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KPf- Z^js

i

WORKS

CAVENDISH SOCIETY.

FOUNDED 1846.

HAND-BOOK

07

CHEMISTRY.

BT

LEOPOLD GMELIN.

VOL. XIV.

ORGANIC CHEMISTRY,

VOL. VIII.

OBOAinc ooHFOfnaa containikg twenty and tw£nt¥-two atoms of ca&bon

TRANSLATED BT

HENRY WATTS, B.A., F.C.S.

O LONDON: PRINTED FOR THE CAVENDISH SOCIETY.

HDCOOUC.

KPE Z^J^

/»^9 ,'f '^' /O,

LONDON:

FBINTED BT HARRISON AND SONS,

BT. martin's lane, W.O.

CONTENTS OF VOL. XIV.

(VOL. VIII. OF ORGANIC CHEMISTRY.)

COMPOUNDS CONTAINING 20 AT. CARBON.

Naphihalm Serie*,

Pag©

Naphthalin, C^H^ .... .... .... .... .... .... 1

Fonnfttion .... .... .... .... ... .... 2

A FfipftTBuOIl .... .... .... ...a .... .... «S

Panfic&tiOD .... .... .... .... .... .... 5

A EwPCrQCo ...« .••« .... .... .... .... 9

DccompotitiODS .... .... .... .... •••> 7

Combiiuitioiis .... ..m .... .... .... .... 9

Metaaaphthalin, C^H^ .... .... .... .... .... 10

Bodies isomeric with Naphthalin, and obtained by the dry distillation of Bensoatet:

a. Hydrocarbon, C^'H^ melting at 92° .... .... .... 11

b» Hydrocarbon, C^H^ melting at 65° .... .... .... 12

Cotyttffaied Oon^xmndt qfihe Nwleui C^H^

Snlpbonapbthalic add, C*^">2SO' (see also page 606) .... .... .... 13

Solphonaphthalates, C^H^,2S0* .... .... .... 16

Add of Faraday's Smouldering Baryta-salt, C>(>H7Ba,2SO* .... .... 20

Bisnlphonaphtbalic add, C^H^4SO> .... .... .... .... 21

Bisnlphonaphthalates, C*H7M,4SO> .... .... .... .... 22

Hyposttlphoglntic add .... .... .... .... .... 23

Ni^bthalase, C^H'O .... .... .... ••.. •••* •••• 25

Tl

CONTENTS.

Ozjfffen-nucleua C*H*0*.

Naphthulmin, C»H«0* = C»H«0*,02 ?

VaDiUin, C»H»CH = C»H«0',02 ?

Naphthesic add, C»H«08 « (^"H*^,©* ?

Sulphi-nucleus C^H7(S0>).

Salphonaphthalin, C»H7 (SO^

Appendix: SalphonaphthaUde, CS^H^o (S<>>) ? ....

Page

26 26 27

28 29

Bromine^nueleut C^BrH'.

Bromonaphthalin, C^rH' Bromosnlphonaphthalic acid» C»BrH7,2SO* Bromosulphonaphthalates, C303rH*M,2SO*

Bibromonaphthalin, C^Bi^H* BibromoralphoD^phthalic acid, ClBr^H*,2S0*

Bromine-nueleui C^Br'H*.

Terbromonaphthalini C^'Br'H'

Appendix: Bronaphthin, C»H»-»Br3*« ? ...%

Laurent's first Bromide of Bronapbthin, C>(>H***Br>*'3H LauieDt's second Bromide of Bronapbtbin, C»H*-*Bi^'^Br^

Bromme^nueleui C»Br<H^.

Qnadribromonapbtbalin, C^Br*H^

Hjdrobromate of Quadribromonapbthalin, (PBr^H^,HBr ..^

Bibjdrobromate of Qoadribromonapbtbalin, C»Br*H^2HBr

Brwrnne-nueleui C'^i'HS. Bibjdrobromate of Pentabromonapbtblin, C^r<H>,2HBr

31 31

32 33

33 34 34 35

35 36 37

37

CMoHne-nucUus C»C1H'.

Cbloronapbtbalin, C^KHH? .... Cblorosalpbonapbthalic acid, C90(>ih7,2SO* Hjdrocblorate of Cbloronapbtbalin, C^1H^HC1

38 38 39

Chlonne-nucleus C?»CPH«.

Bicbloronapbtbalin, C^Ol^H* Bicblorosnlpbonapbtbalic acid, C^Cl^B^,2SO^ .... Bibydrocblorate of Bicbloronapbtbalin, Oa>^l>H«,2HCl

41 45 46

CONTENTS- VU

Pago Chlorine'-nucieus C^CPH*.

Terchloronaphthalin, C^H^l'H' .... .... .... .... 49

Tcrohlorosulphonaphthalic acid, C»a'H*,2S0' .... .... .... 54

Hydrochlorate of Terchloronaphthalin, C^Cras^UCl .... .... 55

BihydrochlozBte of Terchloronaphthalin, C"^PU*,2HC1 .... .... 56

Appendix: Laorenf 8 Chlonir« de Chlonaphthane, G^V*<H7*s,Cl« 57 Laurent's Chloride of Naphthalin and Chlonaphtheiey CP^WKV^ .... 58

CMonne-nucleua C»a«H^

Quadrichloronaphthalm, C^Cl^H^ .... .... .... .... 59

Chloronaphtone F., C»H*»Cl8-» .... .... .... .... 61

Qnadrichlorosnlphonaphthalic acid, C»C1<HS2S0' .... .... 62

Bihydrochlorate of Qoadrichloronaphthalin^ C^Cl^aS2HCl .... .... 62

CAlorine^nucleui C»a«H«.

Sexchloronaphthalin, C^Cl^H^ .... .... .... .... 63

Chlonaphthalane A., C»C1»«H2-* .... .... .... .... 64

Chlorine-nucleus C^CR

Perchloronaphthalin, C^l^ .... .... .... .... .... 64

Oxyclorine-nucleus C»C1H»0*.

Chloronaphthalic acid, C"^1H»C)3,0» .... .... .... 68

Appendix :

1 . Peculiar add obtained from Bihy drochlorate of Terchloronaphthalin

by the action of Nitric acid .... .... .... .... 67

2. Oxychloronaphthalenose, C"H%1H)>? .... .... .... 68

Oxyeklorine-nudetu C^l^B^O^.

Chloride of Chloroxynaphthalin, C^Q'H^O^ = C^PH<0»,0» .... 68

Oxyehlorine-nucleui CP^Cl'HO^.

Perchloronaphthalic acid« C^l^HO^.O^ .... .... .... .... 69

OxycMorine-nueleus C^CW.

Chloride of Perchloroxynaphthalin, 0»C1«0»,02.... .... .... 70

Brtmoehlortne-nucleM C^BrClH^

Hydrochlorate of Chlorobromonaphthalin, C»BrClH«,HCl .... .... 71

Bihydrochlorate of Bromochloronaphthalin, C"BrClH>,2HCl .... 72

BromocMorine-nueleui C^Bra>H*.

Bromobichloronaphthalin, C^BrCl^H* .... .... .... .... 72

Appendix : Laurent's Chlorebronaphtine, C^H^-^Br^^Cl^ .... 73

nil

CONTENTS,

Bromochlorine^nueleut C»Br*ClH*. Bihydrobromate of TerbromochloroDaphthalin^ C?°BrH:;iH^,2HBr

BromocMorine-nueleua C^Br'CPH^.

Bibromobichloronaphthaliii, C'Bi^Cl'H^

Bibydrobromate of Bibromobicbloronapbthalin, C>^Br>Cl*HS2HBr

Blhydrochlorate of BibromobichloronaphthaliD, C»Br%l'H«,2H01 ....

Appendix :

1. Laurent's Bromare de Chlor^ronapbtine, C*lI***Bi^''CP ?

2. Laurent's Bromide a. — 3 Laurent's Bromide /3

3. Laurent's Radical 6 - C»H»BrCP or C»H<BiaCP ....

5. Laurent's Chlorenbronaphtone B, C»H*-*BrK!P-»....

6. Laurent's BromencUonapbtose A, C"H<Bri**CP**

Bromochlorine-nueleut C>^BrGlsH^

Bromotercbloronapbthalin, C^BrCl'H^

Laurent's Bromanchlonapbtone A, C^H^'^Bi^-Hn^ ....

Bromochlorine-nucleui C»BtK;i'H*.

Bibromoterchloronapbthalin, C^BrK^U* ....

Blhydrochlorate of Bibromoterchloronaphthalin, C*i'Br>a'H>«2HCL... Appendix : Laurent's Bromochlomaphtune B., C"'firCl'*'H'*^

NUro-nucleui C*^XW.

Nitronaphthalm, C»NHW =* C^W Nitrosulphonaphthalic add, C90XH7,2SO* ....

mtro-nucletu C»X2H«.

Binitronaphthalin, C»H«NH)» - C»X«H«

BinitrosulphonaphthaUc acid, C*X'H^2S0*

Niiro-nueleus C»X*H«.

Tcmitronaphtbalin, C»N»H»0» -C»X>H»

4|i|7eiuftjrf Nitronaphthaleise, C»X3**H*-<

Bromonitro-nueleus C^'BrX^H*. BromobinitronaphthaUn, 0»H»BrN20« - C»BrX«H» ....

Azo-nucletu C*NH'.

Naphthylamine, C»NH» « C»NH7,H« ....

Phosphate and Metaphosphate of Naphthylamine Sulphate of NaphthyUmine, C^NH',HO,SOS .... Hydrobromate, C^^H^HBr. — Hydrochlorate, C^^H*,Ha..

Page 73

74 76 76

76

77 77 77 78

78 79

80 81 82

82 84

86 87

88 91

92

93 98 99 99

CONTENTS. IX

Page

Nitrate, Chloromercarate, and Chloroplatinate of Naphthylamine .... 100

Oxalate : Neutral 2(C»NH9),C*H90» 100

„ Acid, C»NH«,C<H20> 101

Appendue to Naphthylamine :

Oxynaphthylaminc, C»NH»0» = C»NH7,2H0 ? 101

Lepidme, C»NH» - C«^H7,H' .... .... .... .... 103

Hydrocfalorate of Lepidine, C»NH',HC1. — Nitrate, C»NBP,HO,NO«. — Bichromate, C»NH»,HO,2CrO». —

Chloroplatinate, C»NH^HCl,Pta' .... .... 104

Aio-nOrotiMiucleua C»N(NO>}H«?

Nitroronaphthalin, C»H«N«02 - C»N(NO»)H«.H« 105

Ninaphthylamine, C»H8N»0» « C»N(NO*)H«,H« ? 106

Amidazo^nueieus C'NAdH*.

Seminaphthylamine, C^WRW « C»NAdH«,H» 107

Phofphate. — Snlphate, C^WH" 2HO,2SO* .... .... 108

Hydrochlorate, C»NSH">,2HC1. — Chloroplatinate, C^N^H^ 2Ha,

2PtCl'. — Oxalate.... .... .... .... .... 109

Ctn^ugated confounds qf C^NH?, or qfnmUar nuelH,

Snlphonaphthylamic acid, C*>NH9,2SOS .... .... .... 109

Naphthionic add, C3(^H^2SOS .... .... .... .... .... 110

PotB8sium.8alt, C"NH«KSK>« .... .... .... .... 112

Ammoninm-salt — Sodinm-ialt, C^'NH^aSK)' + 8Aq. .... 112

Bariam-aalt. -— Caldnm-salt, C^^NIPCaSK)* + 8Aq. — Magnesiam-

salt, C?»NH»MgS«0« with 8Aq. ? and lOAq. 113

Zinc-Balt. — Lead-aalt, C^NH^PhSK^ + 2Aq. — Cuproos-ialt ? 114

SUTcr-salt, C^NH^AgS^O* + 2Aq 114

SilTer-ialt with Ammonia, 2NH>, C»NH«AgS^O« + 2Aq.... 115

Tbionaphthamic add, C^H^S^O* .... .... .... .... .... 115

Ammoninm-aalt — Potasnam-calt, C»NH"KS>0*. — Sodivm-aalt —

Barinm-salt, C»NH8BaS«0« + 3Aq .... .... .... 116

Caldnm, Magnednm, and Leadrsalts .... .... .... .... 117

Thionaphthamate of Lead with Acetate of Lead, C"NH>PbS>0* +

\^ JCX xO\J^ .... .... ..a. (*.. .... JLJL/

Formylnaphthalide, C"IPNO» - C»(C5H)AdH«,0« ? 117

Methyl-lepidine, C«NH" - C«(C»H»)NHMI« 118

Naphthalocyanic add, C«NH'0» - C»CyH7,0* .... .... .... 118

Naphthaloanlphocyanic acid, C»NHW - C»CyH7,S« .... ^.. 119

Naphthyl-urea, C"NW«0» - C»CyAdH«,HH)« 119

Ethyl-naphthylamlne, C"NH» - C*(C*H«)NH«,H« 120

CONTENTS.

Page

Ethyl-lepidine, CJ»«NH» = C»(Cm»)NH«,Ha 121

ChloroplaUnate, C»NHW,HCl,PtCl* .... .... .... 121

Allyl-naphthyUsulphocarbaiDidc, C«H"N»S« - C»(,C«H»)CyAdHSH«S2 122

Amyl-lepidine, C»NH» « C»(CWH»)NH«,H2 122

Sulphocyanide of PhenyUnaphthylamine,

CMH"N«S» = C»(C»2H»)CyAdHs,H«S2 123

Conjugated Compounds containing 2AtC^NH7.

Carbonaphthalide, C^HWN^O^ = C«CyNH",HW 123

SulphocarboDaphthalide, C^H^N^S* = C«CyNH",H«S3 124

Mcnaphthylaminc, C«H»7N» = C«CyNAdH«,H2 125

Phosphate — Sulphate — Hydriodate — Hydrobromate — Hydro- chlorate, O^Hi^N'.HCl. — Nitrate .... .... .... 126

Chloroplatinate, C2*Hi7N',HCI,PtCT .... .... .... 127

Bicyanomenaphthylamine, C^HW* « C«Cy»Ad8H",H3 127

Oxaaaphthalide, C^H«N^O< = C«(C<H02)NAdH«,08 128

Menaphthoximide, C^H^NW = (^0(C*HO3)CyNAdHi2,O2 ? .... 128

Tcmaphthylphospbamide, C«H«*N»PO* = C»N3(P03)HW H«(?) .... 129

Primary-nueleut C»HiOj Ojyy«i-ntte/«w C»H«0*.

AlUarin, C"H«C)« = C»H«0*,02 ... .... .... ..„ 129

Sources. —■ Formation .... ... .... .... .... 130

Fkeparation, A. From Madder .... .... .... .... 133

B. From Rubian. 1. By boiling with acids .... .... 133

2. By boiling with Alkalis .... .... .... .... 134

3. By Fermentation .... .... .... .... 135

Preparation of Higgin's Xanthin .... .... .... 136

Properties of Alizarin .... .... .... .... .... 136

Decompositions «... .... .... •••. •'•• .... lo/

Hydrate of Alizarin .... .... .... .... 138

Compounds of Alizarin with Metallic Oxides .... .... .... 139

Primary nueUua C»H^.

Paranicene, C*H" .... .... .... .— .... 1^2

Cuminic alcohol, C»H»W = C»H",HW.... 143

Cuminol. C»H«,02 .... .... .... .... .... 144

Cuminol-potassinm .... .■•• •••• —• •••• l^'

Compounds of Cuminol with Alkaline Bisulphites .... .... 147

Cuminic acid, C^^H",©* .... .... .... —• •••• ^^^

Cuminates, C»H"MO* .... .... .... .... . •• 150

Ozycuminic acid, O^H^^O* .... .... •'.» .••■ •••• 1^1

Silver-salt, C»H"AgO« .... .... .... •• 152

Chlorocumol, C"H^CP .... .... •..• ■••• • •• 1^2

GOIiTENTS. xi

Page Cot^fuffated Compounds qfthe Primary Nucleus C^IF'.

Acetate of Cumoglycol, C^WH)» « 2C4H80»,C»Hi»02 X53

Benzoate of Cnmoglycol, C*»WHy « 2C'<H«0»,C»H«0« 154

Camyl.C«Hao« - CmH"(C«'H"02)02 154

Cuminate of Etbyl, C**HP«04 = C*H«0,C»H"0» 155

Acetocuminic Anhydride, C^H^O* = C^H>02,C»H"0» 156

Cuminate of Phenyl, C^WH>* = C»H«0,C»H»08 157

Benxocuminic Anhydride, C«H"0« « C"H«0»,C»H"O» ..,. 157

Cumosalicyl, C«H»H)« = C"H»08,C»H"0S 158

Cuminate of Methyl-saUcyl, C»HW08 = C2H»0.C»H»0S,C"H*01... 159

Ocnantho-cuminic Anhydride, C«H«0« = CWHW08,C»H»0» .... 159

Cuminic Anhydride, C«HaO« «C»H»iOS,C»H»W 159

Cuminuric add, C«NH«0» = C"Adff»0»,0* 160

Oxygen-nucleus QP^W^^,

Sassafraa-camphor, C»HW02,0' 161

Appendix: Oil of Sassafras .... .... .... .... .... 161

Oxygen-nucleut C»H*0.

Pjrroxanthin, C»H80< ? 163

Appendix: Pyroxanthogen .... .... ..,. .... .... 164

Bromine^nucleua C^OBrH".

Bromocominol, C»BrH",0».... .... .... .... .... 165

CMorine^micleui C^CIH".

Chloride of Cumyl,C»ClH»,0« 165

Chlorocuminol, C»C1H", 02 166

Chlorme-nucleui C^CPH^.

CUoronicene, C»CPHM 167

OxybronUne-nueleut C^Br^IPO',

Brom-aasMfras ofl, C»Bi«H20»,0s 168

Oxychlorine-nuekut C^Cl'HO*.

Chlor-sassafras oiJ, C»CPH0»,02 169

mtro-nucleua C»XH".

Nitroparanicenc, C»NH"0< = C»XH»i I69

Nitrocuminic acid, C»NH"0« = C»XH»,0* 170

Binitrocuminic acid, C»N2HW0» « C»X2H^o,0< 171

Binitrocuminate of Ethyl, C«N«H"0>3 « C*H»0,C»X*H90»; 172

XU CONTENTS.

Page Niirochlonne^nuoleui C^X^CISH".

Nitrochloronicene, C»N3C1«H808 = C^X^CPH* 172

Amidogenriiueleus, C^AdH".

Cuminamide, C»NH»0» - C»AdH",0» 173

Amidocaminic add, C»NH"0< = C»AdH",0* 174

Sulphate of Amidocummic acid, C»NHiH)^,HO,SO>. — Hj- drochlorate, (T^H^HD^^HCl. — Nitrate. ^ CUoroplatinate^

0»NH"O<,HCl,PtCP 175

Amidocuminate of Ethyl, C^NH^CH - C*H»0,C»AdHWO» 176

Amidogtn-nueleui (?°A.d?U^. Biamidocuminic add, C»N»H»H)< = C»Ad»HM»,0* 176

Conjugated Amide* qfthe Cfumnie Seriei.

CumaniUde, C«NH»708 =» C*(NH,CmH«)H»0« 177

Cumyl-sulphpohenyUmide, C»NH»7S«0« = C»(NH,C»H»0»)H»S>0* .... 177 Camyl-salphophenyl-argentamide,

C«NHMHgS«0« « CM(N.Ag.C»H»0»)H«S»0* 178

Ciimyl-sulphophenyl-argent-hydrobiamide,

C»N«Hi9S«0« - C«(N.Ag.0»H"O»)H»S»CH + NH» 178

Cnmyl-benxoyl-solphophenylamide,

C«NH«S?08 - C'«(N.C?»H"0«.C"H»0>)H»S«CH 179

Cumyl-saUcylamide, C«NHVO« = C»(N.CWH«0<)H"0«? 179

Aio-nucleui C*WH".

Oumonitrile, C*NH" .... .... .... .... .... .... 180

Paranidne, C»NH» - C»NH",H« .... .... .... .... 181

ChlorazO'amidoffen.nueleu8 C^Cl'NAdH'. Cailoronidnc, 0»N«CPH» - C»Cl«NAdH»,lP 182

Primary''fiiueieut C**H".

CyncDe, C^H'^ .... .... .... .... .... .... 183

Appendiuc : a-Cyinene .... .... .... .... .... 186

Caryophyllin, C»Hi«0» - C*»H",2H0 187

Cm^aied Compoundi qfthe Nueletu C^H^^.

Solpbocymenic add, C»H"S«0« - C»H",2S0» 188

Soda-ialt, C»H"NaS»0« + 5Aq 189

Baryta-sail, C»Hi*BaSSO< •»- 2, 3, and 4Aq .... .... .... 190

lime-salt, C»Hi»CaS»0« + 4Aq.... .... .... .... 191

Copper and Silyer-salta .... .... .... .... .... 191

• ••

CONTENTS. Xlll

Page Oayffen-nucleus C^H^O'.

Anethol or Ajiiae-camphor, (J^WH^ .... .... .... .... 191

Appendis to anethol:

Oils almost wholly composed of Anethol :

wii 01 Aiuse •••• (••• .... ...• .... .... X90

Oil of Fennel .... .... .... .... .... 196

Oils of Star-anise and Tarragon .... .... .... .... 197

Anisoin, C»H^O* .... .... .... .... .... .... 197

Metanethol- camphor .... .... .... .... .... .... 199

Metanethol .... .... .... .... .... .... 199

SulphometenetHc add, C»H»S«0» - Q^W^Cfi,2^Cfi 200

Eugenin, C»H»20«,02 .... .... .... .... .... 200

Eugenic acid, C»HMO< = C»HK0«,02? 201

Eugenstcs, C»H"MO< and C»H»M0SC»H»«0* 202

Eugenate of Ammonia. C»(NH*)H"0^ .... .... .... 204

Engenate of Potash ; acid ? C»H»KO*,C»H»aO< 205

Engenate of Soda, C»H"NaO^. — Eugenate of Baryta, C»H"Ba0< 205

Eugenates of Strontia, Lime, Magnesia, Lead, Iron, and Copper .... 206

Appendix to Eugenie acid :

1. PyroUviUc acid, C^OR^O* = CP^WW + Aq (?) 206

Lead-salt, C^H»K>*,2PbO 207

2. Carmnfellic acid .... .... .... .... .... 208

3. Volatile Oils containing Eugenic acid :

a. OilofCloyes .... .... .... .... .... 209

h. Oil of Cinnamon-leares from Ceylon, — c. Oil of Pimento. — > d. Volatile Oil of Brazilian Clove^n-

namon. — e. Oil of Canella alba .... .... 210

Eugenate of Ethyl, C?*B}K^ « C<H«0,0»H"0« 211

Bcnzoeugenic Anhydride. C"H«0»,C«H»0» .... 211

Toluo-eugenic Anhydride, Ci«H70»,C»H"0» 212

Aniso-eugenic Anhydride, C"H70«,0»H"0» 213

Cumino-eugenic Anhydride, C»H"0«,C»H"0» 213

Bromine-nueleue C^'^BrH'',

Hydrobromate of Bromocymene, C20BrH",HBr (?) .... ... 214

Chlorine^nucleus C»C1H".

HydrochlorateofChlorocymene, C»C1H'»,HC1(?) .... .... .... 214

Oxyhromine-nueleue C*^Br*H>0'.

Terbromancthol or Bromani8ol,^C«'Bi^H»0^ .... .... 215

XIV CONTENTS.

Page

Osyehhriiie^nueleut CS^CPH^O'.

Terehloranethol or ChloraniBol, CCPH^O^ .... .... .... 219

Appendix: Chloride of Draconyl, C^CI^ITK)* (?) 216

Nitrocymene,C?*Nir»CH - C»XH» .... .... .... .... 216

NUro-nueUu* VJSm^.

BinUrocymene, C^HMN^O* - C»X«H» 217

Oxynitro-nucUui C^X'HWO*.

Binitraniioin, C»HWNK)W - C«X«HWO« .... 218

Azo-nuchM, C»NH».

Cymidine, C»NH« « C»NH",H* 218

Azo-nucleus C»N»H».

Nicotine, C^N^H" « C»N>HW H« .... -.. 219

Formation and Sources .... .... .... w.. 220

Jrrepftrsuon .... .... .... ...• •••• .... »«i

Estimation of Nicotine in Tobacco .... .„. .... 223

Decompositions .... .... .... .... .... 224

Hydrated Nicotine — Aqueous Nicotine .... .... .... 226

Phosphate of Nicotine — Sulphate, C»N'HM,H0,S0». — Add lodate — Hydrochlorate, C^N^RW.HCl. — Nitrate — Double

salts of the Hydrochlorate .... .... .... .... 227

Nicotine with Mercuric Iodide, C»N«H",2H|rI 228

Nicotine with Mercuric Chloride, C««N«H",2HgCl A C«N«H",6Hga 228

Chloromercuratc of Nicotine, C»N*H»,HCl,ttga .... .... 229

Nicotine with Mercuric Chloride and Cyanide :

CWN'H" 4HgCl,2HgCy (?) 229

Nicotine with Nitrate of Silver :

2C»N2HW NO«Ag and C»N2H",N0«Ag 229

Chloroplatinite of Nicotine :

C»N»H",2HCl,2l»tCl and C«N2H",4HCl,PtCl 230

ChloropUtinate of Nicotine, C»N2H».2HCl,2PtCP 231

Acetate of Nicotine — Oxalate of Nicotine .... .... .... 231

Tartrate and Purpurate of Nicotine .... .... .... 232.

Appendix to Nicotine i

a, Nicotianine or Tobacco -camphor .... .... .... .... 232

h, Empyreumatic oil of Tobacco.... .... .... .... 234

Methyl-nicotine, C^NH' « CM>(C«H»)NH*.H« 235

Hydriodate,C»NH»,HI. — Chloromercurate, C«NH«,HCl,4HgCl.

— Chloroaurate, C»NH»,HCl,AuCl« .... 235

CONTENTS. XV

Page

Chloroplatinate of Methyl-nicotine, C»NH^,Ha,PtCls .... .... 236

Ethyl-nicotine, Ci*NH" = CW(C<H5)NH*,H» 236

Hydriodate, C"NH",HI.—Hydrobromate—Hydrochlorate— Nitrate

— Chloromercarate, C»^NH",HCl,3HgCl .... .... .... 237

Chloroaurate, C?<NH",HCl,A.uCl». — Chloroplatinate, C"NH",HC1,

X^v\^X •••« •••• •••• •••• #••• •••■ ^OO

Amylnicotine, C»NHi7 = C«>(CWH")NH*,H« 238

Primary Nuelew C»H".

Oil of Turpentine, C»H^* .... .... .... .... .... 239

oOurocB .... ...• .... .... .... .... •••. w4v

Extraction and Purification .... .... .... .... 241

Modifications : French, English, German, TempHn-oil, Venetian .... 242

ITTw &/Cr Vies •••# ■••• •••■ *■•• •••■ ••«• m4^

Decompositions .... .... .... .... .... .... 245

Interpolation — Terebcntic acid, CWH»0»o (.') .... .... 255

Compoundg qf Oil qf Turpentine.

V^ith Oxygen :

Hydratcd oxide, C»HW02,2HO 256

Ozonised Oil of Turpentine (see algo page 608) .... ^ .... 256

With Water :

Turpentinecamphor, C^H^O-* « C»H»6,4HO .... .... .... 258

The so-called Liquid Turpentine-camphor, C^^HWOS ^ C»H",2HO 263

Tcrpinol, C»H»«,HO or C«H»,2HO 264

With Hydrochloric Acid :

Monohydrochlorate : Artificial Camphor, C«>H",HC1 .... 265

Bihydrochlorate, C-*H»8,2HC1 .... .... .... .... 268

With Hydrobromic acid, C»H»8,HBr .... .... .... .... 269

With Hydriodic acid, C^^H^, HI .... .... .... .... .... 269

Solutions of other bodies in* Oil of Turpentine .... .... .... 270

Solutions of Oil of Turpentine in Alcohol, Acetone, Wood -spirit, &c 271

OILS ISOMERIC WITH OIL OF TURPENTINE. A. Products of the trantformatixm qf the Oil qf Turpentine :

1. Camphene. — 2. Isoterebentiiene .... .... ,..., 271

3. Metaterebenthene .... .... .... .... .... 272

4a X 6i cUVUlS •••■ •••• ■■•■ •■•• •«•• •••• a/O

Hydrochlorate of Terebene, 2C»H",HC1 and C»HW,Ha .... 274 Hydrochlorate of Terebene with Bihydrochlorate of Turpentine- oil, C»H»«.2HC1 + 2(C»H«.HC1) 275

Hydrobromates of Terebene, 2C»H«,HBr and C«H»«,HBr .... 276

Hydriodates of Terebene, 2C«HW,Hl and C^H" HI .... 276

XVI

CONTENTS.

••<•

SiUphotcrcbkj acid, C»HWS»0« (?) 5* Cunphileoo ..•• •••• ••••

Colophene, C^H^

Colopbene from Camphor ....

6* TorcDiIooo ..•• •••• •••• ••*<

B. Natural OiU^ or others related to them:

1. Oil of Bergamot

Hydrated Oil of Bergamot, C»H»0* Hydrochlorate

2. Carvene

Hydrochlorate, C»H»»,2HC1 Chlorocarvcne, C»«H»3Cl*(?)

3. Indifferent Oil of Clovei.

4* Oil of Copaiba. .... •••• •••• ••••

Hydrochlorate, C»Hi«,2HCl Hydrochlorate of Copahilene

5. Para-copaiba Oil

6. Oil of Clemi .... •••• •••• •••■

Hydrochlorate. C^H", 2HCI

Liquid Hydrochlorate .... .... ••••

7. Gaultherylene .... .... •«•

8* Oil of Gomart •... .... .... ••••

Hydrochlorate, C»HW,2HC1 9. Oil of Hopi ....

10. Oil of Juniper-berries

Hydrochlorate, C»H«,HC1 + C^HS.HCl Juniper*camphor .... •••• •••*

11. Laurel Oil of Guiana

Hydrate : Laurel-turpentine-camphor, C»H»0*

12. Oil of Lemon .... •..• •••• ••••

Hydrate,C»H»0*

Hydrochloratee, C»HW,Ha and C«H",2HC1 ....

I^emon-camphor .... .... •••• ••••

13. Citrene .... .... •••• ••••

14. Citrilene .... .... •••• •••• ••••

15. Oil of Lime .... ...« •••• ••**

16. Oil of Mandarin .... ....

Bihydrochlorate .... ,%»•

17. Oil of Orange-peel ....

Hydrocliloratea, C»Hi«,HCl and O^H" 2HC1

18. Oil of China Orange

19. Oil of Parsley ....

20. Oil of Pepper

21. Pepper-oil from Long Pepper

22. Oil of Peucedanum Oreoeelmum

23. Hydrocarbon from Oil of Roman Chamomile

••■•	Page 277
	277
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• •••	280
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••••	284
	285
■ •■•	285
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• •••	287
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*•••	288
	289
«••«	290
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• ••«	290
	291
•«••	29
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■ •••	292
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■ ■••	295
	296
«•••	296
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»•••	300
	300
	301
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«•••	304
	304
• •••	305
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•••	306
	306
• ••«	307
	307
• •••	308
	308
• •••	309

CONTENTS. XVli

Page 84. Oilof SaTin .... .... .... .... .... 310

■SO. A oyiiidiO .••• ...I .li. .... .!•• *•.. oix

3C0. AOicue .... .... •••• ...a ••• .... oiw

27, Valerene or Bomeene .... .... ... .... .... 312

A. Valerene from OU Valerian .... .... .... 313

B. Boraeoie from the Camphor-oil of Dryabalanops Camphor 313 C Madder-bomeene from Madder Toael-oil ... m.. 314

Appendix to Valerian : Crude Oil of Valerian .... .... .... 314

28. Xantfaozylene .... .... .... .... .... 315

Ajqtendix to OiU leomerie wiih Oil qf Iktrpentine.

Oil of Wormseed .... „.. .... .... .... .... 816

Cinsphane, C»H* ..„ .,„ .„. .... .... .... 318

Cintephone^ C^H^.... mm .... .... .«.. .... 319

Cuuebeney 0**H" .... .... .... .... .... .m* 319

Hydnted Cinnbene, C»H»0*. — Hydriodate, 2C?^B}^,m .... 320

Cyncne, C»H" .... .... .... ..„ .... «.. 320

Cinwphenc, C»H« or C«H* .... 321

Cinacrol, C«H"0" ..^ .„. .... .... .... .... 322

C. Volatile Empyrewmatic Oils.

\jmX Oi Amoer .... ..«• •*«. ,,., ..,« ....

Empyrenmatic Oil of Birdi

waomcniTi .... ..•. i..« .... .... ....

Hydrochlorate, C^^H^'^HCL — Hydrobromate and Hydriodate

Affpendis to Caoutchim

1* Chlorocaoutchin ..m .««. •.•« .... ..••

2* laoprenOy C^ H' *... ..•• .... ....

v/xioey \j oL \j ..•• .... .... ...« ...I

Borneo^ or Bomeol^aloohol, C»H»OS » C»HM,2H0

Compounde Isomeric with Bomeol.

1. Laero-rotatory BomeoL — 2. Oil of Cajeput

3. Oil of Coriander

4. Oil of Osmitopsifl .... •... .... ..«•

Camphor, 0»HWO> - C»HM,0»

Appendix to Camphor :

1. lodo-camphor .... .... .... .... ....

2. Bromide of Camphor .... .... .... ....

8. Qnadrochloro-camphor, C^H^^Cl^O^ ....

4. Sexchloro-camphor^ C»H«>aH)« ....

Compounds Isomeric with Camphor :

1. Lero- camphor. •— 2. Non-rotatory-eamphor. — 3. Oil of Worm-

WOOO ...a .... .... .... .... .... VvV

VOL. XIV. h

	323
....	324
	326
....	329
	330
*..«	331
	331
....	332
	334
....	336
	387
M..	338
	347
....	348
	349
.«*.	349

• ••

XYm G0HTXNT8.

Page

4. Volatile Oil of Ptt/e^'ttmHteroN/Aiim .... .... .... ^52

5. Oil of Pennyroyal .... .... .... .... •».. 852

Camphic acid C*H>*,0* .... .... .... .... .... 853

Hydrochlorate of Borneol, C^ir*,HCl .... .... .... 853

Benxoate of Bomcol, CWH«0* - C"H»0«,C»HWO

Appendix to Bomeene : Oil of DryabaUmop§ Oampkora .-. .... 355

Volatile oil of Xaunw OarmjiAorA.... .... .... .... 356

Appendix to the Primary'^meleui C^H^.

Oil of Acacia. — Volatite oil (Aeiiie de amaeejf) .... .... .... 356

Volatile oil of Acorns. — Alyxia-camphor. — Oil of Angelica. — Oil of

AngoBtora .... .... .... .... .... .... 357

Oil of Anim^. — Oil of Ants. — Oil of Arnica .... «... .... 358

Oil of Asarum.— Oil of Balm.— Basil-camplior, C^WKi^ « C»HiS6H0 ? 359

Oil of Bay .... .... .... .... ,,., m*. 360

Volatile Oil of Beans. — Oil of Birch-leayes .... .... .... 361

Volatile Oil of Botany Bay resin. — Camphor of BuphiMmum fmarUwium.

— Oil of Cardamom. — Oil of Carrot .... .... ..«• 362

Oil of Cascarilla. — Oil of Convolvulue eeopariue .... .... .... 363

Oil of Cnlilawan. — Oil of CaAtoroan. *- Camphor of Cat-thyme. — Oil

01 v/eiery .... .... .... ,,,. .,,. m.^ «>d«

Oil of Wild Chamomile.... .... .... ...« ,^ mm. 365

Oil of Chenopodium ambronoldee. — Oil of Coffee .... .... 366

Oil of Curcuma. — Oil of Curcuma Zerubet. — Oil of Dahlia ...• -.. 367

East Indian Grass Oil. — Oil of Elder-flower .... .... .... 868

Oil of Feyerfew. — Oil of Galanga. — • Oil of Gale .... .... .... 369

Oil of Oeum urbanum, — Oil of Ginger .... .... .... 870

Oil of Hedwigia. — VoUtile Oil of Hemp. — Oa of Hyssop 371

Camphor of /myform/tna. — Jasmin-camphor .... .... .... 372

Oilof Jonquil. — Volatile Oil of Lan9on Balsam .... .... .... 373

Oil of Layender .... .... „.. .... ..., ,.., 374

Ledum-camphor. — Oil of Lilac.... .... .... .... .... 877

Camphor of LUy of the Valley. •— OU of Lmie^wer. ...* ..... 878

Oil of Marjoram. — Maijoram-camphor .... .... ..... .... 379

OilofMasBoy .... .... .... .... ^, .^ 380

Oil of Masterwort .... .... .... ..„ .... .... 381

Oil of Matico. — Neutral Oil of Meadow-sweet .... .... .... 382

OU of Mecca Balsam. — Volatile Oil of MentAa viridie, — Oil of Mereu-

rialia anmui, — Oil of Mignonette .... .... .... 383

Oil of Millefoil. — Oil of Noble MiUefoU 384

Oil of Mugwort — Oil of Myrtle. — Oil of ITasturtium .... .... 385

OU of NeroU .... .... .... .... .... .... .... 386

Neroli-camphor .... .... .... ..., ,^ .^. 337

OilofNigdla.... .... .... ..„ .... .^ .... 388

Oil of Nutmeg.— Nutmeg-camphor .... .... .... .... 389

CONTBNTS. XIX

Page

Oil of Nutmeg-flower (mace).— Oil of Olibttitttt' ..m .... .... 390'

Oii of Ong^mnt-^Oitt^Parmeliaparietina .».. .... 391

Oil of Pelargonium. — Oil of PimpineUa. — Oil of Poplar-buds .«.; .:.. 392

Raspberry-CBinphor.—' *Otl of Roae .^m ..^ .4.. 393

Rose^camphor .... .... .... .... ..« ..«• 894

Oil of Roaemary .... .... .... .... .... .... 325

Oil of oaffron.... .... «... .... ,,.. .... .... 39/

C/ii 01 Sage •..«• ..<* ...k ..M' ...• .... ovo

Sage^camphor .... .... .... •«• .... .... 399

Oil of Sweet Sedge .... .«. .... .... .... 400

OU of Serpentaria. — Oil of Squill. — Oil of Sjringa. — Volatile Oil of

Tagetea gUmdul09a .... .... .... ..« .... 401

Oil of Tanay.— Oil of Tea .... .... .... .... .... 402

Oil of Wild Thyme.— Oil of Vitiveria .... .... .... .... 403

Oil of Fine-leftTed Water-drop.— Oil of Water Horehound .... 404

Second Appendix,

Ferment-oils of ChmrophyUum syhestre, Chelidonirtm mqfiu, Oonium

maculatum, Brythraa Centaurium, Echium vulgare .... .... 405

Fouent-oils of Erica mUgaria^ Tuaailago farffsta^ M»mJkwm vulgarep

Achillea Mill^lium .... .... .... .... .... 406

Ferment-oils of various species of Phmtago ; of Qtc^rctw Bjohver, Sali4f

peniandra. Salvia pratensiSf TYifbHumflbrinufA .... .... 407

Fement-oils of Urtiea urene, Vitie vinifera, diseased Apples (iisloS/e) 408

Thymol, C»H"0* .... .... .... .... .... .... 409

OU of Myrrh, C*»H"0» 413

Carvol, CaofliK)*.— Caryacrol, C»BP*0» .... ...* .... .... 414

4^«u2i4r ^0 Caroo/ : Crude oil of Caraway .... ..^ 416

Hydrosulphate of Carrol, C»H"0»,H8 417

Appendix: Hydrosulphate of Sulpho-carrol, C^H^^S^.HS .... 418

Sulphothymic acid, C»H»W,280" 419

Sulphacetothymic add, C»H"S?0M = C*H»0>,C»H"0,2S0» .... 420

Oxggen-nueleus O^H^O*.

Quassiin, C»H»0» - C«^WH>*,CP ? 420

Oxygen-nuclmu C^H^K)^.

Opianyl, C*>H>0O8 - C»IP0O«,O3 422

Appendix .- Mechloic acid. — Meoonin-resin .... .... .... 425

Opiansulphurous acid, C»HW08,2SO* ? .... .... .... 426

Opianic acid, C»H»«0«» - C"H»<>0«,0« 427

•Opiittates of Ammonia; Baryta; Lead, C>9H'PbOi«-l-2HO ; and Silrer,

l>*'H AgO** .... ..•• .... .... .Mf .... 429

52

CONTENTS.

Hcmipinic add, C»HM0» - C»HW0»,0<» ^ .... 430

Hemipinates of Ammonia : Potash, C^IPKO"; Lead; and SHrtr,

Appendix to Hemipinie acid : Add pxodaoed by iti deoompodtion,

V/ XI \^ •••• ..•« .... *•.. ...a ,,«( 4vA

Sulphopianic add, C»HW0«,S20» .... .... .... „.. 432

Conjugated Compounde qfthe Optan-eeriee*

Opianate of Ethyl, C»«H"0"> = C*H*0,C»H»0» 43S

Ethyl-hcmipmic acid, C^^HMQ" = C<H«a»,C»H80» 434

OpUmmone, C^H^NO" = C«Hi7AdO",0« 435

Appendix : Xanthopenic add .... .... .... ^^ 436

Teropiammone, C"H»NO» - C«HVAdOW,C»H«»0» .... ^ 436

OxyiodO'Wueleue C^IH'O*. lodopianyl, C^IHW.CP .... .... .,.. .... .... 437

Bromine-nueleue C^Br^H°.

Brominated Oil of Tarpentine, C*^Br*H" .... .... .... .... 437

BnNBoterebcn6> C^BrH*' .... .... .... .m. .**. 438

Oxybromme-nueleue C^BrH^O". Bromopianyl, C'^BrEPO^yO" .... .... .... .... .„. 438

Chhrine'nueleut C^PW^. Bichloroterebene, C^^U** .... .... .... .... .... 439

Chlorine-nucleue C»C1*HU.

Chlorinated OU of Turpentine, C»a4H» .... .... .... ..., 439

Qoadridiloroterebene, C^Cl^H^ .... .... .... .... 440

Oxyckiorine-nneleue C^IHK)*. Chloropianyl, C»aH»0»,0« .^ .... .... .... .... 441

OtyeMortne-nueliue C?^'E}^C3^. Tcrdilorothymol, C»CPH"0* .... .... .... .... 441

O»ychlorine^nueleu$ C'^^H'O*. Qnintochlorothymol, C^Cl^HH)'.... .... .... .... .... 442

OMynHro^nueleui C^XH^O*.

Nitropianyl, C»H«N0m - C»XH«0«,0« 443

4lV«iiJMr; Meconin-hyponitricadd, C^H^O" .... .... 443

CONTENTS.

Osynitro-nueletu OVH^H)*. Binitrothymol, C»HMNH)i» - O^m^O^ 444

0*ynitrO'Wueleu9 QP^^W^C^. Teniltrothymol, C»HUN»Oi< « C»X»H"0^ ..^ 446

Primary Nucleui C»H«.

M6iitfaen6> C/^H^ «... .... •••• .... ••.• •i.^ 445

Hjdrochlorate, C^H^^Cl? .... .... .... .... 446

SduSdiiy IT*!* »..« .... •••• .... .... >•.. 44/

Cunpaiiiy G'li^ .... .... .... .... *•.. *.•• 44o

Jfipendix: CKmphO'reda,C^B}^} .... .... 449

Peppermint-camphor, C»H»0« « t^H^«,2HO .... .... .... 449

Appendix : 1. Crude Oil of Peppermint .... .... .... 451

2. Chlorinated Peppermint-camphor .... ..^ .... 453

CamphoUc acid, U**H",C)* .... .... .... .... .... 453

Ume-salt, C»H»7CaO*,HO .... .... .... .... .... 454

SilTe^salt, C*>H»?AgO* 455

Oxyffen-nueleui C^H^^O*.

Camphoric acid, C"HM08 - C»HmO»,0« 455

Camphoratee of Ammonia, C»HiHNH^)>08 and 3C?0HUO>,4NHS 456 Camphorate of Potash, C^Hi^KH)^. — Camphorate of Soda»

C»H"NaK)8. — Camphorate of Baryta, C»H"BaHy». — Cam-

phonlte of Strontia .... .... .... .... 459

Camphorate of Lime, C^H^HTa^O^ + 16Aq.-- Camphorate of Mag-

nesia, C«>HMMg>08 + 15HO> also + 24HO and + 27HO ;

—also C»H"MgO» .... .... .... .... .... 460

Camphorates of Alnmina, Uranium, Manganese, Zinc, Tin, Lead,

C»HMPb»08, Iron (ferricum), Nickel, and Copper, C»H"CuK)« 461 Mercnroua Camphorate, C^H^^HgK)^. — Basic Ammonio-mercurous

Camphorate. — Mercuric Camphorate, C^H^^HgH)^. — - Basic

Ammonio-mercuric Camphorate .... .... .... 462

Camphorate of Silver, C^^H^^Ag^O^ — Camphorate of Platinum .... 463

Itomerie Modifications qf Camphoric acid :

1. LsTO-camphoric acid. — 2. Paracamphorie add .... .... 463

Methylcamphoric acid, C^W^O^ « C»HW,C»H"0« 463

Camphorate of Ethyl, C»H«08 - 2C<H»0,C»H"0» 464

Ethyl-camphoric acid, C«H»0» - C*H«0»,C»HW0« 465

SUver-salt, C"H»Ag08 455

Chlorinated Camphoric ether, C»H»ci408 « 2C*H»0,C»Hi<0« .... 466

O^gen-nucleui C^H^H><.

Camphoric Anhydride, C^H^^O'yO' .... .... .... m.. 467

CONTENTS.

Pago Osugen-nucleut C^WH)^.

CaAtharidin, CMH«08 «C»H«0«,0»? 469

Appendix : Volatile Acrid Principles of Plants .... .... 471

Picrotoxin, C^ffW = C»H»20«,02 ? 473

Appendix: Brown acid from the Husks of Coocalus-grains, C*^Ii^O^ 477

Oxygen^nucleut C»HiW.

Oenolin^ C»Hi0O8,O» .... .... .... .... .... 478

Rosite. — ^ Pourprito .... .... •••> •••• •••• 460

Chlorine-nucleus C»C1*HW Qnutichloromenthene, C^V'H^ .... .... .... .... 460 '

Otfy-amidogeu^nueleui C^AdH^O^^

Ca»q)lioramic acid, C»NHi70« « C»AiiH"0»,0* ^. 481

Camphoiamates, C^NH^'^MO' .... .... .... .... 482

Ojey-amidoffen-nueleue C^Ad^H^H)^. Camphoramide, C*»N5Hi80< = C»Adair*02,0» 482

(kn^ugaied Amidee qf Camphoric acid,

Camphoranflic add, C»NHaO« « C»(Ci«NH«)H»08,0* ; 48S

Camphoraml, C^H^NO* - C»(C»NH6)HmO* (?) 484

Oa^-azo-nucleus C^NH^^O^* Camphorimide, C^NHWQ* = C»NH"0«,0» 484

Primary nucleus CP^R^,

Capric acid, C*H",0* .... .... .... .... .... .,., 485

Caprates of Ammonia, Soda and Baryta, C^H^BaO* .... 487

Caprates of Strontia, Lime, Magnesia, Lead, Copper and Siivar^

^ 'd- • Agv/^ •... .... .... .... ...a .,,, 4oO

Caprate of Ethyl, C«H«0* = C*H«0,C»HWO» 489

Appendix to Capric Acid :

Oil of Rne .... .... .... .... .... .... 489

Metacaprol, CWfl^O'C?) 493

Ojcysien-nucleue C^W^Q^,

Sebacic add and Tpomaic add, C^W^Cfi = C»HWO»,0» • 493

Sebatcs, 0»HMM209 and C»H»7MOS 497

Sebatcs of Ammonia. — Sebatcs of Potash, C»H"BP08 .... .... 497

Sebate of Soda. — Sebate of Lime, C^WH^tK)^. — Sebate of Lead, C»H»Pb208.— Ferric Sebate.— Cupric Sebate, C»HWCu«08.—

Sebate of SilTcr, C»HWAg»08 498

500

500

CONTENTS. xxm

Page

SebateofMethyl,C«H«0«-2C»Hi»O.C»H»W 499

ScbateofEthyl, C»H«08- 2C*H»0,C»Hi«0« 499

Sebin, C»H»0" = 2C«H70*,C»H»«0«

Nitro-nueleus C»XH>».

Nitrocapric acid, C»NH»0> = C»XHW,0*

AnUdogen-nucletu C*AdH^*. Capramide, C»NH»0» «■ C»AdH'^OS „„ .... .... .... 601

Oxy-nmidogen-nuel^M C^AdH^^QS. Sebsmic add, C»NH"0* = C»Adff'02,0« .... .... .... 601

Oxy-amdogen-nueletu C«Ad»H^«0». Sebcmide, C?»H»N«0* « C»Ad«H»«03,0»..., .... ... .... 503

Anitfoic acid, C»HW0» - C*0H"O»,O< - 603

Aniioates, C^H^^O'' .... .... ...• ..~ .... 604

ADDENDA TO COMPOUNDS CONTAINING 20 AT. CARBON.

Decompodtioii-product of AmaKc acid, C^N^fi>'^» .... .... 505

Solpfaite of Chloronaphthalin, C^H7C1,2S03 .:.. .... .... 505

Sulphonaphthalate of Ethyl, 0»H7(C*H«),2SO» .... .... .... 506

Naphthionamidc, C»NH»820< - C»AdH7,2S03 , 507

Argento-napbthionamide, C^NH^AgS^O^. — Benso-napbthionamide, CWNHMSW « 0»NH8(C"H5O2)SK)*.— Argento-benio-napb-

thionamide, C'0NH7Ag(C"H*O«)S2O* 507

Cumylamine, C»NH« « C»AdH",H« .... .... .... .... 608

Bicamylamme, C«NH27 - C»AdH»(C»Hi»),!P .... .... 508

Tricumylamine, C«>NH» « C*AdH»(C»H«)2,H» 50S

Oxidising properties of Oxygenated Oil of Turpentine .... .;.-. 508

Volatile Oil of dtrut Lumia .... .... .... .... 509

Amber-campbor .... .... .... .... .... .... 510

Oil of Cajepnt .... .... .... .... .... .... 510

Cajpmtme; C^H^' .... .... .... .... .... .... 510

Isocajputene, C«HW — Paracajpotene, C^^H" .... .... 51 1

Hydrates of Cajpntene :

Monobydrate, C»H",HO .... .... .... .... 512

Bibydrate, C»H»«,2HO .... .... .... .... 512

Hcxbydrate, C«>H",6H0 .... .... .... .... 513

Cbloride of Cajpntene, C«»HW,a* .... .... „.. 614

Monobydrocblorate, C^Hl^Ha. — Bibydrocblorate, C^Hi^2HCl .... 514

Bromide, C^H^'fir^ .... .... .... m.« .... 615

Hydriodates, C»HW HI and C»H",HI + HO 515

XXIV CONTENTS.

COMPOUNDS CONTAINING 22 AT. CARBON. ***

Primary nucleut C^H^ ; Oxygen'tiueleui C^H^O^. Gmphitic acid, Cafl^OM - C«H<0»,0* « 517

Azo-nucieui C^H'. Cryptidine, C«NH" - C»NH»,U« ^ 519

Primary nueUms CH" ; Oxygen-nucleui C'HW.

limettic add, C»H«0»" = C»H«0«,0« 619

Oyxyen-nucleut, C^H^^^O^. Rottkrin, C«H»0« - C»H«K)*,0» 620

Prtrnmy nucleut C^"j Oxygen^nueleui C*"H"0*.

Sinapie acid, C«H»OW = C»HiW,0« .... _ .^. 621

Sinapate of Potaah. — Sinapate of Baryta, C«HMBa«0«» .... .... 622

Interpolation : Sincaline, C^WHy « C»NH"0»,H> 623

Co^fuyated Compo%tndt of Sinapie acid.

Binapine, U"ti-*NO" .... .... .... .... .... .... 524

SiUpbatea: Neutrat.-^Acid, C«H»NO» 280»,2HO.— Hydrochlorate.

Nitrate. — Chloroplatinate] .... .... .... .... „., 527

Hydroaulphocyanate, C«H»NO>o,C«NHS« 628

Appendix to Sinapine :

1. Acrid principle of White Mustard .... .... .... .... 528

2. £mcine .... .••• •— *»«. •••. .... 629

Unknotim Primary nucleus C^H**.

Enodic Aldehyde, C«H«0« ^ 53O

Digitaloic add, C»H»0* .... 53O

Appendix:

1. Digitaltn-fat .... .... .... ..,, .... 53X

2. Acrid prindple of Digitalis A. — 3. Acrid prindple of

Digitalis B .... .... .... .... .... 532

4. Digitaloemin .... .... .... .... .... 533

Oscygen-nucleus C»H'«0«. Volatile Oil of Aristolochia Clematitie, C«H«0« (?) 533

COMPOUNDS CONTAINING 20 AT. CABBON.

Naphthalin Smes.

Napbtlialin. C^H'.

Gardrn. (1820.) Thorn. Ann, 15, 74; J. Phys. 90^ 238; Pogg,

7, 104. KiDD. PhU. Tram, 1821 ; Schw. 34, 420 ; Pogg. 7, 104. Urb. PhU. Trans. 1822, 473. Chamberlain. Phil. Ann. 6, 135 ; Pogg. 7, 106. Faraday. PhU. Tmns. 1826, 140; tichw. 47, 335 and 459; absir.

Pogg. 7, 104. Reichenbach. Schw. 61, 175 ; Schw. 68, 233 ; Pogg. 28, 484. Saussurb. N. Gfehl. 4, 69. Fremy. Ann. Chim. Phys. 59, 18.

A. CoNNBL. N. Edinb. PhU. J. 1832, No. 26, 231 ; Schw. 61, 104. BnooKB. Eepert. 38 265. Mansfield. Chem. Soe. Qu, J. 1, 248. Pelletier 8c Walter. Ann. Chim. Phys. 67, 274. LiEBiG & W5HLER. Pogg. 24, 169 ; Berzel. Jahresber, 13, 358. Laurent. Ann. Chim. Phys. 49, 214 ; Pogg. 25, 376 ; absir. Schw. 05^

86 ; Ann. Pharm. 3, 9 ; Ann. Chim. Phys. 52, 275 ; abstr. Ann.

Pharm. 8, 8; Pogg. 29, 77; Schw. 68, 816; Ann. Chim. Phys. 61,

113; abstr. Ann. Pharm, 19, 38 ; J. pr. CJhem. 8, 18 ; Ann. Chim.

Phys. 61, 125; abstr. •/, pr. Chem. 8, 201; Ann. Chim. Phys. 66^

124; Ann. Chim. Phys. 74, 26; abstr. Ann. Pharm. 35, 292;

Mtv. sc. 6, 76; abstr. Ann. Pharm. 41, 114; Sev. sc. 11, 361;

ibid. 12, 193; ibid. 13, 66 and 579; Und. 14, 313; Gompt. rend. 14,

318; jRev. sc. 14,818; abstr. J. pr. Chem. 27, 29; Compt. rend.

29, 363; Pev. sc 15, 739; ibid. 21, 36; Compt. chim. 1850, 1 ;

abstr. Pharm. Centr. 1850, 310 ; Ann. Pharm. 76, 298 ; Liebig &

Eopp's Jahresb. 1850, 497. Dumas. Ann. Chim. Phys. 50, 182; Ann. Pliaim* 5, 6; Pogg. 20,

517 ; iS^cAw. 66, 89. Dumas & Stass. Ann. Chim. Phys. 76, 40 ; N. Ann, Chim. Phys. 1, 42. LiEBio. Ann. Pharm. 25, 19. WosKRBSSENSKY. Ann. Pharm* 26, 66. Mitscherlich. Pogg, 31, 631. E RDM ANN & Marchand. J^ pr. Chcm. 23, 177. BER2ELIUS. Pogg. 44, 377 ; -4»n. Pharm, 28, 9. Mariqnac. ilnn. Pharm. 38, 18.

TOL. XIV. B

fc*' •

2 PRIMARY NUCLEUS C^H^.

Magnus. Pogg. 90, 1 ; Phil. Mag. J 6, 420 ; abstr. Berl. Acad. Ber.

1853, 446 ; Ann. Fharm. 88, 349 ; J.pr. Ckem. 60, 86; Fkarm. Centr,

1853, 597 ; Instit. 1853, 416 ; Liehi^ & Kopp's Jaliresb. 1853, 525. Bkrthelot. jN'. Ann. Chim. 33, 295; abstr. Ann. Fharm. 81, 108;

J. pr, Chem. 55, 76; Fharm. Centr. 1851, 861 ; LUbig & Kopps

Jahresh. 1851, 437, 504; Compt. rend. 33, 210; N. Ann. Chim.

Phys. 53, 69 ; abstr. Compt. rend. 43, 236; Ann. Pliarm. 108, 188 ;

J. pr. Chem. 70, 253; Chem. Centr. 1858, 535. H. Kopp. Ann. Fharm. 95, 329; abstr. Fharm. Centr. 1855, 771 ;

Liehig & Kopp's Jahretb. 1855, 37. ScriWARz. Dingier, pol. J. 147, 229 ; abstr. Chem. Centr. 1858, 55%.

Coal-tar camphor ; Naphtum or NaphtaUne. (Laurent.) Two-fifllu hydrocarbon^ Decaoctyl. (BerzeUus.) Normal-Naphten. (Gerhardt.) Hydride qfNaphiyl. (Kolbe.)

Discovered in coal-tar oil, by Garden (1820) ; recognised by Reichenbach as one of the products of decomposi^n by heat, of the distillate from coal. Faraday determined the composition of naphthalio, and, as well as Berxelius and Laurent, investigated its derivation.

Formation. A. Very frequently produced in the dry distillation of organic bodies, especially when decomposition takes place at a very high

temperature.

1. From ElJiylene. At a red heat, olefiant gas splits up into marsh- gas, and tar of various degrees of volatility, but containing on the average 93'3 p. c. C and 6*5 p. c. H, (and accordingly having nearly the composition of naphthalin). — This tar sometimes deposits crystals of naphtbalin^ especially when the more volatile part is evaporated off :

8C<H< - C»H8 + ec^u*.

The marsh-gas is mixed with undecomposed olefiant gas and hydrogen, the latter having been formed by the decomposition of the tar into hydrogen and carbon; at a white heat, olefiant gas yields only these two products, but no tar. (Magnus.)

2. By passing the vapour of alcohol, ether, rock-oil, or of essential oiis through a red-hot porcelain tube. (Saussure, Berthelot.) Charcoal and enipyreumatio oil are likewise produced in this operation. (Reichenbach.) Benzene, phenylic alcohol, and other products are likewise formed, and, as well as the naphthalin, are in part simply condensed and partly collected in nitric acid, and obtained as nitrobenzene, nitro-naphthalin, &e. (Berthelot.)

3. From Acetic Acid. If vapour of acetic acid be passed through a red-hot porcelain tube filled with fragments of pumice, naphthalin and a large quantity of undecomposed acetic acid condense in the receiver, together with a brown oil which forms picric acid with nitric acid. (Berthelot.)

4. Naphthalin is found amongst the decomposition-products of cam- phor, the vapour of which has been passed over strongly ignited lime,' and condenses in the receiver in fine, perfectly pure crystals. (Fremy.)

5. Naphthalin is found, in quantity varying according to the circum- stances under which the decomposition takes place, amongst the pro- ducts of the dry distillation of coaU, (compare ix. 135.) (Grarden, Laurent) ; of fat oils when illuminating gas is prepared from them (A . Connel) ; of resins, when fused and dropped into red-hot cylinders (Pelletier & Walter). Naphthalin is produced, not by the carbonization of coal, but by the decomposition of the first formed distillation-products,

4 NAPHTHALIN. 3

'wben these products in tlie state of liquid or vapour come in contact with the red-hot sides of the retorts (vapour-carbonization). It is for this reason that no naphthalin is obtained on distilling coal in iron retorts^ of which only the bottom is heated, while the sides are protected from the heat; or when the products of distillation are repeatedly rectified, or cooled to — 20^; or acted upon by chlorine (as Dumas affirms) (Reichenbaoh). Neither is naphthalin produced by distilling tarry residues or wood (Reichenbach), or lignite (Schwarz), if a very strong heat be avoided. —Naphthalin exists ready formed in commercial coal-tar (Garden, &o.); but not invariably (Laurent), (which is owing^ not, as Liaurent supposed, to varying age, but to the different modes of preparation) (Reichenbach). Coal-tar sometimes contains \ of its weight of naphthalin, and sometimes only traces (London tar contains large Quantities) (Mansfield, C^tn, Soc, Qu. J, 1,248). Tar prepared by aistilling coal in iron retorts (in the manner formerly adopted for the preparation of gas), contains but little naphthalin. If retorts of Char- motte clay are employed instead of iron, the tar contains considerable Quantities of naphthalin, and a little volatile oil, formed either by the aecomposition of the naphthalin, or of the gas itself. (Scliwarz.) —« Kidd obtained naphthalin by dropping coal-tar upon red-hot iron cylinders. — Naphthalin is found in lamp black, to which it imparts its peculiar odour, and may be separated by simple distillation, or by dis- tillation with water. It is also found in the soot obtained by the burning of wood-tar (Reichenbach); likewise in the vapour which penetrates into rooms from leaky stove-flues (Berzelius), since a deposit of soot is pro- duced by the red hot flue. (Reichenbach.) — Dumas believed tha6 naphthalin exists ready-formed in coal, but Reichenbach showed that this is not the case.

B. By iynthens, from inorganic substances. Since olefiant gas may be formed from inorganic materials,— and from defiant gas, alcohol and then acetic acid may bo produced, the modes of formation of naphthalin A, 1, 2, and 3 may be regarded as syntheses of titis description.

1. If a perfectly pure and dry mixture of bisulphide of carbon vapour and sulphuretted hydrogen, or a mixture of these two gases and carbonic oxide, be passed over porous copper or iron at a dull red heat, the pro- ducts obtained are : a little naphthalin and empyreumatic oil, much hydrogen, marsh-gas, and defiant gas, and a residue of sulphide of copper mixed with charcoal. (Berthelot.) Perhaps this mode of for- mation is identical with that from defiant gas (A, 1), defiant gas being probably produced, in the first instance and yielding naphthalin (Carius), by its decomposition.

2. When vapour of dichloride of carbon (viii, 160) mixed with hydrogen, is passed through a glass tube filled with fragments of pumice, at a bright red-heat^ it yields large quantities of naphthalin. (Berthelot.)

Preparatum. Naphthalin is obtained in large, but varying quantities as an almost useless by-product in the distillation of tar on the large scale, especially of that from coal ; but it is also a product of the distillation of wood, lignite, and animal oflal. (Gomp. Benzene, zi, 135.)

1. Tar (whether produced from wood, coal, or animal refuse) is first distilled with steam, as long as naphtha (light napk^ui), of sp. gr. 0*91 at . the utmost, is obtained, and afterwards with the aid of heat, whereupon water and oil of naphthalin {dead oU, heavy naphtha) pass over, until this latter attains a sp. gr. of 0*99. Every 100 gallons of the distillate

B 2

4 PRIMARY NUCLEUS C»H .

last obtained are now intimately stirred up with 15 gallons of oil of vitriol (sp. gr. 1*83) and allowed to settle, after whicb the clear upper liquid is decanted. This is stirred up with one-tenth of its volume of caustic alkali-solution of sp. gr. 1'35, and after it has been completely neutralized^ the whole is allowed to settle. The upper layer is then

? cured off and distilled alone, until the distillate attains a sp. gr. of 0*94. f this first distillate be now mixed in a still with quick lime (1 pound of lime to every gallon of oil), and distilled at a gentle heat, it yields, first a light oil till the sp. gr. reaches 0*91; and if the receiver be then changed and the remainder collected by itself, and cooled to — 4° C, it deposits naphthalin, which may be purified by filtration and pressure. If the distillation of the crude oil of naphthalin be continued in another still, as long as anything passes over, the purified heavy oil of naphthalin is obtained, which, if treated in a similar manner with lime, yields an additional quantity of naphthalin. (G. Shand & A. Maclean, C/um. Gaz. 1854, No. 270; Dingier pol. J. 133, 309.)

The black flaky masses which are deposited on the ground in place? where coal-tar is heated in open pans in order to free it from water, con- sist, according to Schwarz, of almost pure naphthalin. Coal-tar which has been subjected to heat in the above-mentioned process, yields by distillation two oils, one of which distib at 160° C and contains 0'46 p. c. naphthalin, while the second passes over between 160^ and 220° 0. and contains 0*65 p. c. naphthalin. Crude tar, which has not been previously heated, yields by distillation, first a light oil together with strongly ammoniacal water; then between 210° and 230° C, after the water has been driven off*, so large a quantity of naphthalin, that the distillate, if collected in a separate receiver, assumes at ordinary temperatures the consistence of butter. (Schwarz.) — Garden obtained naphthalin by distilling coal-tar, the naphthalin passing over with the enipyreumatio oil, from which it was afterwards deposited. — When coal-tar is distilled,' but little naphthalin passes over at first, the quantity gradually increasing till the operation is half over, and then a^in becoming less ; the greatest amount passes oyer with the last portions of the distillate, insomuch that thes^ become completely solid in the receiver (the final products contain sulphur); 100 gallons yielded 5 lbs. naphthalin. If the distillation be hastened a larger quantity is obtained ; but if oil of vitriol be added to the tar, little or no naphthalin is produced. ^Chamberlain).

2. Coal-tar is boiled m a copper kettle till all the water is driven off (which would otherwise cause the retort to crack), and then distilled in a glass retort to half its bulk. The naphthalin is separated from tlie distillate : a by cooling to — 10° C, whereupon large quantities of naph- thalin, mixed with a small quantity of a yellow unctuous substance, are deposited. The product is collected on fine linen and pressed. — b. The following is a better method : the distillate is placed in a tubulated retort through which chlorine gas is passed for four days, whereupon it becomes hot, evolves hydrochloric acid gas and yapours having an ofieu- sive odour (if the condenser be cooled to 0^ C. these vapours condense to a wine-red liquid), and finally assumes the dark colour of tar. The product is washed with water, which reraoyes hydrochloric acid and bad smelling bodies, and distilled alone, the distillate being collected in two portions. Both of these, when cooled to — 10° C. deposit large quantities of naphthalin. (Laurent, Ann, Chim. Fhys. 49, 214.)

3. When commercial coal-tar oil is submitted to fractional distillation, the portion passing oyer between 170^ and 190° C deposits a very large

NAPHTHAUN. 5

amoant of naphtbalin ^20 lbs. of oil yields 5 lbs.) wbich may be collected on a filter, drained, and aistilled. (Laurent, ^. Ann. Chim. Phys. 8, 296.) 4. Coal-tar is passed tbrongli red-faot iron tubes, and the thin tar, obtained by the condensation of the vapours, is distilled, whereupon first water and oil, then naphthalin pass over. (Kidd.) — 5. Coal-tar (espe- cially such as has been long exposed to the air) is heated with chloride of lime, water, and oil of yitriol. Much naphthalin is eyolred with the steam. (Brook.)

Purification. Commercial naphthalin, or naphthalin prepared by any of the above described methods, is generally contaminated with varying proportions of an erapyrcumatic oil which turns brown on exposure to the air (as well as by a yellow unctuous substance, Laurent). To free naph- thalin from these impurities, the following processes may be employed :— -

a. SublimaUon, 1. The naphthalin is gently heated in retorts or other suitable vessels, and the vapours are collected in wooden chambers, wherein thev condense in white fiakes. (G. Shand & A. Maclean.) — 2. About half a pound of crude naphthalin is gently heated for several hours on the sand-bath in a large porcelain dish, over which a sheet of filter-paper has been pasted ; after the whole has cooled, the dish is found to be full of dazzling white crystals of naphthalin. These are removed and the remaining cake of naphthalin pressed with blotting paper (in order to soak up the oil), and again heated, the operation being repeated as long as any sublimate is obtained. The last portion is yellow. This is the only method of obtaining pure, colourless naphthalin. (Otto, Ann, Pharm. 93, 888.)

b. Washing with cold alcohol and recryttaUxzing from hot alcohol. (Garden, Laurent.) The most convenient method is to put the powdered naphthalin upon 4 or .5 funnels (without paper) placed one aoove the other, and to pour the alcohol upon the uppermost ; by this means 1 \ lb. alcohol are sufficient for 5 lbs. naphthalin. (Laurent.)

Properties. Brilliant white scales, soft to the touch. Crystallizes in 6ix*sided tables. (Kidd, Chamberlain.) — More frequently in rhombic tables of 100*^ — 105^ HCidd). Regular crystals maybe obtained but only with great difficulty, by sublimation or from alcohol; they are rhombic tables of about 122^ and 78^ the acute angles being generally truncated, so that the crystals appear hexagonal. By very slow spon- taneous evaporation from ether, it may be obtained in crystals which are often of considerable size and completely developed ; they are prisms belonging to the oblique prismatic system, generally like Fig. 106, but reduced to the tabular form by the predominance of the /-faces, u' : u' = 82° : «' : t = 111°; u' : t ^ \2y ; t : < = 94° 30'. (Laurent.) — Crystallizes from oil of turpentine in prisms terminated by pyramids. (Cnamberlain.) Naphthalin when slowly sublimed, forms such an ex- tremely light bulky mass, that sometimes \ gramme will fill a litre-flask. (Handw&rterb, 5, 432.) — Heavier than water (Kidd). Sp. gr. 1 048 (Ure); 1*153 at 18° (the naphthalin had been fused, but was still some- what porous: — Reichenbach) Melts at 84° 5' (Garden), between 77° and 82° (Kidd), at 75*5° (Ure), forming an oil which on cooling solidifies in a mass consisting of flexible interlaced laminsD ; melts at 79 (Dumas), at 79 '2° (H. Kopp). — (The naphtlialin used bj Kopp for his determination was absolutely pure; when it was melted and allowed to solidify slowly, the thermometer remained constant at 79*2**.)

« PRIMARY KUCLEUS C»H».

Sp. gr. of liqaid napbihalin at its melting-point (water at 0^ C. being taken as unity) = 0*9778 (arerage). The true Yolame at 8^ aboire the melting point is giyen by the formola :

V = 1 + 0000747 X 8 + 0-0000018095 x 8»

Spec. Yol. =: 149*2 at the boiling point (caleulated, aooording to Kopp = 154) (H. Kopp). Boils at 210^ (Kidd), at 212" (Damas), at 220"* (Gerhardt); boils constantly between 216*4° and 216*8° (barometer at O-in 7476), or at 218*0° (barometer at 760™°*) (H. Kopp). (Determined by Kopp's method, and rectified aax>rding to the corrections proposed by him.) Sublimes even at a low temperature (Garden), bat more slowly than common camphor ; heated alone, it snblimes in brilliant flakes (Ure), without previous fusion. (Laurent.) Thrown into a red-hot crucible, it volatilises undecomposed, and condenses in the air in snowy spangles. (Laurent.) May be distilled with water (Ure, Chamberlain); when heated with water, it rises to the surface in oily drops, and then evaporates with a motion similar to that exhibited by common camphor. (Ure.)

Smells aromatic, like the narcissus, (Garden and others.) Tastes aromatic and pungent. (Garden.) Neutral to vegetable colours. (Kidd.) Vapour-density = 4*528 (Dumas), 4-621 (average, Woskres- sensky, Ann. Fhatin, 26, 66), 4*46 (Natanson, Ann. Pharm. 93, 801). Consequently, 1 litre of vapour weighs 5*882 grammes (Dumas), 5*939 grammes (Woskressensky).

		Faraday. Oppmnaim. a. b.	Laurant* mean.
20 C 8 H	.. 120 .... 93*75 8 .... 6-25	93-75 .... 93-484 .... 94-39 .... 6*25 .... 6-516 .... 5-61 ....	94 00 6-10
e-^H^	.. 128 .... 100-00	10000 .... 100000 .... 10000 ....	100-10
	Dumas. Mitscherlich.	Woakres- Marchand. Erdmwm & sensky. **■**-»"»"• Marchand.	Damas & Stass.
20 C .. 8H ..	mean. 94-2 .... 94*39 .... 94-41 .... »3-65 .... 93-58 .... 6-5 .... 6-21 .... 6*07 .... 6-35 .... 6-27 ....	average* 93-83 6-30

G»H« 100-7 .... 100-60 .... 100-48 .... 10000 .... J99-85 .... 100*13

VoL Density.

■ C-vaponr 20 8-3200

^ ■ H-gaa 8 0*5544

Naphthalin-vapour 2 8*8744

Jl ........ 4 4d/A

The composition as stated by Faraday has been proved to be correct. Thomson regarded C'H^, Ure (?H as more probable. According to Woskressenslcy's analysis, the formula is C'H (with which, however, his determination of the vaponr-density does not agree: Gm.), in which case, naphthalin would be isomeric or polymeric with idrialin, and probably also with paranaphthalln, scheererite, and pyrene. The analyses made in Liebig's laboratory, gave as the average, 94*4 p. c. C, and 6-15 p. c. H, from which we get C'^H^ after making the correction for hydrogen. (Liebig, 1838 ; Ann. Pharm. 25, 19.) — Faraday supposed the atomic weight of naphthalin to be C*'!!^, (which has since been found to be the only admissible formula) ; Berzelins supposed it to be C'^H^; the last supposition was once made by Laurent (Ann. Ckim, PhyB. 61, 124).— According to Marignac, naphthalin may be regarded aa a compound of two hydrocarbons :

C»H« = CWfl* + C*H*,

for the following reasons : a. The formation of chlorine-compounds which are very analogous to those formed from olefiant gas (the chlorine removing only halif

NAPHTHALIN. 7

the hydrogen from the naphthalin ?) ; b. The reeolntion of naphthalin into oomponndfl of the two hydrocvbons in the formation of nitrophthalic acid, C^'XH'O^ and of phthalic acid, together with the compound C^X^CP (ii, 360). According to Kolbe, it is hydride of naphthyl » C^H^H (comp. Ann, Pharm, 76, 39.)

Decompositions, Naphthalin yields by sublimation a liquid which at first tastes sweet and aromatic, afterwards pungent, and from which a considerable quantity of prussic add may be obtained ; Chamberlain,) \. When naphthalin is heated in the air, the vaponr is difficult to set on fire ; when once ignited, it 6w*n« very rapidly with a thick smoke. (Kidd.) — 2. Naphthalin vapour, passed- over red-hot hydrate of baryta, yields carbonate of batyta and hydrogen. — (Pelouze and Millon, ^nn. PAa;*m. 33, 182.) — 3. Chlorine forms new compounds with naphthalin, heat being evolved and hydro- chloric acid sas produced. (Laurent, Ann. Chtm. Phys, 49, 214.) The naphthalin melts, but solidifies again if the action of chlorine be continued ; the solid mass contained 44*69 p. c. C, 312 p. c. H, and 5219 p. c. CI, corresponding to the formula C*<>C1*H* (Dumas). Dry chlorine acts im- mediately and with great violence at ordinary temperatures. The naph- thalin melts, and if the stream of chlorine be rapid, sublimes in part as bihydrochlorate of bichloro-naphthalin, while hydrochloric acid is evolved. The mass gradually thickens, and becomes like solidified olive oil. The products formed in this reaction are hydrochlorate of chloronaphthalin, C^CIH^HCI, and bihydrochlorate of bicbloronaphthalin, C»C1»H«,2HCI (modification a and /3); by the further action of chlorine and heat, new chlorides are formed from the first, with fresh evolution of hydrochloric acid gas, especially bihydrochlorate of trichloronaphthalin, C*dPH*,2H01. (Laurent) Chlorine replaces the hydrogen of naphthalin, atom for atom, but the resulting hydrochloric acid remains in combination with the new radical (comp. also vii. 21). The chlorine which these compounds contain, outside the radical, may be removed in the form of hydrochloric acid, either by distillation or by treatment with potash, while the chlorinated raaicals thus set free cannot be further decomposed by dis- tillation or by treatment with potash. (Laurent.^ If these radicals are Bgain treated with chlorine, the hydrochlorates oi new radicals, richer in chlorine are formed, which, in their turn, may be set free by distillation or treatment with potash, and are finally converted by chlorine into perchloronaphthalin. (Laurent.) The number of the chlorine-compounds obtained by Laurent is very much increased by the fact that almost all of them vary in physical properties when prepared in different ways. (Tbiii seems to be frequently caused by impurities.) (Carius.) Besides such radicals and their hydrochlorates as only contain whole atoms of CI and H to 20 At. C, others are described by Laurent, containing a fractional namber of CI and H atoms, as well as Br and H, or ClBr and H together; the whole of these are probably mixtures of two or more compounds. (Carius.) Several of these raaicals, and likewise their hydrochlorates, bear a great resemblance to one another ; thus bihydrochlorate of bicbloronaphthalin and bihydrochlorate of trichloronaphthalin (the latter recrystallised from alcohol) are isomorphous. (Laurent.) Laurent dis* tinguishes the isomeric compounds of like composition by the letters A, B, &o., and even compounds of different composition, when agreeing in certain properties, e, g,, crystalline form, are denoted by the same letters. Thus all radicals marked A are soft, like wax, ana crystallise in regular six-sided prisms of 120°. (Laurent, Rev, Sclent. 14, 74.)

4. Bromine acts violently upon naphthalin, with rise of tem- perature and evolution of hydrobromio acid, leaving oily bromo-

8 PRIMARY NUCLEUS C-ni\

naplithalin. From tltia it appears that the bromine replaces the hydrogen, while the free radical is formed with evolution of hydrobromic add. (Lanrctlt.) By the further action of bromine upon bromonaphtbalin, bydrobromic acid and bi- or tri-bromonaphthalln are formed^ and from the latter, the hjdro- bromates C»Br*H\2HBr, and C»Br*H*,HBr (from which the radical C^Br^H' may be separated by distillation or by potaeh), and as the final product of the action of bromine, bihydrobromate of pentabromonaph- thalin is formed — C*^Br'H^2HBr. (Laurent.) The bromine-compounds /generally bear a great resemblanoe to one another and to the chlorine- compounds^ €. g., isomorphism^ and like these last, occur in different isomeric modifications (Laurent.) The chlorine-compounds which still contain hydrogen, are converted by bromine into radicals containing both bromine and chlorine, or into their hydrochlorates and hydrobromates. On the other hand, by the action of chlorine on the bromine compounds, the hydrochlorates of radicals containing bromine (or bromine and chlorine) are obtained ; but the latter, as well as the radicals which may be separated from them, are not identical with those obtained by the action of bromine on the chlorine-compounds, but isomeric, and generally isomorphous with them at the same time. (Laurent.) — 5. Naphthalin melts with iodine at a gentle heat to a brown liquid, which solidifies to a graphitoidal mass on cooling, dissolves readily in alcohol, and is preci- pitated therefrom by water. (Ure.) Iodine is without action upon naphthalin ; on warming them together, they melt, but separate on cooling. (Laurent) Phosphorus, sulphur, and chloride of carbon aro equally inert with naphthalin. (Laurent.) 6. Hydrochloric acid docs not act on naphthalin (Reichenbach); it dissolves naphthalin, and assumes a dark colour. (Lowig. Chemie der, erg. Verb, 2nd. pt. 2, 865.) — 7. Chloride of Sulphur (which %) heated with naphthalin, produces bichloronaphthalin, with separation of plastic sulphur and evolution of hydrochloric acid gas. (Laurent) — 8. Cyanogen does not act upon naphthalin. If chlorine gas. be passed over a powdered mixture of naphthalin and cyanide of mercury made into a paste with weak alcohol, an odour of chloride of cyanogen is evolved, mercurous chloride is formed, and the naphthalin is replaced by a yellow oil which is partly dissolved and may be precipitated by water. (Laurent) — 9. A mixture of hicJtro- mate of pota^ and sulphuric (or hydrochloric) acid, acts but slightly on naphthalin, if much water is present ; but if the quantity of water bo small, a violent action takes place, and the naphthalin is partly converted into naphthesic acid (C^H^O®). (Laurent, Bev. scient. 14, 560). —According to another statement of Laurent {Comp. rend, 21, 36), a beantifnl rose-coloared sub* stance is formed in the abore msnner, y'a,, Carminaphthone ; C^H^O', soluble in alkalis and reprecipitated by acids.

10. Strong nitric acid does not act upon naphthalin in the cold (Laurent); it forms nitronaphthalin, in the course of 5 or 6 days, without evolution of red vapours. (?m&, ^. Ann. Chim, Fhys, 31, 217). On gently warming the liquid, a brown oil is formed, which afterwards dis- solves; the liquid on cooling deposits yellow crystals (Garden), readily decomposible and inflammable. (Kidd.) Naphthalin evolves red vapours on boiling with nitric acid, and forms a mixture of nitronaphthalin and an oil, which floats on the liquid in the fluid form; hence 1 At. H in the naphthalin is replaced by 1 At. 0, with formation of water, and the resulting compound then combines with the residue of the nitric acid :

C»H» + NO* = (C»H70 + NC) + HO (Laurent). On continuing the boiling with nitric acid, binitronaphthalin, C^X'H*

NAPHTIIALIN. 9

(ond sitronaphthaleifle C»X2-«H*-») is produced. (Laurent.) By boiling with nitric acid for several days, ternitronaphthalin, C^X'H*, nitro- napLthale, pbthalic aud oxalic acids (Laurent), and nitropbthalic acid (Marignac, Laurent) are formed.

11. Nitrous acid acts violently in the cold and forms nitronapbthalin and an oil. — 12. Aqua regia acts slowly in tbe cold i in tbis reaction, an oil is formed, wbicb by distillation leaves a residue of carbon, and yields a distillate of nitronapbthalin and an oil.

13. (HI of vitriol dissolves naphtbalin very slowly in tbe cold, forming a brown liquid (Reicbeubach) ; at a moderate beat, snlpbonapbthalic acid is formed, and another acid, which is distinguished from tbe first by tbe fact that its traits do not bum with flame. (Faraday.) Oil of vitrioK when gently warmed, dissolves naphtbalin without evolution of sul- pbarous acid, and forms a brownish red liquid, which, after complete (saturation with naphtbalin, is clear and viscid when cold. Water precipitates from the solution unaltered naphtbalin, together with sulphonaphthalin and a little sulpbonapbthalide, while tbe solution contains sulpbonapbtbalic acid, C*'^Ii*,2S0', and bisulpbonapbtbalic acid, C^®^^4S0^ and acquires a red colour. (Berzelius.)

With sulphuric arikydridey naphtbalin melts to a dark red mass, which turns blackish-green, and contains principally sulpbonapbtbalic acid (Liebig and Wbhler) ; in this reaction, sulphurous acid is always evolved, even when naphtbalin is placed with sulphuric anhydride under a bell-jar; the products are the same as those obtained by the action of sulphuric acid ; only the colouring matter, bisulpbonapbtbalic acid, and sulpbonaphthalide are formed in larger quantity, and hyposulpboglutic acid is likewise obtained. (Berzelius.)

Warmed with phosphoric anhydride^ naphtbalin volatilizes unchanged (Laurent); it is not attacked by concentrated acetic or oxalic acid; or by caustic potash-solution even on boiling (Reicbeubach) ; or by fused potassium (Laurent).

1 4. When equal parts of naphtbalin and iat are exposed to the air for a week, the mixture absorbs oxygen, which, together with part of the oxygen of the fat, is taken up by tbe naphtbalin, giving rise to naph- tholeic acid and a hydrocarbon ; at the same time, a little carbonic acid is evolved and the mixture turns black. Naphtholeic acid, extracted from the mixture by ether, is a semi-fluid body becoming fluid at 20° C, yellowish, and transparent, and smells like crude naphtbalin ; it contains f;5'65 p. c. C, 14-22 H, and 20*13 0, and forms soaps with the alkalis, uncrystallisable salts with baryta, strontia, lime, lead, copper, and silver; and decomposes partly at 75^, evolving strong sufibcating vapours. (Rossignon.) It is rancid fat. (Gm.) — The hydrocarbon remains in the residue when the mixture is extracted with ether, and is purified by washing with ether, pressing between blotting paper, and crystallising from boiling alcohol. Forms thick silky flakes, soft to the touch, softening between the fingers, its consistence varying according to the nature of the fat; contains C and H in the proportion of 2:2*5 (basnet been analysed!) (Rossignon, Compf, rend, 14, 61.) — It is impure naphtbalin. (Gmelin.)

Combinations. 1. Naphtbalin does not dissolve in cold vater^ or in aqueous alcohol. (Garden.) It dissolves slightly in boiling water; tbe solution deposits most of the naphtbalin on cooling, but remains turbid, and in that state passes through the filter. (Kidd.) — 2. Dissolves very

10 PRIMARY NUCLEUS C»H».

mpidlj iu bisulphide of carbon, (Reichenbaoh.) — 3. Dissolres in alcohol^ eapeciallj in hot alcohol, and is precipitated from the eolation bj Water (Crarden, Reichenbaoh) ; the solution in 4 pts. hot alcohol yields on cooling a solid crystalline mass, the solution in 1 1 pts. yields fine crystals. (Kidd.) — 4. In ether it dissolves more readily (Kidd, Ure), and yery rapidly. (Reichenbach.) — 5. Dissolves in aqueous oxalic and acetic acids with bright red colour, the warm-saturated solution solidifying in a crystalline mass on cooling. (Garden, Kidd.) 6. Dissolves in oiS both fat and vokUUe (Garden) ; in oU of turpentine, the temperature falling 4*2^, and the hot solution on cooling yields fine crystals. (Chamberlain.) Dissolves slowly in eupione, gradually in creosote, slowly in picamar and in cold olive-oU. (Reichenbach.)

Insoluble in aqueous alkalis. (Garden.) Does not absorb amrnonia- gas. (Kidd.)

7. With Picric acid, — I. A mixture of naphthalin and picric acid IS dissolved in warm alcohol (or in benzene) ; and the golden yellow needles which separate on cooling are washed with a little alcohol, gently pressed between blotting paper, and dried by exposure to the air. — 2. This compound is precipitated in much smaller crystals than those obtained according to 1, when the oold-satnrated solutions of nuphtlialin and picric acid in alcohol are mixed. — Golden-yellow crystals, melting at 149^ to a clear orans;e-yellow liquid and at the same time evolving a little naphthalin. I^ is superficially decomposed by cold water, which removes picric acid, and more freely by boiling water, part of the naphthalin passing off in vapour ; nevertheless microscopic needles of the compound are obtained from the filtered solution. It yields all its picric acid to warm dilute aqueous ammonia. Dissolves in alcohol, ether, and benzene, separating out undecomposed on evaporation. (Fritzsche, Fetersb, Acad. Bull 16, 120 ; J. pr. Chem. 72, 282.)

Fritzsche.

1 At. naphthalin C»H8 128 .... 35*84

1 At picric acid C»2X»H30S 229 .... 6416 6440

C»H* + C»X«H>0» 857 .... 100-00

Appendix to Naphthalin.

An Metanaphthalin. cr^H".

Pellbtibr a Walter. (1837.) Ann. Chim. Phys. 67, 269 ; Po(/*/.

44,81. Ddmas. Compt. rend, 6, 480 ; Po^^g. 44, 110 ; J, pr. Chem, 14^^ 214.

Reiiaerin, (Pelletier and Walter.)

Formation. Found accompanying naphthalin in the tar formed when illuminating gas is prepared bj dropping melted pine-resin into red-hot iron cylinders ; it probably exists also in many other empyreumatio products. (Pelletier & Walter.)

Preparation, Resin is submitted to distillation ; the buttery mass passing over towards the end is collected apart ; all adhering liquid is removed as completely as possible by pressure between blotting paper;

BODIES ISOMERIC \fITH NAPHTHILIN, &C. 11

and the residue is dissolved in absolate alcohol. The solotion, treated with animal charcoal at a temperatare a little abore 40"" 0., then filtered and allowed to oool, yields crystals of metanaphthalin, which may be purified by repeated recrystallisation. (Pelletier & Walter.)

Properties. White nacreous crystalline flakes, unctuous to the touch, having a feeble odour of wax but no taste. Melts at 67^ C. ; distils over at 325° as an oil, which solidifies in a crystalline n\asfl on cooling. Unafiected by light and air. (Pelletier & Walter.)

20 C 120 .... 93-75 93-72 .... 93-4

8 H 8 .... 6-25 6-72 ..,, 70

C»H« 128 .... 100-00 100-44 .... 100-4

According to Damas, the formnla is perhaps C^H^*, which requires 93-2 p. c. C and 6*8 p. c. H.

Decompositions, 1. Metanaphthalin is not acted upon by aqueous chlorine, but if chlorine gas be passed into the melted substance, it is converted, with evolution of hydrochloric acid gas, into a green resin, which is not crystaUisable, and is still less soluble in absolute alcohol than metanaphthalin. (Pelletier & Walter.) — 2. Cold niirie acid acts but slightly upon metanaphthalin ; heated acid converts it into an ochre- yellow resin which decomposes by heat, without volatilising. (This distinguishes it from naphthalin.) (Pelletier and Waiter.^ 8. Oil of vitr'm does not act in the cold or on gently warming ; out if meta- naphthalin be boiled with a large excess of oil of vitriol, it becomes carbonized. No sulphometanaphthalic acid appears to be formed in this reaction. (Pelletier & Walter.)

Coffibinations. Insoluble in water, — Dissolves sulphur by heat.

i Pelletier & Walter.) — Metanaphthalin is not attacked by potassium or »y other metals ; neither does it combine with the alkalis, — Dissolves slightly in cold, and very abundantly in hot alcohol, crystallising there- from on eooling; it is still more soluble in e^er (paranaphthaliu is insoluble in ether), and most soluble in rock-oil, oil of turpentine, and other hydrocarbons, (Pelletier & Walter.)

B, Bodies isomeric with Naphthalin, and obtained by the

dry distillation of the Benzoates,

Laurent & Chancel. Gompt, ehim. 1849, 117 ; J. pr. Chem. 46, 510 j

Liebig & Kopp's Jahresb. 1840, 326. Chancel. Campt. chim. 1849, 87 j Compt, rend. 28, 83; Instit. 1849,

19; Ann. Fhaim. 72, 270; Fharm. Centr, 1840, 216; Liebig k

Kopp's Jahresb. 1849, 326 ; Further, Compt. ehim. 1851, 85 ; Ann.

Fharm, 80, 285 ; «/. pr. Chem, 53, 252 ; LiAig & Kopp's Jahresb.

1851, 432. List & Limpricht. Ann. Fharm. 00, 200.

a. Hydrocarbon C*H', mdiing at 02°.

12 PRIMARY NUCLEUS C»H\

Foftnation, Formed tofi;ether with b, in the preparation of benzone (xii, 40), by the dry distillation of benzoate of lime ; on rectifying the crude liouid, a and b are obtained in the portion which passes over up to S\5^ by before the benzone. — a. and b, are doubtless secondary pro- ducts formed by the decomposition of benzone (Chancel.)

2C»H»W - C^O* + C»H» + C»H».

JPrq>at*cUum. The varions products from the dry distillation of benzoate of lime are dissolyed in oil of ritriol, whereupon the hydro- carbon a rises almost instantly to the surface of the liquid. This substance is removed, washed with water, repeatedly pressed between blotting paper, and recrystallised once or twice from boiling alcohol. (Chancel!)

FroperUes, Crystallises readily in fine needles, melts at 912'', and volatilizes at a high temperature only (Chancel).

2e c 8 H	120 .... W-75	Chance*. averagf, .. 93-46 ... 6*49
C»H»	128 .... 100-00 .....	... 99-95

From the high boUiiig point of a (tn^ h)t Chancel conclndes that the atomic weight of a (and of 5 as well) mutt be very high ; perhaps C'H" or C^H'^

Dissolves more readily in alcohd and in d^er, than &. (Chancel.) h. Hydrocarbcm, C^ll\ melUng at QS".

Formattan. (Comp. p. 11.) 2. By passing the vapour of ben- zoate of ammonia over red-hot baryta, much benzonitrile, C'^NH* (xii, 161) being at the same time produced. (Laurent & Chancel.) — 3. By the dry distillation of benzoate of potash. (Chancel). — 4. When benzoate of copper is submitted to dry distillation (see zii, 43), the products there mentioned are obtained, together with an oil boiling at 260^ which, by heating with oil of vitriol, is resolved into sulpho-carbolic acid and crystals, the latter separating out as the sulphuric acid solution cools, and more completely by the addition of water. These crystals appear to be identical with Chancel's hydrocarbon b, (List & Limpricht.)

Preparation, 1. The following is the best method. When benzoate of lime is mixed with potash-lime, and submitted to dry distillation, a solution of ( in benzene is obtained. The solvent is removed by distil- lation in a water bath, and the residue is purified by cr3rstallisation from alcohol (Chancel). — The vapour of benzoate of ammonia is passed tlirough a tube containing red-hot baryta, and the small quantity of crystals obtained together with benzonitrile, is purified by sublimation and ciystallieation from alcohol. (Laurent & Chancel.)]

Properties. Colourless (nacreous, iridescent (List & Limpricht) laminsa, crystallising with difficulty, and melting at 65° (69*^ accorfling to List k Limpricht). Volatilises without decomposition at a very high temperature. (Laurent & Chancel). Has a faint agreeable smell of roses.

SULPHONAPHTHALIC ACID. 13

Chancel. Laurent & List & average. Chancel. Limpricht.

20 C :. 120 .... 9375 93-54 .... 939 .... 93-41

8H 8 .... 6-25 6-47 .... 6*4 .... 6'66

C»H8 128 .... 100-00 10001 .... 1003 .... 100-07

According to Gerhardt {TraiU 3, 984) the body ii perhaps C**HW» phenyl (by calcnlatioD, 93*5 p. c. C, 6*5 p. c. H).

Forms a crystallisable sabstance with bromine (tliis distinguishes it from napbthalin). f Chancel.)

It is far less soluole in alcohol and in Hher than a, (Chancel.)

Conjugated compounds of the nudeue C^H^.

Snlphonaphtlialic Acid.

C»H*S«0« = C«H«,2S0«.

Faraday. Phil. Trans. 1826, 140 ; Sckw. 47, 355 and 459 ; Extr.

Poffg. 7, 104. Bebzblius. Fogg, 44, 377 j Ann. Pkarm. 28, 9 ; abstr. Be^^z, Jahreih.

18, 468. Reqnault. Ann. Ckim. Phys. 65, 87 ; J. pr. Chem. 12, 99. LiEBio & W&HLER. Pogg, 24, 169. Gregory, jinn. Pkarm. 22, 272. WoHLER. Ann, Pharm. 37, 197. Laurent. Compt, rend. 21, 33 ; Compt. chim. 1849, 390; Extr. Ann.

Pha^m. 72, 297.

8ulph(mapkikaUeaeid(FtniBMy); Hypoeulphanapktkalie aeid (Berseliat); Sulpko* naphikimie aeid (Laurent) ; JHthiononapkihplie acid (Kolbe). — First prepared and inTestigated by Faraday.

Formation. Prodoced bj meltinff naphthalin with oil of vitriol (Faraday), or with sulphuric anhydride (Liebig h Wohler), or with Nordhausen sulphuric acid, -— bisulphonaphthalic acid, sulphonaphthalin, sulphonaphthalides, and a red colouring matter, being in all cases simul- taneously formed. (Berzelius.) — The last four products are obtained in larger quantity, when Nordhausen sulphuric acid or sulphuric anhydride is employed (in which case hyposnlphoglutic acid is formed, and sulphurous acid is always evolved), the proportion increasing with the violence of the reaction. (Berzelius). — When oil of vitriol is employed, a particular acid is likewise formed, yielding with baryta, Faraday's tmonUdering barpta-ealt, (Faraday.) Regnanlt did not obtain this salt, but Berzelius produced it in small quantity. — > If an excess of sulphuric anhydride is employed, no nndeeomposed naphthalin is left. (Liebig & WShler.) If oil of vitriol is used, the whole of the sulphuric add does not pass into combination, even when the naphthalin is in excess and the mixture is warmed for several hours (Faraday) ; on the contrary, when 14 atoms of boiled oil of vitriol are digested at 100° C, for 12 hours, with an excess of naphthalin, 5 At. of sulphonaphthalic add at the most are formed, and there remain 4 At. of 3|-hydrated sulphuric add, which is no longer capable of forming sulphonaphthalic add. Bi- and even terhydrated sulphuric acid still form a certain quantity of sulphonaphthalic acid. (Regnault.)

Preparation, A. Free acid. 1. The thick liquid which is obtained by saturating the most highly concentrated oil of vitriol at 90"" with

14 CONJUGATED COMPOUNDS OF THE PRIMARY NUCLEUS C»H«.

napbthalini and does not solidify ^hea kept from the air, is alloweil to absorb moisture from the air, whereby it is converted after a few days into a dirty violet mass. The same reaction is produced, by directly mixing the thick liquid with a little water. When the solidified mass has been sus far as possible freed from adhering sulphuric acid by spread- ing it upon a porous tile, and then by pressure between two other tiles, it yields almost white talc-like scales, which are a mixture of sulphonaph- thalic acid, bisulphonaphthalic acid, and a little free sulphuric acid. (Wohler.) — 2. May be obtained pnre^ when prepared as above from tho baryta or lead-salt, either by decomposing the lead-salt with sulphuretted hydrogen (Regnault), or by decomposing the baryta-salt with sulphuric acid (Faraday), removing the excess of sulphuric acid by carbonate of lead, and precipitating the lead from the solution by sulphuretted hydrogen ; the filtered solution, evaporated in vacuo over sulphuric acid, yields a syrupy liquid, which after several days solidifies in a crystaUine mass. (Berzelius.)

'" B. Baryta-saU. a. WUh Oil of Vitinol, 1. Seven hundred pts. of naphtbalin are melted with 520 pts. oil of vitriol, and the whole shaken together. After the mass has become solid, the cake of crystals is removed from the liquid beneath it, and melted with 300 pts. more of naphtbalin. On cooling, an opaque liquid is obtained, which separates into two strata. The lower stratum is wanned and shaken with -j- of it<s bulk of water, whereby most of the excess of naphtbalin (and the rest on further dilution) is precipitated, after which the liquid is diluted with more water and neutralized with carbonate of baryta, whereupon tho slight coloration of tho liquid completely disappears. The whole is then filtered and the precipitate slightly washed. The precipitate contains, besides carbonate and sulphate of barjta, Faraday's smouldering baryta salt, which |may be extracted by boiling water. The filtered solution yields on evaporation sul- phonaphthalate of baryta. (Faraday.)

2. Naphtbalin is di^sted with 2 pts. oil of vitriol between 70"^ and 80^ for several hours, and the resulting dark-red solution is diluted with water^ neutralized with carbonate of baryta, filtered hot, and crystallised by cooling. The mother-liquor yields more crystals on evaporation, and the residues on the filter when boiled with water, likewise yield a little more of the same salt. The baryta-salt is purified by recrystallisation. (Regnault.)

3. The hest method, Naphtbalin, freed from water by melting at 100°^ is added in small portions to oil of vitriol which has been distilled and perfectly dried by prolonged heating, and the whole heated in a water bath to 100^ C. (90** Wbhler), whereupon the naphtbalin melts, and dissolves, without evolution of gas, forming a yellowish red solution Naphtbalin is continually added till the liquid, after being warmed for half-an-hour, deposits undecomposed naphtbalin when diluted with water; further addition is superfluous. The liquid, which when cool is homogeneous, red and viscid, is diluted, and the naphtbalin, part of which is deposited immediately and the rest in the form of scales on cooling, is separated by filtration. The residue on the filter partly dissolves in the wash-water (the soluble portion appears to consist of naphtbalin together with sulphonaphthalic acid.) Tho bright brown-yellow filtrate contains sul phouapo thalic acid, bisulpho- naphthalic acid, free sulphuric acid and a red colouring matter. To purify the first two and to separate them from one another, either of the following methods may be adopted. (0.) The impure acids are

SULPHONAPHTHALIC ACID. 16

saturated with carbonate of baryta ; the baryta is precipitated from the

filtrate by sulphttric acid, where open the red colouring matter is likewise

precipitated : and the now colourless filtrate is again saturated with

carbonate oi baryta, filtered^ concentrated by evaporation, and mixed

with twice its volume of alcohol, whereupon the mixture becomes turbid,

and deposits for several hours a pulverulent precipitate of bisulphonaph-

thalic acid. The greatest part of the alcohol is then distilled ofiT from

the residual solution, which on cooling deposits part of the suplhonaph-

thalate in brilliant scales. On evaporating down the mother-liquor and

adding alcohol, a fresh portion of the nearly insoluble bisulphonaphthalin

is deposited ; and the filtrate, which when treated with acetate of lead

gives only a slight precipitate after long standing, deposits sulphonaph-

thalate of baryta in scales. — (6.) The impure acids are completely

freed from sulphuric acid by carbonate of baryta, and the solution only

half neutralized with carbonate of baryta, whereupon the liquid solidifies

in a thick mass of small scaly crystaJs. In this manner, only the stronger sulpbonsphthalic add is neutralieed of which the baryta-salt being, almost insoluble in the cold add liquid, is separated; but if the whole were completely neutralized or merely warmed, the precipitate would redissoWe. The salt is collected on a

filter, washed with cold water, and dissolved to saturation in boiling water, from which it crystallises in scales on cooling. In this way, pure eulphonaphthalate of bar3rta is obtained (the concentrated solution of which is not precipitated by alcohol, and only after several days by acetate of lead), blsulpho- naphtbalic acid remaining in solution. (Berzelius.)

h. With Sulphunc Anhydride, The vapour of sulphuric anhydride is passed into a receiver, wherein naphthalin is kept in fusion. The mass, which at first turns red, and afterwards dark brown, is dissolved in boiling water, and the naphthalin, which partly solidifies on the surface, and partly crystallises out on cooling, is separated by filtration. The sulphonapnthalic and bisulpbonaphthalic acids thus obtained, are purified and separated by methods a or 6.

Properties* Known only as a bihydrated acid. — White, solid mas3, hard and brittle when completely dry. (Faraday.) Solidifies in an irregular crystalline mass when the aqueous or aloohoHc solution is evaporated (Regnault). Melts below 100^ without decomposition and solidifies in a crystalline mass on cooling (Faraday). Melts between 85^ and 90'' (Begnault). Tastes bitter^ acid, and somewhat metallic, like copper salts.

Regnault. in vacuo,

20 C 120 .... 63*08 63'71

10 H 10 .... 4-43 4-69

8 O 64 .... 28-32

2 S .^2 .... 14-17

C»n8,2SO>+2Aq.... 226 .... 10000

Pulphonaphthalic acid is a compound of unaltered naphthalin with sulphuric acid » C3B{]8 ^ 2S0*. (Faraday, Laurent.) Contains hyposulphuric acid, and is formed by the simple combination of naphthalin with sulphuric acid :

0»H8 + 2S0» « C»H78?0«,HO,

the 1 At. of water being replaceable by bases. (Regnault.) Contains hyposnlphnrie acid, as is rendered probable by the behaviour of the potash-salt when boiled with

16 CONJUGATED CO\f POUNDS OF THE PRIMARY NUCLEUS C»H\

potash, and of the mtztare when evaporated to dryness and strongly heated. If the acid (according to Regnault) » C^H^S^O^HO, the baryta salt shoald give on analysis 22*61 p. c. water; Regnault obtained 23'73» Berzelius 24*65 p. c. (average) of water; hence the formula of the acid =- C^H^S^O^HO. The formation of sulphonaphthalic acid by the action of sulphuric acid upon naphthalin, is not so simple as Regnault supposes, since other products are always formed as wdl as this acid. — The acid may also be Tiewed as a compound of 1 At. svlphonaphthalin with 1 At. sulphuric acid. (Berzelius.)

I>ecomp(mtion8. Melts between 85^ and 90^ evolvinG^ part of its water of crjJBtallisation, but deoomposes before all the water bas been driven off; at about 120° C, it begins to smell of napbthalin; at a higher temperature, it swells up and leaves a very brittle shining residue of carbon (Regnault). At a gentle heat, sulphonaphthalic acid turns red^ without evolution of sulphurous acid, gives off a little water, and then contains free sulphuric acid ; if a stronger heat be applied, it evolves a little naphthalin^ and assumes a dark brown colour, carbonization then suddenly setting in from the bottom of the vessel, and spreading rapidly through the entire mass ; at a still greater heat, naphthalin, sul- phurous acid, and charcoal are obtained ; but even after ignition, the residue still contains a little sulphonaphthalic acid. (Faraday.)

If the concentrated aqueous solution be warmed, it first turns yellow, then brown, and is found to contain a yellow colouring matter^ which also passes into most of the salts ; it can only be separated from the baryta-salt, by adding a few drops of sulphuric add, and afterwards treating the solution with a little oxide of lead. (Berzelius.)

2. The aqueous acid placed in the circuit of the voltaic battery ^ gives off hydrogen at the negative pole, and oxygen and sulphuric at the positive pole ; the sulphuric acid acting upon the naphthalin, produces a dark yellow colour. (Faraday.)

3. Nitric Acid converts it, first into nitro-sulphonaphthalic acid, and afterwards, by prolonged action, into binitrosulphonaphthalic acid. (Laurent.)

4. The potash -salt, boiled for a long time with an excess of potash^ yields neither naphthalin nor sulphuric acid, but crystallises out un- changed on cooling. If the mixed solution be evaporated to dryness and the residue of potash-salt and potash bo heated till naphthalin begin.9 to sublime, and the mass turns dark, its solution in water smells of creosote, a blackish brown residue remains undissolved, and the dark yellow solution gives with hydrochloric acid, a whitish precipitate of fine, slowly subsiding crystalline scales. More of this substance is extracted by alcohol from the residue ; the solution acidified with hydro- chloric acid, smells of sulphurous acid, and evolves that gas on boiling. (Berzelius.)

5. The potash-salt, heated with sulphide of hydrogen and potassium, yields a very foul-smelling liquid which is soluble in water and does not precipitate lead-salts (naphthaliu-mercaptan) (Gregory).

Combinations, » The acid deliquesces in the air, and is very soluble in watet% (Faraday.)

SnlphonaphthakUes. The acid neutralises alkalis. The concentrated solution precipitates chloride of barium, but the precipitate dissolves on addition of water. The formula of the salts is C^H7MS'0^ Submitted to dry distillation, they yield first water and a little naphthalin, then sulphurous and carbonic acids, and leave a residue of sulphate, sulphide, and charcoal. Heated in the air, they burn with flame, and leave a

SULPHONAPHTHALIC ACID. 17

residue of salpliaie mixed with charcoal. (Faraday.) They deflagrate violently with nitre; do not give off naphthalin when boiled with potash ; decompose slowly when the dried residue is strongly heated, (Regnanlt.) They are all soluble in water, and mostly soluble in alcohol. (Faiaday.)

Sulphonaphthalaie of Ammonia. Ill-defined crystals having a cooling saline taste. Melts and blackens by heat, bums with flame, and leaves a residue of acid sulphate of ammonia mixed with charcoal.. If the aqueons solution be e^'aporated at ordinary temperatures, even when containing an excess of ammonia, it acquires the property of reddening litmus. Beadily soluble in water^ but not deliquescent (Faraday.)

SulphonaphtAalcUe of FotaA. Obtained by decomposing the baryta salt with sulphate of potash. (Regnault.) Colourless, soft crystals, unctuous to the touch, sometimes transparent, sometimes opaque, occa- sionally forming efflorescences composed of small needles. (Faraday.) Small, white, very brilliant flakes, giving off in vacuo 3*78 p. c aq. (1 At. =3*53 p. a) (Regnault.) Permanent in the air; taste bitter and saline. (Faraday.)

20 C	In vacuo* 120-0	.... 48-73 ... .... 2-84 ... .... 19-16 ... .... 12-99 ... .... 16-28 ...	Regnault. 48*98
7 H	7-0	3-04
KO 2 S	47-2 32-0	19*09 ..... 13-24
5 0		15'65

C»H7K,2SO" 246-2 .... 100-00 10000

The salt bums with flame In the air, and leaves a residue of sulphate of potash having a very feeble alkaline reaction. (Faraday.) Dissolves reaidily in water ; the colourless solution is not decomposed by repeated evaporation and crystallisation. Dissolves in alcohol, forming a colour-. less liquid, (Faraday.)

Soda-sait, — White nacreous crystals permanent in the air and having a peculiar and decided metallic taste. (Faraday.)

Sulphonaphthalaie of Baryta, {Burning wUhJlame, Faraday.) Pre- paraHtm (comp. p. 14.) Crystallises in tufts when the aqueous solution is slowly evaporated (Faraday), in cruciform laminoe resembling prehnite (Regnault). Deposited in grains on cooling the hot aqueous solution (Faraday). Crystallises in foliated masses from the hot solution (Reg- nault). CrystaUises from boiling alcohol in largo transpai'ent scales, which, on drying, cohere in a mass having a silvery lustre. (Derzelins.) After drjdng it appears white and tender, soft to the touch. Tastes bitten Permanent in the air. The salt dried in vacuo, as well as that dried in the air, still contains 1 at. water, and gives oft* at 100", 3-485 p. c. water = 1 at (Regnault.) Contains 1 at. of water of crystallisation, which is completely expelled at 50^ (Berzelius.)

YOL. XIV. O

18 CONJUGATED COMPOUNDS OF TUB t*RtMART NUCLEUS C»H«.

20 C	120 .... 43-55 7 .... 2-54 76-5 .... 27-76 32 .... 11-61 40 .... 14-54	Rcgnault. ^^'«^f Faraday. at 160«. at 100*. 43*80 .... 43-40 .... 41*90
7 H	2-66 .... 2-86 .... 2-86
BaO 2 S	.. 27*59 .... 26*58 .... 27*57 11-76
5 O	14-19
C»H7B«,2SO*	975-ft ..». 100*00	....i... 100*00

Beneliiis obtiined on the ayerage 41*83 p. e. tvlphato of barjiA tnm tlit nit dried at 100"**

Sulphonaphthalate of baryta, heated in a tabe, eyolves naphthalin, but not till the temperature exceeds 260° (a non-inflammable gas is evolved according to Regnanlt), then sulphurous acid and k Httle tarry matter, and at a very high temperature, leaves a blackish mixture of charooal, sui{yhate of baryta, and sulphide of barium. (Faraday and Regnattlt.) — Heated on platinum foil, it bums with a brilliant| very smoky flame, and leaves the same blackish residue. — Not decomposed by boiling with moderately strong nitrio or nitro-hydrochloric acid, so that no sulphate of baryta is precipitated from the solution ; if, how- ever, the acids are very concentrated, sulphuric acid is then liberated and other special decomposition-products are formed. (Faraday.) — Chlorine does not decompose the dry salt, unless heat is applied, where- upon the chlorine acts upon the naphthalin as it is liberated. — Soluble in alcohol, insoluble in ether.

SidphonaphthcUate of Stfontia. -» White, imperfectly crystalline substance, resembling the baryta-salt j it is permanent in the air. Burns with a brilliant, but not red flame, leaving a residue similar to that of the barytansalt. Soluble in water and in iQcohol. (Faraday.)

Suphonaphthatate bf Lime crystallises imperfectly llnd h^ A bitier taste. Heated in a tube, it yields the satne products as thd baryta-salt. Bums with flame. Dissolves slightly in water; soluble in alcohol. (Faraday.)

SulphmaphihakOe irf Ma^esia. -— White^ crystallisable salt, of raoilerately bitter taste. Behaves like the baryta-salt when heatCKi in a tube; burns with flame. (Faraday.)

SulpIionaphAdUUe of Manganese is nentnJ, hits an astringent taste» and gives the same results on heating as the baryta-«alt» Diieolres in water and in alcohol. (Faraday.)

Sulphanaphthalafe of Zinc. — Obtained by diisolvin^ Ihe fnetal (in which case hydrogen is evolved), or the hydrated oxide, in iulpho- naphtbalic acid. White, bitter needles, permanent in the ftir, and burning with flame. Soluble in hot water. (Faraday.)

SulphonaphihcUate of Lead is prepared by dissolving oxtde of lead iu the free acid. (Regnanlt.)

SULPHONAPHTHAUC ACID. 19

a. Neutral, White salt, permanent m the air (Faradaj) ; crystallises still more irregularly than the barjta-salt. (Regnault.) Exactly like the baryta-salt, but more soluble ; crystallises by spontaneous evapora* tion in crystals which may be split into plates like mica. (Bersselius.) Tastes bitter^ metallic, and slightly sweet

20 C	• • ... 120 .... 38-63 ... .„ Ill-; .... 35-93 ... ... 32 .... 10-29 ... .. 40 .... 12-89 ...	Regnault. at 180'. 38-50
7 H ;	2-40
PbO	35-75
2 8 .„	..... 10-21
5 0	1314
C»H'Pb,2SO»	.. 310-7 .... 10000 ...	100-00

Behaves like the other salts when heated. (Faraday.) Decomposes by heat with increase of volume^ and forms ramifications in all directions. (Regnault.)

Dissolres in water and in alcohol. (Faraday.) It is less soluble in w»fer oontaining free acid, than in pure water; the warm-saturated eolation solidifies on cooling in an interwoven mass of scales. (Berielias.)

ft. Ba$ic. The nentral salt a is dissolved in water, and the solution boiled for some time with oxide of lead. The diluted solution on cooling deposits the new salt in crystalline flakes. Contains 53' 81 p. c. oxide of of lead, which is expressed by the formula : C»HTb,2S0' + PbO. (Regnault)» - - • •

c. When the Bolution of h is boiled for a eonsiderable ttme longer with massicot, the decanted liquid deposits an abundant white powder, and scarcely anything remains in solution. (Regnault, Berzelius.) Regnault found 70-36 p. 0. oxide of lei^^ corresponding to thp &i:mula, C*^H^Pb« 2SO» + 3PbO.

Berzelius obtained a fourth basic salt pf lead by prolonged boiling of the neutral salt with oxide of lead. A mass was deposited insoluble iu water, soft and viscid when warmed, but becoming hard on cooling.

FerrouM SulphonaphthalcUe is obtained by dissolving the molal (hydrogen being evolved), or the hydrated ferrous oxide in the acid. Crystal lisable. The aqueous solution absorbs oxygen from the air. (Faraday.)

SidphonaplUhahie of Nickel. — - a. Neutral. Formed by dissolving tho carbonate of the base in the acid. Green crystals decomposible in tho ordinary way by heat ; soluble in water. (Faraday.)

5. Bade. Insoluble in water.

SulphonapJUhcUaie of Copper is prepared by dissolving hydrated oxide of copper, in the acid. Laminsa united so as to present a radiated appearance; very pale green. Contains water of crystallisation, which- it partly loses in dry air. Melts by heat, and burns with flame attended with the usual phenomena. (Faraday.)

Mereuratu SfdphanaphUuilate,^ — Formed by dissolving the freshly pre- cipitated carbonate in the acid. White, lightly crystalliae salt, having

c2

20 CONJUGATBD COMPOUNDS OF THE PRIMARY NUCLEUS C»H\

a metallio taste and feebly acid reaction. Destroyed bj heat. When dissolved in water or alcohol, it leaves a yellow basic salt. (Faraday.)

Merciiric Sulphanaphthalate. — The eolation of the recently precipi- tated oxide leaves on evaporation a yellow deliquescent residue. May be set on fire in the air. (Faraday.)

Stdphonaphthalate of Silver, — When the freshlv precipitated hydrate<1 oxide is dissolved in the acid, the almost neutral, brown solution, leaves on evaporation a brilliant, white, crystalline salt, permanent in the air, and having an intensely metallio taste. (Faraday^ Mioaceous lamina) soluble in 97 pts. water at 20^ C. (Regnault) Regnault found 36*03 p. c. AgO (calculation, C**H^Ag,2S0* = 36*84 p. c. AgO). The aqueous solution deposits by prolonged boiling a black insoluble mass and then yields by evaporation abundant yellow crystals. (Faraday.) Does not decompose, even after several hours' boiling. (Regnault.) Burns with flame, leaving as final residue pure metallic silver.

Sulphonaphthalic acid dissolves in alcohol^ slightly in ether. Dissolves in oil of turpentine^ otive-^U, and melted naphthalin, and in greater pro- portion the more anhydrous it is. The solution in naphthalin forms on cooling two strata, the upper of which is a solution of the anhydrous acid, the lower a solution of the hydrated acid in naphthalin. (Faraday.)

Add of Faraday's Smoolderuig Baryta-salt

0»H*,2SO«t

TiJUDAT. PhO. TrOM. IBM, 140 ; Schw. 47, 355 and 459 ; abstr*

Pogg. 7, 104. BBBZBLZua. Poffg. 44, 877 ; Ann. Pharm. 26, 9»

^ FomusHan and Preparation, By acting on naphthalin with sulphuric acid, Faraday obtained, besides sulphonaphthalic acid, a second acid, which, be says, is formed in proportionally smaller quantity^ as the oil of vitriol is allowed to act upon the naphthalin at a lower tem* perature and in smaller quautity. The baryta-salt remains upon the filter, after the saturation of the impure sulphonaphthalic acid, together with the sulphate of barjrta and a little sulphonaphthalate of baryta. The matter is extracted with boiling water, and the two baryta-salts are seoarated by crystallisation. (Faraday.) To obtain the acid, the lead- salt is decomposed with sulphuretted hydrogen, and the filtrate evaporated in vacuo over sulphuric acid. (Berzelins.)

Mass crystallising in scales, soft to the touch, tasting acid and bitter like sulphonaphthalic acid.

Does not absorb moisture from the air, but gradually turns yellowish* brown by the action of sunlight.

The potoBh-eaU crystallises in scales, readily soluble in alcohol. It is not decomposed by boiling with concentrated potash-solution, but ciystallises out unchanged on cooling.

BISULPHOKAPHTHALIC ACID. 21

Baryta-Mtt. — Small^ tTanslaoent prisms^ grouped in tafUr, perfectly neutral, and almost tasteless.

Fanday. a/ 100%

20 C 120 •... 43-55 42-40

7 H 7 .... 2-54 ..M..., 2*66

BaO • 76-5 ,.^ 27-76 28-08

2 8 32 .... 11-61

5 0 40 .... 14 54

C»IFBa.2S0» 275-5 .... 100-00

Since this salt is jost as neutral as that of solphonaphthalio acid, it appears to differ from the latter only by a slightly lower percentage of naphthalin. (Faraday.) The baryta-salt contains exactly as mach baryta as the common snlphonaphthalate ; hence it is probable that the add contains hyposulphnrie acid in combination with an isomeric modification of naphthalin. (Berzelias.)

The baryta-salt, heated in a tube, evolves only a little naphthalin toother with a vapour havin/i^ an empyrenmatic odour, and a little sulphurous acid, and leaves the same residue as snlphonaphthalate of baryta. Heated on platinum foil, it gives only a slight flame, but rather smoulders away like tinder. The salt, heated for three hours to 227'', increases by only 0*8 per cent, of its weight in the air» Soluble in water, but much less than the snlphonaphthalate of baryta. (Faraday.)

Lead'Balt* — Exactly like the baryta-salt (Berzelius.)

Bisulphonaphtlialic

C«>H»S*0» = C"H»,4S0».

BER2ELnj8. Pogg. 44, 393 ; Ann. Pharm, 28, 9 ; abstr, Ben. Jahresb*

1 8, 468. Laurent. Gcmpt, ehim. 1845, 177; Ctmpt. rend. 21, 33; Ckmipt. chim,

1849, 390 ; abstr. Ann. Pharm. 72, 297 ; Liebig & Lapp's Jahn^.

1849, 440.

ffjfponUphonapkHalie acid. (Bereelins.) 8%UphonaphthaUe aeid^ TkUmt^hikalie acidy TAi<maphthyl'DithUm$ehuf^eUdure. (Kolbe.) DiniffimiiqfhtatintHure.

FormaHon, Comp. p. 14. {Sulphofuqjththalie add.)

Preparation. The bisulphonaphthalate of baryta precipitated by alcohol in the preparation of sulpbonaphtbalate of baryta (p. 14, 3, a), 18 washed with alcohol, dried, and dissolved in boiling water, whereby a yellow solution is generally formed. In order to get rid of the colour, part of the baryta is precipitated with sulphuric acid ; the acid solution is saturated with carbonate of lead and filtered ; the oxide of lead re-

{precipitated by baryta, and filtered ; and the liquid free from oxide of ead, is slightly acidified with dilute sulphuric acid, then filtered, and evaporated down, whereupon the baryta-salt crystallises. The crysUils ^re washed with alcohol till the liquid ceases to redden litmus. The acid

22^ CONJUGATED COMPOUNDS OF THE PRIMARY NUCLEUS C»H«.

mother-liquor, OTfiporated almoat to drynesfl, mixed with tb« wash- alcohol, and then washed with fresh alcohol, yields a fresh portion of the salt. The har3rta-salt is dissolved in water, and precipitated hy sulphuric acid ; the excess of sulphuric acid is removed by carbonate of lead, and the lead in solution is precipitated by sulphuretted hydrogen. Tbe filtrate is first evaporated on a water-bath, till the snlphuretted hydrogen is driven ofl*, and then in racuo over sulphuric acid. The solution acquires the consistence of Byrup, and then dries np to a lamino-crystalline, slightly yellow mass. (Berzelius.)

In the solid form, bisulphonaphthalio acid feels soft like powdered talc, and tastes acid aud bitter, like suphonaphthalic acid. It becomes coloured by exposure to the air, especially if repeatedly allowed to absorb moisture and afterwards dried in the sun.

Bisulphovaphtkalates, Bisulphonaphthalio acid is hihasic. Its salts = C»H«M»,4S0'i according to Berzelius, they are C"H*-*0,MO,SH)». They resemble the sulphonaphthalates and have the same bitter taste. They require a very high temperature to decompose them, and then yield naphthalin and sulphurous acid. They are not changed by boiling with concentrated potash, but if tbe mixture is evaporated aown till the residue chars, tbe solution therefrom treated with sulphnrio acid, evolves sulphurous* acid. The salts are readily soluble in water. To ascertain whether a small quantity of one of these salts is mixed with a sulphonaphthalate, the substance is dissolved in alcohol of sp. gr. 084 and a few drops of acetate of lead are added to the solution, whereupon a precipitate is formed, bisulphonaphthalate of lead being almost insoluble in alcohol. (Berzelius.)

Bisulphonaphthalate of Ammonia exactly resembles the potash-salt; evaporated at a gentle heat, it becomes coloured, and the residue contains free acid.

Bisulphonaphthalate of Potash , IB obtained by spontaneous evapora- tion, as a white granular massj crystallises from a warm solution of aqueous potash, in scales united in arborescent groups. Readily solublq in water, slightly soluble in alcohol.

Bitulplwnaphthalate of Soda does not afford good crystals by sponta- neous evaporation ; it is more soluble in alcohol than (he potash-salt,

Bisvlphonaphthalate of Baryta is deposited, by evaporation of the solution on a water-bath, in crystalline crusts on the bottom of the vessel and on the surface of the liquid. If the hot Bolution be allowed to cool slowly, the liquid becomes filled with a non-cryitallme woolly vegetation of the salt. — Snow-white substance, resembling chalk.

The anhydrous salt, exposed to heat, 3Hields a snblimata of naphthalin, but not till charring has commenced, and gives aoid vapoars which however do not smell of sulphurous acid. Dissolves very slowly in water, even at the boiling heat. The solution may be evaporated down to a considerable extent before yielding any deposit; it generally turns yellow on evaporation, but, when containing free acid, deposits a white salt ; if however, it is neutral, it deposits a coloured salt, which leaves a small brown residue when dissolved in water.

HYPQSULPHOGLUTIC ACID, 23

Very slightly soluble m alcohol^ and precipitated from the aqueous solntiou bj fucohol.

Beneliut, ut 100\

80 C „„ 120 ..., 28-97 2924

. 6H , 6 ,.., 1-42 1-78

2BaO,SO> 233 .... 56-08 5093

2 80" 64 ..., 15-13

CJ»H«Ba»,4S0» 423 .... lOQ-00 ^

According to BerzeUns, the formula is CiiH^H),6aO,S<0* (palcaUtioi) requires 51*18 p. c. BaOfSO*), oomp. p. 22. The discrepancy betireen bis analysis and the formnU assigned, cannot easily be accounted fbr.

JBimlphonapkthalaie of tend is exactly like the barjta-salt, It dissolves in water, but is so little soluble iu alcohol, that it is almost completely precipitated thereby from its aqueous solutiou. (Berzelius.)

rarts with 7 p. c. water at 220** C. (4 At. = 6-82 p. c), and then contains 60*6 p. c. PbO,SO' (calculated, 61*5 p. c). (Laurent.)

90 C 120

10 H 10

2 PbO,SO» 303-4

2 8 , 32

8 O 04

	Laurent,
	«/ lOO*".
.... 22*65 ...	28-00
1*89 ...	1-67
«... 57*33
„.. 604
..„ 1209

C»HMpb«,4S0«, + 4A<| 529-6 .... lOO-OO

Hypostdphoglutlo Acid.

fi^zBUus. Pog^' 44, 87T ; Ann. Pha/rm, 28, 9.

Preparation. 1. When the red sulphate of baryta^ obtained in the preparation of sulphoaaphthalic acid (p. 14), is boiled for a long time with an excess of carbonate of soda, hypoeulphoglutio acid, is extracted* together with a red colouring matter and a resin. The liquid, at a certain degree of concentration, deposits impure hyposulphoglutate of soda, in brown, viscid, glutinous masses^ which however redissolve on dilution. The liquid filtered fron^ baryta is concentrated and separated from the glutinous deposit, a small quantity of which still remains dissolved ; the mother-liquor is mixed with a large quantity of sulphuric acid, wherebjr th^ byposulnhoglutic acid still in solution is precipitated, and the precipitate is washed with hydrochloric acid, in which it is insoluble. The viscid resinous soda-salt is dissolved in as little water as possible and treated in the same way as the mother-liquor, and the precipitated acid is dried. To purify the product, it is dissolved in ammonia; the excess of ammonia is expelled by evaporation ; and the- solntion is filtered and precipitated with acetate of lead, whereupon a brownish-yellow preoipitate is formed, whil^ the pure lead-salt remains

24 CONJUGATED COMPOUNDS OF THE PRIMAKY NUCLEUS C»H«.

in solution . The filtered solution is heated till the precipitated lead-salt redissolves, tben concentrated, and precipitated with basic acetate of lead, and the precipitate is washed and decomposed by sulphuretted hydrogen. The precipitated acid is coloured brown by sulphide of lead ; the liquid is therefore digested for 24 to 48 hours between 60^ and 80^ in a well corked flask, and then filtered. (The brown undissoWed lead-salt, treated in a similar manner, yields a clear yellow liquid, containing the same acid, but contaminated with a resin and a colouring matter.) It is best to evaporate the acid thus freed from lead, in vacuo over sulphuric acid, since it becomes coloured in the air. — 2. The acid may be obtained from the mother-liquor of sulphonaphthalate of barrta (p. 14, 3, a), which dries up to a gummy mass. This gummy mass is dissolved in water, and precipitated to a certain extent with subaoetate of lead ; the precipitate is decomposed by sulphuretted hydrogen, and the filtrate concentrated and mixed with fuming hydrochloric acid, whereby the acid is precipitated almost colourless, while sulphonaphthalic acid remains in somtiou. (This process yields but little acid, since most of the acid is contained as baryta-salt in the sulphate of baryta employed in the first method of preparation.)

Propertia, Transparent, uncrystallisable, slightly yellow mass, fissured like glass (when spontaneously evaporated in the air, it forms a yellow mass without cracks). Dissolves after the glass has been com- pletely dried. Inodorous, and bitter, like sulphonaphthalic acid, but nas a slightly acid taste. Reddens litmus.

Dissolved by nUrie acid, and decomposed on boiling ; water precipi-> tates from the solution a pale yellow substance, insoluble in water; the filtrate is colourless, and fives sulphate of baryta with chloride of barium. If the potash-salt be fused with excess of potash until charring begins, and the mass be then treated with dilute sulphuric acid, it evolves sulphurous acid ; hence it contains hyposulphuric acid.

With a small quantity of water, it forms a viscid glutinous substance. Dissolves readily in water, and is precipitated from the solution by sulphuric or hydrochloric acid (but not by nitric acid) as a viscid, glutinous mass.

The BypondphogltUateB are destroyed by ignition, with formation of sulphates ; they are slightly soluble in cold water, more abundantly in warm water; the portion which remains undissolved melts by heat and becomes opaque.

^ The potash,^ soda, and ammonia-salts, resemble in appearance the free acid. If caustic alkali or carbonate (carbonate of ammonia in the case of the ammonia-salt) be added to their solution, the greater part of the dissolved salt is precipitated in white scales, which gradually unite into a glutinous mass. The solution of the ammonia-salt yields by evaporation a residue which reddens litmus, still contains ammonia, and exactly resembles the free acid«

ByposulplioglutaU of Baryta. — Melts below 100° Dissolves in warm water, and is precipitated on cooling ; dissolves in warm alcohol. Leaves when ignited 37-3 p. c. BaO,SO*.

HyposulphoglutaU of Lead, Melts below 100"*. Dissolves in warm water, and is precipitated on cooling. Dissolves in warm alcohol

Hyposulphoglutic acid is soluble in alcohol, less soluble in ether.

NAPHTHALASE. 25

Oxygen-nudeui C*H'0 ?

Naphthalase. c»H'0?

Laurekt. Ann. Chim. Phyi. 59, 826 ; Bev. $eieni. IB, 68.

Farmatian. By heating nitroDapbthalin with hydrate of lime or hydrate of baryta.

Freparaiion, 1. Nitronaphthalin is heated (as slowly as possible^ lest it should take fire, and bat little product be obtained), with from 8 to 10 pts. of hydrate of lime in a retort filled up to the neck, where- upon ammonia is erolved and a brown oil (containing much naphthaliu) and nndecomposed nitronaphthalin pass over, while a thick oil condenses in the neok of the retort, and solidifies on cooling. The lime is blackened from separation of carbon. The neck of the retort is cut off near the bulb and washed, as well as the condenser, with ether, which leaves naph- thalase undissolved. — 2. A mixture of 1 pt nitronaphthalin and 8 to 10 pta. hydrate of lime or baryta, is distilled by small portions ; the naphthalase eondensing in the neck of the retort is collected, washed with ether, and distilled ; and the solidified distillate is again washed with ether.

F}'opertie8. Yellow snbstance, which begins to sublime at 250% but does not melt till a stronger heat is applied, when it begins to boil. The vapour is yellow and condenses in small spangles, which are deposited on the neck of the retort in long, yellow needles. When melted, it solidifies in a fibrous mass on cooling.

	20 C	120	•••• Do'o ... .... V & ..• >... O X ...	Lanrent. 85-9
	7 H	7	4'8
	O :...	8	9-3
	C»H70 .....	....•,. lOw	.... lOO'O ...	..... 100*0

The analysis should be repeated. Perhaps t At nitronaphthalin forms with 1 At. water of tiie hydrate of lime, 1 At. naphthalin, while another portion is converted into naphthalic and nitric acid, the latter being immediately decomposed by the excess of lime.

CinrUnnaiians. l^aphthalase dissolves in water. — It dissolves in cold oil of vitriolj even in the smallest quantity, with a very intense and beautiful bluish violet colour. The solution in hermetically sealed tubes does not change colour even after two years. On the addition of a little water, the colour turns reddish-violet, and on the addition of more water, pure naphthalase is precipitated, which may again be turned blue by oil of vitriol. The solution m oil of vitriol may be evaporated down for a few moments without losing its colour ; but it gradually turns red, and then brown. Even if the naphthalase be first heated with nitric acid or treated with chlorine, the blue colour is still produced on dis- solving it in oil of vitriol.

Insoluble ip cUccM, scarcely soluble in ether.

2ft 0XYGBN-NUCLBU8 C?«H«0».

Naphthuliida.

SoHUTZENBEBOER & WiLLM. Compt. rend, 46; 894 ; J". ;?r. CAmi. 74, 75.

il^rmalion and PT^^po^'o^Jon. When bjdrechlorate of napbftbalidine 18 treated with aaaeous nitrite of potash, a large qnantitj of nitrogen ia evolved, and a light brown substance insoluble in water is formed, which, when treated with alcohol or with ether, yields a red sabstance, nitrosonaphthylin, taming blue with acids. There remains a tolerably bulky, ulmin-black, non-azotised residue, which is naphthulmin, and may be purified by solution in oil of vitriol and precipitation with water.

20 C 6 H	... 120 ... 6 ... S2	.... 75-95 . S'79 . .... 20*26 .	Schtitzenberger & Willm. 76-18 ^'1%
4 0	20*03
C»HHy	... 158	.... 100-00 .	10000

It is therefore the hjdride of ozynaphthyl, or at least isomeric (?) with that Bubstanoe. (SchUtsenberger & l^illm.)

^ Insoluble in almost all solvents, especially in aeids fmid aUcaU/f, Dissolves in ail ^ vitriol with indigo*blue oolcmr, iMud i^ pr^oipitat^d tlierefrom in its original state by water.

Vanillin.

C*^H«0* = C»fi«0*,OM

GoBLBY. (1858.) I^. J. Phai^, 84, 461 . Am. ViB. N. J, Phaiv^, 34, 412.

(?iMv d§ PtmUk. Mistaken by BvchhoU (Revert. 2, 253) and by Vogel for ben, so'io acid, previonsly by Oobley for coamarin, and by others for cinnamic acid : first recognized as a distinct body by F. L. Bley {Br, Arch. 28, 132).

Source. In vanille, the fruit of Vanilla aromatica, -r- It constitutes the crystals which effloresce from the pods (Qobley, V^e) j and is deposited from tincture of vanille which has been kept for a long tim^

Preparation. The tincture of vanille, prepared with alcohol qf S5 p. c, is evaporated to the consistence of extract, diluted to a syrup with water and shaken up with ether, as long as that liauid takes up colooring matter. The ethereal extracts leave on evaporation a brown^ strongly smelling residue, from which boiling water extracts the vanillini to be purified by animal charcoal and recrystallisation.

NAPHTHBSIC ACID. 27

Properties. Colourless, long, fonr-sided, acicular prisms. Has a strong aromatic odoar of vanille, and a hot pungent taste. It is hard and cracks between the teeth. Melts at 76^ and volatilizes almost com- pletely at 150° in small, brilliant, white crystals. Neutral. (Goblej.) The yanillin effloresced on Tanilla-pods melts between 77 and 78°., and reddens litmus (V6e), very slightly (Gobley).

Gobley.

20 C 120 ..., 75-95 75-22

6H 6 .... 3-79 3-98

4 0 82 .... 20*26 20-80

C»H«0* 158 .... 10000 10000

Almost insoluble in cold, readily soluble in boiling water, (Gobley,

Diseolves without decomposition, in dilate (icids^ with yellow colour inwlof vitriol. (Gobley.) Dissolves easily in caustic potasky from which it is precipitated unchanged by acids. It does not expel carbonic acid from alkaline carbonates, even on boiling j neither does it combine with bases. (Gobley.)

Dissolves readily in alcohol, etkcr, and in oils both fat and f/olatiU, (Gobley.)

Naphthesic Acid.

C»H«0« « C»HH)*,OM

Lavrbnt. Eev. seient, 14, 560. Nttphisstmurs*

jFhrmation and Preparation. (See page 8.) Naphthalin placed in contact with bichromate of potash, water, and sulphuric acid, is violently attacked if little water is present, slightly If much water be present. If, after the reaction is over, the mass be treated with water, and the solution filtered from undecomposed naphthalin, and left to itself for one or two months, crystals of chrome-alum are deposited, at first pure, but afterwards covered with white granules of the size of a pin's head. When these granules are dissolved in alcohol, they remain, on evapora- ting the filter^ solution, as a crystalline mass, which may be purified by sublimation.

Properties. Crystallises in rhombic needles of 58° and 122°; melts below 100°.

20 C 6 H	120 6	.... 63-14 ... .... 3*1 0 •(.! .... o<S*70 ...	Laurent. 62-94 2-93
8 0	64	3413
C«*H«0«,0«	.... 190	.... lOO'OO ...	10000

According to a preliminaiy experiment, the atomic weight is m\ioh lees than is expressed by Uiis formala. (Liaarent.)

Very slighUy soluble in water.

28 SULPHI-NUCLEUS C^HyCSC).

Sulphi-nucleus, (^H'(SO»).

Sulphonaphihalin. C»ir(SO«).

Berzjslius. Ppgj. 44, 404 ; Anrt. Pkarm. 28, 9. Begnault. Ann. Chim, Phys. 05, 87 ; •/. pr, ChenL 12, 90. Laurent. Comiyt. chim. 1849, 390 ; abstr. Ann, Pharm, 72, 297. Gebike. Ann, Pharm. 100, 216; Liebig & Kopp*$ Jahredferushi, 1856, 613 (note).

Oside qf ThiononapMhyl. (Kolbe.)

Formation, (p. fi.) 1. Produced, to^etber with snlphonaphthalide, by the action of fuming^ sulphuric acid or salphuric anhydride on naph- tbalin. (Berzelius.) 2. By dissolving naphthalin in warm sulphuric acid, whereby only a small quantity of snlphonaphthalide is formed. (Berzelius.)

Preparation, Naphthalin is treated with sulphuric anhydride, as in the preparation of sulphonaphthalic acid (p. 16), and by the addition of water to the red product, a mixture of sulphonaphthalin, snlpho" naphtha] ide, and undecomposed naphthalin is precipitated. The last is Tolatilised by prolonged boiling of the mixture with water. The residae is fatty, sticks to the glass vessel Irnd dissolves very slightly in boiling water, which then becomes opaline on cooling. The residue is treated with cold alcohol, which dissolves scarcely anything but sulphonaphthalin, and the solution is crystallised by spontaneous evaporation. If the solution be evaporated by heat, it becomes turbid on coolinfif, and deposits a pulverulent mixture of both products, whilst the liquid contains merely traces of sulpho- naphthalide. (Berzelius.)

Properties. Soft, laminated nodules (Berzelius); crystalline (Gerike). Melts far below lOO'' (Berzelius); at 70" (v. Fehling, Handworterb. v. 439); between 90° and 95° (Gerike), to a yellowish liquid, solidifying in a transparent (gummy, Gerike), highly electric mass. (Berzelius.)

20 C 7 H	120 .... 75-47 ... 7 .... 4*40 ...	Berzelius. 74-974 4-879
S	16 .... 10-06 ...	10-000
2 O	16 .... 10-07 ...	10-147

C»H7(S02) 159 .... 100-00 100-000

According to Berzelius, sulphonaphthalin consists of C^H^ oomhined with 1 At. SO' ; it is not probable however, that naphthalin exists as such in the compound ; neither can it be determined whether sulphonaphthalin is CHHD' + S, or C^^^O^SO, or C^H^fSO'. (Berzelius.) It appears to be analogous to sulphobenside, and therefore its formula u probably 2(C^H7|S02). — (Gericke.)

Decompositions. Heated above its melting point, it gives off fumes, and sublimes as a mealy substance, portions of which are crystalline ; the product is partly decomposed sulphonaphthalin. Heated in small tubes, it distils partly in drops, and then evolves sulphurous acid and turns

SULPHONAPHTHALIDE. 2 9

yellow, brown, and finally black* (Berzelius.) Sublimes partly nnde- composed. (Gerike.)

2. Decomposes with fuming nitric (zeid; water precipitates white flakes from the solution. (Gerike.)

3. Aqua regia does not form sulphuric acid, even after prolonged boiling ; but dissolves the substance after 24 hours* boiling ; water pre- cipitates from the solution a substance which exactly resembles sulpho- naphthalide, and partly dissolves in ammonia with dark yellow colour, (Berzelius.) 4. Alcoholic potash does not decompose it at a high tern* peratare* (Gericke.)

ComJbinations. 1 . Does not dissolve in water (Gericke), boiling water dissolves only a trace of it, and becomes opaline on cooling (Berzelius). — 2. Dissolves in cold alcohol^ especially in anhydrous alcohol (Berzelius); scarcely in cold, and somewhat more m hot alcohol. (Gericke.) It is precipitated on cooling from the boiling saturated solution in the form of powder; but if separated before the liquid has cooled down below the melting point of sulphonaphthalin, it is deposited in drops, just as when the solution is evaporated by heat. (Berzelius.)

4 Appendix to Sulphonaphthalin,

SulphonaphthaUde. C^H'^SOM

BsRZBLius, Pogg. 44, 404; Ann* Pharm, 28, 9 ; «/. pr. Chem^ 12, 99.

Formaiion and Preparation, Formed, according to Berzelius, together with sulphonaphthalin, when naphthalin is treated with sul- phuric aoid, and in still greater quantity, when sulphuric anhydride is employed. The residue left on treating sulphonaphthalin and sulpho- naphthalide with cold alcohol (p. 28), is dissolved in boiling alcohol, whereupon the sulphonaphthalide separates on cooling out as a snow- white powder.

Properties, Colourless ; becomes strongly electric when rubbed or stroked with the back of a knife. Melts at a temperature much above 100° C. to a colourless liquid. Does not lose weight at 100°.

Berzeliiu.

24 C 144 .... 77-72 77146

10 H 10 .... 5-29 6-131

S 16 .... 8-50

2 O 16 .... 8-49

C"H"SO* 186 .... 10000

AcoordiBg to ▼. Fehliug (Handwdrterb, v. 439) it is a mixture of a little naph- thalinwith sulphonaphthalin. Gerhardtwas of the same opinion (TV. 3, 460). This is rendered very improbable by the much higher melting point of sulphonaphthalide* (Curias.)

Deccmpoeitions, !• Heated above its melting point, it fumes and sablimes with decomposition as a partly crystalline powden This subli-

80 BROMINE^NUCLEUS C^BtW.

mate melts and eolidifies in a ciyBtalline mass on oooling ; if die subli- mate be dissolved in alcohol^ it crystallises out by spontaneous eyapora* iion in small, short, needles acuminated at both ends, and appearing like elongated octahedrons ; they have a slight vellow tinge^ and are insoluble both in dilute acids and in canstio alkalis. Heat^ in a glass tube, sttlphoni^hthalide behaves like sulphonaphthalin,

2. Sulphonaphthalide is but slowly attacked by ciqua re^; it coheres, then melts on the surface, and slowly evolres nitric oxide. After prolonged boiling, it dissolves completely, if enough nitric acid is present; and the solution gives with water a white precipitate which assumes a lemon colour on the filter. The filtered liquid does not contain a trace of €ttlphuric acid, eren when heat has been applied for several days ; hence the sulphonaphthalide nmst be converted into another sulphurised body.

3. Heated with nitraU of baryta, it volatilises without oxidation of the sulphur. — 4. On heating it with Morate of potash and carbonate of sodOf a partial decomposition is effected, and the solution of the residue contains sulphuric acid.

ComhinationB, Insoluble in water, concentrated nitric aeid^ and caustic potash.

Dissolves very slightly, if at all, in cold, and slightly in boiling absolute alcohol, separating out for the most part, on cooling. Very slightly soluble in etJier.

Bromine-nucleus C*BrH^.

Bromonaphthalin. C»BrH'.

Laurent. Ann. Chim, Phys, ,59, 216; Ann, Fharm. 12, 187; Pogg^ 81, 320 ; Further, Rev. scient. 12, 195.

Bromonophtalate, Bronapktase, (Lanrent) Bromide t^f fuqfhthpl, (Kolbe.) Bro- minated naphthalin. (G«rh«rdt.)

Formation and Preparation, Formed when bromine is brought in contact with excess of naphthalin, a violent action taking place, heat being developed, and hydrobromic acid evolved. With excess of bromine, bibromonaphthalin is likewise formed, and is very diflicult to separate from bromonaphthalin, since both are equally soluble in alcohol and ether. They may be incompletely separated by distilling the crude oily mixture, bibromonaphthalin passing over towards the last.

Properties. Colourless oil, volatile without decomposition. The

crude oil, not previously purified, gave on analysis 50*90 p. c. C. and

2*95 p.c. H, (Laurent.) In accordance with this analysis, Laurent considers the crude oil to be a mixture of 1 At. bromonaphthalin, C^BrH', and 1 At. bibromonaph- thalin, C»Bi«H«.

DecomposUums, 1. Bromonaphthalin is not attacked by alcoholic potash. — 8. Bromine converts it into bibromonaphthalin and other brominated products, hydrobromic acid being evolved. — 3. Chlorine forms hydrochlorate of bromochloronaphthalin and an oily compound containing bromine and chlorine. •— 4. Suiphurio acid converts it into bromosnlphonaphthalie acid.

BROMOSULPHONAPHTHALtO ACID. 81

ChnjugaUd compcnmd of the Brcmine-nudem, G^BrH\

Bromosulphonaphthalic Acid.

LAURtiNf. Cofnpt. rend. 21, 33; Contpt chim, 1849, 3d0; abstr. iinn. FhatTn. 72, 297 ; Liebig & Kopp's Jahrah. 1849, 441.

BrwHinaphHHnieKwrfeUdttre; BromonaphthylodiihitmicBeiis Brominuted SutphO" naphikalie acid.

Known only in combination with bases*

Ponnaiion and Preparation of the Potash-salt Bromonaphllialin is heated with fuming snlphuric acid till complete solution takes place, after which the liquid is diluted with water and neutralised with potash. The whole is then heated to boiling, filtered from a little free bromonaphthalin, and allowed to cool. The crystalline mass which now separates out is washed on a filter and dissolved in boiling alcohol. On cooling, the potash-salt is deposited in crystals.

})ecompositton. By boiling nitric add. It the solution of the potash- salt be eyaporated to dryness with nitric acid, and the residue taken up with water and neatralised with potash, a yellow powder, almost insoluble in water, separates out, which deflagrates when heated in sealed vessels, and is therefore probably a nitro-compound.

Brom<mUphonap?Uhalate of Potash. •— Colonrless, crystallises in nodules.

Lanrenh

KO,80S

^ i38'0 .,M f3*3 87-2 .... 267 ...*%!..

85*95

C«BrKH«,2SO* .... 325*2 .... 1000

Bromosulphonaphthalate of potash produces in a moderately dilute solution of chloride ofecUciuni, a white precipitate ; also in acetate oft^d. It does not precipitate salts of magnestum, manganese, cobalt, nickel, zinc, or silver.

JSromosulphonaj^hataie of Baryta obtained by double decomposition, separate out f^m its warm and slightly dilute solution as a ciystalline ptecipitate.

Laurent.

C«BrH«80« 2380 .... 673

BaO,80< 116-5 .... 327 .,....- 324

- -'— ' ■ - '

C»BrBaH<,2S0" .... 3545 .... 1000

i2 BROMINE-NUCLEUS C»Bi*H«.

Bramine^ucletis (?*^Bi!*H*.

Bibromonaphthalin- Ci*»Br>H«.

Laurbnt. Ann. Okim. Phys. 59, 216 ; Ann. Fharm. 12, 187 ; Pogg. 31, 320 ; Further, Eev, scient. 12, 204.

. BronmaphtaUte, BronapAte$e* (Laurent.) DekahexylbromUr, (Berzellos.) BfO^ mide qf bromonaphthyl (Kolbe).

Formation and Preparation. Bromine is added to naphthalin or to bromonaphthalin till no more hjdrobromic acid is evolved ; and the mass, which solidifies when the reaction is completed, is dissolved in alcohol and left to crystallise. Abo formed whea Laurent's first bromure de bronaphiine U heated, together with free bromine and terbromonaphthalin. (Comp, p. 34.)

Properties. Long, white, inodorons needles, whose section forms a hexagon with two very acute angles. Melts when heated and solidifies in a fibrous mass when oooled to 59^ Volatile without decomposition.

Laurent.

20 C 120 ...• 41-95 42-17

6H 6 .... 2-ia 2*25

2 Br ., 160 .... 55-93

C»Bi»H« 286 .... 100-00

Deeompontiona. Heated on platinum-foil in the flame of a lamp, it hums witn a smoky flame, which goes out as soon as the lamp is taken away. — 2. Chlorine does not act upon it in the cold; bnt on heating, quad- rich loronaphthalin is formed. 3. Cold nitric acid does not attack it; the boiling acid decomposes it. — 4. Sulphur dissolves in bibromonapbthalin when heated ; on cooling, both bodies separate in crystals. If heat be applied till the mixture of the two bodies assumes the colour of bromine, it remains fluid for a long time after cooling to 10". If the mixture be ultimately heated to boiling, it evolves hydrobromic and hydrosulphuric acids, and deposits charcoal. — 5. Sulphuric acid appears to be without action on bibromonapbthalin, even when warmed, but chars it slightly. Fuming sulphuric acid forms bibromosulphonaphthalic acid.

— 6. Potassium decomposes it slightly at a gentle heat, and becomes covered with bromide of potassium; at a strong heat, decomposition suddenly takes place, with evolution of light, and charcoal is deposited.

— 7. It is not attacked by hydrate of potash.

Combinations, Insoluble in water; very soluble in alcohol and in elher.

TERBROMONAPHTHALIN. 33

ConjugaUd compounda oftlht Bromine-mideuB C*Br*H*.

Bibromosulphonaphthalic Acid.

Laurent. Compt. rend. 21, 33 ; Compt. chim. 1849, 390 ; abstr. Ann. Pharm, 72, 297 ; Liehig & K<ypp'$ Jdhresb. 1849, 441.

Bibromanaphihylodtthionic acid; Bibrominated atUphonaphthalic add. Known only in combination with bases.

Formaiicm and Preparation. Prepared from bibroinonapbthalin witb fuming snlpbnrio acid, in the same way as bromosnlpbonapbthalic acid from bromonaphtbalin. The solution is diluted witb water, neutralised witb potash, and heated to boiling ; and the liquid is filtered from the free bibromonaphthalin, and allowed to crystallise by cooling. The bibromosulpbonaphthalate of potasb thus obtained is purified by recrys- tallisation.

Potaah-ioit. Laurent.

C»Br»H«S03 817 .... 784

K0,S03 87-2 .... 21-6 21-5

C»Br2KH»,2SO» 4042 .... 100.0

£ibramo8ulphonaphthala(e of Baryta is obtained by mixing tbe solu- tion of the potasb-salt with a very dilute, boiling solution of chloride of barium. Deposited on cooling as a flocculent precipitate, consisting of microscopic crystals.

Laurent.

C»Bf«H5S0« 817 .... 73-2

BaO.SC 116-5 .... 26-8 26-6

C»Br2BaH»,2SO» 433-5 .... 1000

Bromine-nucleus C«^Br»H».

Terbromonaphthalin,

C»Br»H*. Laurent. Rev. meni. 12, 213; 13, 95.

Bromnaphtalue, Bronaphtue. (Laurent.) Bromide of hibrmimaphthyl.

Formation and Preparation. 1. Bibromonaphthalin is heated with excess of bromine. — 2. Laurent's first bromure de bronaphtine is heated in a retort, whereupon bromine is evolved and a crystalline mixture passes over, consisting of bi- and ter-bromonaphthalin, which are separated by ether. By spontaneous evaporation, tbe terbromonaphthalin crystal- lises first, mixed however with bibromonaphthalin.

VOL. XIV. ^

34 APPENDIX TO TBRBRONAPHTHALIN.

Properties. Fine yellow needles; melts at about 60°, and then does not sometimes solidify till it has cooled down to the common temperature.

Laurent.

20 C 120 .... 32-87 3430

5 H ft .... 1-87 ,. 1-46

3 Br 240 .... 65'76

C»Br»H» 365 .... 10000

It still contained a litcle bibromonaphthalin.

Very slightly solable in alcohol, moderately solable in ether.

Appendix to TerbromonaphtihaUn,

Bronaphthin, C"H»-»Bi*»f

Laurent. Bev. tcient. 12, 204.

Formation and Preparation. Formed, together with several other products, by pouring bromine over bibromonaphthalin. The mixture is extracted with ether and the compound is obtained in crystals by spon- taneous evaporation.

Properties, Opaque, white, microscopic needles, united in slightly radiated scales. Melts at 48°, and volatilises undecomposed.)

Laurent.

20 C 120 .... 37-40 3817

5-5 H 5-5 .... 1-75 182

2-5 Br 200 .... 60*85

■ - . ■ . '

C»Bi^-*H»-* .... 325-5 .... 100-00

It ifl perhaps » C^Br^H" + C»Bi«H».

Laurent's First Bromide of Bronaphthin.

C«H»-»Br»-», Br*.

Laurent. J^ev. sdenl. 13, 95.

Formation and Preparation. When bibromonaphthalin is exposed to sunshine, with an excess of bromino, hydrobromic acid is evolved, and after one or two days, a crystalline mass is deposited, which either con- sists wholly of the bromide, or contains the compound C'"Br*H^2HBr as well. If enough bromine has been used, the bromide crystallises in prisms which may be picked out with a pair of forceps. Should the compound

.QUADRIBROMONAPHTHALIN. 38

C*^Bi^H',2HBr hav0 been likewise fonued, th^ mixture^ afi^r repeated wa«hing, must be triturated with ether and dissolved therein^ the solution allowed to evaporate slowly^ and the crystals picked out*

Propei-ties. Right rhombic prisms, {Fig. QSy, * : < = 115° 30'j tt': < = 109°; «': t* = 142°.

Lfturent.

20 C 120 .... 18-59 19-40

6-5 H 5-5 .... 0-85 0*88

6.5 Br 520 .... 8056

.CJ»HS4Br«-« .... 645-5 .... 100-00

According to ▼. Fehling (IfandwdHerh, 5, 456), it is a mixture of C»Br*H*,2HBr and C»PBr»H»,2HBr* It is decomposed by distillation, bromine being evolved and a mixture of bi- and terbromonaphthalin passing over. (Laurent.)

Laurent's Second Bromide of Bronaphthuti

C*»H»-»Br»-«, Br«. Laubent. Eev. scient. 13, 97.

Formation and Preparation, Bibromonaphthalin is heated with excess of bromine, and allowed to stand for two days, the whole being repeatedly heated. A body very slightly soluble in ether is formed, apparently of the same formula as the first bromide of bronaphthin, but crystallising in a different form.

Oblique rectangular prisms m: t = 90"; y : « = 90°; y : m = 127°. Sometimes the angles ^, m, t are truncated by the faces a, which oblite-> rate all the others, a : m = 1 30°; a : ^ = 1 20°.

Laurent's analysis gave 18*94 p. c. C and 0*86 p. c. H.

Evolves bromine and a little hydrobromic acid when heated, and leaves an oil which solidifies in needles on cooling.

Bromine^wiLem C^Br*H^

Quadribromonaphthalin*

C»Bi*H*. Laurent. Rev, sdent, 12, 221.

Bronaphiote, (Laurent.) Bromide of trihromonaphfhyt*

Formation and Preparation. When the bromide C*Bi*H*,2HBr \9 distilled, hydrobromic acid and a little bromine are evolved, and a white substance distils over, which is a mixture of qaadribromooaphthalin with

d2

36 BHOMINE-NUCLEUS C»Br*H<.

another body. In order to effect their separation, they are washed with ether, then warmed with ether in a strong sealed tube placed in a water bath at 100®, an<l after the whole has cooled, the short brilliant prisms of qnadribromonaphthalin are picked out from the other substance, which crystallises in very fine needles.

Properties. Oblique prisms with oblique base, exactly resembling quadrichloronaphthaliu 6. Inclination of tne lateral edges =101° dO'> Inclination of the base to either side = between lOl*' SO' and 102**. Volatile without decomposition.

Laurent. Prismi, mean.

20 C 120 .... 27-45 2717

4 H 4 .... 0-91 0-93

4 Br 320 .... 7164

C»Br<H* 444 .... lOO'OO

Hydi*ate of potcuih has not the slightest action on this compound. It is slightly soluble in alcohol and in ether.

The substance crystallising in fine needles which accompanies qnad- ribromonaphthalin, is probably isomeric with that compound. The angles of the needles are of 1 20°; the crystals are very elastic, brittle, and very slightly soluble in ether. (Laurent.)

Hydrobromate of Qaadribromonaphthalin.

C«»Br»H* = C«Br*H*,HBr. Laurent. Rev. scient. 13, 94.

Sottihromwre de hronaphtite, (Laurent.) Bromure de naphtaline tribromSe, (Gerhardt.)

Foi'mation. Sometimes formed, together with the compound C^Br*H^2HBr, when bibromonaphthalin is treated with bromine. To separate the mixture, it is boiled with ether, in which the bromide (^Br^H^HBr chiefly dissolyes, and is deposited in microscopic needles by the spontaneous evaporation of this solution.

Needles, Laurent.

20 C 120 .... 22-85 23-61

5H 5 .... 0-95 ........ 1-00

5 Br 400 .... 76-20

C»Br*HSHBr 525 ... 10000

Decomposed by distillation, evolving bromine with a little hydro- bromic acid, and yielding a crystalline sublimate very slightly soluble in ether (quadribromonaphthalin ?)

BIHTDROBROMATE OF PJSNTABROMONAPHTHAUN. 37

Bihydrobromate of Quadribromonaphthalin.

C»Br«H« = C«Br*HS 2flBr. Laurent. Bev, 9cient, 13^ 94.

BnmaphtesbromUrf DecahexyUuperbromid.

Formation and Preparation, By pouring bromine oyer naphthalin or bibromonaphtbalin. Sometimes after a few boars a wbite powder is deposited^ wbich is washed with ether.

Properties. Crystallises by spontaneous eraporation from its boiling ethereal solution, in microscopic rhombic tables.

Tables, Lanrent.

20 C 120 .... 19-80 20-49

6 H 6 .... 0-99 1-01

6 Br 480 .... 79*21

C»Br*H«,2HBr 606 . .. 10000

Deeompositions, 1, Deoomnoses by distillation into hydrobromio acid^ a little bromine, and quaaribromenaphthalin, which condenses in the neck of the retort. — 2. Decomposed with great difficulty by alooholie potash, with formation of bromide of potassium.

Very slightly soluble in boiling ether.

Bromine-nueUus C^Bz^H*.

Bihydrobromate of Fentabromonaphthalin.

C»Br'H» = C^'Br^H', 2HBp.

Laurbmt. £ev. sclent, 13, 579.

Bromure de bronaphiue, (Lanreot.) Quadribromnaphtylbromitr'bibromwiU'' serstoff, (Kolbe.)

Formation and Preparation, By the prolonged action of bromine on bibromonaphtbalin or on naphthalin, at a gentle heat, and finally in sun- shine. The substance is recrystallised fromether, and the czystals picked out with forceps.

Properties, Crystallises in prisms belonging to the doubly oblique prismatic system, yery closely resembling prisms of the oblique prismatic system; like Fig. 112, together with the sides a; u : u = 110°; %\h nght = 132^ left = 130** 30'; i : a left = 120°; t : w = 105°.

Priims. Laurent.

20 C 120 17-52 .... 18-01

5H...... 5 0-73 .... 0-75

7 Br 560 81-76

C»Bf»H»,2HBr 685 .. lOOOO

38 . CONJUGATED GOMPOUNDS OF THE CHLORINE-NUCLEUS CP^aH'.

Decomposed by distillation, bromine being eYolyed and another pro- dnct formed which has not yet been investigated* Very slightly soluble in etker.

Chlorine-nudeua C^Clff.

Chloronaphthalin. C«C1H'.

Laurent. Ann* Ckim. Fhyt* 59j 196 ; abstr. Ann. Phamk B, S; Ben, Jdhrefh. 16^ 350. — Rev, scient. 13» 78^ <fe 92. — ZiNur. J.pr. Chem, 83, 36.

ChiomaphialaSf Chlomaphtat. (Laurent.) Ikodekates»erylehlorUr. (Berzelins.) Naphialine chlorie. (Gerhardt.) Chloronaphihalid, (Mitscherlich.) a- Chloronaph' thalid. (Uwig.)

Forma;^<m and Preparation, 1 . Hydrochlorate of chloronaphthalin is repeatedly distilled over hydrate of lime. — 2. Hydrochlorate of chloronaphthalin is boiled with alcoholic potash, and the oily compound thus liberated is precipitated by adding water, and purified by distilla- tion. (Laurent.)

Properties. Colourless, transparent oil; combustible; distils without decomposition.

Laurent. Oil. mean*

20 C 120 .... 73-84 ., 72-75

7 H 7 . .. 4-31 400

CI 35-5 .... 21-85

C»C1H7...! 162-5 .... 10000

Deeompoeitiani. 1. Heated with oil of viliHol, it is concerted into chlorosulphonaphthalic acid (Zinin); it is not attacked by sulphuric acid (Laurent). 2. Decomposed by bromine with violent effervescence ; hydrobromic acid being evolved, and bihydrobromate of terbroraochloro- naphthalin (C»Br»ClH*,'2HBr), being formed. — 8. Chlorine converts it into a peculiar oil which is changed into a-terchloronaphthalin by hydrate of potash. If the action of the chlorine is aided by a gentle heat, ter- or quadricliloronaphthalin is directly formed. — 4. Kot attacked by hydrate of potash. (Laurent.)

Conjugated compounds of the Chhrine-nudeus C*C1H'.

Ghlorosulphonaphfhalic Acid.

0««C1H^2S0». Zinin. J. pr. Chem, 38, 36.

Chlonu^onaphiaKnsaure, Chlorohypiftulphonaphthalasie acid. (Laurent.) Acide tulfimaphtalique chlori. (Gerhardt.)

Fwrnaiion and Preparation. 1 vol. of purified chloronaphthalin is mixed with 2 yols. of sulphuric acid, and the mixture heated for a

UYDROCULORATB OF CHLORONAPHTHALIN. 39

quarter of an hour in an oil-bath to 140^. A transparent^ brownish liquid is thereby obtained, which is not changed by cooling, but on the addition of a fbw drops of water, solidifies in a white, buttery, crystalline mass, which must be placed upon a porous tile to absorb the excess of sulphuric acid. (Zinin.) The same aCid is also probably obtained by treating hydrocblorate of chloronaphthalin with fuming sulphuric acid, hydrochloric acid gas being eyolredi (Laurent.)

ProperHei. Melts by heat to a brownish liquid, and then decomposes, diffusing an odour of naphthalin.

OombincUioiu, Readily soluble in water.

Forms with bases chiefly soluble saUs; with ammonia, a %hite, easily soluble, non-crystalline mass ; with potash, a dull, white powder, but slightly soluble in water and in alcohol i this gare accoitiing to Zitain's analysis^ 16*71 p. e. KO, (the formula C*^C1&K,2S0* requires ld8p.c. KO).

Chlorostilphanaphthdlate of Baryta, Dull white, microscopic needles, diffionltiy solnblv.

20 c 6 H	120 .... 38-69 . 6 .... 1-94 .	2inin. at 150*. 38-77 i 2-13
CI BaO	35*5 .... 11-48 .. , 76*6 .... 24-69 .	11-18 25-65
5 O	40 ...» 12-90 ,	i, 11'96
2S	32 .... 10-32 ..	10*31

C»»C1M«B«,2S0> SlO'l .... 10000 10000

Cuprous dihroiutphonaphlkalate is a white flocculent precipitate ; the eupHe salt is bluish and readily soluble ; the lead-salt a white, almost insoluble body; the silver-salt a white, curdy, precipitate, slightly soluble in water, and decomposing at 100^ C.

Chlorosulphonaphthallc acid dissolves easily in alcohol.

Hydrocblorate of Chloronaphthalin.

C*C1«H« = C»C1H^HC1.

Laurent. Ann, Cliim, Phys. 52, 275; Ann. Chim. Phys. 59, 196; Ann. Pharm, 8, 8; Pogg. 29, 77 ; abstr. Brrz. Jahresb. 16, 350; Pev. scient. 13, 76.

Hydroehlorate qf Chlortumhihalate, or Chlonapkihase. (Laurent.) Bichloride qf naphthdUn, (Berxellas.) NaphtalidchlorHtr. (Mitftcherlicb.) Naphtylehlor&r'Chlor^ wasHr^iof. (Kolbe.) Chlttrure de naphtdiine. (Gerhftrdt.)

fornidtion. Hydrocblorate of chloronaphthalin is the first product of the action of chlorine upon naphthalin.

Preparation. 1. When dry chlorine gas is passed at the common temperature over naphthalin, a yiotont action immediately sets in ; the

40 CONJUGATED COMPOUNDS OF THE CHLORINE-NUCLEUS C»aH".

naphtbalin melts, and when the stream of chlorine is rapid, partly sub- limes as solid C'^*'C1'H®,2HCI, hydrochloric acid being liberated at the same time. The mass gradually thickens, owing to the formation of a granular substance, and after a while assumes the consistence of solidified olive oil. The same product is formed, when, in preparing naphthaliu according to the method given at p. 4, chlorine is passed too long into the tar. If all the naphthalin has not been attacked, the mass must be gently warmed till it melts, and again treated with chlorine. After the reaction is terminated, the mass consists of solid and liquid hydrochlorate of chloronaphthalin ; it is shaken up with ether in a glass tube, the liquid decanted, and the mass treated in the same way three or four times, and then filtered. The whole of the ethereal solutions are distilled till the greater part of the ether is volatilised, and the residue, which still contains ether, is maintained at a temperature of — 10°, as long as it continues to deposit solid chloride. The oily chloride is now removed with a pipette from the crystals, and the ether is evaporated by a gentle heat. The fluid chloride thus obtained, invariably contains a small quantity of the solid chloride. (Laurent, Ann, Chim, Fhys, 52, 275.)

2. The following is a better method. Chlorine is passed oyer naph- thalin, till the resulting oily compound, which had become heated during the reaction, begins to deposit a white granular mass. The oily liquid thus formed is a mixture of naphthalin, the oil C^C1H'',HC1, and the crystalline body C'*'C1*H',2HC1. (If an attempt were made to convert all the naphthalin, there would he a risk of transforming the two chlorine-compounds into other compounds closely resembling them.) In order to partially remove the naph- thalin, the mixture is heated in a dish for a long time between 50° and 60°; the residue is afterwards dissolved in ether, and the solution is kept for some time at — 10°. The residual ethereal solution is mixed with alcohol and exposed to the air in an open beaker, until f of the oil have been deposited ; this portion contains the oily chloride. The third-fifth is collected apart ; it is the solid chloride in a state of perfect purity; while the -| still in solution contain naphthalin. (Laurent, Ann, Chim. i%«. 59, 196.)

Properties. Pale yellow oil, heavier than water, and smelling like the solid bihydrochlorate of bichloronaphthalin (C«°C1»H«,2HC1).

Laurent. Oil. Ist analysis. 2nd analysis.

20 C 120 .... 60-30 61-435 .... 60-60

8 H 8 402 3-625 .... 3-60

2 CI 71 .... 35-68

C»CIH7,HC1 199 .... 100-00

Decompositions. 1. Hydrochlorate of chloronaphthalin cannot be made to bum of itself, but must first be mixed with some combustible body, such as paper or wood, when it burns with a green-edged smoky flame. — 2. Decomposes partly by distillation, hydrochloric acid gas being evolved and chloronaphthalin (C"CIH') being formed. When redistilled six times, whereupon a little hydrochloric acid is each time evolved, it is converted into a colourless oil, which has the composition of a sub-hydrochlorate, since it contains 67'81 p. c. C and 386 p. c. H,

BICHLORONAPUTilALlN. 41

and probably oorresponds to the formula 2 (C^G1H''),H CI; it may how- ever not be a pure product, since it loses by repeated distillation as much hydrochloric acid as it had already parted with . (Laurent.) — 3. Hydro- chlorate of chloronaphthalin is decomposed very slowly by potassium, even at the boiling heat, into chloride of potassium and an oil ; it was for this reason that Laurent {Ann. Giim. Phys, 52, 275) formerly supposed that it was not decomposed by potassium, but that the formation of chloride of potassium was owing to decomposition of solid chloride contained in the liquid. (Laurent.) 4. Distilled over fra^i^ents of potash, it parts with hydrochloric acid ; the decomposition is more complete than by distillation per se, chloride of potassium being formed and chloronaphthalin obtained' as distillate ; but to decompose the oil effectually, it is necessary to repeat the operation three or four times. (Laurent, Ann. Ohim, Phys, 59, 19G.) Alcoholic potash decomposes it readily and completely into chloride of potassium and chloronaphthalin. (Laurent, Rev, Scient. 13, 76.) — 5. By bromine it is converted into chlorenbronaphtone B (?).*— 6. Chlorine conTorts it slowly into solid C^C1*H^2HCI; but when heat is applied, bihydrochlorate of terchloronaphthalin is formed. This last body is produced in this reaction in two modifications :

C»C1H7,HC1 + Cl< = HCl + C»C1»H»,2HC1.

If too great a heat be applied during the action of the chlorine, terchloro- naphthalin A is also formed, or the products of its decomposition by the action of chlorine. (Laurent.)

7. Niiric acid slowly converts it into a yellow, glutinous, and viscid mass. — 8. Dissolves in hot fuming sulphuric acid, with evolution of hydrochl6rio acid gas; the resulting liquid diluted with water and saturated with carbonate of baryta, yields an almost insoluble salt. (Laurent.)

Comlfinations. Insoluble in water. Dissolves readily in alcohol, still more and in every proportion in ether.

aOarine-nucleuB C*>Cl*H*.

Bichloronaphthalin. C^Cim\

Laurent. Ann, Chim, Phys. 59, 196 ; abstr. Ann. Pharm. 8^ 8 ; Bert. Jahres. 16, 350 ; Further, Compt. rend. 21, 35 ; Eev. scient. 12, 196 j Compt. chim. 1850, l &7 ; abstr. Ann. Pharm. 76, 399.

Chlomaphtalete, CMomaphtete. (Laurent.) Dekahexyleklori^. (Berzelias.) Naphtalidchhrid. (Mitecherlich.) Napthaline bichlorie. (Gerhardt.) Chloride of ehhronaphihyl. (Kolbe)

Formation. According to Laurent, bichloronaphthalin exitts in seven different modijlcations. It is formed : 1 . from o- hydrochlorate of bichloro- naphthalin ; a. by distillaiion, in the modifications A, C, F, and X; — h. by decomposition with potash, in modifications E, and AD — c. by alcoholic ammonia, in the modification C. — It is formed : 2. from $- bihydrochlorate of bichloronaphthalin; a. by distillation, in the modifi- cation C. ; — b. by decomposition with potash, in the modification F, together with an oil. — Formed : 3. in the modification G, by treating binitronaphthalin with chlorine.

42

CHLORINE-NUCLEUS C»Cl*H«.

Chitf characteriitici of the BtMoivnaphthalins. (Laurent. Serf.

seierU. 12, 203.)

	A.	C.	AD.	E.	F.	X.	Y.
Form	Fluid	Needles of	Needles	Needles	Tables	Fluid	Sab.
		112* 30'	of 122"	of94*'	103«		limed laminsB
Meltmff	tika	60*"	28 -80'	31»	101*
point
JFbmuvnth	OilyA-bihy-	Bihydrochlo-	Trichloro-	•<••	Lamins	OilyX-bihy-
chlorine	dro chlorate	rate of quad-	naphtha-		of chlo-	drochlorate
	of quadri-	richloronaph-	linAC		naph-	of quadri-
	chloronaph-	thalin C			tone	chlotonaph-
	thtdin, which					thalin,
	i» ooDTerted					Which is
	by potash					oonyerted
	into A' quad-					by potash
	richloronaph-					into £ quad-
	thalin					richloro- oaphthalih
Formi	• •••	Bihydrobro-	Bromo-	!•••	Bibro-	AnoU
with irO'		mateofbibro-	bichloro-		mobi-
mine		mobichloro- naphthalin	naphtha- lin A		chloro- naphtha-
					lin B

a. Isomeric bkhloronaphihalins formed hy the distUlfUion of a- C*CPH*, 2HC1.

1. Modification C. Obtained by the distillation of a- Cr»Cl»H*,2HCl, hydrocbloric acid gas being OTolved. It is obtained mixed with a peculiar oil (the quantity of which increases with the rapidity of the distillation), and with undecomposed chloride ; for this reason, the distillation must be repeated in order to decompose the latter* l*he product is pressed between blotting paper^ dissolved in alcohol at the common temperature, and crystallised by cooling the fiolutiou to — 5° or — 10* C. (Laurent, Ann. Chim. Phys. 59, 196.) — 2. The oily distillate of a - C«>C1*H«,2HC1 deposits, after varying intervals of time, at first chiefly rhombic tablets of bichloronaph thalin F, from which the oil is decanted, and then needles of C. — Bichloronaphthalin X, which is likewise present, but in very varying proportions, is removed with a pipette when the quantity is considerable; the crystals are further pressed Between blotting paper, dissolved in ether- alcohol (more advantageously in ether, if the suostance still contains rhombic tablets); and the liquid is allowed to evaporate spontaneously in a flat-bottomed flask. As soon as all the ether is evaporated, but not the small quantity of alcohol, the crystals are thrown upon paper, and if any rhombic tablets are mixed with them, they are picked out with forceps. ( Lauren t. )

8. Chloride of sulphur (which ?) is heated in a flask, and naphthalin gradually added, whereupon hydrochloric acid is evolved. After the action has ceased, water and ammonia are added, whereupon a soft.

BICHLORONAPTHALIN. 43

brown mixture of salpbnr and a crystallisable sabstance ia produced, from wbicb bichloronapbthalin C is extracted by boiling alcobol and crystallises out on cooling. (Laurent.)

Frapefiies. Crystallises from alcobol in long transparent needles baving a rbombic section (of 111° or 1 12°) and terminated by very acute pyramids. Generally two such prisms are joined together lengtbways, so tbat hemitropby results, just as in tbe case of spbene. The crystals obtained from ether, though tolerably large, are nevertheless extremely irregular. Melts about 50^ to a colourless oil, solidifying at 44° in a fibrous mass. Distils without decomposition. Inodorous and tasteless.

Laurent. average* Needlee, a. h,

20 C 120 .... 60-87 6162 .... 6073

6H 6 .... 304 2-90 .... 2*96

2 CI 71 .... 36-09

C»Cl«H» 197 .... 100-00

b was prepared by the third method*

DecompofUionB, 1. Forms witb chlorine at ordinary temperatures, bihydrochlorate of quadrichloronaphthalin ; by beat, chiefly tbe modifi- cations h and c of quadrichloronaphthalin. — 2 With bromine at ordinary temperatures it forms bihydrobromate of bibromobichloronapbtbalin. — 3. Nitric^ hydrochloric and sulphuric adds are without action upon it.

— (Laurent.) Fuming sulphuric acid dissolves it when heated, with formation of bichlorosulphonaphthalic acid (Zinin, J. pr. Chem, 33, 37.)

— 4. It is not attacked by potassium in the cold, but between 30° and 40° it is decomposed, witb eyolutlon of li^bt and deposition of carbon.

— 5. Very concentrated solution of potash does not attack it, even on boiling.

Insoluble in water; very soluble in alcohol and in etJier, 2. Modification F, is contained, according to Laurent, In tbe oily distillate from the chloride a- C^C1'H*,2HC1 (see modification C; prepara- tion 2, p. 40). The oil above tbe rbombic tablets is decanted; tbe crystals are dissolved in ether; and the solution is placed in a flat-bottomed flask, and allowed to evaporate very slowly. After two or three days beautiful rhombic tablets are formed, mixed with a few acicular groups of C; these latter are first picked out as completely as possible, and the crystals are then washed with ether, whicb dissolves tbe tablets less rapidly than tbe needles. The tablets are finally recrystallised once or twice from ether. (Laurent.)

Properties. Colourless, inodorous, rhombic tablets, with angles of 77^ and 103^ Melts at 101'', and on cooling solidifies in a soaly mass. Distils without decomposition.

Laurent.

20 C 120 .... 60-85 60-45

6 H 6 .... 3-05 3-08

2 CI 71 .... 36-10

C?»C1>H» 197 .... 10000

Decompositions^ 1. Not attacked by alcoholic potash, — 2. Converted by bromine into bibromo-bicbloronaphthalin 5. -^ 3. Forms a substitution-

44 CHLORINE-NUCLEUS C»C1«H«.

prodact with chlorine, — 4. Dissolyed by warm /umtn^ wlphuric acid; the solation is not precipitated by water. Dissolves readily ia alcohol and in ether,

3. Modification X is produced, together with the two preyioas modifications C and F, by distilling a- C'^PH*,2HC1 and forms the oil- decanted from these two. According to Laurent, the more rapid the distillation, the more abundantly is the oil formed; but he does not mention how this liquid modification X, is to be separated from the oily modification A (4), which is also produced in the distillation. K)ariu8.) Sometimes the distillate does not solidify on cooling, or only becomes partially solid. In order to purify the decanted oil, it is dissolved in alcohol; the solution is cooled to — 8° or — 10^ and decanted from the crystals hereby deposited; and the oil is precipitated by the addition of water. (Laurent.)

Properties. Distils without decomposition. Contains 60*5 p. o. C andd'Op.c. H. (Laurent.)

Converted by chlorine into oily bihydrochlorato of quadrichloronaph- thalin X. — It is not decomposed by akolwUc potash.

4. Modification A is obtained by redistilling the chloride a C*^CPH*,- 2HC1 four or five times, whereby the modification C is completely decomposed.

Properties. Oil, not decomposed by distillation, and containing 60*5 p. c. C. and 3'2 p. c. H. (Laurent.)

Converted by chlorine into oily hydrochlorate of quadrichloronaph* thalin A. — Not attacked by hydrate of potash.

' h. Isomeric bichloronaphthcUitis obtained by decomposing a-bihydro- chlorate of bichloronaphthalin with alcoholic potash.

5. Modification AD. Parachloronaphthalose (Laurent), a-bihydro- chlorate of bichloronaphthalin is distilled upwards for an hour in a long- necked flask with concentrated alcoholic potash; the liquid is precipi- tated with water ; and the precipitated oil is redistilled with alcoholic potash in the same way, then reprecipitated by water, freed from adhering potash, chloride of potassium and alcohol by washing with water, and finally dried. The colourless or faintly yellowish oil thus obtained, gradually solidifies in a white nacreous mass, which is purified from adhering oil by pressing between blotting paper, and then dissolved in ether-alcohol. By cooling the solution to — 5 or — 10®, crystals are obtained, which are separated from the mother-liquor and dried. The crystals may sometimes contain a little bihydrochlorate of bichloronaphthalin ; in this case, the ethereal solution, by slow evaporaiion, first deposits this substance in rhombic laminae which are less readily fusible and less soluble in ether than AD. f Laurent.)

Properties. Colourless, acute laminsd, or rather long rhomoic neeales of 122° (Laurent, Rev. scienL 13, 72). Melts between 28 and SO""; but does not solidify till cooled to 1 8° or 20°, and then forms a nacreous, but not fibrous mass. Volatile without decomposition. Inodorous.

Needles or lamina, Laurent.

20 C 120 .... 60-87 6135

6 H 6 .... 304 2-90

2 CI 71 .... 36-09

C»a«H« 197 .... 10000

BICHLOROSULPHONAPHTHAUC ACID. 45

DecamposUicns. 1. UnaU!icked by acids, — 2, Faming sulphuric acid behaves with this compound a« with the isomeric compound C- bichloronaphthalin. — 3. With chlorine it forms, when warmed, ter- ohloronaphthalin AC. — 4. With bromine, hydrobromate of bromobi- chloronaphthalin A, with evolution of hydrobromic acid. — 5. Decomposed by potassium between 40** and 50°, with evolution of light and separation of carbon. — 6. Not attacked by hydrate of potasli.

Insoluble in water; very soluble in alcohol and in ether.

6. Modification E is found in the alcoholic mother liquor from which AD has crystallised by refrigeration (comp. p. 44), and is obtained by spontaneous evaporation.

Properties, Very well defined, brilliant six-sided prisms of 94**, larger than the crystals of AD. Melts at 31^ and distils unchanged. Laurent found 60*76 p. o. C. and 3*06 p. c. H.

Decompositions. 1. Treated with bromine, it evolves hjrdrobromic acid. — 2. Behaves with sulphuric acid like the other modifications of bichloronaphthalin. — 3. It is not acted upon by hydrate of potash.

e. Bichloronaphthalin formed by treating binitronaphtJialin with chlorine gas.

7. Modification Y. Chlorine is passed through fused binitronaph- thalin. If the heat does not exceed the melting point of binitronaphthalin, and the decomposition is not thoroughly effected, a mixture of undecom- posed binitronaphthalin, oily hydrochlorate of terchloronaphthalin, and oichloronaphthalin Y is obtained, nitrous fumes being evolved. If more

chlorine is used and the temperature raised higher, terchloronaphthalin A is formed. First the oily chloride is removed with a little ether, and then the bichloro- naphthalin is extracted from the residue by more ether, (the hinitronaph- thalin remains undissolved), and it is purified by recrystallising once or twice, and finally sublimed or distilled. (Laurent, Hev. sdent. 12, 202.)

Properties. Forms by sublimation, white needles, the exact form of which cannot be determined. In order to obtain fine sublimed scales, the substance is put on a small dish and placed on a sand-bath heated to 100°, the whole being covered with a low bell-jar. It melts at 35^ and crystallises in needles on cooling. Laurent found 60*45 p. o. C. and 3 03 p. o. H.

Of all the modifications of bichloronaphthalin, this is the least soluble in alcohol and in ether.

Chnjugated Compounds of the Chlorine-nucleus C**C1*H*.

Bichloro8ulplionaplithalic Acid.

C»CPH«S*0» = C«>C1»H«,2S0». ZnviK. J, pr. Chem, 33, 37.

Chhrohypotulphonaphihalerie acid. (Laurent.) BichloronapkthyloditMonic acid. (Kolbe.) Acide iulfonaphtalique bichlori. (Gerhardt.) Bichlomaphtalinschwefel' sUure.

Sulphuric acid acts upon bichloronaphthalin as upon chloronaphthalin, and forms a white buttery acid, somewhat more consistent than chloro- sulphonaphthalic acid. (Zinin.)

46 CONJUGATBO COMPOUNDS OP THB CHLORINE-NUCLEUS C»C1«H«.

The afMiionith^aU is exceedingly sol able.

The poUuh-ioU forms small needles having a fattj lustre, sparingly soluble. Contains 14*74 p. c. KO.

BarykhwU, Small, white needles haying a £Ekttj lustre ; sparingly soluble.

20 0 ... 5H ...

2 CI ...

BaO

6 O ....

2S ...

		Zinin.
		at 150^
120	.••• fj\*oA „.,	.... 34-85
5	1*46 ....	.... 1-50
71	.... 20-60 ....	.... 20-57
76-6	.... 22-20 ....	.... 2207
40	.... 11-63 ....	.... 11-42
32	.... 9 «af ....	.... 9-59

C»Cl-H«Ba,2S05 3446 .... 10000 10000

Silver-^alt. White, brilliant laminae sparingly soluble. Zinin found 29*89 p. 0. AgOj the caJonlation requires 30-23 p. o.

Bihydrochlorate of Bichloronaphihalin.

C»^H«C1* = C»»CPH», 2HC1.

Dumas. Ann, Chim, Phys, 50, 182.

Laurknt. Ann, Chim, Fhys. 52, 275; 59, 19G ; Further, Rev, sclent, 6,

29 ; 13, 72 ; Further, Ann. Chim, Fhys. 74, 26 ; Further, Compt.

rend. 21, 35 ; Compt, chim. 1850, 1 ; abstr. Ann, Phartn, 76, 298;

Liehig & Kopp'$ Jahresh, 1850, 497. De Marignao. Ann, Phai^m, 38, 40.

Hydrochlorate de chloronapkialete. (Laurent.) Bichlorure de napMaline. (Ger- hardt.) ChlomaphtylchlorHr-bichlorwaaaeratoff, (Kolbe.)

Formation, By the action of chlorine upon naphthalin. If the stream of chlorine-gas be not too lon^ continued, hydrochloric acid gas is eyolved and a buttery mass resembling frozen olive-oil is obtained, which, togetlier with undeoomposed naphthalin, contains hydrochlorate of chloronaphthalin, and the modifications a and p of hxhydrochlorate of bichlojvnaphthalin, (Laurent.)

1 . Mbdifieation a.

Preparation, The buttery mixture of the chloride (see formation) is washed four or five times by deoantation with ether, collected on a filter, pressed between blotting paper, dried and fused. (Laurent, Ann. Chim, Phys, 52, 275; De Marignac.) Since the chloride may be converted by excess of chlorine into new compounds closely resembling it, the stream of chlorine must be interrupted before all the naphthalin is decomposed; and in order to partly remove the Utter, the product is warmed for a long time in a dish, between 50* and GO*" C, then dissolved in ether, and the solution maintained for some time at a temperature of — 10*C, whereupon the greater part of the solid chloride separates out; or the product is mixed with a little ether, in order to make it more liquid ; the oil is decanted after 24 hours } and the residue is repeatedly washed on a filter with ether. (Laurent.)

To purify the product, it is either (a.) dissolved in boiling ether, the substance yielding on cooling, very white, more or less crystalline chloride.

BIHTDROCHLOBATB OF BIHTDROCHLOHQNAPHTHALIN. 47

Or^ (5. a obeaper metliod^ since less ether is required for solation) the mass^ after being washed with ether^ is dissolved in rock-oil, which dissolyes the chloride yory abundantly, and on cooling rapidly deposits it at eyen a few degrees below the boiling point, and when quite cold retains only traces in solution. The crystals are collected on a funnel and washed with a little ether, (Laurent, £ev, vAent, 13, 72.)

Properties, Obtained either as a white, shining powder, or, when crystallised from ether, in transparent, yitreous, rhombic laminsB. As how. ever only a small quantity of the chloride ia dissolyed by ether, it is better to heat it with 30 or 40 times its balk of ether, in a sealed flask to a few degrees above the boiling point of ether, and then to cool the solution slowly. (Laurent.) Ciystal-

lises from rock-oil in crystals resembling rhorabohedrons^ with the cracked laminated appearance of calc-spar. Crystallised from ether, it forms oblique rhomboidal tablets; — Lateral angles = 109°, inclination of bases to side = 108° 30' (Laurent, Compt.rend, 20, 363); or in oblique rhombic prisms; — Angles of the rhombic base = about 75° and 105"^, the obtuse angles being truncated. (Laurent, Ann, Chim. Phys, 52, 275.) Heated with ether to 100° in a sealed glass tube, it crystallises on cooling in the form of fig. 113; a and a much more upright, the faces h being wanting; faces «, u, vf predominating ; A- faces are always present ; on the other hand, hmes a, m, and a, (which are wanting in Fig. 113) seldom occur, uiu^z 109° (hence they more resemble ^g, %Q: Gm.), t : w = 108** 30'; * :/ (behind) 121° 40'; h: h (below) = 118°; w : A = 129° 50'; i : t (y : w) = 113°; t :/ = 147"*; t : a = 144° (about); m (Fig. 115) : a = 139° 30* or, on the other side, 137** 30'; i : m left = 92° and right = 88^ (Laurent, Pev, scient, 13, 72.) Melts at 160°, and solidifies in a crystal- line mass on cooling. (Laurent.) If a crystal thereof be thrown into the partly fused chloride, the whole mass solidifies at about 150° in perfectly weU defined rhombic tablets. If, however, the substance has been completely fused, and is then allowed to cool without adding a crystal, the mass solidifies sometimes at 150° in rhombio crystals, sometimes between 110^ and 100° in radiated needles. Very brittle, pulverisable, inodorous, and permanent in the air. May be yolatilised nndecomposed in a glass tube through wliich a stream or gas is passing. (Laurent.)

Laurent. Dnmaf, Marignac.

.... 44-48 4513 .... 44-69 .... 44-72

.... 2-96 2-49 .... 812 .... 3-04

.... 52-61 .... .... 52-20

20 C	120
8 H	8
4 CI	142

C»CPH«,2HC1 273 .... lOO'OO 99-96

Laurent formerly considered the chloride to be bihydrochlorate of blchloronaph* thaliD i afterwards CX^HH:!*,

Decompodlioru, 1. Strongly heated in a retort, it begins to boil, eyolyes hydrochloric acid, and yields an oily distillate, which soon solidifies in crystals, and is a mixture of the four bichloronaphthalins C, F, H, and A (occurring in different proportions^acoording to the tem- perature at which the distillation takes place), and a little nndecomposed chloride. There remains in the retort a small quantity of porous char- coal, amounting, after washing with alcohol, to 1 or 2 p. c. of the chloride employed. (Laurent.) 2. It is not combustible of itself, eyen in the gaseous state; melted on paper, and lighted, it hx/ms with a

48 CONJUGATED COMPOUNDS OP THE CHLORINE-NUCLEUS C^CPRS.

fuliginous, deeply green-edged flame. (Laurent.) — 3. Bromine converts it in sunshine into bibromo-tercbloronaphthalin and other compounds. (Laurent.) 4. It is converted by chlorine, at a gentle heat, into bihydro- chlorate of chloronaphthaliu, taking op 2 At. chlorine, and parting with 1 At. HCl; at a higher temperature, other products are likewise formed.

— 5. The chloride is attacked only by boiling nitric acid, and yields (even when a portion still remains nndecomposed) phthalic and oxalic acids, a thick oil being at the same time obtained, from which ether pre- cipitates oxychloronaphtalose, C*^H*CI*0* (Laurent). During the re- action abundant nitrous fumes are evolved, and a little chloride of binitromethylene (C'X*,Cl*) passes over with the nitric acid (vii, 360); the acid in the residue appears to differ from Laurent's phthalic acid (Marignac). — 6. HydroMoric acid is without action on this compound.

— 7. Sulphuric acid is also inert in the cold ; but on prolonged boiling, decomposition takes place, with evolution of hydrochloric acid, and formation of : — 1, a substance which is insoluble in water, soluble in ether, leaves a transparent varnish on the evaporation of the ethereal solution, and is decomposed by heat, yielding an oil which on cooling solidifies in a transparent fissured mass; 2, a substance which remains dissolved in the sulphuric acid — the solution saturated with baryta yielding a salt resembling sulphonaphthalate of baryta. (Laurent, Ann, Chim. Phys, 59, 196.) — 8. Heated with fuming sulphuric acid, it evolves hydro- chloric acid; — the liquid, diluted with water, saturated with baryta, filtered and evaporated down, yields a yery soluble baryta-salt, which crystallises with difficulty, and contains both chlorine and sulphur. (Laurent, Hev. scient. 13, 72.) — 9. Decomposed by potassium aX, or a little above, the common temperature, with slight explosion and evolution of light, chloride of potassium being formed and much carbon separated; Laurent, by performing the experiment in a glass tube, obtained a small quantity of a gas which burned with a green flame. — ]0. It is not attacked by potash in the cold; on boiling, chloride of potassium and a new crystal lisable substance are formed. (Laurent.) It is decomposed by boiling alcoholic potasli into chloride of potassium and the two modifications £ and AD of bichloronaphthalin. (Laurent, Rev, scient. 13, 72.) — 11. Decomposed by alcoholic ammonia, but slowly, bichloronaphthalin C being apparently formed. (Laurent.) — 12. Boiled with alcoholic sulphide of ammonium, it forms a new compound, soluble in alcohol and in ether, and containing sulphur, chlorine,' and oxygen. (Laurent.)

Combinations, Insoluble in water. Scarcely soluble in cold, and very slightly soluble in boiling alcohol, from which, on cooling, it is almost completely deposited in small scales* It dissolves somewhat more freely in f/W, especially at 100° fin a sealed tube). Dissolves very sparingly in cold, and abundantly in boiling rock-oil, (Laurent.)

2. Modification p.

Formation (p. 46).

Preparation, That portion of the buttery mixture, obtained by the action of chlorine upon naphthalin, which remains liquid after coolinjr, is dissolved in a little ether, and maintained at 0° for 48 hours, whereupon the mixture solidifies like frozen olive-oil. The deposit is collected at 0^ on a piece of fine linen, and the mother-liquor again cooled, whereby more of the solid product is obtained. Both portions are pressed and

TERCHLORONAPHTHALIN. 49

dissolved in a little ether oontaining \ or ^^ of alcohol. The solation^ allowed to stand in an imperfectly closed vessel, deposits in the coarse of a few- dajs a crystalline mass, which is filtered off and pressed. This is a mixture of the modification a, which is slightly soluble in ether, and scarcely soluble in alcohol, and of the modification fi, which dissolves readily in alcohol, and still more in ether. The whole is dissolved in boiling alcohol, and very slowly cooled, and the modification a, which erystallises first> is separated by decanting the liquid; this liquid, by spontaneous evaporation, yields first the modification a, and then mix- tures of the two modifications, which are treated separately with a little ether, whereby the modification fi is dissolved immediately, and the modification a more slowly in proportion as the crystals are larger. The product is now repeatedly recrystallised, till the crystalline mass is dis- solved by ether immediately and without residue. (Laurent, Compt, Chim. 1850, 1.)

Properties. Colourless, inodorous ; crystallises in small flakes, often united in large balls. When fused and cooled to 10^ C, it does not solidify immediately, but gradually, in radiated spheres often more than an inch in diameter.

Laurent.

30 C 120 .... 44-51 4411

8 H 8 .... 2-95 2-83

4 CI 142 .... 52-54

C»CPH«,2H01 270 .... 10000

Decompasitums. 1. Resolved by distUlcUion into hydrochloric acid and oil, and bichloronaphthalin C. (needles of 112*'). — 2. Bromine con- verts it into bihydroehlorate of bromochloronaphthalin, C^ClBrH^,2HCl. — 3. Decomposed by boiling alcoholic potash into chloride of potassium, an oil, and bichloronaphthalin F. — 4. If alcoholic sulphide of ammonium be poured into a boiling alcoholio solution of the chloride, the liquid turns brown, becomes turbid in a few seconds, and deposits an abundant precipitate resembling flowers of snlphur, and containing chlorine, sulphur, and oxygen.

Cfilo7'ine-nucleu$ C*»CPH».

Terchloronaphthalin. C»C1W.

Lavrekt. Ann, Chim. Phyn. 66, 152, and 199 ; Further, Rev. sclent 12, 206; Further, Compt rend. 15, 739; Further, Compt. rend. 21, 35; Compt. chim. 1850, 1 ; abstr. Ann. Pharm. 76, 300 ; Liebi^ & Kopp's JahreA. 1850^ 498.

ZiNiN. J. pr. Chem. 27^ 152.

CJdomaphUMst Chlomaphtis. (Laurent.) Deiapenfykhhrid. (Benelius.) Naph* imUmt triehlorSe. (Gerhardt.)

Obtained hy Laurent in seven dif event modifications, formed under diftrent circumstances. — Laurent {Ann. Chim. Phys. 66, 152) states his belief that he had often previously obtained terchloronaphthalin; but S3 tbe crystals were soft like wax, he mistook them for a mixture of qnadrichloronaphthalin with an oil, and indeed he was ultimately of opinion that, in every case in which he formerly supposed that he had

TOXi. XIV. B

50

CHLORIKR-NUCUUS C»Cl«H».

obtained qaadrioliloronaphthaliii by the action of oUorine on Tarioas GonipouDds, the compound, described as sach, was really terchloronaph- tbalin, with the exception of that obtained by the deoompoaition of bihydrochlorate of quadrichloronaphthalin.

Formation. 1. Modification A. 1. Obtained by treating hydro- chlorate of chloronaphthalin with chlorine^ and boiling the oily product with potash. (Laurent.) 2. By treating nitro- or binitro-naphthalin with chlorine. (Laurent.)

2. Modification AC. By treating fused bichloronaphthalin with chlorine, hydrochloric acid being evolved. (Laurent.)

3. Modificaticm D, is formed together with A, when bihydroohlorate of terohloronaphthalin is distilled.

4. Modifications C^'and (5) G are formed simultaneously, together with A, when bihydrochlorate of terohloronaphthalin is boiled with potash.

6. Modification AD. Obtained by Laurent by decomposing the bihydrochlorates of hi- and terchloronaphthalin with potash.

7. Modification AE is formed, together with A and an oil, with evolution of hydrochloric acid, when bihydrochlorate of bichloronaph- thalin is warmed with fuming oil of vitrioL

Chief characteristics of tfie TercJdoronaphthaUns. (Laurent, jRee.

scient, 12, 213.)

	A.	AC.	C.	G.	D.	AD.
Form	e.sided prisms of 120"	6-8ided prisms^ rhombus of 113**	Long needles, rhombus of 113*	Prisms ter . minated by needles,rhom- buaof laO**	Like G, rhombos of 124"	Needles of silky lustre, rhombus of laf
Hardness, &c.	Soft	Soft	Elastic, brittle	Unelastic, britUe	LikeG
Melting- point	75*	66«	Between 78* & 80**	Between 69° & 70°	Between 88« & 90'*	160*
State after fusion •	Soft reC' tangular parallelo- grams.	Like A	Transparent rosettes, be- coming slowly opaque when left to them- selves.	Transparent rosettes, be- coming sud- denly opaque by friction with foreign bodies	Needles, with moirated surface transparent, becoming opaque on standing.	Transpartnt rosettes, becoming opaque on
In ether	Exceed- ingly so- luble.	Very soluble	Soluble	Soluble	Soluble	Slightly sol«Ue
In alcohol	Very sUghtly soluble.	Soluble	Solublo	Soluble	Solubto	SHghtly BohiUe

TERCHLORONAPHTHALIN. 51

1. Modificaiion A. 1. Chlorine gas is passed over napLtbalin ; and the oily hydrochlorate of chloronaphthalin (p. c)9) is separated from the Bolid chlorides by means of ether, and again treated with chlorine, either with the aid of heat, or in the sun. A thick mixture of oily hydro- chlorate of terchloronaphthalin, solid bihydrochlorate of terchloronaph- thalin, and other solid chlorides is obtained. — In order to separate the products, they are mixed with ether, and the whole is maintained for seyeral hotfrs at 0°, whereupon the solid chlorides separate out. —(Amongst these, Laarent disooyered a new chlorids crystaUisiDg ia right priame with rectangular base ; this form does not in an j other instance occur in the aeries of chlorides of naph- thaline and could be isolated only by picking out the crystals with the aid of a magnifying.glass.) The oil is decanted and boiled with alcoholic potash, which is renewed two or three times. Aboye ^-ths of the oil employed are obtained. (Laurent.) — 2. The oily hydrochlorate of terchloro- naphthalin may also be subjected to distillation, whereby hydrochloric acid gas is evolved. The chloride thus prepared is, however, not pure, but must be separated from a little oil by dissolving in 3 or 4 pts. ether and 1 pt alcohol, with the aid of heat Crystals are obtained b^ the cooling of the solution, and still more by spontaneous evaporation in an open vessel. The crystals must be recrystallised once or twice from ether-alcohol, and can be obtained colourless only by recrystallisation from equal pts. of ether and alcohol, or rather more ucohol. (Laurent, Ann, Okim. Fhy$, 66, 197.) — 3. By treating nitro- or binitronaphthalin with chlorine, with the aid of heat. (Laurent, Ann. Chim Fhys. QQ^ 152.) — 4. Zinin obtained terchloronaphthalin by treating chloronaph- thalin (he afterwards thought that it contained the terchloronaphthalin ready formed) with oil of vitriol at 140° C, as a clear oil, which on cooling became solid like wax and floated on the brown liquid containing chlorosulpho-* naphthalic acid. (This part of Zinin's research has not since been noticed; it seems to show that Zinin's compound is identical with Laurent's terchloronaphthalin A ; its formation in Zinin's experiment may be explained by supposing that chloronaphthalin is converted by chlorine into compounds of the nucleus C^Cl'H'. (Carius.)

Prtjfperiiei. Inodorous, tastelelss. Crystallises from boiling alcohol in crystals grouped like the feather of a quill (Laurent) ; in long, flexible crystals of silky lustre (Zinin). It may be obtuned by very slow evaporation of the ethereal solution in long, striated, irregular, six-sided prisms of 120^ — Soft like wax; the crystals soften by being pressed together, and yield a transparent mass. (Laurent, Zmin.) Melts at 75^ (Laurent); at 74^ (Zinin), and solidifies in crystals on cooling. Begins to boil at 200" (Zinin), and distils without decomposition. (Zinin^ Laoxent.)

Zinin. iiaiireot.

Crytialt. average,

20 C .-M 120 .... 51-90 „ 52-61 .... 52*32

5H 5 .... 2-16 2-36 .... 2-25

»Cl 106-5 .... 45-94 44-12

C»H*C1« 231-5 .... 100-00 9909

Since terdhloronapliflialhi ia formed by treathng the oily chloride with hydrate of potHrik^tlw latter oU matt have Che 4x«ipocitioiiC3i<3Hl* 4 HC],or + 2HCH (Laurent).

1. The oonapoBod is dissolved by warm fiiTMang mlpkmic qM; ^9im ^oes Aot fcodnoe a precipitate with the £olation

B 2

52 GHLOBINE-NUCLEUS C»asH*»

as long aa it is warm, bat on cooling it assumes a gelatinoos appeamnoe, and a crystalline body is obtained (Laurent). 2. With chlorine, aided by beat, it forms a new compound, probably G'^l^H^HCi. (Laurent.) 3. Nitric acid is without action. (Laurent.) 4. Fotamum decomposes it with evolution of light 5. It is not attacked by aqueoxis potash; by alcoholic potash it is dissolved, and deposited unchanged. (Zinin.)

Terchlorouaphthalin A is insoluble in water.

Ether dissolves more than its own weight of it ; in alcohol^ on the contrary, it dissolves but sparingly, even on boiling, and is therefore precipitated by alcohol from its ethereal solution. (Laurent.)

2. Modification AC is obtained by passing chlorine through fused bichloronaphthalin AD, whereby hydrochloric acid is evolved; it is purified by one or two recrystallisations from ether.

Properties. Fine 6-sidea needles (inclination of the faces = 113"^ ; it is soft like wax, and the crystals may be bent in all directions. (Laurent, Rev. scient. 14, 74.) Melts at 66% and on cooling crystallises like A, Distils without decomposition.

Laurent found 51*6-8 p. c. C and 2-16 p. c. H.

Unacted upon by hydrate of potash. — Fuming sulphuric acid behaves with this modification as with A.

Dissolves more readily in alcohol than A ; very soluble in ether,

3. Modification D. When bihydrochlorate of terchloronaphthalin A is distilled, it is completely decomposed ; hydrochloric acid is evolved and modifications A and D of terchloronaphthalin are obtained, a small residue of carbon being left. A is first extracted from the mixture by ether; the residue is dissolved in ether with a little alcohol ; and the solu- tion allowed to evaporate spontaneously, whereupon D crystallises out. (Laurent, Eev. scient. 12, 211.)

Properiiet. Beautiful brilliant needles, the section of which forms a rhomb of 124°; it resembles terchloronaphthalin G. Melts between 88^ and 90% and on cooling solidifies in a transparent mass of long needles ; in this state it is soft like wax, but gradually becomes hard and opaque. Distils without decomposition.

Laurent found 51*5 p.c. C and 2*2 p. c. H.

Behaves with sulphuric cuiid like the other terchloronaphthalins ; and is not acted upon by hydrate of potash.

Dissolves very readily in ether , much less in alcohoL

4. Modification G. If powdered crystallised bihydrochlorate of ter- chloronaphthalin be boiled with alcoholic potash, it is decompoeed^ with formation of chloride of potassium ; and on adding water to the solution, a precipitate of the three modifications A, G, and G of terchloronaphthalin IS proouced. In order to effect their separation, the modification A is first removed with a little ether (or alcohol might first be used, which dissolves G and G more readily than A), and the residue dissolved in ether with a little alcohol. The solution is placed in a loosely covered vessel, and allowed to evaporate spontaneously. G, which is present in greater quantity than 0, first crystallises ; the solution is poured off from the crystab and aMin left to evaporate spontaneously, and this treat- ment is continued as long as homogeneous czystals are obtained.

TERCHLORONAPHTHALIN. 53

Finally G and G crystallise together; G in gronps of very brilliant crystals^ C in fine regular needles^ vhicli trarerse the liquid in every direction. The crystals are picked out and recrystallized. (Lanrent, Bev. soienL 12, 209.)

Properiieg. Brilliant, colourless, transparent prisms, the section of which is a rhomb of 50 and 130^ The crystals are brittle^ unelastic, and may be readily pnlyeiised. Melts between 69° and 70° C. If one gramme of the substance be melted on a ^lass plate, it solidifies on cool- ing in a slightly transparent mass, which, by examination with the microscope, is found to consist of small striated rosettes ; after a minute or so, the mass becomes perfectly opaque. If touched with a hard body immediately after solidification, it will be found to be soft, like the modifi- cation A j but as soon as it has become opaque, it is found to be brittle and easily pnlyerisable. If the transparent mass be touched with a feather, it suddenly becomes ox>aque (Laurent) .

Laurent found 51 '60 p. c. C, and 2*14 p. o. H.

It is not decomposed either by distillation, or by potash.

Dissolves in vtam fuming sulphuric add; and on addition of water, a precipitate is formed which redissolves in warm water.

Dissolves readily in ether, less readily in alcohol,

5. Modification C is obtained mixed with G (p. 52), by boiling solid bihydrochlorate of terchloronaphthalin with alcoholic potash. It is separated from G by picking out the crystals, and purified by one or two recrystallisations from ether-alcohol.

Properties, Long, brittle, elastic needles, the section of which forms a rhomb of 1 1 3°. Melts between 7S^ and 80° and exhibits on cooling the same phenomena as G.

Laurent found 51*45 p. c. C and 2*22 p. o. H.

6. Modification AD is obtained by boiling bihydrochlorate of hi- and terchloronaphthalin with alcoholic potash. The solution is precipitated by water and the precipitate treated with a little ether, whereupon the modification AD alone remains in the residue. (Laurent, Bev, scient 12, 212.)

Properties, Crystallises from ether in needles of silky lustre. Does not melt till about 160° C, and solidifies on cooling in microscopic, slightly transparent rosettes ; it is then soft like wax, but gradually hardens and becomes opaque.

It has Dot been analyBed.

Beadily soluble in alcohol, moderately in ether,

7» Modification AE. The crude oil, obtained in the preparation o bihydrochlorate of terchloronaphthalin (p. 55) is treated with gently warmed fuming sulphuric acid (whereupon hydrochloric acid gas is evolved), and the brown solution is precipitated with water and left to cool. After a few hours, a brown semi-plastic mass is deposited, which is first washed with water, then with a little alcohol, and afterwards dissolved in ether. On evaporation, a deposit is formed which is a mixture of the terchloron aphtha! ins A, AE, and of a small quantity of an oil. Since A, as well as the oil, is more soluble in ether than AE, the product is crystallised a second time from ether^ and afterwards twice recrystallisei} from ether-alcohol.

64: CONJUGATED COMPOUNDS OP THB CHLORINE-NUCLEUS C»C1«H».

Pr9periie». Fine, colourless needles^ the section of which ia a heXftgon^ deriyed from a rhomb of 122°. Melto at 93^ and on cooling crjatairiees like A in rectangular parallelograms, crossed by two diagonals. After cooling, it remains soft like A^ but becomes hard and brittle after a time. Distils undeoomposed.

Laurent.

20 C 120 .... 61-90 51-50

5 U 6 .... 2-16 210

3 01 106-5 .... 45-94

C»Cl'H» 231'5 .... 100-00

Decompoiitiotu. 1. In contact with bromine, it evolves hjdrobromic acid, and gives rise to a crystalline and almost insoluble substance. — 2. With faming sulphuric acid it forms terchlorosnlphonaphthalio

acid.

It is less soluble in ether, but more soluble in alcohol than the modifi- cation A. (Laurent, Compt, rend. 21, 35; further Compt. chim. 1850, 1; extr. Ann. Fharm. 76, 300; IMig <fc Kopp'B Jahre^. 1850, 499.)

Conjugated compounds of the Chlorine-nucleus, (?%1'H^

Terchlorosulphonaphthalic Acid.

C«<3PH»SK)« = C?»CPH»,2S0*.

Laitrbnt. Compt* rend» 21, 33 ; Further, Compt chim. 1849| 390 ; abstr. Ann. Pharm. 72, 298 ; Ziebig & Kopp's Jahrtsb. 1849, 441.

ChlorohypatulphorugtAtAalie acid. (Laarent) TriehloronaphthylodithUmic add, (Kolbe.) Acide suiftnuiphttdiqtte triehlorS. (Gerhardt.) TVichionugfhtM^auckwe' ftU'dwre.

Formation, Obtained by treating terchloronaphthalin with fuming sulphuric acid. In preparing terchloronaphthalin AE by means of fuming sulphuric acid (p. 53) part of the terchloronaphthalin is directly converted into this acid.

Preparation, Terchloronaphthalin is dissolred in warm fuming sul- phuric acid, and the solution is diluted with water and neutralised with potash, whereby an abundant gelatinous precipitate is immediately produced; the whole is then heated to boiling and filtered. On cooling, the liquid, even when very dilute, solidifies as a transparent jelly, appearing under the microscope to consist of long and exceedingly fine needles, which being interwoven give to the salt its gelatinous appear- ance. The salt is thrown on a filter, washed with cold water, then dissolred in boiling water and poured into a solution of acetate of lead.

HTDROCHLORATB OF TERCHLORONAPHTHALIN. 55

whereupon a white, gelatinous precipitate, consisting of microscopic needles, is formed. If this be decomposed nnder water by dilute sul- phuric acid, the solution filtered from sulphate of lead solidifies on cooling as a transparent jelly of terchlorosulphonaphthalic acid, consisting of microscopic needles, which, when dried and dissolved in boiling alcohol, is deposited on cooling, as a crystalline magma.

It displaces the strongest acids from their compounds, and precipitates the dilute solutions of sulphate and nitrate of potash, soda, magnesia, or oxide of nickel, as well as chloride of barium or calcium.

Ammama-MU. Readily soluble in water and in aqueous ammonia.

Potask-saU, Opaque, microscopic lamlnse; readily sol able in boiling, and almost insoluble in cold water. It is but slightly dissolved by boiling alcohol.

Baryk^nU. When a dilute, boiling solution of chloride of barium is decomposed by terchlorosulphonaphthalate of ammonia; a gelatinous piecipitate, consisting of microscopic needles, is deposited from the solu- tion on cooling. Contains 31-5 p. o. BaO,SO' (C»CPBaH^2S0* = 30*6 p, 0.) Dissolves in from 300 to 400 pts. of boiling wateif,

Lime-$aU. The ammonia salt added to a warm dilute solution of ofaloride of oaloium, throws down a transparent starch-like jelly.

CuprammoniumritalU Prepared by pouring the ammonia-salt into aoetate of copper, adding ammonia, and heating. On cooling, the solu- tion solidifies in a thready jelly. The washed salt is lilac-blue, and

becomes blue on drying. Its water cannot be estimated, aa it parta with ammonia on drying.

Laurent found 6*3 p. c. N and 9-1 p. o. CuO; the formula C^CPCuH*,- 2S0' + 2NH» + 4H0 requires 67 p. c. N and 0 5 p. c. CuO.

Hydrochlorate of Terchloronaphthalin.

C««1»H»,HC1.

Laubsnt, Ann. Ohim* Fhy9. 66, 199.

If chlorine-gas be passed through crude oily hydrochlorate of chloro- naphthalin (p. 39), and its action promoted by warming or by sun-light, a thick oil is obtained, from which a mixture of solid chlorides is pre- cipitated by a small quantity of ether at 0°. The decanted ethereal solution contains an oil, which Laurent supposed to be hydrochlorate of terchloronaphthalin, since it is resolved by boiling with potash or by distillation, into hydrochloric acid and terchloronaphthalin A (see also Preparation J, p. 51).

56 CONJUGATED COMPOUNDS OF THE CHLOBINE*NUCLEUS C»CPH^

Bihydrochlorate of Terchloronapliihaliiu

C*»C1*H»,2HC1. Laurent, £ev. zciewt, 13, 78.

Chloride qf Ckloronaphtkcte. (Laurent.) Biehhrure de tugthUtUne eklori^* (Gerhardt) Bichlomaphiylchlor^r'Bichlorwanenif^ff, (Kolbe.) Zweifach-HydrQm ehloT' JVichlomaphtalin,

Formaium. Foists in two diferent modijieations, which are simtsl- taneously formed when bihydrochlorate of buMoronaphthalin is treated with chloriite-gas,

A. Solid modification. 1. Fused bihydrocblorate of bichloronapbtlialia is treated witb cblorine-gas. It is difficult to conduct tbe operation success- fully, since if the temperature be too low no reaction takes place; and if too strong a beat is applied, tbe cbloride formed is further decomposed. — 2. Crude bydrochlorate of cbloronapbthalin is treated with chlorine- gas. After tbe solid bihydrochlorate of bicbloronapbthalin has been separated by ether from the buttery product of the action of chlorine on napbtbalin (p. 46 ; preparation) and the ether expelled by beat from the oily cbloride, chlorine is passed through the oil for two or three days; if tbe liquid thereby becomes too thick, it is gently warmed. A few drops of ether are now added, to render the mass more fluid, and it ia allowed to stand in a cool place, whereupon a crystalline precipitate, exactly like C^C1'H',2HC1 a, is formed. The supernatant oil is decanted, and the deposit thrown on a filter, washed with a little ether, and finally dissolved in boiling ether. The solution is allowed to stand for seTenu days in a wide-mouthed vessel covered with paper. The crystals which are then deposited on tbe bottom of the vessel, are sometimes a mixture of C«'CPH«,2HC1 and C«C1'H»,2HC1. The crystals of the last compound being much larger than those of tbe first and easy to distinguish, may be readily picked out. The selected crystals are dissolved in the mother- liquor by a ffentle beat, then recrystallised, again picked out, and finally recrystallised once or twice from ether.

Properties. Crystallises from ether in rhombic prisms (Fig. 68), the obtuse lateral edges being truncated; u' :u =^ 70^ 15'; u' : u over t = 109° 45'; < : t = 115° 55'; t : t* = 111° 25'. Sometimes several other bevelling faces occur, belonging to different acute and obtuse horizontal prisms, as well as the octahedral faces a. The crystals are transparent and colourless. Crystallised from alcohol it presents an entirely dissimilar form, viz., an oblique rhombic prism (Fig. 91); a:a = 110° (about); t : u between 118° and 119; a:u == between 127° and 128°.

Melts at 105°, and when completely fused may be cooled down to 84^ without becoming solid ; it then crystallises slowly in nodules formed o£ concentric rings; tbe last portions remain fluid, or rather viscid, until they reach tbe common temperature. If tbe substance has been melted at 105° or 110^, and a crystal is then thrown into the liquid, it rapidly solidifies at 105° in beautiful oblique rhombic tablets. If the liquid becomes solid between 105® and 54°, a mixture of both forms is obtained, «.«., nodules and tablets, but the latter much more acute than those previously obtained. (Laurent.)

ULURBNT'S CHLORURE BE CHLONAPHTANE. 57

Laurent. mean,

20 C 120 .... 39-41 39-43

7 H 7 .... 2-30 2-31

6 CI 177-5 .... 58-29

C»C1>H»,2HCI.. 804-5 .... 10000

DeeomposUions, I. Completelj decomposed by distUUUion, evolying hydrochloric acid^ yielding the terchloronaphthalins A and D^ and leaving no residue. — 2. Conyerted by boiling nitric acid into chloroxynaphthalic phthalic, and oxalic acids, together with crystalline oxychloronaphthalose. — Conyerted by boiling alcokoltc potash into chloride of potassium and the terchloronaphthalins A, C, and O.

Insoluble in water ; slightly soluble in alcohol, rather soluble in e^A^r (more readily than the chloride C»C1*H<^HC1).

B. Liquid ntodifieatUm, — This is the oil obtained in the preparation of the solid modification (p. 54, 2).

LaureDt.

20 C ................... 120 «.. 39-41 38-30 '

7 H .,.. 7 .... 2-30 2-30

5 CI 177*5 .... 58-29

C»CPH»,2HC1 304-5 .... 100-00

It is completely conyerted by distUlation into hydrochloric acid and terchloronaphthalin A, mixed with a little oil. With boiling alcoholic potash, it yields the same products as the solid modification A.

Appendix to the Chlorine-nucUuSf C**CPH".

Iiaiireiit's Chlomre de Ghlonaphtane,

C»°CP-»H'-»,C1*.

Laurent. Rev. sclent. 13, 77.

Found I : — in crude hydrochlorste of chloronaphthalin prepared by the method described at page 89; secondly, in the ethereal mother-liquor, from which bihydrochlorate of terchloronaphthalin has been crystallised. (Comp. p. 5Q.)

Preparation. Crude hydrochlorate of chloronaphthalin (p. 89) left for seyeral weeks in a cool place, deposits a white granular mixture of the chloride 0'^*H*,2HC1 and of chlomre de chlonaphtane. The oil 18 decanted ; the crystals are laid upon paper, until the paper no longer shows grease spots; and the product is treated with a little ether, which dissolyes the last traces of oil together with all the chlorure de chlonaphtane and a small quantity of bihydrochlorate of bichloronaph- thalin. Chlorure de chlonaphtane then crystallises from the solution, the oil remaining dissolyed. The crystals are treated with alcohol|

I

58 APPENDIX TO CHLOEINS-VUCLBUS C»CI>H».

which does not diisolve the bihjdrochlorate of chloronaphthalin, and the crystals obtained by evaporating the alcoholic solution are purified by recrystallisation .

Properties. Crystallises in needles. Melts at 57^ C, and does not solidify on coolings but if a crystal of the chloride be added to the liquid it is immediately converted into a transparent mass of crystals.

Niediei, Laarent.

20 C 120 .... 41-77 42*20

7-5 H 7-6 .... 2-61 2*75

4-5 CI 160 .... 55-62

C»H'-»Ol^-* 287-5 .... 100-00

DecompotiHons. 1 . Decomposed by repeated diHillation into hydro- chloric acid and three substanceSi the first of which crystallises out after the distillate has stood for a long time, and appears to be the wax-like terohloronaphthalin A. The second crystallises from alcohol in needles ; the third is oily; both appear to be modifications of bichloronaphthalin and to hare been formed as represented by the equation :

2 0»H7-»Cl<-« - 4HC1 + C»H*Cl» + C»H«C1«.

2. Decomposed by alcoholic potash into chloride of potassium and a sub- stance which is perhaps C^l***!!*-*.

Chlorure de chlonaphtane cannot be a mixture of the chlorides C*»C1»H«,2HC1 and (?°C1*H»,2HC1, since both are much less fusible and less spluble in ether and in alcohol, (Laurent)

Laurent's Chloride of Naphthalin and Chlonapthtise.

C~H»C1»*.

Laurent. Bev. ecient. 1 d, 83.

Preparation. Difficult to prepare. Chlorine is passed through fused bihydrochlorate of bichloronaphthalin. If insufficient heat be applied, the substance is not attacked, and too great a heat decomposes it. If the action of the chlorine be too long continued, bihydrochlorate of quadri- chloronaphthalin is formed. If the operation has been conducted success- fully, the double chloride is obtained, mixed with bihydrochlorate of quadrichloronaphthalin and some other crystaliisable and oily substances. These last are extracted by cold ether, and the residue, consisting of the two first substances, is dissolved in boiling ether, and the solution allowed to evaporate spontaneously in an imperfectly closed vessel. In a few days, rhombic tablets of the double chloride and right rhombic prisms of bihydrochlorate of quadrichloronaphthalin are obtained. The first is picked out with a forceps, redissolved in ether, allowed to crystallise, and the rhombic tablets are a^ain picked out. These are finally dissolved in boiling alcohol and crystallised by cooling the solution.

Crystals : &g. 86 without the faces m and /; iih behind = 120'^ (about); tt:AT>elow = ISO** (about); i:u =: about 110"; and accord-

QUADRICHLORONAPHTIIAUN. 59

inglj it has the same form as bihydrochlorate of bichloronaphthaUn a. Melt8 at 160^ (Laurent.)

Laurent

80 C 480 .... 40*55 40-52

29 H 29 .... 2-46 250

19 CI 674-5 .... 56-99

C»H«C1» 1183-5 .... 100-00

Hence it has the composition of a compound of 3 At bihydrod&lorato of tercblo* xonapbthalin ^C^H^CF, and 1 At. bihydrochlorate of bichloronaphthalin ^O^VKlK — It is not a mixture, since on distillation, it yields terchloronaphthalin A, and an oil, together with hydrochloric add gas. Boiled with alcoholic potash, it parts with 2 At. hydrochloric acid, and yields microscopic needles, which are not obtained from a mixture of the two chlorides. Its melting point is also higher than that of chloride. (Laurent.)

Chlarine-nucleui C»C1*H*.

Quadrichloronaphthalin. C»Cl*H*.

Laurent. Ann. Chim. Fhys, 59, 196 j Farther^ Ann. Chim. Phys. 66, 203 ; Further, Eev. sclent. 12, 218.

Tetraehloronaphtaline, Chlorotu^htalose, CKUmaphtose. (Laurent.) DeiatetryU chlorid. TBenelius.) Chloride (^ tirehhronaphthyl. (Kolbe.) Nt^ktalina qnadri- ehlorie. (Gerhardt)

Formation. BxtsCM, according to Laurent, in four different mcd^fiea^ tioM. A, fi, E, and K, which are formed in diferent ways.

Chuf a^araeteriftici of the QuadrichloranaphthcMni. (Laurent, J?0if«

scUnt. 12,221.)

	A.	B.	E.	K.
Elasticity	Soft	Brittle	Flexible	Flexible
Form	6-sided prisms of 120*	Oblique prisms with oblique base of 100**, 101*, 1 03«	Long needles, rhombus of 94°	Short needles, rhombus of 100**
Melting-point	106**	124*	170»	125*
Crystalline form i^erjiuion	Microstopic rosettes	Needles	Needles	Rosettes
Jn ether	Very soluble	Very slightly soluble	Very sliriitly soluble	Very dightly soluble

1. Modification A. Formed when naphthaliu, or one of the first products thereof bj the action of chlorine, iB heated to boiling and treated with chlorine-gas.

60 CHLORINE-NUCLEUS C»C1<H<.

FrepanAvm, Chlorine is passed through fused terchloronaphthalin A. — 2. (Very adraiitagcoiii.) ChloriDO is passed through impure hrdro- chlorate of chlorouaphthalin, until the mass, which has been kept rased, solidifies when slightly cooled, and the white crystalline product, which generally contains an admixture of oil, is recrystaUised two or three times

from boiling alcohol. Thus prepared it Kometiines still contains perchloronaph- thalese, which may be easily recognisied by its crystalline form. .— . 3. On distilling

bihydrochlorate of quadrichloronaphthalin, hydrochloric acid is evolred and a mixture of quadrichloronaphthalin A and B passes oyer, from which A is extracted by ether.

Fropei^ties. Long, white or yellowish needles. Crystallises in 6-sided prisms of 120^; the crystals are yery like those of terchloronaphthalin A, but are more brilliant, and are not terminated by needles, but generally ronnded at the angles; almost all the crystals have an opening parallel to the axis. Melts at 106°, and on cooling solidifies in microscopic rosettes. Soft like wax and plastic. It sublimes at higher temperature unchanged in small needles.

Laurent.

20 C 120 .... 45'12 . . 44-5

4H 4 .... 1-51 1-5

4 CI 142 .... 53-37

C^C1*H* 266 .... 100-00

DecompoiUiotu. 1 . Heated on a combustible body, it hwiis with a green-edged, smoky flame. — 2. With chlonne at a gentle heat it forms hexachloronaphthalin. 8. It is not attacked by boiling €tcid9. 4. Con* yerted hy fuming stUphurie acid into qnadrichlorosulphonaphthalie acid. — 5. When it is heated with potcLssium, light is eyolyed and carbon deposited. — 6. l^ot decomposed by boiling alcoholic potash. It may be melted and yolatilised on fragments of potash, without undergoing decomposition. If its yapour be passed over lime heated nearly to red- ness, carbon is deposited and chloride of calcium formed.

Combinations. Very slightly soluble in boiling alcohol. It requires four or fiye times as much ether for its solution as terchloronaphthalin.

2. Modification B. (Preparation, vid. sup,)

Properties. Highly lustrous prisms of the doubly oblique prismatio system. Fig. 124, without 9-faces; y : u = 100''; y : v = 101^ 30'; v : u = 103^ Melts about 125**, and solidifies in beautiful needles on cooling. Distils without decomposition.

Laurent found 45*00 p. c. C and 1 '50 p. c. H.

It is not attackea hj potash. Pissolyes yery slightly in ether, less than A.

8. Modification E. (Paraehloronaphialote. Lanrent.)

Formation. By distilling bihydrochlorate of quadrichloronaphthalin X, hydrochloric acid being eyolyed; or by boiling the same substance with alcoholic potash.

Freparation. Oily bichloronaphthalin A (p. 41) is cooled in order to free it from the accompanying solid modifications, and chlorine is passed through it in the cold for a long time (whereupon it acquires the consist-

CHLORONAPHTONfi F. 61

enoe of bonej); it is then warmed and treated with more ohlorine. The product^ after standing for 4 dajrs, does not yield a deposit, but when shaken with half of its volume of ether^ it gives a white pulverulent pre- cipitate. It is the cryrtaUised modification of C»C1«HS2HC1, since the oil oontained a little bichlorbnaphtbalin C. When the ethereal liquid is evaporated^ and the residual X-C^C1*H^2HC1, boiled with alooholic potash, which is renewed four or five times, it yields a crystalline substance, contaminated with a brown oil. The same product is likewise formed when the chloride is distilled. To separate the crystals from the oil, they are pressed between blotting paper and boilea with ether-alcohoL The product is finally distilled.

Fraperties. Crystallises from ether or rock-oil in microscopic silky needles. Melts at 170^, and solidifies in a radiated mass. Distils without decomposition. Inodorous.

NeedUi. Laurent.

20 C 120 .... 4512 45-79

4H 4 .... 1-51 1-65

4 CI 142 .... 53-37

C»Ci*H* „ 266 .... 10000

It is not attacked hypakuh.

It is but very slightly soluble in boiling aleohcl, and not much more in warm ether; the accompanying brown oil considerably increases its solubility.

At tne ordinary temperatures, it is almost insoluble in rock-oil, but readily soluble at the boiling point; on cooling, the solution becomes completely filled with long needles.

4. IfodifieatUm K. Ciystallised bihydrochlorate of quadrlchloro- naphthalin C is boiled with alcoholic potash as long as chloride of potassium is formed ; the whole is then diluted with water, the residue washed with alcohol or with ether, and dissolved in boiling ether or rock-oil. The solution deposits crystals on cooling.

Properties. Very fine and short needles, forming nodular groups; their section is a rhombus of 100° 4- 80^ Melts at 125^ and on cooling solidifies in an opaque mass. Distils without decomposition.

Laurent found 44 '90 p. c. C and 1'50 p. c. H.

It is not attacked b^ potash. Dissolves very sparingly in alcohol and in boiling ether, likewise in cold rock-oU, but to a greater amount in boiling rock-oil. The solution in rock-oil deposits on cooling nodular grouped needles, which occupy but a very small portion of the liquid.

Ajfpindije to Qfuutrieklorowi^ktkalin.

Chloronaphtone P. c»H«ciw.

LAmuBNT. Rev. eeient. 12, 215.

Formation 8l Preperation. Bf passing chlorine through ftiaed bichlonmaph* tlialin F, hydrodilorio add being evoWed; purified by recrystdlisaUon from daiUn^ slcohoL

62 CONJUGATED COMPOUNDS OF THE CHLORINE-NUCLEUS C»a<H*.

ColottrlMf kmln». It is the only radictl without definite form. After fenoa, it lolidiAes in a fctlj meu. Distils without decomposition.

Lsurent found 48*0 p. c. C, and 2'0 p. c. H; by calculation, 48*3 p. c. C, sad 1-8 p. c. H.

It is possibly an isomorphous miiture of the unluiown modifications F, of bi- and terefaloronaphthalin. (Laurent.) Somewhat readily soluble In alcohol, very solnble in ether.

OonjugaJUd compound of the Chlortne-wuekui, C^l^H*.

Qnadrichlorosulphonaphihalic Acid.

(P^H^Cl^'O* = C»C1*H*,2S0».

Laurrnt. Compt. rend. 21, 83; further, Compt. chim. 1849, S97 j abstr. Ann^ Fharm. 72, 300 ; Lidng & Kopp'a Jahresb, 1849, 442.

Quadriehloronaphthylodithionie acid. Acide tuffbnapktaligue quadrichlori. (Ger- hardt.) QiiadrichhmaphtaHneekwefeleUure,

Known only in combination with potash.

FormcUion and Preparation. Produced by heatins qaadricliloro- napbtbaliii with fuming sulphuric acid. When the whole is completely dissolved, the liquid is diluted with water, neutralised with potash, heated to boiling, and rapidly filtered. On cooling, the potash-salt is deposited in crystalline flakes, which are washed on a filter and dried. These contain 22*0 p. c. KO, S0», corresponding to the formula (7°C1*KH',2S0* which requires 22*6 p. c. KO,SO'. Almost insoluble in cold and only slightly soluble in hot water; readily soluble in boiling alcohol.

The alcoholic solution of the potash-salt does not precipitate acetate of baryta; but the liquid ia rendered gelatinoua by the addition of water.

Bihydrochlorate of Quadrichloronaphthalin.

C«HK)1* = C»H*C1*,2HC1.

Laurent. iV. Ann. Chim. PAy«. 58, 196; 66, 196 and 203; further (complete desenptiou of the three modifioatioiifl), Jiev. soient. IB, 85.

PetehiorcmaphtaUee, Chhnire de ekUmt^hieee. (Laurent.) Dekakerple^per- chlorid. (Berselins.) Trichlomaphtylchlorilr'Bichlorwatseratqf. (Kolbe.) Biehlorure de naphtaline bichlarSe. (Gerhardt.) Zwei/ach-Hydrochlor'Quadriehlomaphtaim.

Formation, Produced hy treating hichloronaphthalin with chlorine, and in three different modi/icationa, according as the modificcUtone C, A, or X are employed.

1. Modification G. 1. Bichloronaphthalin G is kept in fusion and treated with chlorine ; no hydrochloric acid is evolyed. The product im purified by washing with a little ether, dissolving in boiling ether, and orystailising. — 2. Ghlorine is passed through the crude mixture of biohlorona^thaliB obtained by distilling 0%PH^2HC1 (p. 42) ; ihe thick transparent product is diluted with a little ether; and the wUte

8BXCHL0R0NAPHTHALIK. 63

eiysialHne powder^ whioh is deposited after a few minntes^ is reerystal- lized from boiling alcobol.

Properiiei, Crystallises from ether on cooling, or better by slow eTaporation^ in small, brilliant, oblique, rhombic prisms : fig. 99; with faces m and without i j t^ : tt = between 90^ and 91*^ ; a? : a; = between 122'' and 123'"; a; : u = between 128"" and 129°. Colourless, inodorous. Melts at 141°; and after complete fusion, solidifies in needles; when only partly melted, it crystallises in prisms, and apparently at a higher temperature.

PrUfM. Laurent.

20 C 120 .... 35-40 35-38

6H 6 .... 1-77 1-89

6 CI 213 .... 62-83

C»C1*H*,2HC1 .... 339 .... 10000

DeeompoaitUms, 1. By distillation, it evolves hydrochloric acid and yields a small quantity of quadrichloronaphthalin A, and much B. — 2. With boiling alcoholic potash it forms chloride of potassium and quadrichloronaphthalin K. — 3. Fotassium decomposes it at a gentle heat, with evolution of light and deposition of carbon.

Slightly soluble in ether, still less in alcohol,

2. Modification A. Bichlorcnaphthalin A is treated with chlorine, whereupon only a very small quantity of hydrochloric acid is evolved.

Pi'opertifs, Oily liquid.

On distillation it evolves hydrochloric acid and yields quadrichloro- naphthalin Af together with traces of an oil. Boiled with alcoholic potash, it is resolved into chloride of potassium and quadrichloronaph- thalin A«

3. Modification X. Bichlorotiaphthalin X is treated with chlorine, whereupon no appreciable quantity of hydrochloric acid is evolved. The oil becomes yery viscid, owing to the formation of small quantities of modification 0, which are separated by shaking up the liquid with a Bmall quantity of ether. The ethereal solution is evaporated.

Properties. Oily liquid.

On distillation, it evolves hydrochloric acid and yields quadriohloro- naphthalin E: the same products are obtained with alcoholic pota^.

Chlorine-nucleus C»C1W.

Sezchloronaphthalin. C»c;i*H*.

Laurent. JRev. scient. 12, 233 ; further, CompL rend. IG, 861.

Chkmep^iMlase A. (Laurent) Chloride qf quiniichloronaphthyl, (Kolbe.) Sech*' faeh' Chlomaphtalin,

JPormaiion and Freparution. Terehloronaphthalin A isk treated with eblorin^ for a long time at an elevated temperature. If the product

64 CHLORINE-NUCLEUS C»CP.

contains perohloronaphthalin, it is extracted with ether, wherein thd last substance is but sparingly soluble.

Properties, Six-sided prisms with angles of 120''. Soft like wax and may be bent in everj direction. Melts and solidifies at 143°. Distila without decomposition.

Priamt. Laurent.

20 C 120 .... 35-88 3600

2H 2 .... 0-60 0-66

6 CI 213 .... 63-52

C»Cl«H» 335 .... 100-00

DecomwmUons. It is not attacked b^ potash, or by dilute sulphui^ or hydrochloric acid. It is dissolved spanngly by warm oU of vitrioL — Boiling nitric add converts it slowly into oxide of chloroxynaphthalise. C»CI«0*,0». (Laurent.)

Soluble in about 20 pts. dher ; dissolves more abundantly in rock-^, scarcely at all in alcohol.

Appendix to SexcUoronaphthalin.

Chlonaphthalane A. C«»Cl'-«H«-»

Laurent. Sev. scient, 12, 232.

Mrmation and Preparation. On treating bichlorouaphthalin C with chlorine, aided by a gentle heat, a mixture of sexchloronaphthalin A and of chlonaphthalane A is obtained, which is separated by crystal- lisation from its solution in ether mixed with a little alcohoL By spontaneous evaporation, fine needles of sexchloronaphthalin crystallise out, then fine as well as thicker needles. The liquid is then decanted, and diloronaphthalane is obtained on further evaporation.

Properties. Six-sided prisms of 120'', pierced parallel to the axis. Slightly yellow, and soft like wax. After melting, it crystallises at 131° C in microscopic resetter Volatile without decomposition ; not decomposed by hydrate of potash.

Laurent found 37'53 p. o. C, and 0*83 p. c. H ; calculation, B7'7 p. c C and 0-8 p. c. H.

Dissolves in ether, but less freely than quadrichloronaphthalin A ; scarcely soluble in alcohol.

Chlorine-nucleus C^Cl*.

Perchloronaphthalin. C^OV.

LimiBNT. Hev. sclent. 12, 234.

ChhnmaphiMlU A, (Laurent.) Chloride rf pSTMwwMpMkgU (Kolbe.) Nq^Ataline perchlorie. (Gerhardt.)

Formation and Preparation. Chlorine is allowed to act for a long time upon t^rchloronaphthalin A kept in fusion* The eezohloronaphthalin is

CHLORONAPHTHALIC ACID. 65

remoyed from the product hj means of ether, and the residue is treated with boiling rock-oiL

Properties, Light yellow, easily friable, acicniar prisms with angles of 112*30' and eT"* 30'. Melts at 172**; yolatile without decom- position.

PrtMnu, Laurent.

20 C 120 .... 29-75 29-88

8 CI 284 .... 70-26

C»C1» 404 .... 100-00

Laurent obtained in his analysis 0*06 p. c H, in addition.

The compound is not attacked by potash.

Very slightly soluble in boiling alcoJiol and eiher,

OxyiMorine-nudeus C*»C1H»0".

Chloroiiaphihalic Acid.

Laurent. Compt. rend. 1 6, 861 ; Ann. Chim. Phys. 74, 26 ; Sev. scienU

13, 592 ; abstr. Ann. Pharm. 35, 292. WoLPP & Strecker. Ann. Pharm. 75, 14.

Aeidt ehhronapAlisi^ue, (Laurent) Aeide cMoroxynaphtalique. (Gerhardt.)

Fo)'mation. By boiling hydrochlorate of terchloronaphthalin with

nitric acid j Laurent afterwards obtained only chloride of chloroxynaphthalin, and therefore thought it probable that the acid was formed from this substance when the two bodies were separated by very dilute alcoholic potash.

2. By boiling chlorozynaphthalin with concentrated alcoholic potaeh:

C^CPH^O* + KO,HO = C»aH»0« + KCI.

Preparation. Bihydrochlorate of terchloronaphthalin (Laurent) is boiled with nitric acid, till a yellow oil, which becomes very thick on cooling, is formed. This is mixed with ether, wherenpon a yellow sub- stance (chloride of chloroxynaphthalin with or without chloronaphthalio acid) is precipitated ; on boiling the latter with alcoholic potash, it dissolyes completely. The liquid is diluted with a small quantity of water and neutralised with an acid, whereupon chloronaphthalio acid gradually crystallises out on cooling. (Laurent.) — Wolff & Strecker onco obtained by this method an acid, which did not yield the common golden-yellow baryta-salt, but a purple-red salt, perhaps bi- or ter- chloronaphthalio acid. (Wolff & StrecKer.)

Properties. Long, yellow, transparent, inodorous, very delicate needles, permanent in the air ; their ends show under the microscope re-entering angles, because they consist of two twin crystals. Sometimes short irregular crptals are met with, which, howeyer, also show the re-* entering angle. Melts about 200° C, and on cooling crystallises in laminsp, which, being composed of rectangular prisms, likewise exhibit a re-entering angle at their ends. Distils without decomposition. (Laurent.)

TOL. xiy. F

/

66 OXTeHLOWNB^NUCLBUS C»C1H*0«.

20 C ft It	120 5 35*5 48	.... 57-6 .... 2-4 .... 16-8 .... 23-2	LafurettL at 100^ in vacuo. mean, 57-00 2-45
a	16-68
6 o	23-87
c»aH»o«	208*5	.... 100-0	10000

This compound is alizarin, in which 1 At. H is replaced by 1 At. CI* as is evident from the analogy between the two substances, in eomposition, properties and decompo- sition-products, especially with nitric acid. (Wolff & Strecker.)

DecomposUums. Resolved by boiling nUrtc acid into phthalio, oxaliCy and hydrochloric acids (unless perhaps a chlorophihalic acid^ C^'CIHH)*, is formed : Wolff & Strecker) :

C»C1H»0« + 4HO + 60 = CWH«0« + OHW + HCl. (Laurent.)

2. Chloronaphthalic acid cannot be reduced to alizaric acid either by Melsens' method (redaction by patataium-amnlgam, ix, 211), or by that of Kolbe (redaction in the voltaic circuit, vii, 295). The aqaeons acid produces with potaBsium-amalgam the dark red solution of the potash-salt, which does not appear blue by reflected light ; ftnly a small quantity of the acid is decomposed in this reaction. The potash solution of the acid becomes light in the eleotrio current. (Wolff it Strecker.)

Combinations, It does not dissolve appreciably in water. Dissolves in strong dulphujic acid, and is precipitated therefrom by water.

With Bases. — ChloronaphtkaUUes. The acid forms very beantiliil salts, varying between yellow, orange, and carmine-red. A pieoe of paper saturated with the aqueous solution of the acid, is immediately turned red by ammonia- vapour. The salts yield by distillation a new crystalline substance^ and leave a residue of metallic chloride and char- coal.— Hydrochloric acid precipitates the aoid from them.— They are almost insoluble in water, and are, with the exception of the potash-aalt, obtained by double decomposition from the solution of the ammonia-salt in 30 pts. water.

Ckloronaphthalale of Ammonia, The acid is added to a hot dilute solution of ammonia in alcohol or water, whereupon the salt orystallisea on cooling in radiated crimson needles. By distillation it yields much carbon and a white sublimate. (Laurent.)

CMoronapkthdtate of Potash. Hydrate of potash is heated to boiling with 10 or 15 pts. water or alcohol, and the acid is added till the alkali is saturated. Crystallises on cooling in striated oarmine-eoloured needles, which most be washed with a little alcohol. Dried at lOO"* in vaoao, it contains 1807 p. c. KO, corresponding to the formula (?°G1KHH)' + Aq. Calculation = 18'46 p. o. KO* (Laurent.)

ChloronaphtKalate of Baryta, Chloride of barium preoipiiates from the ammonia-salt ^when dilate, after a short time) very friable silky needles, whicn are orange-coloured when dry, and beceme rod

PECULIAR ACID OBTAINBD FROM BIHYDROCULORATB, &a 67

under the burnisher. Dried in vacuo at 100^, it contains 27*27 p. o. BaO, corresponding to CClBaH^O*. (Laurent.) (By calculation ss 27*7 p. c. BaO.)

Chloride of Strontium precipitates orange-yellow needles.

Chloronaphthalate ofZinie. When chloride of calcium is added to a solution of the ammonia-salti the liquid after a few minutes becomes filled with long orange-yellow needles.

The ammonia-salt immediately yields with potash-alum an orange- yellow precipitate; with sulphate of cadmium, an instantaneous brilliant yermilion-red precipitatei which under the microscope is seen to consist of yellow cruciform crystals.

With acetate of lead, it forms an orange-yellow precipitate. The solution of the acid in boiling alcohol, forms with alcoholic acetate of lead, beautiful, silky, orange-coloured, four-sided needles. It precipitates mhacetate oj lead, orange-red ; ferrous and ferric sulphates, brown ; with chloride of cobalt it produces an instantaneous crimson-red precipitate, which is blood-red after drying, and then becomes vermilion-red under the burnisher. It yields a crystalline carmine-coloured precipitate with cupric acetate; with mercuric chloride a reddish -brown ; and with nitrate of silver a blood-red precipitate, which is dense when precipitated from hot solutions, and, when examined with the microscope, is found to consist of carmine-red needles.

Chloronaphthalic dissolved with difficulty in boiling alcohol and in ether. It does not dye fabrics either mordanted with ^umiua or oiled and mordanted for Turkish-red. (Wolff & Strecker.)

Appendix to Chloronaphthalic Acid*

1. Peculiar acid obtained firom Bihydrochlorate of Terchloro- naphthalin by the action of Nitric Acid.

Laurent. Ann. Chim. Phys. 74, 26.

Formation and Preparation. Formed by boiling the oily modifica- tion of bihydrochlorate of terchloronaphthalin for two or three days with 6 pts. concentrated nitric acid. The acid liquid is separated from the oil, then eyaporated, and the phthalic acid, which now cnrstaUises out, is separated from the solution, which is further eyaporated till the residue Bolidifies in a crystalline mass. This neutralised with aqueous ammonia, eyaporated to dryness, taken np with boiling water, filtered from a brown, yiscid substance, and again eyaporated, leaves a residue, which, being dis- solyed in boiling alcohol, deposits after 24 hours a yery small quantity of a sparingly soluble, scarcely crystalline salt, which has not been farther investigated. The remaining solution is precipitated by chloride of calcium, the precipitate after standing 24 hours, thrown on a filter^ washed with a little cold water, then heated to boiling with 20 pts. water, whereby only a part is dissolved, and oxalic acid is gradually added till the salt is almost completely decomposed. The liquid is then

F 2

68 OXYCHLOWNE-KUCLfiUS C«CPH*03.

filtered and eyaporated^ wbereapon it separates into an aqaeous and an oily stratum ; the latter, on being dissolved in etber, filtered from a alight residue, and evaporated, yields a peculiar oily acid.

Yields by distillation a substance which crystallises on cooling, is insoluble in water, but soluble in ammonia.

The acid dissolves in water^ and separates by evaporation as an oily stratum.

Forms crystallisable salts with ammaniOy potaA, and litne.

2. Oxychloronaphthalenose, C«H*CTOM

Laurent. Ann. Chim, Fhys, 74, 26.

Formaiion and JPreparation, In the preparation of chloride of cbloroxynaphthalin with nitric acid from oUy bihydrochlorate of terchlorouaphthalin. The ethereal solution, filtered from the chloride of cbloroxynaphthalin (q, v.)y deposits by spontaneous evaporation, small colourless prisms and a yellowish substance. The oil is decanted (it is almost completely converted by distillation into tercbloronaphthalin), and the crystals are washed with a little ether, then with alcoholic potash, and dissolved in boiling alcohol. On cooling, oxychloronapb- thalenose crystallises from the solution.

Properties. Oblique rhombic prisms or needles, colourless, and yery brilliant. Melts about 160'', and distils at a higher temperature apparently without decomposition.

18 C 8 H	.... 108	.... 31*80 ... .... 01-/ft# ••! 4-65 ...	Laurent. 31-00 ..... £ £ti 6107 5-71
6 CI	.... 213
2 O	.... 16
CWH8C1«0» ....	.... 345	.... 100-00 ...	100-00

Insoluble in ioaier,, — Dissolves in strong svUfliuriG add without coloration, slightly in alcohol and in ether.

Oxychhrine-ntuleiu C*»CPH*0*.

Chloride of Chloroxynaphthalin,

c»cra*o* = c»cPH*o«,o».

Laurent. Compt, rend. 16, 861 ; Ann. Ohim. JPhys. 74, 26 ; Bev. 9cieni» 13, 592 ; abstr. Ann. Fharm. 85, 299.

Oxyehloronaphtalose, Oxide qf Chloroxenaphto»e. (Laurent.) CMorure de ehloT" bsynaphtyle. (Gerhardt.)

Formation. By boiling bihydrochlorate of tercbloronaphthalin with nitric acid. (Laurent.)

PERCHLORONAPHTHAUC ACID. 69

PrepartUuyiu Crystalline bihydrocfalorate of terchloronapbthalin is boiled witb nitric acid, till a yellow oil, becoming very viscid on cooling, bas been formed. (Phtbalio acid crystallides from tbe acid solution on evaporation.) Tbe oil mixed witb a small quantity of etber, yields a polyerulent deposit, wbicb, after standing for one or two days, is purified by decantation and wasbing witb etber on a filter, and tben dissolved in a large quantity of boiling alcobol. On cooling, needles of cbloride of cblorozynaphtbalin are deposited from tbe solution :

C«CPH»,2Ha + 40 - C»CPH*0* + 8HCL (Laurent.)

In tbe first preparation, Laurent obtained tbe cbloride of cbloroxy- napbtbalin mixed witb cbloronapbtbalic acid, bibydrocblorate of quadri- cbloronapbtbalin and anotber crystalline substance; afterwards {Rev, 9ciefU, 13, 592) be obtained only tbe above-mentioned oil, wbicb contains only cbloride of chlorozynapbtbalin, but in a very small quantity.

Properties. Brilliant, yellow needles, bent like tbe knee. Melts at 98^ ; and sublimes at a bigber temperature, without decomposition, in rhombic tablets.

20 C 4H	120	.... 62-87 .... 1-76 .... 31-27 .... 14-10	Laurent. 63-3 1-8
2 CI 4 0	71 32	14-2

C«CPH^O< 227 .... 100-00 lOO'O

Laurent found previously 56*04 p. c. C, and 2-54 p. c. H.

Decompantians, Blackens on exposure to ligkt.^^ 2. Converted by boiling nitric acid into pbtbalic acid. — 3. It is instantaneously turned carmine-red by (dcoholio potash ; the whole tben dissolves in ivaAer as cbloride of potassium and chloronaphthalate of potash.

ConMnations. Insoluble in water. Dissolves in oU of vUriol with mahogany colour, and is precipitated therefrom by water in its state.

Dissolves very slightly in alcohol or in ether.

OxyehlorifiMiueleus G^GPHO^

Ferchloronaphthalic Acid.

C»C1»H0* = C»C1»H0»,0*. Laubskt. Compt, rend, 18, 861 ; Sev. scient, 13, 596.

ChUfroxenaphthdUste acid, (Laurent.) Acide perehloroxynaphiaiigue, (Gerhardt)

FormaUon and Preparation, When cbloride of perchlorozynaph- thalin is treated with potash, a very beautiful carmine-red substance is

/

70 OXYCHLOKINE-NUCLEUS C»CI«0«.

instantaneously formed, from wbiob percbloronaphthalio acid Beparates on the addition of an aoid :

C»Cl«04 + KO,HO = C»C1*H0« + KCL

The product is purified by dissolving it in etherj evaporating the solution, dissolving the crystalline deposit in alcohol, and adding potash, whereby a precipitate of carmine-red needles is immediately formed. These being coUected on a filter, washed and decomposed by an acid, yield perchloronaphthalio acid, which may be finally recrystaflised from alcohol or from ether.

Pn^ptrtim* Yellow, crystalline,

Laurent.

20 C 120 .... 34'6 35-0

H 1 .... 0-3 0*5

5 CI 177*5 .... 51-2 50-5

0 O 48 .... 13-9

C»Cl*HO« 846'6 ... 100*0

Hence it is formed from chloride of perchloroxynaphtbalin, in the same manner as chloronaphthalio add from chloride of chloroxynaphthalin. (Laurent.)

C(>mbmatU>iM, When added to boiling alcoholic solution of potash or ammonia^ it forms red or carmine crystalline salts, which appear to dissolve to « slight extent only in boiling water.

Chloride of Ferchlorozynaphthalin,

C»C1«0* = CWPO*,0».

Lattrbnt. Compt. rend. 16, 861 ; Ann. Cfhim, Phy9. 74, 26 ; Riv. $cimU 13, 595 j abstr. Ann. Pharm. 35, 292.

CMaroxenaphtaUsoanfd (Laurent) ; Chlorure de Perchhroxynaphiyle (Gerhardt).

Formation. Formed by boiling sexchloronaphthalin with nitric

acid, (together with chloropthalic acid, which remains in the add solution, also an oilj and a crystalline snbstanqp, neither Qf whi^ have beoa farther investigated) :

C»ci6H2 4- 6 0 - C»C1«0< + 2 HO. (Laurent.) « Preparation, Sexchloronaphthalin is but feebly attacked by nitric acid, 10 grammes thereof require boiling for 8 or 4 days, whereby a yellow resin, melting in the boilinj? nitric acid, is formed. The whole is diluted with a little water, boiled, and decanted. The resin is pal* yerised, and after the oil has been extracted by digestion with ether, the residue is dissolyed in boiling rock-oil, from which the chloride of per- chloronaphthalin is deposited a few degrees below the boiling point, and agaiii recrystallised from rock-oil

HYDROCHLORATB OF CHLOROBROMONAPHTHALIN. 71

The rock-oil solution, when perfectly cool, deposits a second substance, which appears under the microscope to consist of orange-coloured granules, and, according to Laurent, is gradually decomposed by boiling rock-oil, which thereby acquires a brown colour.

Frcpertiet. Gnrstallises from boilinff ether or from rock-oil in light, yellow, highly brilfiant laminte. It melts at a rather elevated tempera* ture, and then volatilLses, for the most part undecomposed.

			Laurent.
20 C	120	• ... dS V •••	••... oo*3
6 CI	213	• •1. vO*« ...	66-7
	32	••«• 9 9 •••	lO'O
C»C1«CH ...	365	.... lOO'O ...	100-0

DecompotiUiyM. 1. Gonyerted by boiling niiric acid, probably into ohlorophthalio acid. 2. With potaJk or ammonia it forms a chloride of the metal and perohlotonapbihalio acid.

Ineoluble in 100^ and in alcohol; yery slightly solable in boiling eiher, sparingly in boiling roek'oU.

JBromoMorine'nueleus C^BrClH^

Hydrochlonte of ChlorobromouaphihaliiL

C»ffBrCP = 0»BrClH«,HCl-

Laubbrt. Rev. icimU. 18, 580.

9ubM>rid§ if BrompkiMa$e, (Laurent.) Chlorun de nrnphtaUn^ bromSi* (Ger- hardt.) HydrochhT'Chlorbromnaphtalin,

Formation and Preparation, When chlorine is passed into crude bromonaphthalin, the liquid gradually thickens, and deposits a crystal- line substance. The product is diluted with a small quantity of ether, and allowed to stand for 24 hours : the oil is then decanted, and the crystalline powder is washed with ether and dissolred in a large quantity of boiling ether, whereupon it crystaUises by spontaneous eyaporation.

Properties. Rhombic tables, deriyed from an obli<^ie rbombie prism, resembling bihydrochlorate of bichloronaphthalin. (/V* ^^0 Tabular, owing to the predominance el the f-faoe ; u' :%=• between 121° and 122^ Melts at 166% and on eooling ca7stallise6 in well-defined rhombic taUem

7^le$, Laurent.

20 C 120 .... 43-2 43-0

7H 7 .... 2*5 2'«

2 CI 71 .... 25-5

C»BrClH«,HCl 278 .... 100-0

By diMkUiou it eyolyee bromine and a hydracid«

1

72 BROMOCHLORINB-NUCLEUS C»BrCPH».

Bihydrochlorate of Bromochloronaphthalin.

C»H»BrCl» = C»BrClH«,2HCl.

JiAURENT. CompU rend. 21, 25 ; C<mpt. chim. 1850, I ; absir. Ann* Ffiarm, 76, 399 ; Liehi^ & Eopp'a Jahresb, 1850, 498.

Bichlorobromwe de naphialine (Gerhardt).

MmuUion and Freparaiion. Bromine is poured over bihydio- chlorate of bicbloronaphthalin fi, and tbe liqaid is left to stand in a closed flask for 48 hours ; tbe excess of bromine and the undecomposed chloride are then remoyed by lukewarm alcohol, and the residue is dissolred in boiling ether, from which the new product crystalliaes on cooling.

FropeHies. Colourless four or eight-sided rhombic prisms, the acute lateral edges of which are generally truncated by irregular £ftce6 {Fig. 81), t : tt = lOd"" d(X ; u' :tif=^ about lOd'' ; hence it is bomoxphous with bihydrochlorate of bicbloronaphthalin /3. (Laurent.)

Pri9m$. Lanreiit.

20 C 120 .... 38-20 3806

8 H ., 8 .... 2-55 2-56

Br 80 .... 25-47

3 CI 106-5 .... 3378

C»BrClH«,2HCl 3145 .... lOO'OO .

It is decomposed by alcokolic potash, as well as by distUlatum.

Dissolves more readily in ethef than common bihydrochlorate of bicbloronaphthalin a, and less readily than the modification fi of the same chloride.

BromocKhrine-nwleus C?®BrCPH^

Bromobichloronaphthalin. C»BrCPH».

Laurent. £€v. scieni. 12, 214.

CMorhronaphiise A (lAunnt). Nii^hiatine bromohichhrSe (Qerkudt). Ckhride qf chlorobromonaphthifl (Kolbe).

Formation and Freparaiion. A slight excess of bromine is ponred over bicbloronaphthalin AD, and the whole is allowed to stand for one or two davs in an imperfectly closed vessel, whereupon hydrobromic acid is evolved. The excess of bromine is first removed by washing the pro- duct with a small quantity of alcohol and a little ammonia^ and the residue is then dissolved in boiling alcohol. The compound crystallises on cooling, while any bicbloronaphthalin that may be present remains in the alcoholic mother-liquor.

Frcperties. Colourless ; of the consistence of wax. Crystallises from alcohol in fine needles^ and by spontaneous evaporation of its ethereal

BIHTDROBROMATB OF TERBROMOGHLORONAPHTHALIN. 73

solution, in six-sided needles, with angles between 120° and 121°. Melts^ at about 80% and on cooling solidifies in rectangular parallelograms, crossed by diagonals* When it is perfectly cold, the surface of the mass has a moirM appearance. It distils without decomposition.

Laarent.

20 C 120 .... 48-5 44-5

5 H 5 .... 1-8 1-9

Br 80 .... 29*0

2 CI n .... 25*7

C»BrCPH» 276 .... lOO'O

Unattacked by potash.

Sparingly soluble in alcohol; readily in ether*

Appendix to the BrcmoMorme-^ucUue C^BrCPH*.

Laurent's Chlorebronaphtine.

C~H»-«Br°-»Cl\ Lavhent. Rev. scient. 12^ 205.

Formation and Preparation, Bichloronaphthalin X is treated with bromine, and the resulting oily bromide is boiled with alcoholic potash (whereby bromide of potassium is formed), and the oily product, which speedily solidifies, is precipitated by water. The mass still contains an oil, from which it may be freed by pressing between paper and repeated recrystallisation from ether-alcohol.

Properties, Colourless needles. Melts at 47% and solidifies in rectangular parallelograms crossed by two diagonals bristling with needles. Volatile without decomposition. It is not attacked by

potash*

Laurent found 51*1 p. c. C. and 2*3 p. c. H. ; by calcolation, 51*0 p. e. C. and 2'3 p. e. H.

It is not a niztare of the radicals C^PH> and C^Bra^^ first, because the bichloronaphthalin oonld only be the modification X, which is liquid; secondly, because otiier compounds corresponding to this chloride exist, which are not mixtures* (Ijaurent.)

Bromoehlorine^udeus C*^Br*ClH*.

Bihydrobromate of Terbromochloronaplithalin,

C»Br»ClH« =s C*>Br»aH*,2HBr, Laurent. Bev, seient, 13, 92 j further, Compt, chim, 1850, 8.

Bromttre de chlorobrfmaphtese (Laurent). JBt^ontifrc de naphtaUns bromo-ehhris (Gerhardt).

Formation and Preparation, The first distillate of chloronaphthalin is treated with bromine. A lirely effervescence then ensues, owing to

74 BROMOCHLORINB-NUCLBUS OBfiiH:PH«.

6Tolatioii of bydrobromio aoid, and with excess of bromine^ oiystals are fomie<l on standing. These are dissolved in a very large qaantitr of boiling ether, which on cooling deposits very small, highly brilliant prisms of the componnd.

Properties, * Prisms belonging to the donbly obliqae prismatic system. Fig. 132, without u- and defaces; with g-tftces; tr : v = 96"*; y : w = 85°; y : V = 102'*30'; v \ e i=i 125^ ; y : « = 135^; w : « = 124°; e : g = 114°; t/ : ^ = 121°; w : ^ =s ]20°; v : g =s 186°. (Laurent, Cofnpt, chim, 1850, 8 ; corrected detcriptioii.)

Lftweiit. PritvM. miwn*

20 C 120 .... 21*38 — .. 21-87

F 6 H .: 6 .... I'Or 1-17

CI 35-5 .... 6-33

5 Br 400-0 .... 71'22

C»BrK;iH*,2HBr 561'5 .... 100-00

It turns red before melting ; eyolyes bron&ine yapour at 100° ; melts about 110°, and then eyolyes a large Quantity of bromine and hydro- bromic acid, leaving an oil which on cooling crystallises in quadrilateral figures, crossed by two diagonals bristling with needles (as is the case with terchloronaphthalin).

Brmoehhrine-nudeus G^fir*Cl*H^

BibromoblchloronaphtlialiiL

(?°Br»Cl«H*,

LiURBirr. Bev. ideni. 12, 222 ; further, Campt, rend. 14, 380.

FormaUofL It easiiU, acGording to Laurent^ «f» two itomeric mod^fice^- tiotu I modification a (MorebronapkUm b, Laufent) obtained by tk6 aetUm of bromine upon hichloronaphikalin^ and modification /3 {Jbromecklonapihtooe 5, Laurent), by the action of Morine on bibromonaphiheUin.

1. Modification a. Bromine is poured orer bichloronaphthalin F, whereupon hydrobromic acid is eyofyed, and after a few minutes the liquid solidifies in needles. These are washed with etber, and diasolved in a small quantity of warm ether.

Properties. Small, brilliant, doubly oblique prisms. Facial angles = 101°30'tol02°5e'andl01''15'. Melts at about 1 70°. Crystallises in needles on cooling, and exhibits dimorphism, like the terchloronaphthalins ; for, if a portion be again melted, part of the fused mass crystallises again in needles; but at the same time, a second eryatallisation may be observed, of opaque four-sided bodies, which coyer the needles. If the whole be melted, no more needles are obtained.

Laurent.

20 C 120 .... 84-25 84-43

4 H 4 .... 1-14 1-26

2 Br.2Cl 231 .... 6461

C^BfKJPH* SM ...• 100-09

BIHTDROBROMATB OP BlBROMOfilCHLORONAPHTHAUN* 75

It is not decomposed by didtUatidn, or by pota$h. Scarcely solable in ether and in (Ucokol, eren on boiling.

2. Modificat«>» fi. Obtained by heating bibtomonaphthaUn with ehlonne.

Propertiee. It is deposited by the spontaneous eraporation of its etbereal solntion^ in small doubly-oblique prisms, which are much longer than they are broad. Inclination of the faces = 102* 10' -* 108* -^ 101 ''20'. Melts at 160^ and distils unchanged; solidifies on cooling in a fibrous mass.

Laurent found 38''90 p. e. C. and 1*11 p. e. H.

It is not attacked by potash.

Scarcely soluble in ether and in boiling aloohol.

Bihydrobromate of Bibromobichloronaplitlialin.

(?°H*Bi*CP = C»Br»Cl«H*,2 HBr, Laurent. Ann. Chim, Phys. 59, 196 ; further^ Sev. ecient, 6, 79 ; 13, 87.

Bramur§d€ekhiu^hi^M(ljnLrtgki). Deiahesyltuperhtomid (BtmHuB), CMordi" ir9mmaphiyibromilr''Bibromw(User4tqjf (Kolbe)* Bibromure de fu^hiaiine bieMorSe (Gerhardt).

Formation and Preparation. Bromine is poured upon bichloronaph- thalin in a stoppered bottle, and the stopper is firmly tied down* The bichloronaphthalin first dissolves in the bromine, and then the whole gradually Decomes one solid crystalline mass. On opening the bottle, no hydrobromic acid is evolyed. The excess of bromine and any unattacked bichloronaphthalin that may be present are remoyed by washing the product with ether ; the residue is dissolved in alcohol or in boiling ether, or heated in a sealed glass tube with ether to 100^ (but not higher), and crystallised by cooling the solution.

Properties, Small, brilliant crystals, very like bihydrochlorate of bichloronaphthalin ; Fig. 83; «': « = 101 "^ 80'; » : « = 94° 30' ; some- times the a-faces are completely removed by the enlargement of the faces f ; a : u = 133*"; a : f s between 121'' and 122^ It is colourless.

Laurent.

20 C 120 ... 23-99 23-50

6H :.. 6 .... 1-05 1-0&

2 CI 71 .... 13-83

4 Br 320 .... 61-13

€?«>CPBi«H*,2HBr 617 .... 10000

Decompositions. 1. Melts a little above 100% immediately turning red and evolving bromine-vapour. If heat be applied as long as bromine continues to be evolved, bichloronaphthalin C remains in the residue, which may be reconverted into the bromide by means of bromine. — 2. It is decomposed with difficulty by boiling aleoholio potash; a sub- atance is then precipitated by water from the solution, which, when from ether-alcohoC yields needles, while an oil remains in

76 APPENDIX TO THE BROMOCULORINE-NUCLEUS C»B|4CPH*»

eolation. The needles melt at 55^, Tolatilise without decomposition, are very readily soluble in alcohol and in ether, and contain 41*8 p. c G. and 1*7 H. ; hence Laurent considers them as C^H^|Br1^Cl', or as a mixture of 5 At. C*°BrCl>H* and 1 At. C*»Br»Cl»H*. Hence potash acts in the same way as heat, i. «., it removes the bromine as such, and not aa hjdrobromic acid, and forms a radical or a mixture of two radicals, which cannot be decomposed by distillation. — 3. If the bromide be heated with ether in a sealed glass tube between 120^ and 130°, it losea the property of crystallising on cooling, and on evaporation needles are obtained, which appear to be bichloronaphthalin C. Sparingly soluble in cold alcohol, and in cold etJier.

Bihydrochlorate of Bibromobichloronaphthalin.

(?«H*Br»Cl* = C»Br»Cl«H*,2HCU Laurent. Eev. scierU. 13, 582.

Chiorure de bronaphUie. (Laurent.) Bicklorobronme^hiyl'Biehlorwuttntqfi (Kolbe.) Bichlorure de naphialine bibromU. (Gerhardt.)

Preparation. By passing chlorine over fused bibromonaphthalin a very tnick oil is hereby formed, which when diluted with a small quantity of ether, deposits the chloride as a crystalline powder. In this reaction, another oil is formed which, when treated with excess of chlorine, yields the chloride, together with bihydrochlorate of bibromo* terchloronaphthalin and a new oil.

Froperiies. Long, colourless, oblique prisms; Fiff. 79, without the i-faces ; uiu = between 90^ and 91° ; a :x = between 122° and 123^; u: a =: 129°. Melts about 155°, and solidifies in prisms on cooling.

Laurent.

20 C 120 .... 2803 28-14

6 H 6 .... 1-40 1-51

2 Br,4Cl 302 .... 70-57

C»Br^Cl«H^2HCl 428 .... lOO'OO

It is decomposed by distUlationy yielding bromine, a hydracid, bromo- terchloronaphtnalin /3, and quadrichloronaphthalin A. — Alcoholic potash converts it into a product crystallising in needles, and rather soluble in ether.

Very slightly soluble in alcohol and in ether.

Appendix to the BromoMorine-nudem C°BrH/l'H\

1. Laurent's Bromure de Chlor6bronaphtine,

C»H8.»Br*-*CP ? Laurent. Rev, sclent, 18, 89.

Formation and Preparation. Bichloronaphthalin C is treated with excess of bromine, and exposed for several days to the sun, whereupon

LAUnENT'S CHL011BNBR6NAPHT0NE B, 77

crystals are deposited^ which are -washed with ether^ then dissolved iu ether in a sealed tube at 100°^ and allowed to cool. Those crystals are selected which have the following shape : Fig. 65 ; t : t = 108°; i t u behind t = 102°; iivf =z 120°; t* : t* = 102^30'; ♦ right : u = 125^ Hence thej do not belong to the right prismatic system^ bnt to the obliqae or donbly oblique prisnuitic system.

Laurent.

20 C 120 .... 21-56 2209

6-5 H 5-5 .... 1-00 M 111

4-5 Br,2Cl 431 .... 77*44

C»H««BH-»CP 556-5 .... 100-00

The analTsiB shoald be repeated, nnce the experimental composttioD, as well aa the properties of the body, resemble those of bihydrobromate of bibromobichloronaph- tfaaUn.

It evolves bromine by heat^ together with a small quantity of white

vapour, and leaves an easily fusible substance.

It is scarcely soluble in ether.

2. Laurent's Bromide a. This compound crystallises from the ethereal solution together with the above-mentioned substance. Right rhombic prisms ; Fig. 63 ; m' : t* = 106° 30' ; p:y=^ 135°. Evolves bromine on application of heat, and leaves an oily residue which solidifies very slowly.

It is almost insoluble in boiling ether,

3. Laurent's Bromide fi is found mixed with the crystals of the bromide a. Fig. 75 ; without faces m. Right rhombic prisms : u' :u:=2 100° ; y : y = 126^ ; i*' : i* = 61°.

Evolves bromine and white vapours when heated. Insoluble in ether,

4. Laurent's radical h is likewise mixed with the preceding. Oblique, rhombic prisms. Fig. 121 ; y : w = 109°; y\v^ 107° 30' ; t* : v = 108°. Volatilizes without decomposition, and must therefore be a radical; perhaps C*H»BrCl« or C»H*Br»CP; probably the ether had taken up oromine at 100°.

Almost insoluble in ether.

5. Laurent's Chlorenbronaphtone B.

C«^H*-*Br»CP». Laurent. Bev. scierU. 12, 215.

Formation and Preparation. When bromine is mixed with crude hydrochlorate of chloronaphthalin, a hydracid is evolved, and after 24 hours, the bottom of the vessel is found covered with small crystals, which may be easily purified by washing with ether after the oil has been poured off.

Froperties. Brilliant, colourless, transparent and very small oblique prisms, with oblique base. Angles of faces = between 100° and 103% inclination of base to one of the sides = about 100°. Volatilises without decomposition .

Laurent found 36*00 p. c. C. and 1*36 H. ; by calculation^ 35*9 p. a C and 1-3 H.

78 BROMOCHLORINB'^MUCLBUS CnxCPB*.

According to Laurent, this compoand m&y have been formed from hydrocblorate of chloronaphthalin ; but since it is produced only ia Terj small quantity, he considers it probable that the chloride may hare contained a small quantity of chlonaphthene, C^^Cl^'^H***, and that it may hare been derived from this body.

Almost insoluble in alcohol and in ^Aer^

6. Bromenchlonaphtose A. (Laurent.)

C»H*Br*'»Cl»-».

Laurent. £ev, scient 12, 228.

Formation and Preparation. Fused bibromonaphthalin treated with chlorine, yields amongst other substances, an oily product. If this be separated from the solid product by. standing under a small quantity of ether for several days and the ether then driven off; the oil again treated with chlorine with the aid of heat ; the liquid portion separated from the solid by ether ; and after the ether has been driven off, treated with chlorine in sunshine: a very thick oil is obtained (probably: 0»Br»-*Cl»'*H*,HCl or Cr»Br»-»CP»H*,2HCl). If this be now separated from the solid products by ether, and boiled with alcoholic potash, it. deposits a mixture of bromenchlonaphthose A (very soluble in ether), and of bromenchlonaphthose B (almost iniBoluble in ether), which is separated by means of ether, and purified by reorystalUfiHation from ether.'

Properties, It bears a close resemblance to terchloronaphthatin A ; crystalUses in six-sided prisms or in needles of 120^ the apices of which are rounded off. Soft like wax, and melts when preased together. Melta at 115° C, and on cooling crystallises in microscopic rosette& Volatile without decomposition. It is not decomposed by hydrate of potash.

Laurent.

20 C 120 .... 36-4 3617

4 H 4 .... 1-2 1-65

1-5 Br 120 .... 35-6 ., 33-65

2-5 CI 88-75 .... 26-8 27-99

C»Bri-«Cl»-»H* S32'75 .... lOO'O 9936

Very soluble in ether, slightly soluble in akokoL

Bromochlorine-nucleua C^BrCPH^

Bromoterchloronaplifhalin. C^BrCPH*.

Laubbht. Compt. T€nd. 14, 380 ; further, Sev, scicnt. \2, 225.

Formation. Eseiate according to Lanrent in tktm diferent modifieaiixyiu, formed under diferent drcufMtaneee.

1 . Modification a. (Chloribronaphtose a, Laurent.) Bromine is poured over terohloronaphthalin a, whereupon this compound dissolyea witboot

0

I

B^MAKCHLONAPHTONB A, (LAURSNT.) 7»

deooiopofiing. When the eolation is exposed to the Bun for toveral da^e, it eyolves hydrohromic acid, and yields bromoterohloronaphthalin, whioh 16 purified by repeated recrystalliBation from ether-alcohot

Propertiei. Goloarlese, six'sided prisms, with angles = 117° 30^ and two =: 125^. It is soft, Hke wax, and may be bent in every direction withont breaking. After it has been melted, it crystallises between lOST and 106° in microscopic rosettes. Volatile without decompositiont

Laarent.

20 C 120 .... 38'99 ........ 38-91

4 H 4 .... 1-29 1-29

Br,3Cl 186-5 .... 59-72

C^BrCl'H* 310-5 .... lOO'OO

2. Modification /S. (Bromachlonaphtose a, Laurent.) A stream of bromine is passed over bichloronaphthaliu, which at first is heated till it melts. A thick oily mixture of bihydrochlorate of bibromobichloronaph- thalin and an oil is obtained. If this be mixed with ether and allowed to stand, it yields crystals of the solid chloride, while the oil remains in solution. On boiling the crystals with alcoholic potash, bromoterchloro-, naphtha] in is formed, and may be purified by repeated crystallisation from ether-alcohol.

Properties. It exactly resembles quadrichloronaphthalin A, except that the crystals are far more beautiful and well-defined. Six-sided prisms, whereof four angles == 120^ 80', and two angles = 119°. Soft, like wax ; after fusion, it solidifies at about 1 1 0° in microscopic rosettes. Volatile without decomposition. It is not attacked by potoA.

Laurent fonnd 38*91 p. c. C. and 1*30 p. o. H.

It is rather soluble in ether, but less than the modification a ; scarcely soluble in alcohol, , *..".. * '

8. Modification 7. (Bromaehlonaphtose b, Laurent) When bihydro- bromate of bibromobichloronaphthalin is distilled, bromine and acid Tapours are evolred, and a mixture of terchloronaphthalin A and bromo- terohloronaphthalin 7 condenses in the receiver. * Ether extracts ter- chloronaphthalin from the mixture, and leaves a white powder which is boiled with more ether. This solution, when left to evaporate, deposits small, brilliant, perfectly defined prisms.

Properties. Oblique prisms, with oblique base. Inclination of the sides = 102° 30^ ; inclination of the faces to the base = lOl"* and 103°. Volatile without decomposition.

Lttoreat found 39'04 p. e. C. and 1*48 p. e. H.

Dissolves very slightly in alcohol and in boiling cCAfr.

Bromanchlonaphtone A. (Laurent.)

C»H*-»Br»*CP ?

Laurent. Bev. Bcieni. 12, 216.

Formatum and Preparation. Chlorine is passed into bromonaph- thalin, and after a short time the oil thus obtained is freed from solid

80 BHOMOCHOLRINE-NUCLBUS C»Br«Cl*H«*

matter by mixing with a little ether, and after the ether has been drireii off, the oil is gently warmed and again treated with chlorine till it deposits crystalline matter afresh. This is removed by ether, and the oil is boiled with alcoholic potash. (The oil is probably C»Br»-*Cl»H*-» + HCl or + 2HC1). The product is purified by crystallisation from boiling ether containing a little alcohol, and by spontaneous evaporation.

Properties. It bears a dose resemblance to terchloronaphthalin A, but forms much finer crystals : they are six-sided prisms of 1 20°, the cleavage being parallel to the axis. Soft^ like wax, and may be bent in every direction. Melts at 106^, and solidifies in microscopic rosettes. Distils without decomposition.

Laurent.

20 C 120 .... 44-45 44-03

4-5 H 4-5 .... 1-66 1'62

0-5 Br,3Cl 146-5 .... 53-89

C»Br»-*Cl»H*-» 271-0 .... 10000

(0*500 bromanchlonaphtone being decomposed by lime, reqaired 0-710 siWer for the precipitation ; by calculation 0*700 silver. The precipitate treated with chlorine e?olved bromine.)

Dissolves somewhat readily in eth^r, and very slightly in alcohol.

Bromochlorine-nticlem C*^Br*CPH'.

Bibromoterchloronaphthalin.

C»Br«Cl»H^ Laurent. JSev. tdent. 12, 231.

Bromide qf ferehhroirofMnaphthyh (Kolbe.)

Existty according to Laurent, in tv>o isomeric modifications,

1. Modification a. (Brom6chlonaphtuse & ; Laurent.) When bihy^ drochlorate of bibromoterchloronaphthalin is boiled with alcoholic potash, a white powder is formed, which is dissolved in a large quantity of boiling ether, or better still in boiling rock-oil, and allowed to crystallise. The eUiereal mother-liquor contains in solution a small quantity of a substance crystallising in needles.

Properties, Crystallises from ether by spontaneous evaporation in small and very brilliant prisms of the doubly oblique prismatic system. Fig. 124, without 2-faces, with tf-faces; v : « = 101° 30' ; fy : w = lOl"* 30'; y:v=:10P; tf:u=132^i «:y=115°; «:v = 115*^30'. After it has been melted, it crystallises at 1 65° in long prisms. Volatilises without decomposition.

It is not attacked by potash.

Lanrent.

20 C 120 .... 31-13 31-27

3 H 3 .... 0-80 0-90

2 Br,3Cl 266-5 .... 68-07

C»Bi«Cra» 380-5 .... 100-00

BIHTDROCIILORATfi OF BIBROMOTERCHLORONAPHTHALIN. 81

2. Modification fi. (Chloribronaphtase.) Bromine is poured over bihydroohlorate of bichloronaphthalin, and the mixture is exposed for £c»ur weeks to the sun. On treating the mass with ether^ an oil and a crystallisable substance are dissolved out, and a residue of bibromoter- cmoronaphthalin^ which is almost insoluble in ether^ remains :

C»H8Cl* + 6Br - C»BiaCPH« + 4HBr + HCl.

White powder, which crystallises from fusion in rectangular parallelo- gramsy crossed by two diagonals.

Laurent.

20 C 120 .... 30-80 30-90

3 H 8 .... 0-78 1-10

3 CI 106-0 .... 27'35

2 Br 160-0 .... 4107

C»Br»Cl»H» 389-6 ^.. 100-00

Bihydrochlorate of Bibromoterchloronaphthalin.

C*H»Br»Cl« = C»Br>Cl»H»,2HCl.

Laurent. Bev, tdent, 13, 563 ; further^ Compt, chim. 1850, 1 ; abstr.- Ann. Fharm. 76, 301.

Perchhrure de hronaphth^ (the compound was first described by Laurent under this name, and the formula written C^H^Bi^CP). CMorvre de hromichionaphthe (Laurent). Terehlorobrmmutphthylchioriir Biehlonooitertqf^ (Kolbe.)

FormaUon and Preparation, By the action of chlorine on bihydro- chlorate of bibromobichloronaphthalin.

Propej'ties, Prisms of the doubly oblique prismatic system, very similar to those of the oblique prismatic system. Fig, 124 without faces, 7, with faces q, 5, k^ d; uivzs llC; y:k=. US'"; v : y = 101°; k : I = about 77° ; q : d a= 93^; d :t=. 106°. It has also been obtained in rhombic prisms by Laurent. Melts at about 150°, and crystallises in rhombic tablets on cooling. If it be heated a little above its melting point, it remains soft and transparent on cooling, and solidifies but partially, in a non-crystalline mass, which, if gently heated, crystallises m rhombic tablets.

Deeomposition$, On distillation it evolves bromine and a hydracid, and yields three other substances. (Comp. Bromaehlonaphtune B, p. 78.) — It is converted by boiling alcoholic potash into bibromoterchloronaphthalin a.

(Laurent previously obtained in this reaction another radical, ehhrinbrontqthiune C»Bri-H:ras-* ; see Rev. teient, 12, 229.)

Dissolves very sparingly in ether.

VOL. XIV,

82 NITRO-NUCLEUS C»XH7.

Appendix to the Bromochlorine-nudeus, C**Br*Cl*H'.

Laurent's Bromochlonaphtune B.

Laurent. JRev. scient. 12, 230.

Formation and Preparation, When bihjdrochlorate of bibromo- ierchloronaphthalin is distilled^ bromine and a bydracid are evolved, and the following products are obtained: 1. Bromachlonaphtune B ; 2. A chloride or a'chloro-bromide of the series A, crystallising in six- sided prisms of 1 20°, and melting in boiling water ; 3. A very small quantity of a substance crystallising from ether in small opaque nodules ; less soluble in ether than 2, but more soluble than 1. — 2 and 3 are extracted from the mixture by ether ; the bromachlonaphtune is dissolved in a very large quantity of boiling ether, and crystallised by spontaneous evaporation of the solution.

Very minute oblique prisms, with oblique base; Fig. 81, ii : u' = 101° ; i:m = between 100° and 103° ; i:u = between 100° and 103". When fused, it sometimes solidifies suddenly in an opaque mass, some- times in fine needles.

Laurent found 36*33 p. c. G. and 1*11 p. c H. j by calculation, 36*83 p. c. C. and 1*07 p. a H.

Nltro^udeiu C»XHl

Nitronaphthalin.

C^'NH'O* = C»XH\

Laurent. (1835.) Ann, Chim, Phys, 59, 376 ; Ann, Pharm. 19, 38 ; J, pr. Chem. 8, 13 ; Ann. Chim. Phys, ^Q, 152; Rev, scient. 6, 88 ; further, 13, 68. Marionac. Ann. Pharm, 88, 1 . ZiNiN. J. pr. Chem, 27, 140 ; Ann. Phaim, 44, 283. Piria. Compt. rend. 31, 488; Ni Ann. Chim, Phys, 31, 217; Ann. Pharm, 78, 32; J, pr. Chem. 52, 56; Pharm. Centr. 1850,780; Liebig 4s Kopp^s Jahresber. 1850, 500. Bbohamp. N. Ann, Chim, Phys. 42, 186 ; Arm, Pharm, 92, 401.

NUronaphUUa»€t NinaphUue, C?^W (Lsurent) ; Nitrite de tugfkiaUue, CX'H^O.NO' (Laurent, Ann. Chim. Phy$. 66, 152) , Nitrite qf Icodecmttsnryl, C»H3^0,NOS (Beneliiu) ; NaphthylmtrHr (Kolbe).

Formation. 1. Nitronaphthalin was first prepared by Laurent by boiling naphthalin with nitric acid, whereby red vapours aro evolved and nitronaphthalin and an oil are formed :

C»HP + NO»,HO = C»XH7 + 2 HO.

2. From naphthalin and nitric acid in the cold, without formation of red vapours and an oil (Piria). — 3. By the action of hyponitric acid on naphthalin in the cold, whereby a peculiar oil is simultaneously formed ; this oil, after being exposed for some time to the air, aquires the smell of bitter almonds. (Laurent) According to Laurent, an oil is produced

NITRONAPHTHALIN. 83

bj the action of aqua regia on naphthalin in the cold, which on distilla- tion jields carbon and another oil from which a little nitronaphthalin is deposited on cooling.

Preparatwn, From 5 to 6 pts. nitric acid of sp. gr. 1*33 are added to 1 pt. of naphthalin, and the whole is allowed to digest for 5 or 6 days. The matter easily cakes and must therefore at first be frequently stirred. Lemon-yellow nitronaphthalin, without any by-products, is obtained, and is washed on a filter with water. (Piria.) — 2. Naphthalin is boiled with nitric acid, wbereapon red vapours are evolved, till, after 15 or 20 minutes, a yellow oil has been formed, which on cooling solidifies very slowly in a crystalline mass, consisting of nitronaphthalin and a reddish- yellow oil. This is submitted to strong pressure between blotting paper and dissolved in hot alcohol. On cooling, the liquid first deposits an oil which must be removed with a pipette ; afterwards nitronaphthalin crystallises out, and is collected after 12 hours and reerystallised once or twice. The oil which has been removed with the pipette, yields a fresh crop of crystals when redissolved in the alcoholic mother-liquid. (Laurent)

Properties. Brittle, sulphur-yellow, six-sided rhombic prisms, derived from prisms with angles of 100*^ and Sif, the acute angles being truncated. Melts at 43^, the thermometer rising to 54^ at the moment of solidificar tion. A Sew cr3rBtal8 melted on a glass plate, form oily drops which remain fluid for some time at ordinary temperatures, but on slight agitation, instantly solidify in needles. Volatilises without decom- position and sublimes in small needles ; when rapidly heated, a consider- able quantity decomposes with emission of reddish light, and forms a large deposit of carbon. (Laurent)

				Laurent.
				mecm.
				earlier. later.
20 C	120	••••	69*35 ....	.... 69*86 ..M 68-70
tj u	7	• •••	406 .... 810 ....	.... 4*07 .... 4*07
X^ •••••••	14	.... 8-53 .... 8*30
4 O	32	••••	18-49 ....	17-54 .... 18-93

C»XH7 173 .... 100*00 « 10000 .... 100*00

DecompodtwM. 1. Chlorine at a gentle heat converts it into an oil (C*Cl»H*,HCn), which yields with potash terchloronaphthalin A. If the nitronaphthalin be too strongly heated, terchloronaphthalin A or quadrichloronaphthalin A may be directly formed. (Laurent.) — 2. With bromine, aided by a gentle heat, it forms hydrobromic acid and bibromo- naphthalin; the experiment should be repeated. (Laurent) — 3. It is not attacked by iodine, — 4. It dissolves unchanged in fused sulphur; if a stronger heat be applied, the mass begins to boil, evolves sulphurous acid, and the heterogeneous green mass thus formed dissolves partially in ether with green colour ; the portion insoluble in ether swells up by heat and leaves a very bulky residue of charcoal. (Laurent.) — 6. Nitro- naphthalin boiled with pettnaTiganate of potash, yields nitrate and phthalate of potash. (Cloez and Guignet, Compt, rend, 47, 712 j J, pr. Chem. 76, 500.) — 7. Uydrochloric acid is without action upon it — 8. OU of vitriol dissolves nitronaphthalin, and water reprecipitates it unchanged ; on boiling, the solution becomes brown and is no longer precipitated by

G 2

84 CONJUGATED COMPOUNDS OF THE NITRO-NUCLEUS C»XH7.

water; on neutralising tlie liquid with lime, filtering and evaporating, a saline mass, soluble in alcohol, is obtained. (Laurent.) — 9. It is converted by fuming sulphuric acid into nitrosulphonaphthalic acid, C»XH',2S0*. (Laurent, Rev. scient, 13, 590.)— 10. Potamum decom- poses it suddenly at 43^ with evolution of light and deposition of carbon. (Laurent.) — 11. It is but slightly attacked by boiling aqueous pctask; the liquid becomes brown, and on the addition of an acid deposits a few- brown flakes. With alcoholic potash it forms a red liquid ; on testing it from time to time with oil of vitriol, a dark green, blueisfa or violet-blue coloration is obtained ; on continued boiling, the mass swells up, decom- poses, and leaves a very bulky residue of charcoal. (Laurent.) — If nitronaphthalin be heated in a water-bath for 6 hours with a paste of 2 pts. hydrate of potash in as little water as possible, and 1 pt. fresh hydrate of lime, the water being replaced as it evaporates, it is completely decomposed, and yields the potash-salt of nitrophthalic acid, C'^H^NH)^®, which dissolves in water with dark yellow colour, and nitrophthalin, C^H^NO^ to which a brown substance obstinately adheres. (Dusart, N. Ann, Chim. Phys, 45, 332.) — 12. Heated with an excess of hydrate of baryta or limey it evolves ammonia, naphthalin, an oil, and naphtalaae, C~H'0 (p. 25). (Laurent.)

13. When nitronaphthalin is dissolved in alcohol and the warm solution is treated with sulphuretted hydrogen, naphthylamine, C^NH% is formed, and the liquid turns greenish-yellow and deposits sulphur. This decomposition is more rapidly effected by sulphide of ammonium. (Zinin.)

— 14. When 1 pt. of nitronaphthalin is heated to 100° with a moaerately concentrated solution of ferrous acetate (2 pts. iron) for a quarter of an hour, it yields naphthylamine and ferric oxide ; the same reaction takes place with lively effervescence, when 1 pt. nitronaphthalin is heated with H pts. iron filings and sufficient acetic acid to cover the mixture (B6champ); at the same time another base, phthalamine (C^'H'NO^) is formed. (Schiit- zenberger & Willm., Compt, rend, 47, 82; J, pr. Chem. 75, 117.) — 15. When nitronaphthalin in alcoholic solution is boiled for 8 hours with aqueous sulphite of ammonia, it is converted into the two isomeric com- pounds thionaphthamic acid and naphthionic acid, C^E'NS'O*. (Piria.)

— 16. An alcoholic solution of nitronaphthalin, heated with bisulphide of carbon in a sealed tube to 160% yields naphthylamine and sulphur. (Schlagdenhaufen, N, J, Pharm. 34, 175.)

Combinations. Insoluble in water; very soluble in aloohol, ether, and in chloride of sulphur, (Laurent.)

Conjugated Compounds of the Nitro-nudeus C*XH'.

Nitrosulphonaphthalic Acid.

C»H^NSK)" = C»XH^2S0>.

Laurent. Rev. scicnt. 13, 68, 587 and 588 ; Compt. rend. 21, 33; Compt, chim. 1849, 390; abstr. Ann. Pharm. 72, 297; Liebig & Lapp's Jahresber. 1849, 440 ; Compt. rend. 31, 537 ; J. pr, Chem. 52, 68 ; Pharm. Centr. 1851, 157 ; Liebig k Kopp's Jahresb. 1850, 508.

Acide su^aninaphterique and nitrasulnaphthique ,- Aeide tulfbnaphtalique niiri (Laareat); Ntironaphthjflodiihionic acid (Kolhe). NitronaphtaUmeh'wrfeUdure.

Formation, 1. By boiling snlphonaphthalic acid with nitric acid

NITROSULPHONAPHTHALIC ACID. 85

(acide sulfaniDapbt^sique) ; or 2. By dissolving nitronapbthalin in faming sulphuric acid (acide nitrasulnapht^sique). (Laurent.)

Pf'eparaiiorL Nitronaphthalin is heated with fuming sulphuric acid, wherein it dissolves with a red colour, gradually turning to orown ; the solution is then mixed with water, filtered from undecomposed nitro- naphthalin, neutralised with chalk, filtered, and evaporated ; whereupon the lime-salt crystallises out and is purified by dissolving in alcohol, filtering, and evaporating the solution. — 2. Sulphonaphthalate of lime is boiled with nitric acid ; the acid solution is evaporated to dryness ; the residue washed with a little alcohol, then dissolved in weak alcohol, and the solution is decomposed by sulphuric acid; the filtered solution is saturated with baryta, and the excess of baryta precipitated by carbonic acid, and the liquid is filtered and evaporated ; it then deposits crusts of the baryta-salt. — The free acid is separated from the baryta-salt by means of sulphuric acid, care being taken to avoid an excess of acid, or from the lead-salt by sulphuretted hydrogen, and the filtrate is finally evaporated in vacuo.

Fropei'ties. Microscopic, rhombic laminss.

With sulphide of ammonium it yields acide sulfonaphtalidamiqtte (naphth ionic acid ?).

Very soluble in VKUer.

The nitrogulphonaplukalates take fire when heated in closed vessels.

Ammoniaraalt, The solution left to evaporate sometimes yields rhombic laminse, sometimes long needles.

Fotash-scUt May be obtained in irregular crystals by the spon- taneous evaporation of its solution ; slightly soluble in alcohol.

NUrosulphmaphthdUUe of Baryta. Crusts.

20 C

6 H

N

SO»

BaO,80» 116-5

4 O

			Laurent.
			dried in vacuo.
120		37-5	36-43
6		1-8	1*75
14		4-4
32		100	9-60
116*5		36-3	36-36
32		10-0

i.C»XBaH«,2S0> 320-5 .... lOO'O

NUrotHlphonaphihalate of Lime, The salt dried in vacno, loses at 140'' 3-00 p. c. water; 1 At = 3*20 p. o.

20 C .... 7 H ....

NO* 2SO»

CaO

		Laurent.
		m vacuo (mean).
120	.... 42-60	42-00
7	.... 2-48	2-50
46	.... 16-35
80	.... 23-46	28-75
28	.... 10-11	10-22

C»XCaH«,2S0» + Aq.... 281 .... 100H)0 Nifyroiulphonaphthalic add is very soluble in alcohol and in ether.

86 NITRO-NUCLEUS C»X»H«.

KUro-nucleus C^X*H\

Binitronaphthalin.

C»H«N'0« = C~X'H«.

Laurent. Ann. Chim. Phys. 59, 376 ; Ann. Pharm. 19, 38 ; J. pr^

Chem. 8, 13 ; Rev. scient 6, 88 ; 13, 68. Marignac. Ann. Pkarm. 38, 1.

Biniirite de naphtalhe, C»H80>,2NO>; Nitronaphthalhe, Ninapkthe C (Laurent). NttronaphtylnitriSa: (Kolbe.)

Formation. Napbthalin or nitronapbtbalin is boiled for a long time witb nitric acid. (Laurent, Marignac.)

Preparation, Nitric acid is boiled in a large bolt-bead and napbtbalin gradually added as long as it continues to dissolve ; on cooling, tbe liquid deposits pale yellow needles, wbich are wasbed, first with nitric acid, tben witb water, and finally with alcobol. (Laurent) — 2. If nitro- napbtbalin be rapidly boiled down witb nitric acid in a glass bolt-bead, tbe oily stratum at first formed dissolTes in tbe nitric acid, as soon as botb occupy about equal volumes. Tbe bolt-bead is now taken off tbe fire, and on cooling, tbe wbole solidifies in a mass wbicb is first wasbed with hot water, tben witb hot alcobol. (Laurent) — 3. Napbtbalin is boiled with nitric acid for several days in a retort, the acid distillate being poured back in small portions by means of a funnel drawn out to a fine point. After each addition of acid, it is necessary to wait till no more red vapours are evolved, and the mass in the retort must be wasbed oat every evening. In this manner, the following products are obtained : 1. An aqueous solution of nitronapbthalic acid; 2. An insoluble residue, principally of temitronaphtbalin (p. 88), and a small quantity of a yellowisb, viscid resin, insoluble in water; 3. Binitronaphthalin, partly sublimed in the neck of the retort, and partly dissolved in nitric acid in the distillate. Tbe greater part of tbe nitric acid is evaporated off at a gentle heat, and water is then added to the residue, whereby the binitro- naphthalin is completely precipitated. (Marignac.)

Properties. Light powder consisting of microscopic needles; crys- tallises from its nitric acid solution in rhombic prisms of 67° and 113°, (Laurent); and from its solution in a very large quantity of boiling alcobol, in fine, flexible, slightly yellow needles, (Marignac). Melts at 185°, and when heated strongly in small quantities, sublimes without decomposition, in small needles. When large quantities are rapidly heated, or when it is heated in close vessels, it suddenly decomposes, evolves gas witb violence, and yields much carbon witb emission of red light. (Laurent.) Neutral to test-papers.

Laurent. Marignac.

20 C 6 H	120 6	.... 65'05 ... ..a. A #0 ... .... 1 ^ 04 ... .... 29-36 ...	mean. 64-83 2-90 12-70 29-57	.... 54-92
2 N	28	.... 12-46
8 O	64	.... 29-79
C«>X2H«	218	.... 100-00 ...	100-00	.... 10000

Decompontiops. 1 . Treated witb chlorine aided by a gentle heat, it evolves nitrous fumes; and if the action of tbe chlorine is discontinued at tbe proper time, bicbloronaphthalin Y is obtained together witb an

BINITROSULPHONAPHTHALIC ACID. 87

oil, which by diBtillation or treatment with hydrate of potash, yields hydrochloric acid and terchloronaphthalin A, and hence must be a sons- chlorure de chlonapht^e, (Laurent.) — 2. By prolonged boiling with nitric aeid it is converted into ternitronaphthalin, (Laurent, Rev, scierU. 13, 70.) — 8. Fused with tiUphur, it evolves sulphurous acid and sulphuretted hydrogen, leaving a residue of very porous charcoal. (Laurent.) — 4. Binitronaphthalin is but slightly attacked by concentiated aqueatu potash; with alcoholic potash, it forms a red liquid in the cold, and on boiling, rapidly turns brown and evolves ammonia, the reaction being com- pleted in a quarter of an hour. A body resembling ulmic acid, viz., nilixh naphkUetic acid, ■ is precipitated from the solution by nitric acid. (Laurent.) In order to purify this body, it is washed on a filter with boiling water, dried, and treated with ether, which extracts a small quantity of a brown substance. — The acid is brownish black, and tasteless. Laurent found in it 62*2 p. c. C, 23 p. c. H. and 13* 1 p. c. N. Heated on platinum-foil, it decomposes without melting, and leaves a bulky residue of carbon. It is rather easily attacked bv boilinff nitric acid, being converted into a light brown substance, completely soluble in a large quantity of nitric acid. Water precipitates from the solution yellow flakes, which deflagrate by heat, and form salts with ammonia and potash, which decompose with deflagration when heated in closed vessels. The nitric acid mother-liquid from the flakes, yields another crystalline acid by evaporation. Nitronaphthdlesic add is insoluble in water, in alcohol and in ether, and forms salts which ^low when heated in close vessels. Its alkaline salts are brown, crystallisable, and soluble. (Laurent)

5. Binitronaphthalin, heated with hydrate of lime, evolves naphthalin^ ammonia, and a brown oil. (Laurent.)

6. With sulphuretted hydrogen it forms a carmine-coloured base, which melts on warming, and, deflagrates when heated in close vessels; probably nitronaphthylamine (?). (Laurent, CompL rend. 31, 537; J. pr. Chem. 52, 58.) — 7. Treated with sulphide of ammonium, like nitronaphthalin for the preparation of naphthyfamine, it yields fine red needles of semi- naphthylamine, C"N"H". (Zinin, J. pr. Chem, 27, 152, and 33, 29.) — Its feebly ammoniacal, boiling solution is reduced by sulphuretted hydrogen in about thrcie hours to ninaphthylamine, C^H'N'O' (isomeric with nitrosonaphthylin), (Ch. S. Wood, Cuem. Gaz. 1859, 218; Oiem. Centr. 1859, 1836.)

C»X«H« + 8HS-6HO + 8S + C»H8NH)a.

8. Its alcoholic solution is converted by zinc and hydrochloric add into nitrosonaphthylin, C«^H*N»0*. (Church & Perkin, Chem. JSoc. Qu. J. 9, 1; J. pr. Chem. 68, 248.)

Conjugated compounds qf the NUro^udeus C^X*R\

BinitroBulphonaphthalic Acid.

C»H«N«S*0" = C»X"H*,2S0».

Laurent. Compt. rend. 31, 537 ; J.pr. Chem. 52, 58 ; Pharm, Centr, 1851, 157 ; LiMg & Kopp's Jahresb. 1850, 508.

BMironaphtalmichwrfeliHure.

Known only in combination with ammotua.

Formation and Prepamtion. By long continued treatment of sulpho- naphthalic acid with nitric acid.

88 NITRO-NUCLEUS C»X»H».

Binitrosulphanaphthalate of ammonia. Crystallises in beantifal yellow needles, and treated with sulphuretted hydrogen, it deposits sulphur, and yields a new nitro-acid, apparently acide nUfonaphUdidamique nitrS, (nitronaphthionic acid ?).

Tendtronaphthalin. C~H»N>0» = C*»X'H».

Laurent. Bev. scient 6, 84 and 86 ; 13, 71. Marionac. Ann, Fharm. 88, 1.

NUronaphtaiUe, Ninapkiise, (Laurent)

Ibrmaiion. By prolonged hoUing of naphthaUn with nitric add, in three isomeric modijications, o, /9, and 7, which differ only in crystalline form, meUing-point, and solubility.

Modification a, (N'inaphtise G LAurent,) When naphthal in is boiled for a day or two with nitric acid, almost colourless crystals are obtained, which are a mixture of binitronaphthalin, naphthaleise and temitronaph- thalin a and fi, the last being formed in the largest quantity. Binitro- naphthalin and naphthaleise are extracted by ether, and the residue is heated with such a quantity of alcohol, that on cooling about half remains dissolved. This solution yields by spontaneous evaporation, long rhombic laminse of ternitronaphthalm a, mixed with needles, which are separated by shaking up the whole and pouring off the sus- pended crystals. By repeatedly recrystallising the lamina from boiling alcohol and picking out the needles, ternitronaphthalin a is obtained in a state of purity. (Laurent.)

Propeiiies. Pale yellow, inodorous. Crystallises from boiling alcohol on cooling in long rhombic tablets, which are generally very irregular and indented like a saw. If it be heated to 100^ with ether in a sealed tube, six-sided prisms are obtained, derived from a rhombus of 50° and 130®. Melts at 210^ and solidifies in a fibrous mass on cooling. Heated on a glass plate in the air, it volatilises nndecomposed ; but if it be heated in a tube, it takes fire, gives off a brown smoke, and leaves a residue of charcoal.

Laurent.

20 G

5H

I 3N

120

			mean,
120	.••1	45*6 ...	..... 45*5
5	••.•	1-9 ,„.	.... 2-0
42	•>••	160 ....	..... 16*3
96	■•••	36-5 ....	36-2

C^X»H« 263 .... 1000 100*0

Decompositions, 1. By cUorine it is first tamed red, and then com- pletely decomposed. rLaurent.) — 2. Heated with lime, it undergoes combustion. (Laurent.) «> 3. It dissolves in alcoholic potash and forms a red solution, which turns brown on boiling and evolves ammonia. On neutralising the solution with an acid, a voluminous brown precipitate of

TBBNITEONAPHTHALIN. 89

nitronaplitlialesic acid is obtained. This acid resembles nitronapbtbalesic (p. 87) and nitronaphtbaleisic acids, and decomposes with deflagration on beating in a close vessel. Its compounds witb tbe alkalis are brown, uocrystallisable. Nitronapbtbalesic acid contains more carbon tban ternitronapbtbalin ( ? ), (Laurent). •— 4. It dissolves slowly and witb difficulty in a saturated alcobolic solution of ammonia, forming a rose- coloured liquid, which, if saturated witb sulphuretted hydrogen, turns yellowish and reddish brown, and then dissolves a considerable quantity more of the excess of ternitronapbtbalin. The solution turns green when heated but does not deposit sulphur. If the liquid be distilled almost to dryness, and tbe residue treated witb boiling water, it yields a carmine-red solution, which on cooling deposits a reddish-brown powder, not possessing basic properties. (Zinin, •/. pr, Chem. 33, 84.)

CombmcUiorii, 1. Dissolves very sparingly in boiling alcohol, -— 2. It dissolves in nUric add, and oU of vitriol without decomposition, if they be not too strongly heated. (Laurent.)

Modification p, (Ninaphtise GL, Nitronaphtalc, Laurent). All tbe residues from tbe previously described modification are mixed together and boiled witb nitric acid for five or six days. On cooling, beautiful needles are obtained, which are washed on a ninnel (without paper) first with nitric acid, and then witb water and with alcohol. If the crystals be immediately washed with water, a resin is precipitated^ which mixes with the temitro- naphthalin. The crystals when dry must be washed with ether, to remove traces of this resin. (Laurent.)

Properties. Colourless when freshly crystallised, becomes slightly yellow and dull after washing witb water and drying. It closely resembles tercbloronaphtbaliu a, but has a diflerent crystalline form. Heated in a sealed tube to 100° witb ether, it crystallises on cooling in brilliant, yellow, exceedingly small, oblique rhombic prisms : Fig. 93, witb faces «. ttittr^SO"*; t :< behind = 126 ; <:tt = 124; i:t=UO°; i:u=z 9S^ 15'; f lu = 104° 30'. Although the crystals of a and p have one angle in common, yet they cannot be confounded with one another. (Laurent.) Melts at 215°; 0*1 gramme melted on a glass plate, remains transparent on solidifying, and then crystallises suddenly when it is again heated below its melting point, or when gently stirred witb a pointed instrument. Heated on platinum -foil, it appears to volatilise undecom- posed; but when heated in closed vessels, it suddenly decomposes witb emission of light.

Laurent. flrgt analysi*. later.

... 45-6 45-46 .... 45*6

... 1-9 1-92 .... 20

... 160 17-25 .... 16-8

... 36-5 55-38 .... 35*6

20 C 5 H	120 5
3 N	42
12 O	96

C»X»H» 263 .... 100-0 100-00 .... 100-0

Laurent previously considered the compound to be C^H^NH)*^ ; Berselius (Jahrei' hericAt, 23, 534) considered it to be isomeric with temitronaphthaUn a, which Laurent afterwairds found to be the fact.

Decotnpositions. 1. Dissolves readily in hot oii of vitriol without decomposition ; but if tbe solution be too strongly heated, it turns brown

90 NITRO-NUCLEUS C»X»H«.

and evolves sulphurous acid. — 2. It takes fire when heated with hydrate of baryta in a closed vessel. — 3. Boiling alcoholie potash first turns it orange-red, then brown, and decomposes it; the brown solution gives with acids a brown precipitate resembling nitronaphthalislc acid. (Laurent) — 4. Boiling nitric acid decomposes it in a similar manner. (Laurent.)

Of all the nitro-compounds of naphthalin, it is the most insoluble in alcohol and in ether.

Modification 7. Marignac*s temitronaphthalin. The insoluble reei^ due which remains when binitronaphthalin is prepared by boiling naphthalin for a long time with nitric acid (p. 87, 3), is impure temitro- naphthalin 7. To purify it, it is again washed with water, finely pulverised, and treated with cold ether; which thereby acquires a yellow colour and yields a viscid resin on evaporation. (Marignac.)

Properties, Slightly yellow ; it is deposited from boiling alcohol as a crystalline powder. Melts a little above 1 00*'. When carefully heated it volatilises without residue, but often decomposes very rapidly, with slight explosion and reddish flame, leaving a large residue of carbon.

20 C	120	.... «d*D .. .... 16-0 ... .... 36-5 ...	Marignac, mean. 46*12
5 H	5	1*96
3 K 12 0	42 .... 96	16-59 35-33
0»X3H^	.... 263	.... lOO'O ..	100-00

Hence it is C»H503,3NO»^r C»H»,3N0* (Marignac).

Decomposition. Dissolves with beautiful red colour in caustic alkalis and their carbonates, slowly in cujfueotis and rapidly in alcoholic potash. The red alcoholic potash-solution becomes dark or blackish-brown, slowly in the cold, but almost instantly when heated, evolving a large quantity of ammonia ; the liquid having absorbed carbonic acid, effervesces when it is saturated with an acid, and yields a fiocculent, bulky, brownish-black precipitate = C*«H»NO«. The brown body dries up to a hard, black, shining mass, resembling anthracite.

Marignac. mean.

12 C 72 .... 56-21 56-22

3 H 3 .... 2-30 2-69

N 14 .... 10-85 10-79

5 O 40 .... 30-64 30-30

C«H»NO» 129 .... 10000 10000

When the liquid separated from the brown body is distilled, it yields formic acid and exhales a feeble odour of prussic acid, which however cannot be detected in the solution. Since prussic acid is decomposed by potash into formic acid and ammonia, the decomposition is perhaps as follows :

2C»X»H* + HO - 2C«H»N0» + 4CNH + CHO" + 6CO». (Marignac.)

The brown body heated in a tube, evolves water and empyrenraatic vapours and leaves a large amount of carbon; it decomposes when rapidly

NITRONAPHTHALfilSB. dl

heated on plationm-foil^ emitting red sparks* It is not acted npon by concentrated hydrockhrie add, or by dilated nitric and tulphuric acids, bat is decomposed hjoUof vitriol with evolation of salphurons acid. It dissolves in concentrated nitric add, nitrous acid being set free; the yellow solution gives with water a pulverulent precipitate insoluble in water, soluble in ether.

Almost insoluble in tpater and in alcohol, to which it neyertheless imparts a yellow colour. Quite insoluble in ether.

The dry brown substance also dissolves readily in eaustio alkalis and their carbonates, forming brown solutions, without expelling carbonic acid from the carbonates. The solutions yield viscid masses by slow evaporation. When the ammoniaoal solution is boiled, it gradually parts with its ammonia and deposits the brown substance. Salts of silver, lead, baryta, and lime precipitate the brown substance from its solutions in combination with small quantities of the salt employed, or of the corre- sponding metallic oxide; the precipitates have, however, no definite composition, and appear to decompose by prolonged washing. The brown body is precipitated by acids from its solution in alkalis. (Marignac)

CoTnhinations, I. Temitronaphthalin 7 is insoluble in cold water, and only so far soluble in boiling water, that the liquid becomes turbid on cooling.

2. Dissolves slightly in nitric add, and is precipitated therefrom by water.

8. Dissolves sparingly in boiling alcohol. — 4. It is almost insoluble in ether; even in boiling ether.

Appendix to Teimitronaphthalin,

Nitronaphthaleise (Laurent).

Laurent. Rev, scient, 0, 88 ; 13, 70.

Ninaphfine, (Laurent.)

Formation and Preparation. The nitric acid mother-liquid which remains in the preparation of binitronaphthalin (p. S6, 2) still contains a large quantity of that substance in solution; this solution is boiled for several hours in a retort, whereapon, while the whole is still warm, an oily mixture of binitro- and temitro-naphthalin (both of which are scarcely soluble in ether), and nitronaphthaleise (rather soluble in ether) is deposited at the bottom of the vessel. The oil solidifies in a yellow waxy mass; which is washed with alcohol and boiled with ether; whereupon the solution by spontaneous evaporation yields crystals of nitronaphthaleise mixed with a little binitronaphthalin. The mother-liquid still contains some nitronaphthaleise and an oil. The crystals are treated with warm but not boiling ether, the solution is evaporated, and the residue completely pnrified by repeated recrystallisation from alcohol.

Properties, Pale yellow. Crystallises from alcohol or^from ether in

92 BROMONITRO-NUCLEUS C^rX'H*.

small feathery needles. Melta in boiling aloobol (hence it cannot be a mixture of bi- and ter- nitronaphthalin, both of which melt near 200**), and on oooliDfi^

Bolidifiee in an opaqne radiated mass. — Distils partly undecomposed, bat decomposes suddenly after a few moments with erolotion of light

Laurent. mean,

20 C 120 .... 49-90 498

6-5 H 5-5 .... 2-27 2-3

2*5 N 35 .... 14-55 14-8

10 O ., 80 .... 33-28 33-6

C»X«-»H»-* 240-5 .... 10000 1000

It imparts a red colour to alcoholic potash and then decomposes by boiling, evolving ammonia ; the brown liquid gives with acids a brown precipitate of nitronapbthaleisic acid. This compound resembles naph- thalei'sic acid, and forms with alkalis brown uncrystallisable salts which decompose with deflagration when heated in closed vessels. Laurent found in the analysis of nitronaphthaleisio acid, 51-8 p. c. 0. 2*6 p. e. H., and 31-8 p. c. N.

Nitronaphthaleise is insoluble in toater. It dissolves unchanged in nitric ojcid; sparing in hot oU of vitriol^ and is precipitated therefrom by water.

Slightly soluble in alcohol, rather soluble in ether.

BromonitrO'fiticleus C*BrX*H*.

Bromobinitronaplithalin.

C«»H»BrN«0» = C"BrX*H».

Latjrknt. Compt, rend, 21, 35; CompL chim, 1850, 1; abstr. Afoi. Pharm. 76, 298 ; Fharm, Centr, 1850, 310 ; LUhig & Kopp'a Jahresb. 1850, 497.

Nitrobronaphtite, (Laurent.)

Formation and Preparation, When bibromonaphthalin is boiled with nitric acid, a solution is obtained from which water precipitates an oil solidifying in the cold. The product is purified by repeated crystal- lisation from ether. (The acid Uquid, from which the bromobinitronaphthalin haa crjstalliaed, yields by evaporation a miztnre of oxalic and bromophthalio adda.)

Properties, Yellow substance.

20 C 5H Br

2N 80

		Laurent.
120	.... 40-50 ...	40*35
5	.... 1-67 ...	..... 1-55
80	.... 26-90 ...	26-40
28	.... 9-50 ...	10-25
64	.... 21-43 ...	21-45

0»BrX«H» 297 .... 100 00 10000

Thna 1 At« Br and 1 At. H of bibromonaphthalin are replaced by 2 At. X.

When rapidly heated in a glass tube, it explodes.

Insoluble in water; readily soluble in ether, less soluble in altohoL

NAPHTHTLAMINE. 93

Azo-nucUui C^NH'.

Naphthylamine.

C»NH» = C»NH',H».

ZiMiN. (1842.) J. pr. Chem. 27, 140; Ann. Pharm. 44, 283; Berz.

Jahresb, 23, 545. — Petersb. Acad. Bull. 10, 346 ; abstr. Ann. Pharm.

84, 346 ; Chem. Gaz. 1852, 441 ; J. pr. Chem. 57, 173 ; Pharm.

Centr. 1852, 689 ; Liebig <fe Xopp's Jahresb. 1852, 627. PiRiA. SulCazione del edJUo d^ammoniaca tuUa nitronc^kUina, Pisa^

1850 ; Ann. Pharm. 78, 31 ; i\r. Ann. Chim. Phys. 31, 217 ; abstr.

Pharm. Centr, 1851, 380 ; Compt. rend. 31, 488 ; J. pr. Chem- 52, 5^;

Liebig & Kopp^s Jdhre9b. 1850, 500. Bechamp. N. Ann. Chim. Phys. 42, 186; abstr. Ann. Pharm. 92, 401;

Compt. rend. 39, 26 ; J. pr. Chem. 62, 469. Delbos. j^. Ann. Chim. Phys. 21, 68 ; Compt. rend, 24, 1091 ; If. J.

Pharm. 12, 237 ; Ann. Pharm. 64, 370 ; J. pr. Chem. 42, 244 ;

Pharm. Centr. 1847, 637 ; Liebig & Kopp's Jahresb. 1847-8, 610, W. H. Pbrkin. Chem. Soc. Qu. J. 9, S ; Chem. Gaz. 1856, 119;

Jf. Phil. Mag. J. 12, 226 ; Instit. 1856, 300 and 406 ; J. pr. Chem.

68, 152 and 441 ; Chem. Centr. 1856, 394 ; Luhig & Kopp's Jahresb.

1856,538. H. ScHiPF. Prelim, notice : Ann. Pharm. 101, 90; J. pr, Chem. 71, 108;

more detailed : Inaugural dissertation, Gottingen, 1857 ; abstr. Ann.

Pharm. 101, 299 ; J. pr. Chem. 70, 264 ; N. Ann. Chim. Phys. 52,

112; Chem. Oat. 1857, 211; Chem. Centr. 1857, 166 and 362; IMig

& Ktmp^s Jahrefh, 1 857, 389. A. W. HoFMAHN. Compt. rend. 47, 425 ; N. Ann. Chim. Phys. 54, 204. ScHUTZENBERGER k WiLLM. Compt. rend. 47, 82 ; J. pr. Chem. 75,

117; Chem. Centr. 1858, 654; Chim. p. 1, 38.

Naphihdlidam (Zinin) ; Naphthalidine (Piria).

Formation. First prepared bj Zinin in 1842, by treating nitronaph-* tbalin with solpbaretted hydrogen, or with sulphnretted hydrogen and ammonia aided by a gentle heat :

CTXH7 + 6HS - C»NH7,IP + 4 HO •«- 6S.

2. A thionaphthamate is decomposed by an acid, and the thionaph- thamic acid thereby liberated is resolred by water into sulphuric acid and naphthylamine :

C«TNH9,2SO» + HO = C»NH»,HO,SO» + HO,SO»;

the same reaction is produced when a thionaphthamate is distilled with excess of hydrate of lime. (Piria.) — 3. Nitronaphthalin is warmed with excess of ferrous acetate :

a^W + 12PeO -I- 2HO » 6Pc»0» + C»NH',H';

or with iron filings and acetic acid (Bechamp) ; in the last case, phtha- lamine, C"H*NO*, is simultaneously formed, (Schiitzenberger & Willm). — 4. Nitronaphthalin is heated with bisulphide of carbon in a sealed tube to 160% whereby sulphur is separated. (Schlagdenhauffen, ^. J*. Pharm. 34, 175.)

94 AZO-NUCLEUS C»NH'.

Preparation 1. One pt. of nitronaphthalin is difisolyed in 10 pis. strong alcohol, the solution saturated with ammonia, whereupon a little nitronaphthalin may remain undissolved, and then saturated with sul- phuretted hydrogen, till the whole is dissolved and the solution acquires a dirty dark-green colour. The liquid is then allowed to stand for a day, whereupon sulphur crystallises out, the odour of sulphuretted hydrogen ceases, an odo«r of ammonia heeomes perceptible, and the solution now contains hydrosulphate of naphthylamine which decomposes on distilla- tion. A portion of the alcohol is distilled off, whereupon a large quantity oi sulphur is deposited, which causes violent bumping, so that the distillation cannot be continued unless the liquid be decanted from the sulphur; the distillation is now continued till Dumping a^ain occurs ; and the liquid is again decanted and distilled till the portion remaining ia the retort separates into two strata, the lower of which is impure naph- thylamine, the upper a solution of naphthylamine in weak alcohol. Or sulphuretted hydrogen alone is passed into the warm alcoholic solution of nitronaphthalin; and after a time, the pale yellow solution is poured off from the precipitate which has been formed, and submitted to distillation, whereupon a thick dirty green oil is deposited (solidifying in crystals on cooling), and the liquid on standing deposits fine needles of naphthylamine.

To purify the product, either of the following methods may be adopted : a. the impure base is distilled, the fluid yellowish distillate then solidifying in a white crystalline mass. Or, b. sulphuric acid is added to the alcoholic liquid, whereby sulphuretted hydrogen is evolved and sulphur and sulphate of ammonia are precipitated, and on the addi- tion of more sulphuric acid, the whole mass solidifies in a paste of sulphate of naphthylamine. This is purified by one or two recrystallisa- tions from alcohol, dissolved in water and supersaturated with ammonia, whereupon the liquid becomes transiently turbid, and after a few minutes is completely filled with crystals of napnthylamine. (Zinin.)

2. A thionaphthamate, or better still, hydrochlorate of naphthylamine prepared therefrom (p. 99), is distilled with excess of slaked lime. (Piria.)

d. 20 grammes of nitronaphthalin are warmed for 4 hour on a water- bath with tolerably concentrated ferrous acetate containing 40 grammes of iron, in a flask provided with a drawn out tube. The flask is then filled with boiling water, and after the liquid has become clear, it is decanted ; if it deposits needles, these are collected, and only the liquid is poured away. After the residue has been several times treated with boiling water, it is collected on a filter and exhausted with alcohol of 86"^; the alcoholic solution is distilled as rapidly as possible ; and the residue is treated with sulphuric acid, whereupon, if the liquid be sufficiently concentrated, the whole solidifies in a crystalline mass of sulphate of naphthylamine. This is purified by recrystallisation from boiling alcohol or better, from boiling water, (since in contact with alcohol the red mass is formed with peculiar facility,) and its hot aqueous solution is decomposed by ammonia (B^champ). — 4. A mixture of 1 pt. nitronaphthalin (which for this purpose need not be recrystallised from alcohol, but only freed from nitric acid by washing with water: Schif) with l^- pt iron filings in sufficient common acetic acid to cover the whole, is gently warmed in a retort capable of containing ten times as much substance, till the nitro- naphthalin is melted. It is then taken off the fire, lest the mass should go over. When the violence of the reaction has abated, it is distilled on a sand-bath^ the retort being surrounded with sand up to the neckj

NAPHTHTLAMINB. 95

whereupon first the acetic acid, and afterwards at about 300^ the naph« thjlamme passes over and collects under the acetic acid as a yellow liquid, which is purified either by fractional distillation, or as described in method o. ?B6champ.) Considerable quantities of naphthylamine are thus obtained, but impure; it is therefore dissolved in hydrochloric acid, and the filtrate is evaporated to dr3niie8s and distilled with hydrate of lime, whereupon the base passes over perfectly colourless and almost pure. (Perkin.) 5. The operation is conducted as in 4, and after the reaction is terminated, the excess of acetic acid (which aJways contains a little naphthylamine in solution) is distilled ofi*; the residue when cooled is mixed with rather concentrated potash-solution, and allowed to stand for an hour, in order that the mass may become thoroughly saturated with potash; and the bulb, of the retort is then completely surrounded with ignited charcoal, whereupon the naphthylamine begins to pass over at 800°. It is advantageous to place some acetic acid in the receiver, in order that the vapours may be immediately absorbed. As soon as the distillation is over, the contents of the receiver, which always contains a small quantity of undecomposed nitronaphthalin, are repeatedly boiled with dilute acetic acid, and the naphthylamine is precipitated from the filtrate by potash. White flakes are obtained which impart a turbid, milk^ appearance to the liquid, and after standing for several hours unite m long needles. (SchiffJ

JPurifieaticn. Naphthylamine obtained by method 4, (as well as that obtained by method 5, according to Carius), contains an admixture of phthalamine. To purify it, the crude product obtained in the first dis- tillation is treated with sulphnrio acid, and the more insoluble sulphate of naphthylamine is separated from the more soluble sulphate of phtha- lamine by crystallisation from water. (Schutzenbergez & Wilbn.)

Properties, Precipitated from the sulphate by ammonia, it forms fine, white, silky needles, pressed flat together; or when precipitated from the acetate by potash, white flakes, uniting in long needles after they have stood for several hours in the liqnid. (Schifi*.) Melts at 50% and boils at about 300% distilling without decomposition, as a pale- yellow, dear liquid, a single drop of which often remains fluid for some time on a watch-glass, but solidifies suddenly when touched. When, the liqnid is cooled to 0°, it solidifies in a yellowish white crystalline mass. (Zinin.) Carefully and gradually heated, it sublimes in long silky needles (Schifl*), and when kept long in a closed vessel between 20° and 30°, in long, narrow, very thin, flexible and transparent lamina. (Zinin.) It has a peculiar, strong, disagreeable odour, and a strong, pungent, bitter taste; it nas not an alkaline reaction. (Zinin.)

20 C 9H

N

			Zinin.
			mean.
120	• •••	83-91 ....	1.... OO'ol
9	•«••	6-30 ...,	6-51
14	• •••	9-79 ....	I.... «f £1

C»NH» 143 .... 10000 99-63

Deeampositioni. 1. Heated on platinum-foil, it bums with a very smoky, yellow flame, and leaves a large residue of charcoal (Zinin). — 2« Turns violet in the air (Zinin); exposed to air and ligktf it turns

96 AZO-NUCLEUS CWH^,

yellow, and afterwards brown (Sohiff) ; probably ahsofinng oxygen at the same time (Zinin). It becomes more rapidly coloared in the liquid form, and hence more especially after distillation, if it be not cooled to 0° and preserved in hermetically sealed vessels. (Zinin.) Sublimed naphthy- famine becomes coloured only by prolonfifed exposure to the air and sun, and if protected from both, may be preserved unchanged for years. (Schiff.) — 3. It is not attacked by ckhrins in the cold, but in the melted state it is violently attacked, being thereby converted into a resinous substance, while anotner portion forms hydrocblorate of naph- thylamine with the hydrochloric acid produced, and sublimes in the upper part of the vessel. When the aqneons solution of hydrochlorate of naphthylamine is submitted to the action of chlorine, it assumes a violet colour and deposits a brown resin. No chloride of ammonium is formed in this reaction ; but from the solution, which has become strongly acid, a new substance crystallises by spontaneous evaporation in long, transparent, golden-yellow needles. (Zinin.)

4. Naphthylamine, or one of its salts, gives with aqueous/rrte cJUoride^ nUrcUe of sUver, chloride ofgoJdy and in general with all oxidising agents, a beautiful, azure-blue precipitate of naphthameine, which rapidly turns purple ^Piria); the same reaction is produced by mtrous ctcid (Ganahl), as well as by> plcUinic Moride, mercuric chloride^ chloride of zinc, li-^ chloride of tiUf and'by chromic acid. (Scbiff.) The blue precipitate is not formed, as Piria concluded, from naphthylamine by loss of hydrogen and the elements of ammonia, but consists of oxynaphthylamine, C^H*NO' (Schiff). The colour acquired by naphthylamine and its salts by exposure to the air is probably due to the formation of the same substance. (Piria, Schiff.) — 5. Naphthylamine, as well as its salts, is converted by nitric acid, especially if it contain nitrous cund, into a brown powder, which is almost insoluble in water, but readily soluble in alcohol, forming a red or violet liquid. It is deposited on evaporation unchanged, and sometimes together with crystals resembling murexid. (Zinin.) (Hence it is probably nitrosonapfathylin ; Carins.) — 6. Naphthylamine or one of its salts is converted by nitrous acid or by nitrite of potash, into nitroso- naphthylin, C^H^N'O* (Church & Perkin), with evolution of nitrogen gas (Schlitzenberger & Willm); according to Schiitzenberger & Willm {Gompt, rend. 46, 894 ; J, pr, Chem. 74, 75), it is converted into a brown porous mass which is resolved by alcohol or ether, into nitrosonaphthylin, which dissolves, and an insoluble non-azotised substance, naphthulmin, C^H'O^ (Comp. p. 26.) Naphthylamine suspended in water and treated with nttrous acid, yields at first naphthameine, with evolution of gas, and if the action be prolonged, a resin and an acid which dissolves in alcohol with lemon-yellow colour, C*«H«N«0» (xiii, 352) — (Ganahl & Chiozza, Ann. Pharm, 99, 240; J. pr. Chem. 70, 125).

7. When naphthylamine is added by small portions to a mixture of nitric and sulphuric acids, a violent reaction sets in and the whole acquires a dark green colour. Water precipitates from the solution yellowish-red flakes, insoluble in water and hydrochloric acid, soluble with red colour in alcohol, sulphuric acid, nitric acid, and potash, and precipitated from the potash solution by neutralisation and from the other solutions by water; they are probably nitronaphthylamine, G^NXH^H^ From this solution iron and acetic acid precipitate brown flakes of a base resembling in reactions and insolubility Zinin's semi- naphthylamine C»N*H". (Schiff.)

8. Naphthylamine heated on a water-bath with oxychloride of phos^

NAPHTHYLAMINE. 97

phariis, yields ternaphthylphosphamide and faydrochlorate of naphthyl- amine.

PO^CP + 6C»NH9 = Na(P0>)(C»H7)»H» + 3C»NH9,HC1. (Schiff.)

9. When a solution of naphthylamine is anhydrous ether is saturated with gaBeoua cyanic acid-, and allowed to evaporate spontaneously, it yields brilliant yellow laminso of naphthyl-urea, CH^^N'^O*. This urea IS not formed from snlphate of naphthylamine and cpanate of potash, but these substances decompose by prolonged digestion of the concentrated solutions and evaporation in the water-bath, giving rise to naphthylamine, sulphate of potash, and common urea:

S«(C»NH»«)H08 + KO,CyO + 2H0 = C»H*N»08 + 0»NH9 + 2KO,SO»

+ 2 COS. (Schiff.)

this shoold perhaps be :

S>(C»NHW)K)» + 2KO,C70 + 2H0 - C^H^N^Oa + 2C»nH9 +

2KO,SO» + 2CO«. (CariuB.)

When an ethereal solution of naphthylamine is saturated with gaseotis cycmic acid, no naphthyl-urea is formed under certain circumstances, (probably when ether containing water is employed), but a red solution, yielding on evaporation a purple syrupy mass, which is turned violet by acids, and red again by alkalis. Paper saturated with the alcoholic solution gives the opposite reactions to litmus paper; like that formerly prepared by Saco with tincture of madder. These colour-reactions are perhaps connected with the relation of the naphthalin-compounds to the colouring matters of madder. (Schiff.)

10. Alcoholic solution of naphthylamine combines with oU of mustard, forming allyl-naphthyl-sulphocarbamide, C*"H"N*S*. (Zinin.) — 11. A mixture of naphthylamine and gtUphocyanide of phenyl becomes almost immediately solid, phenyl-naphthyl-sulphocarbamide being formed. (A. W. Hotmann.) — 12. An alcoholic solution of naphthylamine yields with bisulphide qf carbon, sulphocarbonaphthalide and sulphuretted hydrogen, (Laurent, iT. ^nn. Chim. Fhys. 22, 104; Delbos); and the same reaction ensues when naphthylamine is heated for several hours with bisolpl^ide of carbon in a sealed tube. (Schiff.)

2C»NH» + 2CS« * C*2N2HWS» + 2 HS.

When the yapours of naphthylamine and bisulphide of carbon are passed through a red-hot porcelain tube, much shining charcoal is deposited ; and hydrosulphocyanio and hydrosulphuric acids are formed ; probably naphtho-siilphocyanic add, C^yH'fS', together with sulphuretted hydrogen, is first formed, aud is then resolved in carbon and hydrosulphocyanio acid. (Schlag- denhaufen, N. J. Fharm, 34, 175.)

18. Naphthylamine behaves with chloride of cyanogen like aniline, (Cahoun & Cloez, GcmpU rend, 38, 354; Ann. Pharm. 90, 91.) If cbloride of cyanogen be passed through naphthylamine in the fused state, as in the preparation of melaniline by A. w . Hofmann's method, Cs\, 351) heat is developed and a substance is produced which on cool- ing becomes a black resinous mass, and consists chiefly of hydrochlorate of menaphthylamine. (W. H. Perkin.)

2C«»H»N + CNCl « C«NH>7,HCl.

14. When naphthylamine is heated with bromide of ethyl for several hours at a temperature between 40^ and dO"", so that the vapour formed yoL. xiy. H

98 AZO-NUCLEUS C*NH7.

condenses and flows back into the flask, a reddish-brown mass is pro- duced, containing hydrobromate of etbyl-naphthylaniine together with excess of bromide of ethyl ; the same reaction takes place at the common temperature in about 1 4 days :

C»NH» + C*H»Br = C«HWN,HBr. (ScMff.)

15. Naphthylamine and iodide of ethyl form hydriodate of ethyl-napfa-' thylamine. 16. ^\\h. iodide of ftfiethyly ^ sticky mass is formed, which cannot be crystallised from either alcohol, water, or ether. (Scbifi*.) — 17. Naphthylamine and aniline do not react apon one another either by distillation or by heating the mixture in a sealed tube in an oil-bath, (Schiff:)

Combinations. 1. Almost insoluble in water. (Zinin.) 2. Appears to combine with iodine, (Zinin.)

Naphthylamine is a strong base, and combines with all oxyacids and hydracids, forming salts, from all of which it is separated by ammonia. The salts of the hydracids are anhydrous, those of the oxy- acids contain 1 At. water, which cannot be expelled without destroying the salt (Zinin.) The salts of naphthylamine are white, and for the most part crystalline. (Zinin.) They turn yiolet on exposure to air and light (Zinin); they turn yellow, afterwards red, and then brown, (Schiff) — probably absorbing oxygen (Zinin), and in consequence of the formation of oxy naphthylamine. (Piria, Sohifi*.) Their solutions give with ferric chloride, nitrate of silver, chloride of gold, and generally with all oxidising agents, a beautiful azure- blue precipitate, rapidly acquiring a purple colour (comp. p. 96): naphthamein, according to Piria; oxynaph- thylamine, C^H'NO', according to Schiff; and with chromic acid, a green, blue, or black coloration, according to the concentration of the liquid. (A . W. Hofmann.) They impart a yellow colour to pine- wood, like aniline, only the colour is more intense. (A. W. Hofmann.)

Phosphate of Naphthylamine. a. Ordinary. Even weak solutions of naphthylamine solidify in a mass of acicular crystals with an aqueous solution of unignited phosphoric acid. These crystals are readily soluble in boiling alcohol and in water ; the salt crystallises unchanged from the alcoholic solution, but is deposited from the aqueous solution as a mass of white, silvery scales. It tnrns red in the air more rapidly than the sulphate. (Zinin.)

6. Metaphosphaie. An alcoholic solution of naphthylamine gives with alcoholic metaphosphoric acid, a white pulverulent precipitate, which is but yery slightly soluble in water and in aJcohoL (Zinin.)

Sulphate qf Naphthylamine. Naphthylamine dissolves in gently heated oil of vitriol, forming a clear liquid, which yields no crystals even at 0^, but when diluted with water, deposits a large quantity of scal^ crystals, so that the liquid becomes solid. The same crystals are obtained by cooling a solution of naphthylamine in dilute sulphuric acid. (Zinin.) If sulphuric acid be added to a solution of thionaphthamate of potash, soda, or ammonia, and the liquid warmed, a crystalline pulp is formed before the liquid begins to boil, provided it is sufficiently con- centrated ; on continuing the application of heat, the crystals dissolve, and on cooling, silvery laroinee are deposited, which may be purified by repeated recrystallisation from water or from alcohol (comp. p. 93.)

NAPHTHTLAMINE. 99

(Piria). White, silvery laminaB, possessiDg in a great degree the odour and taste of the free base. Reddens litmus. When dry, it does not suffer any change in the air; when moist, or in solution, it turns red like the base. The solution stains the skin first red aud then dark brown. (Zinin.) At the temperature of boiling water, it effloresces to a light, mealy, dull powder. Heated in a retort, it melts, decomposes with evolution of sulphurous acid, and leaves a porous, shining charcoal, while part of the base distils over with the water. (Zinin.) It is difficultly soluble in oold water and alcohol ; slowly, but rather abundantly soluble in boiling alcohol, so that the saturated boiling solution solidifies com- pletely on oooling. (Zinin.) It is iesB soluble in water than sulphate of phthalamine, and can therefore be separated from this substance by erystallisation. (Schiitzenberger & Wilun.)

10 H

N

S

40

			Zinin.
			at 100° (mean)
120	• •••	62-49	6200
10	• ■•«	5-21	5-88
14	• ••«	7-29	6-50
16	■ •••	8-34	8-39
32	• • ■ •	16-67	17-23

C^NH«,HO,SO» .... 192 .... 100-00 10000

Bechamp fonnd in the salts prepared by method 3 (p. 94), 22*812 p. c. SO"; Schlltsenberger and Willm, in those obtained by method 4, and separated by crystal- lisation from sulphate of phthalamine, 62*3 p. c. C, 5 '3 p. c. H, 20*8 p. c. SO*, and 8*65 p. c. water of crystallisation.

Alcoholic solution of sulphate of naphthylamine yields with iodide of potasnum, a precipitate of sulphate of potash ; the solution deposits on evaporation a resinous mass containing iodine, burning without residue, and decomposing with hot water. (Schiff.)

Hydrobnymaie of Naphthylamine. A concentrated alcoholic solution of sulphate of naphthylamine mixed with an equivalent quantity of con- centrated solution of bromide of potassium or of barium, yields in the first instance slowly, in the second immediately, a precipitate of sulphate. The coloured filtrate slowly evaporated, leaves a crystalline residue of hydrobromate of naphthylamine, readily soluble in alcohol, but less

soluble in cold water. Schiff found in the salt 35*53 p. c. Br ; the formula C^NH>,HBr requires 35*72 p. c. Br. (Schiff.) Schiff explains the formation of this salt by the equation :

8»(C»NHW)H08 + KBr - C»NH»,HBt + SSKHO>.

HydroMoraU of Naphthylamine. When concentrated alcoholic solution of naphthylamine is mixed with excess of hydrochloric acid, a white, solid mass is produced, which must be carefully freed from moisture by pressure between blotting paper and drying in vacuo over oil of vitriol and lime, and afterwards sublimed in a common beaker-glass placed in an oil-bath. (Zinin.) — A tolerably concentrated solution of thionaphthamate of potash, soda, or ammonia, is heated till it nearly boils, pure hydro- chloric acid is then added, and the whole is boiled for a few moments. If the solution is very concentrated, a crystalline precipitate of sulphate and hydrochlorate of naphthylamine is formed, even while the liquid is still warm; in this case, a little water must be added and the whole

H 2

100 AZO-NUCLEUS CP^W.

wanned, till the precipitate redissolves. The snlphario acid is now precipitated by excess of chloride of barium and the liquid filtered hot; on cooling, hydrochlorate of naphthylamine crystallises out. The mother-liquid yields, on addition of hydrochloric acid, more of the salt, which becomes less soluble therein the more hydrochloric acid is added. (Piria.) Crystallises from alcohol in brilliant scales resembling: the sulphate; from water in asbestos-like needles. (Zinin.) Sublimes almost without decomposition (Zinin, Piria); at 200^ in a lij^ht, woolly mass, consisting of fine needles (Zinin) ; in snowy crystalline flakes (Piria). The sublimed salt is permanent in the air; if moist or in solu- tion, it is rapidly decomposed in the air (Zinin, Piria); it then becomes red more quickly than the sulphate (Zinin), and can no longer be purified by crystallisation from alcohol or from water. (Piria.) Rather soluble in water, more soluble in alcohol and in ether. (Zinin.)

Zinm. sublimed (mean),

20 C 120 .... ^6-85 66-36

10 H 10 .... 5-58 5-74

N 14 .... 7-80

CI 35-5 .... 19-77 19-03

C»NH»,HC1 179-5 .... 10000

Nitrate of Naphthylamine, Naphthylamine dissolves in boiling dilute nitric acid free from nitrous acid, forming a colourless or slightly red liquid, from which the salt crystallises on cooling in small, brilliant scales. (Zinin.)

Chloromercuntte of Naphihylamine, Mercuric chloride produces with alcoholic solution of naphthylamine or of its salts, a yellow curdy pre- cipitate, difficultly soluble in cold alcohol, but completely in boiling alcohol, from which it is deposited in crystals on cooling. (Zinin).

Chloroplatinaie of Naphthylamine, When an alcoholic solution of hydrochlorate of naphthylamine is poured into a solution of platinio cnloride, the liquid turns green ana deposits the salt as a brownish green-yellow powder. Crystallises from the hot solution on cooling; difficultly soluble in water, and still less soluble in alcohol or in ether. (Zinin.)

Dried at 100^, it contains 28*21 p. c. platinum. (Zinin.)

Oxalate of Naphthylamine, a. Neutral, Crystallises in small, thin, silvery laminae, grouped in stars. (Zinin.) Heated in a retort, it first melts, losing water of crystallisation; shortly afterwards, water and equal volumes of carbonic oxide and carbonic acid are evolved with effervescence, naphthylamine and carbonaphthalide, C^N'H^'O', distilling over at the same time :

C«H»N«08 « C«N»Hi«0» + 4 HO + 2 CO J

or better;

2C«H»N»0« ^ C«N»H»«0« + 2C»NH» + 6HO + 4C0 + 2C0«. (Delbos).

The last named compound is a secondary decomposition-product from oxanaphthalide C^N'N^'O^ The neutral salt behaves when heated like

OXYNAPHTHYLAMINE. 101

the acid salt, only that it yields more free napbthylamlne and more oxanaphthalide (Zinin.)

Zinin.

dried in vacuo over

eulph, acid,

44 C 264 .... 70-20 6613

20 H 20 .... 5-32 5-33

2 N 28 .... 7-45

8 0 64 .... 1703

2(C»NH»),C<H208 ^. 376 .... 100-00

h. Acid, Crystallises in clumps of dull, white nodules, soluble in alcohol and in water. (Zinin.) Decomposed by dry distillation, yield- ing a brownish yellow powder, which is insoluble in water, and is depo- sited from its alcoholic solution unchanged. (Zinin.) Heated to com- plete fusion, it yields carbonaphthalide :

2C«H"N08 « C«N«H»«0» + 6HO + 4CO + 2 CO^. (Delbos.)

The well dried substance begins to melt at 200°, then swells up, evolving water and a mixture of 2 vols, carbonic acid and 1 vol. carbonic oxide; after the whole has been completely melted, the liquid residue, which on cooling solidifies in a radiated crystalline mass, consists of oxanaph- thalide and formonaphthalide C^H'NOl (Zinin, Feterfib. Acad, Bull. 16,242 ; Ann. Fharm. 108,228; J, pr. Chem. 74,379.)

Zinin.

24 C 144 .... 61-79 6218

11 H 11 .... 4-73 4-88

N 14 .... 6-01

8 0 64 .... 27-47

C»NHSC<H208 .... 233 .... 10000

Appendix to Naphthylamine,

Ozynaphthylamine.

C*»NH»0> = (7°NH',2H01

PiRlA. C(mpt rend, 31, 488; Ann, Pharm. 78, 31 ; K, Ann. Ckim.

Pkys. 31, 217; J. pr, Chem. 52, 56; Fharm. Centr. 1851, 380; Liebiff

& Kopp's Jahresb. 1850, 500. H. ScHiPP. Ann. Fharm. 101, 90 ; J. pr. Chem. 71, 108 ; Chem, Centr.

1857, 166; Chem. Oat. 1857, 211; Liehig & Kopp's Jahresb. 1857, 389.

NaphihamHne. (Piria.) Oxynaphthalidine.

Formation. 1. A solution of naphthylamine or of one of its salts is treated with an oxidising agent, such as ferric chloride, nitrate of silver, chloride of gold (Piria), or chromic acid, mercuric or stannic chloride, or chloride of zinc; in which reaction neither metal nor chlorine enters into the new compound. (Schiflf.) — 2. By the first action of nitrous

102 APPENDIX TO NAPHTHALAMINE.

acid upon naplitliylainine suspended in water, nitrogen gas being erolved. (Ganahl^ Ann. Pharm, 99,240.) — The violet colour acquired by naph- thylamine and its salts, as well as by the thionaphthamfltes, on exposure to the air, is probably owing to the formation of oxynaphthylamine. (Piria, Schiff.)

Preparation. Hydrocblorate of naphthylamine is dissolved in alcohol, the solution diluted with water, but not sufficiently to cause turbidity, and while the whole is continuously stirred, aqueous ferric chloride is added, drop by drop, until a slight excess is present. The whole is allowed to stand for an hour with repeated stirring, and the precipitate is then collected, and first washed with water, till the wash-waters cease to become turbid with nitrate of silver, afterwards with alcohol, and then dried in vacuo. (Piria.) — Schiff adopts the same method, or he precipi- tates sulphate or acetate of naphthylamine with aqueous chromic acid.

Properties, Light, amorphous, dark purple powder (closely re- sembling Robiquet's orcein, xii, 858.) (Piria.) When moist, it nas a peculiar odour, resembling that of iodine, especially if heated. It cannot be crystallised. (Schiff.)

Schiff.

20 C	.... 120	.... 79-47 ... .... 5-66 ... .... o't$U ... .... 10-07 ...	a, ..*•. /w 4t4 .... ..... w # X .... >.... I)*o4 10-04	b. 74-09 .... 5-70 ....	75-34
9 H	9	5-39
N 2 0	.... 14 .... 66
C»NH»0» ....	.... 159	.... lOO'OO ...	100-00

a was obtained with chromic add, b with ferric chloride; c was precipitated by water from the sulphuric acid solution. Hence it is a simple product of the oxidation of naphthylamine, and not, as Piria thinks, oxidised naphthylamine minus ammonia.

Decompositions. It melts when heated, and immediately decomposes, evolving an aromatic vapour smelling of naphthylamine j and finally leaves a residue of difficultly combustible charcoal, which, however may be completely burned. (Piria.) — Burns when heated in the air, and leaves a difficultly combustible charcoal. (Schiff.) When moist, or if placed under water, it rapidly becomes violet ; hence it is difficult to obtain the dry product of a pure blue colour. (Schiff.)

Combinations. 1. It is insoluble in water. — 2. Dissolves in cold sulphuric acid, forming a blue liquid of the colour of indigo-solution, and is precipitated unchanged by water. — 3. Insoluble in ammonia and caustic potash. (Piria.) — 4. Dissolves sparingly in alcohol, imparting its colour to the liquid. (Piria.) — 5. Dissolves abundantly, with purple colour, in ether, and is precipitated from the solution by spontaneous evaporation as an amorphous powder. (Piria.) — 6. Dissolves in con- centrated acetic acid with violet colour ; the solution is not precipitated by water or by tartaric acid, but oxynaphthylamine is precipitated therefrom by most acids, alkalis, and metallic chlorides. (Pixia.)

It does not combine with acidfl or with bases. (Schiff.)

LBPIDINB. 103

Lepidine.

C»NH* = C«>NH^H«.

Gr. Williams. JEdinh. Boy. Soc. Trans. 21, 2nd pt; Chem, Gaz, 1855, 301 and 325 ; J. pr, Chem. 66, 334 ; abstr. N, Ann. Chim. Pkys. 44, 491. Farther, Edinh, Hoy. Soc. Trans. 21, 377; Chem. Gat. 3rd pt., 1856, 261 and 283 ; abstr. J. pr. Chem. 69, 355 ; Chem. Cenir. 1856, 817 i ZiMff & £opp's JalireS). 1856, 532.

liolated by ^^UamSi after Gorhardt had already coi:^ectnrad its preaence in cMnoline. (Comp. xlii^ 243.)

Formation. 1. By snbmittin^ oinobonine to dry distiUation. — 2. In the dry distillation of coal, passing over in the coal-tar oil. In either case accompanied by many other bases.

Preparation. 1. From cinchonine. The operation is eondncted as described, xiii, 244, and the portion passing over above 270^ (between 266° and 271° J. pr. Chem. 69, 363) is purified by repeated rectifica- tion.— 2. From coal-tar oil. The portions passing over between 250° and 267^ C. in the fractioDSkl distillation of the bases as described (xiii, 244), are collected apart. The portions which pass over afterwards, Le. at 274°, contain cryptidine, CPNH^'.

Properties. Oil resembling chinoline. That obtained from cin- chonine boils between 266'' and 271°, that from coal-tar oil between 252° and 257°, and has asp. gr. of 1*072 at 15°. Both products have the same odour. The vapour density of the first = 5*14, of the second =5*15, at 1 5° above the boiling point, but the last was slightly decomposed.

from Cinchonine. Gr. Williams.

20 C 120 .... 83-91 83*29

M .<M.. ...».••••« 14 ••.« "'oU .•••••«. 10*15

9 H 9 .... 6*29 6*57

C»NH9 143 .... 100«00 10001

Vols. Vapour density.

C-yaponr 20 8-3200

N-gas 1 0-9706

H.gas 9 0*6237

Lepidine Tapoor ........ 2 9*9143

1 4*9571

According to Williams, lepidine obtained by method 1 is probably only isomeric, and not identical with that obtained by method 2, which is rendered probable by the difference in boiling point (and the different behavioars of their salts).

Isomeric with methyl-chinollne (xiii, 252), and with naphthylamine.

Decompositions. 1. Lepidine 1 is slightly decomposed by boiling, yielding traces of pyrrhol and carbonate of ammonia. — 3. The iodides of methyl, ethyl, and amyl, convert it into methyl-, ethyl-, and amyl- lepidine.

104 APPENDIX TO NAPHTHALAMINE.

ComhincUions. Lepidine 1 forms salts, wbich are crystallisable, bat crystallise with difficulty. When bases of lower boiling point are present, the same holds ^ood with lepidine. 2. The salts obtained from the latter smell of naphthaliu.

Hydrochhrate of Lepidine, C*NH',HC1. — Small colourless needles, which do not melt at 100'\

I^itixtte of Lepidine. When lepidine which has passed over between 260° and 266^ is dissolved in moderately dilute nitric acid, it forms a pale red solution, yielding on evaporation a brownish red deliquescent mass. When this has been purified by repeated pressure and crystallisation from alcohol, it forms hard prisms (yellow, if impure) which are per- manent in the air, and do not melt at 100° — Lepidine obtained from cinchonine, and that from coal-tar oil, behave in the same way with hydrochloric acid.

Prisms. 6. Williams.

20 C

10 H

2N

6 O

0»NH9,NO»HO 206 .... 10000

Bichromate of Lepidine is obtained by mixing aqueous chromic acid with lepidine, and recrystallising from water the crystalline powder thus formed. Beautiful, long, golden-yellow needles, which decompose at } 00°, when moist but not when dry, and leave chromic oxide on ignition. Lepidine, prepared from coal-tar oil, does not form crystals with chromic add, but only oily compounds.

120	• ••• do'Zd ••••	.... 57*69 to 58-40
10	• ••• 4 oo •»■«	.... 4-93 „ 4-90
28	.... 13-69
48	.... 23-30

20 C N 10 H	Needles. 120 .... 47-36 14 .... 5-52 10 .... 3-95	6r.	Williams. 47-05 3-89
2 Cr	53-4 .... 21-07	21-27
7 O	56 .... 22-10
C»NHSHO,2CrO»	.... 253-4 .... 100-00

Concentrated solutions of hydrochlorate of lepidine and chloride of cadmium yield a crystalline compound, corresponding to that formed by hydrochlorate of chinoline (xiii, 215). {Chem, Gaz. 1855, 450 ; Liehig ee Kopp^s Jahreah. 1855, 551.)

Ckloroplatinate of Lepidine. — Obtained from lepidine passing over between 2^5° and 271°. If prepared from coal-tar oil, it remains soft for a short time after it has been precipitated, and afterwards becomes crystalline.

6r. Williams.

20 C 120 .... 34-36 34-04

N 14 .... 4-01

10 H 10 ..., 2-86 2-95

Br 98-7 .... 28-27 28-13

3 CI 106-5 .... 30-50

C»NH»,HCl,PtCP 349-2 .... 10000

NlTROSONAPHTHYLm. 105

Jx(hnitro90'nucleu8 C*N(NO»)H« ?

Nitrosonaphthylin.

C»H»N»0» = C«>N(NO»)H«,H».

A. H. Church & W. H. Perktn. Chem, Soc. Qu. J, 9, 1 ; J. pr. Cheni, eS, 248 ; CJiem, Gaz. 1856, 139 ; InsttL 1856, 299 ; Lu^ & Eopp'i Jahresb. 1856, 607.

Formation, 1. Fonned by reducing binitronapbtlialln witb nascent b jdrogen :

(?»H«N«0« + 8H - C»H8N»0« + 6 HO.

2. By the action of nitrous acid in napbtbylamine :

C»NH» + N0> =. C?»H9N'0« + HO; or of nitrite of potash on hydrochlorate of napbtbylamine : C»NHSHC1 + KO,NO» = C2*H8N50» + 2HO + KCL (Chnrch & Perkin.)

In this reaction a large quantity of nitrogen is evolved, and a brown porous mass is formed, which is a mixture of nitrosonaphthylin and naphtbulmin (p. 26). (Schatzenberger k Willm, Compt rend. 46,894, J. pr, Chem. 74,75.) It is also probably formed by the action of nascent hydrogen on nitronaphthylamine. (Church & Perkin.)

Preparation. Nitrite of potash added to hydrochlorate of napbtby- lamine, yields a precipitate of almost pure nitrosonaphthylin. If the precipitate be washed with water, dried, and extracted with alcohol, and the solutiou slowly evaporated, the nitrosonaphthylin gradually crystallises out in small needles.

Properties. Small, very dark crystals having a green metallic lustre, like murexid ; when precipitated from its alcoholic solution by water, it is scarlet Melts and sublimes partly, without decomposition. It imparts to alcohol an intense red colour, which is chauged to a magnificent violet by acids : alkalis restore the original colour. Cotton wool, linen, paper, &c.f may be dyed permanently orange by being dipped into the alcoholic solution of nitrosonapfithylin. When fabrics thus dyed are dipped in acids, tbey acquire an intense purple-blue colour, rapidly changing to orange in a stream of water.

20 C 2 N	... 120 ... 28 ... 8 ... 16	.... 69-77 .... 16-28 .... 4-65 .... 9-30	Church & Pfj-kin. 69-76 16-39
8 H	4-80
2 O	9-05
C?»H8N»02	... 172	.... 10000	100-00

Asfluming Laurent's theory of " substitutions nitres^/' nitrosonaphthalin is 0»H«(NO«)N,H« = naphthylamine, wherein 1 At. H is replaced by 1 At. NO^. The discovery of nitrosonaphthylin and of the analogous nitrosophenylin point to the existence of an entirely new type of substitution-compounds. (Church & Perkin.)

106 AZ0-NITR0S0-NUCLEU8 C»N(KO»)H«,

DeeompatUions. 1. When nitrosonaphtlijlin is strongly heated, part of it sublimes undecompoeed ; afterwards white vapours are erolved^ and charcoal is left behind, — 2. The alcoholic solution appears to decompose gradually ; the amount of carbon in the substance thus altered is raised to 75 p. c. — 3. Nitrosonaphthylin is destroyed by strong nitric acid, — 4. Its colour is not affected by alkalis, but is destroyed by the prolonged action of nascent hydrogen.

ComUnaiions. Insoluble in ipaUr and in dilute acids. Dissolves in fuming sulphuric axnd with purple-blue colour. Dissolves in alcohol with intense red colour^ and is precipitated from the solution by water. Soluble in ether.

Ninaphthylamine.

C»H»N»0» = C»N(NO')H«,H« 1

Ch. S. Wood. (Aem. Gaz. 1859, 218 ; abstr. Chem. Centr. 1859, 836.

Ninaphihalidin.

Formation, By reducing a weak ammoniacal solution of binitro- naphthalin with sulphuretted hydrogen :

C»X«H« + SHS - CSOH'N'O' + 6H0 + 8S.

Jhreparaiion, Sulphuretted hydrogen is passed through an alcoholic and feebly ammoniacal, boiling solution of binitronaphthalin for about three hours, whereupon the greater part of the alcohol distils off ; the residue is then supersaturated with dilute sulphuric acid, heated to boiling, and filtered. — On cooling, yellowish brown sulphate of ninaph- thylamine crystallises out, from the solution of which the base is precipi- tated by ammonia.

Properties, Beautiful carmine-red needles. It is slightly decompose at 100''. It is a base, and differs totally in properties from the isomeric compound nitrosonaphthylin (p. 105).

Sulphate of Ninaphthylamine. C~H«N*O^SO^HO . —• White scales ; decomposed by recrystallisation from its aqueous solution.

HydrochloraU of Ninaphthylamine. C»H8N«0*,HC1. — Acicular ciystaJs.

Chloroplatinate of Ninaphthylamine. C»H W0*,HC1 -h PtCT is preci- pitated in yellowish-brown, rather soluble crystals when platinic chloride IS added to a solution of the base in ether- -alcohol.

SEMINAPHTHTLAMINE. 107

AnUdazo-nueletts C^NAdH*.

Seminaphihylainine.

C»^2iiio -- c»NAdH*,H*.

ZiNiK. (1844.) J. pr. Chem. 33, 29 ; Ann. Pharm. 52, 362; J. pr. Chem. 57, 177 ; Awn. Pharm. 85, 329.

Axonaphthylamme, Semnaphthdlidin9%

Formation. Bj treatiDg binitronaplitlialin with sulpharetied hydro- gen and ammonia. (Zinin.)

Preparation. Binitronaphihalin is dissolyed in a saturated alcoholic solution of ammonia, and sulphuretted hydrogen is passed through the dark carmine-red solution, till, on complete saturation, it has become greenish-brownish yellow. The liquid is then boiled in a retort, where- upon a large quantity of pulverulent sulphur is deposited ; hence in the distillation proper precautions must be taken, as in the case of naphthy- lamine (p. 94, 1.). When no more sulphur is deposited from the residue in the retort, water is added; and the whole is boiled, filtered boiling, and left to cool, whereupon a quantity of copper-red needles crystallise out. A dark brown, resinous mass, becoming yiscid by heat, then remains in the retort, which is several times boiled out with water, as long as the solu- tion continues to deposit crystals on cooling. The crystals are dissolved in hot water, and the filtered solution is left to cool in a well corked flask, whereupon crystals are obtained having an almoot metallic lustre, and yellow colour, with copper- red iridescence \ by repeated crystal lisa* tion from alcohol and water alternately, they may be obtained colourless. The red coloration is due to a resin which is more soluble in alcohol than the base, crystallises from water in fine, dull needles, melts to a red liquid when heated, and distik with partial decomposition, without ex- plosion. (Zinin.)

Properties. Crystallises from alcohol in long and yery brilliant needles. It is not affected by a temperature of 100°, melts at 160° to a yellowish-brown liquid, and sublimes in small quantity. Boils above 200°, partly subliming in the neck of the retort, and distilling partly nn- decomposed, while another part undergoes decomposition, leayes a large residue of carbon, and yields decomposition-products, which impart a brown colour to the sublimate and distillate, and render them impure. Permanent in the air.

JSinia. Average at 100* in dry air.

20 C 120 .... 75-79 75-60

10 H 10 .... 6-31 6-31

2N 28 .... 17-90 18-00

C*NAdH8 158 .... 100-00 99-91

The formula is C^^^H^N, and from its formatioo, the atomic weight of binitronaph- thalin must be halved. ^Zinin.) From binitronaphthalin C^X*H', a compoiind con- taining IOC could not be formed ; hence the formula must be C^H^^N. (Laurent, Con^t. CMm. 1849. 165.)

108 AMIDAZO-NUCLEUS C»NHAdH«,

Decompostiions. 1. The solutions of seminaphtbylamine in water, etber, or in alcohol, especially the last, decompose rapidly in the air, be- coming tnrbid and brown, and depositing a brown powder ; they then yield only a small quantity of dark brown crystals on evaporation. 2. Heated on platinum foil, it bums with a yellow and yery smoky flame, diffusing a not unpleasant odour of naphthalin. — 3. By strong nitric acid it is converted into a violet-brown powder, probably the same sub- stance that is deposited from the solution on exposure to the air. — 4. When chlorine gas is passed through aqueous hydrochlorate of semi- naphtbylamine, the base is converted into a reddish brown powder, which is almost insoluble in water, but dissolves in hot alcohol with dark carmine colour, and is precipitated unchanged on cooling. — 5. By chlorate of potash (snd hydrochloric acid )) it is converted mto a similar, but somewhat lighter coloured powder.

Combinations. Dissolves with difficulty in water, forming a pale brownish red solution.

It combines with acids and forms salts ; those with oxy-acids contain 2 At. water. Dry seminaphtbylamine dissolves in oil of vitriol, forming a dark violet liquid, which remains unchanged for months, but on addi> tiou of water instantly solidifies to a reddish white crystalline mass. The alcoholic solution of seminaphtbylamine is decolorised by all aqueous acids ; the concentrated solution solidifies with sulphuric, phosphoric, or hydrochloric acid in a soft crystalline mass consisting of microscopic white needles or laminsB ; ammonia precipitates from the aqueous solution of these crystals, unchanged seminaphtbylamine in reddish needles.

Phosphate of Seniinaphthylamine. Obtained by mixing the alcoholic solution of the base with aqueous phosphoric acid. It forms brilliant white crystalline scales, more stable than the sulphate. Difiicultly soluble in water and in alcohol, crystallising therefrom almost unaltered.

Sulphate of Seminaphthylamine. Moderately dilute sulphuric acid is added to concentrated alcoholic seminaphtbylamine, but in such quantity that the free base, which may be recognised by the colour of the liquid, is still present. The white precipitate is washed on a filter with alcohol till the washings are almost colourless, then pressed between blotting paper, dried in vacuo over sulphuric acid, and afterwards in a stream of dry air at 100°. Small, white, scaly crystals ; or, when dried, a white, dull powder, permanent in the air. Above 100° it turns red and decom- poses. Dissolves with difficulty and with partial decomposition, in water or alcohol ; the boiling solution deposits brownish laminsa on cooling.

20 C	120	.... 46-87 ... .... 4-69 ... .... 10-93 .... 6-25 .... 31-26 ...	Zinin. at 100^ 4709
12 H	12	4-80
2 N	28
2 0	16
2 SO*	80	31-00

C*'NAdH8,2UO,2SO» .... 256 .... 10000

ffpdrocMorate of Seminaphthplamine. To a cold alcoholic solution o seminaphtbylamine, moderately strong hydrochloric acid is added drop by drop, and the mixture is cooled, lest it should become heated. The liquid solidifies to a thick white paste of silvery laminae. These are

SULPHONAPHTHYLAMIC ACID. 109

"washed on a filter with a small quantity of alcohol, pressed between blotting paper, and dried, first in vacuo over salphuric acid and caustic lime, and then at 100° in a current of dry air. — White crystalline powder which may be preserved unaltered when dry, but decomposes readily in the moist state. It is decomposed by heat, and cannot be sub- limed. Sparingly soluble in water and in alcohol ; the solutions tnm brown in the air.

			Zinin.
			at 100^, mean*
20 C	120	«••. Ol*"!	51-81
12 H	12	.... 6'19 . .... 12-27 .... 30-63 .	5-21
2 N	28
2 CI	71	30-51

C^NAdH8,2HCl 231 .... 100-00

Hydrochlorate of seminaphthylamine forms with mercuric chloride an easily soluble compound, crystallising in rather large, white, silvery laminsd.

Chloroplatinate of Seminaphthylamine, Yellowish brown, difficultly soluble powder. The well dried substance leaves on ignition 34*56 p. o. Pt.; C«i!^»H",2HCl + 2PtCl» = 34-63 p. c. Pt.

Seminaphthylamine does not appear to oombine* with hydrocyanic acid; it does not dissolve more abundantly in the aq aeons acid than in water, and crystallises unchanged from its alcoholic solution which has been mixed with concentrated prussic acid.

. Aqueous hydrosulphocyanic acid dissolves seminaphthylamine, readily and abundantly, especially when heated ; on cooling the solution, bril- liant white laminae of the sulphocyanide are deposited.

Oxalate of Seminaphthylamine. White crystalline powder, sparingly soluble in water, and still less in alcohol and ether. The hot solution deposits on cooling brilliant white laminae.

Tartrate of Seminaphthylamine is prepared like the phosphate. Cry- stallises in fine, white needles, grouped in the form of stars. Rather soluble in water and in alcohol, sparingly soluble in ether ; its solution decomposes ; the dry salt is more stable.

Seminaphthylamine dissolves in alcohol and ether with much darker

colour than in water. (These aUtements of Zinin's refer to ooloared seminaphthyl. amine. Cariiu.)

ConjiLgated compounds (/C'®NH', or of similar nuclei.

Sulphonaphthylamic Acid.

C»NH*S'0« = C?»NH»,2S0».

Laurbnt. Compt. rend. 31, 537 ; J. pr. Chem. 52, 58 j Pharm. Centr. 1851, 157 j Lieh^ & Kopp's Jahresb. 1850, 508.

Aeide wlfonaphtalidamique. (Laurent.) NapAtalidintchwrfelsdure.

Formation, 1. By treating nitrosulphonaphthalio acid, C"XH*,2S0', with sulphide of ammoniam. — 2. By gently heating carbonaphthalide,

no CONJUGATED COMPOUNDS OF C^NH'.

C^N'H^'O^ with oil of vitrol, carbonic acid being eyolred : the acid is precipitated on diluting the liquid with water. '

C«N^H"03 + 4(HO,SO>) = 2 (C»NH»,2SO») + 2 C0» + 2 HO.

It 18 uncertain whether this acid is merely isomeric with naphthamic and with naphthionio acid, G^NH^O^ or whether it is identical with naph- thionio acid, (Carius.)

NapMhionic Acid.

C"NH»S«0« = C»NH',2S0«.

PiRiA. SulCazione del golJUo cTammoniaca mlla nitrcnaftalina, Pisa, 1 850; Ann, Phai'm, 78, 31 ; N. dnu. Chim, JPhys. 81, 217 ; abstr. Gompt. rend. 31, 488; J.pr. Chem, 52, 56; Fhcbrm. ChUr. 1S51, 380; LiM^ & Kopp's Jahre^. 1850, 500.

Formation, Produced, together with the isomeric body thionaph- thamic acid, when nitronaphthalin is boiled with sulphite of ammonia. In this reaction the sulphite of ammonia converts the nitronaphthalin (like ammonia and sulphuretted hydrogen), into naphthylamine, which then eombines with 2 At. SO^ forming about equal proportions of the two isomeric acids. These acids cannot, howeyer, be oonyerted one into the other. (Piria.)

Ftrparation, 1 pt. nitronaphthalin (prepared by Piria's method, p. I), and washed with water till the acid reaction ceases, is warmed with 5 pts. alcohol till completely dissolved, and mixed, while the liquid is kept warm, with 5 pts. aqueous sulphite of ammonia of sp. gr. 1*24. The mixture turns reddish, and then yellow ; and, when kept simmering, deposits crusts of acid sulphite of ammonia on the sides of the flask, and becomes acid, whereby the thionapthamic acid i^ decomposed, and a large quautity of resign is formed, which greatly hinders the formation and purification of the acids. Hence it is necessary, as often as the liquid becomes acid, to add powdered carbonate of ammonia till the crusts re- dissolve completely, and the solution becomes alkaline. After boiling for eight hours, the decomposition is complete. This may be ascertained by adding a drop of the liquid to water, with which it should produce no turbidity. The liquid forms two strata, whereof the upper and more considerable stratum contains the decomposition-products of nitronaph- thalin dissolved in ammonia — the lower stratum, aqueous sulphate and excess of sulphite of ammonia. The upper stratum is decanted, evapo- rated over a naked flame to an oily consistence, and allowed to stand in a cool place for 24 hours, whereupon it solidifies in a mass of orange- yellow laminss of thionaphthamate of ammonia. The mother-liquid contains uncr^stallisable naphthionate of ammonia ; it is heated to 100®, and mixed with excess of hydrochloric acid, whereby naphthionio acid is precipitated as a reddish white powder, and sulphurous acid is evolved from the sulphite of ammonia contained in the liquid. The acid is first washed with water, and then with alcohol, till both flow off colourless ; and by purifying it completely, it is converted into the lime- or soda- salt. The salt is obtained white by recrystallisation, decomposed with excess of hydrochloric acid, and the naphthionio acid washed as much as

NAPHTHIONIC ACID. Ill

possible out of contact with the air^ first with water freed from air bj Doiling, and then with alcohol. In this way, 200 grammes of nitre- naphthalin yield 62 '5 grammes of almost pure naphthionate of soda.

ProperUes, Precipitated from the cold solution of the lime- or soda- salt, it forms a bulky white powder \ precipitated from the hot solution^ small, light, silky crystals. It is tasteless and inodorous, and has an acid reaction. The crystals part with 1 At. water at 100^, but may be heated to 150^ without losing more.

Crystallised, Piria.

20 C 120 .... 51-72 51-54

10 H 10 .... 4-31 4-48

N 14 .... 603 6-14

2 8 32 .... 13-80 14-14

7 O 56 .... 24-14 23-70

C»NH«,2S0» + Aq 232 .... 10000 10000

Decompontions, Naphthionic acid, especially when moist, is readily decomposed by the air^ and by oxidising agents; but presents great stability with most other chemical reagents. — 2. Heated on platmum foil, it bums, evolving sulphurous acid and a combustible aromatic vapour, smelling of oil of bitter almonds, and leaving a difficultly combustible charcoal which preserves the form of tbe substance. — 3. It is not affected by dilute nitric acid, but by concentrated nitric acid, especially if con- taining nitrous acid, or if hot, it is converted into a brown resin resembling that produced by other oxidising agents. — 4. Chlorine passed into an aqueous solution of a naphthionate, turns it brown, and finally precipitates a brown resin. Cliromate of potash acts in a similar manner, especially if it be mixed with sulphuric acid. — 5. Naphthionic acid is neither dissolved nor decomposed by concentrated hydrochloric acid ; neither is it attacked by concentrated soda-ley.

Combinations, — 1. Dissolves in 2,000 pts. cold water; readily iu boiling water, from which it separates in crystals on cooling. — 2. Dis- solves in sulphuric acid, especially with the aid of heat, and is precipitated therefrom by water unchanged ; the solution does not blacken till 220% at which temperature it evolves sulphurous acid.

Naphthionic acid is a strong acid ; it expels acetic acid from its salts, and readily dissolves in a solution of acetate of potash. The salts of the alkalis are neutral, those of the heavy metallic oxides, acid. Mineral acids precipitate naphthionic acid as a white crystalline powder ; acetic acid does not precipitate the aqueous solution, and only partially precipi- tates the alcoholic solution. It is difficult to obtain the naphthionates free from a red colouring matter ; the best way is to recrystallise them from alcohol in the dark. Their solutions exhibit fluorescence like that of quinine, with red, blue, and violet colour; 1 pt. of naphthionate of soda in 200,000 pts. water still exhibits this property. In the solid state, the salts are permanent in the air ; the solutions turn red on exposure to air and light, but not in the dark. — Ferric chloride produces with a solution of a naphthionate, a vermilion-red precipitate turning brown by heat ; nitrate of silver a white, crystalline precipitate; mercuric chloride, a white precipitate, dissolving by heat, and reappearing as the liquid cools ; platinic chloride gives a bright yellow precipitate ; chloride of gold imme-

112 CONJUGATED COMPOUNDS OF C»NH7.

diatelj turns the solation parple-red, and reduced gold is then precipi^ tated ; uo reaction is produced by acetate of lead, chloride of barium, ferrocjanide of potassium, sulphate of zinc, or tartar-emetic.

Naphthionate of Potcuih, The brown solution of crude naphthionio acid in boiling^ concentrated potash, deposits, on cooling, crystals which must be recrystallised twice or thrice from the smallest possible quantity of alcohol. — Small, micaceous, slightly coloured lamins, very soluble in water or in alcohol^ sparingly soluble in aqueous or alcoholic potash. Contains 14*84 p. c. K. and 11*87 p. c. S, corresponding to the formuU C*NH»S'0*,KO ; by calculation 14*98 p. c. K. and 12*25 p. o. S.

NapTuhiimaU of ammonia is exceedingly soluble in water and in alcohol, and crystallises with difficulty.

Naphthionate of Soda. The crude acid is heated with powdered carbonate of soda and a little alcohol of 60 p. c, the solution filtered boiling, and allowed to stand for 10 or 12 hours, whereupon it deposits naph- thionate of soda in beautiful, large, transparent, and but slightly coloured prisms. The mother-liquid yields on evaporation more of the salt, but coloured. The crude salt is powdered, washed in a funnel with con- centrated alcoholic soda (which dissolves the resinous matter very efiect- ually, but not the salt), and the residue is repeatedly recrystallised with animal charcoal from a small quantity of weak boiling alcohol, till colour- less crystals are obtained. — Large, well defined prisms of the oblique-pris- matic system, or, when crystallised from water, ill-defined, indeterminable forms, containing apparently more water of crystallisation. When com- pletely freed from water of crystallisation by heat, it reabsorbs it in moist air, and appears unchanged when dissolved m water, but does not dissolve in alcohol till it has been boiled for a long time, and this solution deposits on cooling a mass of small, ill-defined, cauliflower-like crystals, which are presently converted into thick prisms of the original form : Fig. 81 with A-faces; *:«= 118° 56'; t:^=96°34'; u:ti= 111^55'. Ratio of the axes, a ; 6 : c = 1 : 0*760 : 0*914. — Viewed in masses, it is always slightly yellow. In dry air it does not undergo any change, or lose any water of crystallisation. The solution turns reddish brown in the air, especially in sunshine. Dissolves readily in water and in alcohol, but not in ether, and but slightly in alkaline water or alcohol ; hence its saturated solution is completely precipitated by solutions of the fixed alkalis. Its taste is at first scarcely perceptible, but after a time it is sweet and per- sistent.

Piria. CryttalUsed. mean.

20 C 120 .... 37-85 37*56

16 H 16 .... 505 5-23

Na 23 .... 7-26 7*15

N 14 .... 4-42 4*50

2 S 32 .... 1009 9*76

14 O 112 .... 35*33 35-80

C»NN»H»S«0« + 8Aq 317 .... 100*00 100*00

Contains 8 Ats. water of crystallisation, whereof 7 At. 20*00 p c. (average), by calculation 19*87 p. c. are expelled at about 80°, and the eighth atom, 2*67 p. o. at about 130°. (Piria.)

NAPHTHIONIC ACID. 113

NaphQwofnaJte of Baryta is prepared : 1. By dissolying the acid in baryta-water and remoring the excess of baryta by carbonic acid ; it is then generally coloured deep red by a resinous substance^ and must be purified by washing with cold alcohol, dissolving in boiling water, treating with animal charcoal and crystallising. — 2. (better than 1), 2 pts. cr3rBtallised naphthionate of soda and 1 pt. chloride of barium are dissolved in 10 pts. boiling water. As the solution cools, the salt immediately crystallises in a tolerable state of purity, and may be freed from every trace of chloride of barium by two recrystallisations from a small quantity of boiling water. — Crystallises in two dijBTerent forms, depending on the temperature, and probably with different amounts of water of crystalli- sation. From rather concentrated solutions, micaceous, white, slightly amethystine laminso are deposited while the liquid is still warm. The dilnte solution does not crystallise till it is quite cold, and then deposits large, transparent, rhombic laminae, resembling the lime-salt with which the^ are probably isomorphous. The last-named crystals effloresce very rapidly, become opaque before they are dry, and even when they are placed in alcohol or in water heated above 80°. It is rather soluble in water.

NaphikumaiU of Lime, Crude naphthionic acid is heated to boiling with milk of lime, and the filtered solution is evaporated on a water bath and aUowed to stand from 12 to 24 hours, whereupon large, reddish crystals are deposited. The mother-liquid when evaporated yields more crystals, but more highly coloured. Of all the naphthionates this is the most easy to purify, yiz. by washing the powdered salt on a funnel with eold alcohol, and then recrystallising it from boiling alcohol after previous treatment with animal charcoal.

White tablets having a fatty lustre, imperfectly transparent, appear- ing colourless singly, but rose-coloured when viewed in masses. When diy it is unaffected by the air, but its aqueous solution becomes coloured. Rmuiily soluble in water, almost insoluble in alcohol. Neutral to test papers. Fig. 86 with a- and /-faces, without m. i'.u&tU* = 124'^ 1 9' ; » :/= 115^ 41'; » : a = 116" 30'; i : A = 69° 30'; u : t*' = 117° 4'. Ratio of the axes, a : 6 : c = 1 : 1*355 : 1662. The crystals are mostly reversed twin-crystals with curved faces, in which the inclination of the two i-&ces is about 172° 44^.

20 C		Crystallu 120	td. • ••• ■ ••• • • •• • •ft*	38-22 .... 5-10 .... 6-37 .... 4-46 .... 10-19 35-66	Piria. .... 38-13
16 H		16	.... 5-14
Ca N 2 S		20 14 32	.... 6-33 .... 4*58
14 O	»••••■•••• 9	112
0»NCaH8S»0«	+ 8Aq	.... 314	•«•■	100-00

Gives off 7 Ai (calculation = 20'05 p. c.) water of crystallisation at 100°, and the 8 At. between 100° and 160° (calculation = 2*86 p. c.) ; Piria found an average of 20*00 p. c. and 2*78 p. c. water.

Naphthionate of Magneda is obtained by boiling 1 pt. of carbonate of magnesia with 2 pts. crude naphthionic acid for two hours. As the filtered solution cools, it deposits deep red needles, which may be freed from the

VOL. XIV. I

114 CONJUGATED COMPOUNDS OF THE NUCLEUS C»NH7, &C.

greater part of the colouring matter by repeated recrystallisation from boiling weak alcohol. Crystallises in two different forms, containing different miantities of water of crystaUisation, depending on the tempeiar* tare. a. From concentrated solutions it crystallises on cooling in long prisms probably belonging to the square prismatic system, and having their extremities bevelled with two faces. They contain 3'92 p. c. Mg, and give off 23*15 p. c. water at 150°; hence they are probably C»NMgH^«0' -f S Aq. (calculation = 3-92 Mg. and 23*52 p. c. Aq,> The crystals rapidly become opaque in the air, from absorption of water. — b. The mother-liquid from a, evaporated spontaneously or in vacuo, yields beautiful, large, red, oblique prismatic crystals ; Fig. 91 with /-&^faceB.ti:u'= 76^" 22'; i:t= 132° 51'; iiwandt*' = 114** 57'; i :f = 77° 43' ; Permanent in the air ; becomes opaque in hot water, loses only part of its water of crystallisation at 100°, but the whole at 150** in all 27*56 p. c. ; hence its formula is C»NMgH»S'0« + 10 Aq. (By calculation 27 '78 p. c. water.)

Naphthumait of Zinc, 2 pts. naphthionate of soda are dissolved with 1 pt. sulphate of zinc in a small quantity of boiling water. On cooling (sometimes the cold liquid requires stirring), large nacreous laminso crystallise out, resembling naphthalin, and are purified by first crystal- lising from alcohol and then from water. — Rather long, transparent, red, rhombic laminae ; or when crystallised by cooling the hot aicoholic solution, short, four-sided prisms. Becomes opaque at 90°, but not anhydrous till it has been long heated in a stream of air between 150° and 160°. At a higher temperature, it is decomposed, yielding an aromatic vapour and afterwards sulphurous acid. Dissolves readily in water, and in absolute alcohol, especially when heated.

Naphthionate of Lead* Acetate of lead and naphthionate of soda do not react upon one another. — A solution of nitrate of lead in hot, con- centrated, aqueous naphthionate of soda, deposits on cooling short, red needles grouped about a common centre, or small granules. Its aqueous solution turns red when boiled, and cannot afterwards be msbde to crystallise. Reddens litmus. Dissolves slightly in water, but not in alcohol. In dry air at 150° it parts with 5*15 p. c. water of crystal- lisation ; 2 At. = 5*24 p. c. water.

Cuproiu Naphthionaie 9 A solution of naphthionate of soda turns red on addition of sulphate of copper. If the excess of sulphate of copper be precipitated by alcohol, and the liquid evaporated in vacuo, an uncrys- talline, reddish-brown residue is left, the aqueous solution of which gives with potash a precipitate of hydrated cuprous oxide.

Naphthionate of Silver. Solution of naphthionate of soda produces with perfectly neutral nitrate of silver, a white precipitate, which at first redissolves but afterwards becomes permanent, being converted into a light, white, curdy powder. The salt sometimes remains in this state, and sometimes is rapidly converted into small, heavy, granular crystals of adamantine lustre. It is slightly soluble in water, especially in hot water, from which it crystallises on cooling. It turns grey on exposure to light, without suffering further change. It yields by heat the same volatile products as the other naphthionates, and leaves metallic silver mixed with exceedingly incombustible charcoal.

THIONAPHTUAMIC ACID. 115

Piria.

Cryttalliaed or amorphoug. mean,

20 C ^ 120 .... 34-48 3435

10 H 10 .... 2-88 3-04

Ag 108 .... 31-03 31-38

N 14 .... 4-02 416

2 S 32 .... 9-20 9-22

8 O ., 64 .... 18-39 17-85

C^NAgH«S«0« + 2Aq 348 .... 100-00 10000

It parts with 6*28 p. o. water of crystallisation at 120^; 2 At. = 5*17 p. a

NaphlhionaU of Silver wHk Ammonia, Naphthionate of silyer gives with hot aqueoas ammonia, a dear solution, which, on cooling, deposits whitish grey granular crystals. Resembles the silyer-salt, and is yery little affected by light. Decomposes by heat^ with eyolation of ammonia.

20 C . 16 H.

Ag. 3N. 2B . 8 0..

		Piria.
120	.... 31*41 ....	.... 31-70
16	4-19	.... 4*33
108	.... 28*27 ....	.... 28-85
42	.... 10*99 ....	.... 10*76
82	.... 0-30
64	.... 16-76

2NH»,C»NAgH8SW + 2Aq.... 382 .... 100*00 Naphthionio acid is barely soluble in alcohol.

TMonaphthamic Acid.

C»NH»SW = C»NH»,2S0» (?).

PiBiA. (1 850.) SiM<mone del iolfito d^ammoniaca sulla nitronafkUinaj Pisa, 1850; Ann, Fharm. 78, 31 ; N. Ann. Chim, Fhyi, 31, 217 ; abstr. Compt, rend. 31, 488 ; J. pr. Chem. 52, 5Q ; Fharm. Centr, 1851, 880 ; Iddng k Kopp'9 Jahresb. 1850, 500.

Formation. Obtained as impure thionaphthamate of ammonia, in orange-yellow lamiu®, together with the isomeric compound, naphthionio acid (p. 110), and in about equal quantity, by boiling nitronapbthalin with sulphite of ammonia. The mother-liquid contains the naphthionate of ammonia.

Thionaphthamic acid cannot be separated from the ammonia-salt without undergoing decomposition, being converted on the adilitlon of acids, even of cold acetic acid, into sulphate of naphthylamine, which ciystallises out.

The thionajilUhamaU9 crystallise in large, reddish or amethyst-red, nacreous laminaa. Their solution rapidly turns brownish red in the air, owing doubtless to formation of oxynaphthylamiue (p. 101), by the oxidising agency of the air upon the naphthylamine. (Piria.) This decomposition is especially promoted by the action of heat and light ;

I 2

116 CONJUGATED COMPOUNDS OF THE NUCLEUS C»NH7^ &,c.

alkalis retard it; hence the salts are obtained with less oolonr when they are crystallised from solutions containing a slight excess of alkali. In a state of perfect parity, the salts are probably colourless. (Piria.) From 1 At. salt, 2 At. sulphuric acid are thus liberated, of which only 1 At. is neutralised by the naphthylamiue ; hence free sulphuric acid is formed, which hastens the decomposition. If the solution of the per- fectly neutral ammonia- salt be heated to between 80° and 90°, and the evaporated water replaced^ it becomes coloured, deposits a melted brown resin, turns very acid, and then contains sulphate of naphthylamiue. The potash-salt to which a little caustic potash has been added, it is not decomposed by similar treatment. The salts, distilled with excess of hydrate of lime, yield oily naphthylamine which afterwards orystaUises.

Tkionaphthamate of AmmonitL Obtained in crystals by dissolving the crude salt in 2 pts. boiling water containing a few drops of ammonia (p. 110) and cooling the solution. -— Small, reddish, micaceous laminffi, the solution of which becomes more rapidly colour^ than that of the other salts. Dissolves very readily in water and in alcohol.

ThionavhtheanaU of Fotcuh. The aqueous ammonia-salt is boiled with a slignt excess of carbonate of potash, till ammonia ceases to be evolved ; on cooling, broad, nacreous laminsB, resembling boracio acid, crystallise out. These crystals cannot be obtaine4 perfectly colourless, even by recrystallisation with animal charooaL — It does not lose weight in a stream of air at 150°. Dissolves very readily in pure water, and but very slightly in water containing potash or carbonate of potash ; it scarcely dissolves in alcohol, and very slightly in dilute alcohol

Firiiu

20 C	CryMiaUiatd^ 120	45-97 . 3*06 . 14-98 . 5-36 .. 12*26 . 18-37 ..	mean. 45-84
8 H		3-22
K N 6 O	14	14*83 y, 5-53 12-24 18-34
C»NKH8SK)«	... ••.. 2ol*2 ...	100-00 ..	100-00

Thionaphthamate of Soda is prepared in exactly the same manner as the potash-salt. Crystallises in reddish micaceous laminsB. Dissolves slightly in cold and readily in hot water, and very slightly in water containing carbonate of soda.

Tkionapkthamate of Baryta. Beddish micaceous laminsB, which crys- tallise out on mixing boiling concentrated solutions of thionaphthamate of potash and chloride of barium.

20 c 11 H		CryttaU. 120	.... ol 70 ..•• .... 0 4v .... .... 2I-O7 .... .... 4-41 .... 10*07 .... .... 22*72	Piria. .... 37*32 .... 3-78 .... 21-45 .... 1004 1
Ba N 2 8 9 0		68-5 14 32 72
C»NBaH»SK)« +	3Aq	.... 317-5	.... 100-00

FORMTLNAPHTHALIDB. 1 1 7

Loses at 120^, 8'53 p. o. water of ciystallisation (3 At. = 8*5 p. c). (Piria.)

The Hme' and magnesia^salts resemble the other salts, and are reiy soluble.

Thionapkthamate of Lead. Nitrate of lead is added to excels of the boiling concentrated solution of the potash-salt (if an excess of nitrate of lead be added, a double-salt is formed, containing apparently equal number of atoms of thionaphthamate and nitrate of 1^). The salt which is deposited on cooling is purified by recrystallisation. — Light, reddish, crystalline powder, dissolying yery slightly in water, and scarcely at all in alcohol.

ThumapkikavMiie and Acetate of Lead. When almost boiling con- centrated solutions of thionaphthamate of potash and acetate of lead acidulated with acetic acid, are mixed together, this double-salt crystal- lises out on coolings in reddish, nacreous laminaB grouped about a common centre. Qives with sulphuric acid, acetic acid and the ordinary decomposition-products of thionaphthamic acid. Heated in dry air, it does not part with any water. Slightly soluble in cold, more soluble in hot water.

Crystallued. PIria.

24 C 144 .... 29'51

11 H 11 .... 2-25

2Pb 207-4 .... 42-42 4207

N 14 .... 2-87 2-99

2 8 32 .... 6-66 6-58

10 O 80 .... 16-39

C»NPbH8S«0« + C<H»PbO* 488-4 .... 100-00

Fonnylnaphthalide.

CPH»NO» = C»(C«H)AdH«,OM

ZiNiN. Pelerth. Acad. Bull. 16, 282 ; Ann. Pharm. 108, 228 ; J. pr. Chem, T4t, 379; Rep. Chim.pure 1, 148.

FormatioiK Compare oxalate of naphthylamine a and b (p. 100.)

Preparati<yn. Well dried acid oxalate of naphthylamine, C*^NH*, CH'O^ is heated in a retort carefully and graoDally to about 200°; whereupon it melts and eyolyes with efferyescence, water and a mixture of 1 yol. carbonic oxide with 2 yols. carbonic acid. After the whole has been completely melted, it is left to cool, whereupon the liquid product solidifies in a radiated crystalline mass, genersklly amounting to two- thirds of the salt employed. This is treated with alcohol, which dissolyes formylnaphthalide and leayes insoluble oxynaphthalide, C**H»N»0*

Properties. Ciystallises on cooling from boiling water in long silky

118 CONJUGATED COMPOUNDS OF THE NUCLEUS C»NH7, &C.

needles. Melts at 102^^ and distils almost entirely withont decomposition. It acquires a slight rose tint in the air, especially when moist.

Zinin.

22 C 132 .... 77-19 77*14

9H 9 .... 5-26 6-S4

N 14 1 , ...5

20 16/ •• *^^^

C»(C«H)AdH«,0« .... 171 .... 100-00

DecomposUions, 1. Aqneons and eren dilute boiling paUuh readily decomposes it into naphthylamine and formic acid. 2. It is easily decomposed by strong adds with aid of heat.

Dissolves somewhat readily in boiling VHxUr, and very readily in alcohol*

Methyl-lepidine.

(?»NH" = C*>(C»H«)NH«,H«. Gr. Williams. J. pr. Chem. 66, 340.

Obtained in crystals in combination with hydriodio acid, like hydrio- date of methyl-chmoline (p. xiii, 252). Isomeric with ethyl-chinoline and cryptidine.

Naphthalocyaxdc Acid.

CNH'O* = C»0yH^O».

V. Hall. iV. PMl Mag. J. 17, 304 ; (Mem. Gaz. 1858, 477 ; ZiebigA

Kopps Jakresb. 1858, 350. A. W. HoFMANN. CompL rend. 47, 425; N. Ann. Chim. Fhys. 54, 204.

emanate qfnaphthyl.

Fotmaiion and Preparation. When carbonaphthalide (p. 125) is heated with phosphorio anhydride, a small quantity of cyanate of naphtbyl passes over, while the greater part of the compound is charred. (Hall.) — 2. Menaphthoximide (p. 128) heated to 260° decomposes, puffing out white vapours, which have a very strong peculiar odour, and probably contain naphthalocyanic acid corresponding to anilocyanio acid. (Perkin, Chem. JSoc. Qu. J. 9, 8.)

Properties. Magnificent and very fusible crystals. With chemical reagents, it gives reactions precisely analogous to those of anilocyanic acid. (Hofmann.)

Insoluble in water^ very soluble in alcohol and in ether.

NAPHTHALOSULPHOCYANIC ACID. 119

Naphthalosulphocyanic Acid.

C«H'NS" = C»CyH^S».

V. Hall. If. FhU. Mag, J. 17, 304 ; Chtm. Gag. i65S, 477; Zidng &

Kopp's Jahresb. 1858, 350. A. W. HoFMANN. CompU rend. 47, 425; N, Am- Chim, Thy 8. 54, 204.

»

Sulphocyanide ofnaphthyl.

Formaiion and Preparation, By distSlUng snlpbocarbonaphtbalide, C*»CjNH",H»S». with phosphoric anhydride:

C^aN'HMS* - C»NH» + C»CyH7,8».l

Sniphocarbonaphthalide, obtained by digesting crude naphthylamine with bisul- phide of carbon, is pore enough for the purpose. (Hall.)

Properties, Splendid, readily fusible crystals, having a peculiar odour. (Hall.)

Decompositions, 1. Boiled in alcoholic solution with naphthylamirte, it again forms sniphocarbonaphthalide, which^ from its insolubility in alcohol, may be easily separated from the naphthalosulphocyanic acid. — 2. With aniline it forms sulphocyanide of phenyl-naphthylamine, C»(C"H»)CyAdH»,H«S'. (HaU, Hofmann.)

Insoluble in tpater, readily soluble in alcohol and in elke)'.

Naphthyl-urea.

C»N*H^'>0' = C»CyAdH«,H»0».

H. ScBiFF. Dissertation^ Gbttingen 1857 ; J. pr, Chem, 70, 264 ; Ann, Fharm. 101, 299 ; -A^. Ann. Chim. Fhys. 52, 112 ; Chem. Gat. 1857, 211 3 Chim. Centr. 1857, 166 and 362; Liebig & Kopps Jahresb 1857,389.

Naphthalidinhamttoff ; Napkthylharnstqf ; Naphthylearhamid. (Schiff.;

Formation. From naphthylamine and cyanic acid (p. 97, 9), but not from sulphate of naphthylamine and cyanate of potash.

Preparation. Solution of naphthylamine in anhydrous ether is saturated with gaseous cyanic acid (prepared by heating cyanuric acid), and left to evaporate spontaneously, whereby .brilliant laminie of the compound are obtained. In making this experiment, decomposition once took place, giving rise to a purple- red substance; probably owing to the presence of water in the ether (comp. p. 97, 9).

120 CONJUGATED COMPOUNDS OF THB NUCLEUS C»NH7, &C.

JProperties. Brilliant laminie ; or when obtained by eyapoTating the alcoholic solution by heat, flat^ brilliant, flexible needles. It retains a yellowish tint oven after several recrystallisations.

Schiff.

22 C ..^ 132 .... 70-96 7075

10 H 10 .... 5-38 5-45

2 N 28 .... 1505 14-35

2 O 16 .... 8-61 9-45

C^CyAdHSH*0* .... 186 .... 100-00 100-00

DecomposUions, 1. Detcomposed bv acids. — 2. With nitric acid the eolation evolves gas, and forms a blood-red liquid.

C(ymhinaiion», It is scarcely soluble in water, and insoluble in alkalis. -» 2. Dissolves sparingly in ether, but readily in alookol, — 3. Its con- centrated alcoholic solution mixed with oxal%c acid, yields a crystalline compound.

Ethyl-naphthylamine.

(?*NH» = C»(C*H»)NH«,H*.

ScHiPP. Notice by Limpricht : Ann, Pharm, 99, 117. — J, pr. Ghent. 70, 264 ; Ann. Pharm. 101, 299 j N. Ann. Chim, Phys, 52, 112; Ghent. Gaz. 1857, 211 ; Ghent. Gentr. 1857, 166 and 862 ; Liebig k Kopp'a Jahretib. 1 857, 389.

Vmetug^hthalidin. (6m.)

Known only in combination with hydrobromic and hydriodic adds.

Formation. When naphthylamine is treated for a long time with excess of bromide of ethyl between 40° and 50"", hydrobromate of ethyl-naphtbylamine is formed, from which potash liberates the ethyl- naphthylamine, which at the same time decomposes.

Hydrobronuite of Ethyl-naphthylamine. Purified naphthylamine mixed with excess of bromide of ethyl in a small flask (provided with an upright tube so as to condense the vapours and allow them to flow back) is heated for several hours to the boiling point of bromide of ethyl ; the excess of bromide is then distilled ofl* from the resulting reddish brown mass^ and the residue is extracted with boiling water. The compound crystal- lizes from the cooling extracts, and is purified by recrystallisation :

C»NH9 + C<H»Br » 0»(C*H»)NH8,HBr.

2. Naphthylamine sealed up in a glass tube with bromide of ethyl^ yields in a few days, at ordinary temperatures, a small quantity of crystals, and after 14 days, the tube is almost completely filled with them. Pale, rose-coloured, small needles, grouped about a common

ETHTL-LEPIDINE. 1 21

centre ; tliey beoome less readily coloured in the air tbao naphthjlamine. With potash, it forms a white curdy precipitate of naphthylamine, which after a time is conyerted into needles; at the same time alcohol is formed :

C»(C*H«)NH»,HBr + KO^O - C»NH« + C<H»0« + KBr.

Very slightly soluble in cold water, rather soluble in hot water, alcohol, and ether,

Sebiff.

24 C 144 .... 57-14

14 H . 14 .... 5-56

Br „ 80 .... 31-74 ........ Sl-55

C»(C«H»)NH8,HBr .... 252 .... 100-00

ffydriodaie of Ethylr^aphthylamine is obtained from naphthylamine and iodide of ethyl, and crystallises in brilliant four-sided prisms. It is much more easily decomposed than hydrobromate of ethyl-naphthylamine; and has about the same solubility as the latter.

EthyHepidine.

(?*NH^ = C»(C*H»)NH*,H».

Gb. Williams. Edvnh, Boy. Soe. Trans, 21, 3rd pt., 377 ; Chetn, Oaz. 1856, 261 and 283 ; J, pr, Ohem. 69, 355.

Vitulepidin, (Gm.)

If 1 At. more hydrogen be supposed to be added to this oompomid, it becomes ethjMepidine-ammonium. Known only in combination with adds.

Obtained as hydriodate of ethyUlepidine in the same manner as the hydriodate of methyl* or ethyl-chinoline fziii, 252, 254) in brown needles, which after recrystallisation exhibit a beautiful canaxy-yellow colour, become transiently blood-red at 100°, and have the formuhi C^H'^N,!!!.

Chhroplaiifnate of Eihyl-lepidine, Obtained in the same manner as the chloroplatinate of methyl-chinoline (ziii, 252). It is soft at first, but soon becomes crystalline. It must be washed with ether* alcohol

24 C

N

14 H

Pt

3 CI 106-5

		Gr. Williams.
144	.... 3814	38-00
14	.... 3-71
14	.... 3-71	3-82
99	.... 26-23	26*53
106-5	.... 28-21

<?*NH",HCl,PtCP .... 377-5 .... 10000

122 CONJUGATED COMPOUNDS OF THE NUCLEUS (^fW, &C.

Allyl-naphthyl-sulphocarbamide,

C«H"N*S» = C»(C«H»)CyAdH»,H»S«.

ZnviN. PeUrsb, Acad. Bull. 10^ 346 ; abstr. Ann. Pharm. 84^ 346 ; J. pr. Chem. 57, 173; Chem. Gaz. 1852, 441; Pharm. Oentr. 1852, 689; Liehig & Kopp's Jahreiib. 1852, 627.

Sei^UNaphtdlidin.

Formation, Naptithjlamine combines with oil of mustard, like ammonia.

Preparation. If 30 pts. oil of mnstard be added to 43 pts. uaph- tbylamine, dissolved in 344 pts. alcohol of 90 p. a, the greater part of the compound (51 pts.) is gradually deposited in radiated, hemispherically grouped crystals, which soon form a crust ; the mother-liquid evaporated to half its bulk yields 18 pts. more product.

Properties. Melts at 130° to a clear, colourless liquid, which on cooling solidifies in a granular crystalline mass. Carefully heated, it distils for the most part undecomposed, as an oily, colourless or slightly yellow liquid, which when cool does not crystallise in granules till it has stood for some time, l^eutral.

28 C

14 H

2N

2S

»•••••••«*■■• C%B

			Zinin.
			mean.
168	• •••	69-42 ....	.... 69-66
14	••••	679 ....	.... 5-95
28	• ••■	11-57
32	• •••	13-22 ....	.... 13-00

C»(C«H8)CyAdH»,H«S».... 242 .... 100-00

Deeompoaitions. Dissolves in nUric acid of sp. gr. 1*36, without coloration, if carefully heated, but is soon decomposed, with violent -evolution of red vapours, the liquid turning yellow ; water then precipi- tates a yellow resin. If the solution be still boiled till no more red vapours are evolved, water precipitates from the liquid an orange-yellow powder, dissolving readily in alcohol and in nitric acid, but sparingly in boiling water ; heated on platinum foil, it melts to a brownish red liquid, and then bums with deflagration, leaving a large residue of carbon. — 2. Treated with hydrated oxide of lead, it parts with its sulphur, and forms a new substance crystallising from not alcohol in white silky CTanules. More of these granules are precipitated from the mother- liquid by water, as well as an unctuous substance much more soluble in alcohol than the body granules.

Amyl-lepidine.

C»NH" = C»(C"H")NH«,H«. Gb. Williams. J. pr. Chem. 66, 340.

When lepidine is heated with iodide of amyl for several hours in a sealed tube at 100°, hydriodate of amyUlepidine is obtained in small crystals containing 37*49 p. c. iodine, and but slightly soluble in water. (By calculation 37*24 p. c. iodine.)

CAKBONAPHTHALIDB. 123

Sulphocyanide of Phenyl-naphthylamine.

A. W. HovMAKN. Compt. rend. 47, 425; N, Ann. Ckim. Fhys, 54, 205.

PhenyUnaphthyUSulphoearhamide. (Hofmann.) St^oeyanphenyl-naphtalidin,

FartnaHon and Preparation. 1 . When napbthjlamine is mixed with sulphocyanide of phenyl, the two bodies unite almost immediately to a solid compound (Hofmann) :

C"CyH»S» + C»NH» = C«(C»H»)CyAdH»,BPS«.

2. Naphthalosnlphocyanic acid forms the same compound with aniline. (Hall, N. Fhil. Mag. J. IT, 304.)^

Properties. Crystallides from its boiling solation in spangles : very like snlphocarbanilide, C^7NH*«,H»S«.

Very sparingly soluble m alcohol and in ether.

Conjugated compounds containing t At. C"*NH.

Carbonaphthalide.

C«H"N»0» = C«CyNH",H»0«.

Delbos. N, Ann, Chim. Phys. 21, 68 ; Compt. rend. 24, 1091 ; N. J.

Pharm. 12, 237; Ann. Pharm. 64, 370; J, pr. Cliem. 42, 244;

Pharm. Centr. 1847, 637 ; Ziebig & Eopp's Jahred). 1847-8, 610. ZiNiN. Petenb. Acad. Bull. 16, 282; Ann. Pharm. 108, 228; J. pr.

Chem. 74, 279 ; Pep. Chim. pure. 1, 148.

NapKthaHdam'CarhanUd. (Delbos.)

Formation. (Comp. p. 100 ; oxalate of naphtfaylamine a and h.) — 2. By boiling sulphocarbonaphthalide with alcoholic potash (Delbos) :

C«Hi«N«8» + 2H0 = C«ff«N«0» + 2HS.

3. Oxanaphthalide is heated for a long time above its melting point or submitted to dry distillation, whereupon almost pure carbonic oxide is evolved. (Zinin.)

Preparation. 1. When neutral oxalate of naphthylamine is fused in a retort, it evolves water of crystallisation, and umost immediately decomposes, whereupon water, carbonic acid, and carbonic oxide are evolved with effervescence, and at a higher temperature naphthyU amine and carbonaphthalide distil over, the latter condensing for the most part in the neck of the retort. The distilled vellowish mass is freed from naphthylamine by repeated boiling with alcohol, which leaves a residue of pure carbonaphthalide. It would be more advantagsoiis to

124 CONJUGATED COMPOUNDS CONTAINING 2 AT. C»NH7.

intemipt the distiUatioii immediately after the eTolation of carbonic oxide and carbonic acid, lince a large quantity of carbonaphthalide is decomposed by distiUation; bat then a product would be obtained contaminated with nndecomposed oxalate of naph- thylamine. (Delbos.^ — 2. Best method : Acid oxalate of Daphthylamine ib heated till it melts completely^ and' is parified as in method 1 ^also from simultaneoQsly formed naphthalide and nndecomposed oxanapnthalide). (Delbos, Zinin.)

Properties. Pure white, light, and slightly silky mass. Distils above 300, undergoing partial carbonisation. Turns rapidly red in the air. (Delbos.)

Delboi. dried at 100^

42 C 252 .... 80-76 80*17

16 H 16 .... 513 4-98

2 N 28 .... 8-98

2 O 16 .... 5-13

C«CyNHMPO» .... 312 .... 10000

Decompositions, 1. Distilled with phosphoric anhydride, it yields amongst other products, a small quantity of naphthalocyanic acid (p. 118.) (Hall, N. PhU. Magi J. 17, 304.) 2. It is not aflfected hj dilute iwids. (Delbos.) — 3. Dissolyes without decomposition in dlcoholvc potash, and is precipitated therefrom by water. (Delbos.^

Insoluble in water. Dissolves very sparingly in boiling alcohol (less than oxanaphthalide, Zinin), from which it is deposited on oooling as a white powder consisting of microscopic needles.

Sulphocarbonapthalide.

C«H"N«S* = C«CyNH",H«S«.

Delbos. N, Ann. Chim, Phys, 21, 68 ; Compt, rend, 24, 1091 ; N. J, Pharm. 12, 237; Ann, Pharm, 64, 370; J. pr. Chem. 42, 244; Pharm, Centr. 1847, 637 ; Liebig & Kopp's Jahresb. 1847-8, 610.

Napkthtdidam^sulphoearhamid, (Delbos.)

Formation, From naphthylamine and bisulphide of carbon (comp. p. 97, 12.) — 2. From naphthalin and naphthalosulphocyanic acid, (comp. p. 119, 1).

Preparation, Bisulphide of carbon is mixed with a solution of naphthylamine in absolute alcohol. After one or two days, the liquid deposits sulphocarbonaphthalide, on the sides of the vessel, as a white crystalline vegetation. The mixture blackens if allowed to stand for three or four days, owing to the formation of sulphide of naphthalidam. By using a very dilute solution of naphthylamine in absolute alcohol, sulpho- carbonaphthalide is obtained in brilliant, colourless needles. (Delbos.

^ Properties* Snow-white crystalline mass, or small and yeiy briUian prisms.

42 C 16 H	252 16
2 N	28
2 8	32

MBNAPHTHTLAMINE. 125

Delbos.

76*83 78-86

4-87 4-59

8-54

9-76 9-69

C«CyNHM,H'S' .... 328 .... 10000

DecamposUiofu. 1. By boiling with alcoholic potash^ it is converted into carbouaphthalide (comp. p. 123. Delbos). 2. By dry distiUaUon it is decomposed, naphtbylamine being liberated and the sabstance at the same time becoming charred. (Delbos.) Distilled with pkosphmnc anhy' dride it yields naphthalosolphocyanic acid, (p. 119. Hall.) — 4. It is not affected by dilate adds. (Delbos.)

Insoluble m water^ alcohol, and bistdphide of carbon, (Delbos.)

Menaphthylamine.

C«H"N» = C«>CyNAdH",H«.

W. H. Perkin. Chem. Soc. Qu. J. 9, 8 ; Chem. Gaz. 1856, 519 j iiT. FhU, Mag, J. 12, 226 ; ImtU. 1856, 800 and 406 ; Arm, Pharm. 98, 236 ; J. pr. Chem, 68, 152 and 441 ; Chem. CerUr. 1856, 394 ; Liebig k Kopp's Jahresb, 1856, 538.

MemaphtuHdim,

Formation, From naphtbylamine and chloride of cyanogen (oomp. p. 97). (Perkin.)

Preparation. By A. W. Hoiinann's process for preparing melaniline, (zi, 351). A number of glass tnbes arejpartly filled with naphtbylamine maintained in fusion by a gentle heat, and gaseous chloride of cyanogen is drawn through them by means of an aspirator. As soon as the reaction commences, heat is developed ; the liquid thickens, so that the passage of the gas is impeded; and at the end of the operation, the mass must be carefuUy warmed to keep it sufficiently fluid. The mass, which after cooling is black and resinous, and consists principally of hydrochlorate of menaphthylamine, is boiled with a large quantity of water, and the menaphthylamme is precipitated by ammonia or potash from the filtered solution, as a white precipitate, which is washed with water in order to free it from chloride of potassium or chloride of ammonium, and purified by one or two recrystallisations from alcohol.

ProperHcB, Small, white needles, inodorous and having a bitter taste. It becomes coloured in the air; and restores the colour to reddened litmus.

Perkin. mean*

42 C 252 .... 81 0 80-89

17 H 17 .... 5-4 6-54

3 N 42 .... 13-6

C«OyNAdH»,H« .... 311 .... 1000

126 CONJUGATED COMPOUNDS CONTAINING 2 AT. C»NH7.

Decompositions, 1. Melts at about 200° to a transparent pale yellow oil; and decomposes at 260^, whereupon pure naphthy famine distils over, and a brown mass remains in the retort. Thii brown residue has probably a compositioii analogous to that of the substanoe formed under similar circumstances from melaniline. (Perkin.) — 2. It appears to form neutral compounds with chlorine, bromine, and iodine, 3. Menaphthylamine treated with fuming sulphuric acid becomes pasty, from formation of sulphate; the mixture becomes liquid again when heated; and if it then be diluted with water and treated with carbonate of lead, the soluble lead-salt of a new acid is obtained, which, however, decomposes partially every time its solution is evaporated. Sulphuretted hydrogen precipitates sulphide of lead from the solution of the lead-salt, and leaves a colourless solution, which on evaporation, yields a soluble alkaline and an insoluble neutral body as decomposition-products of the acid.-i- 4. JFuming nitric add reacts very violently on menaphthylamine, giving rise to a series of substitution- products. — 5. Chi'omic acid acts but slowly. — 6. Cyanogen gas, passed into an alcoholic or ethereal solution of menaphthylamine, turns it first yellow, and then red, but gives no precipitate even after standing for a long time. Menaphthylamine suspended in ether and treated with caseous cyanogen, dissolves completely, and the solution after a time deposits dark-yellow, crystalline bicyano-menaphthylamine. (Perkin.)

C«Hi7N» + «C«N » C«Cy»Ad»H",H».

Comhinations, It is almost insoluble in loater. It unites with aeidsy forming salts of menaphthylamine, many of which are amorphous or but very slightly crystalline; all of them are but sparingly soluble in water and neutral to litmus paper. The salts are precipitated from their solu- tions by acids and by saline solutions ; potash and ammonia precipitate the base as a pure white powder.

Phosphate of Menaphthylamine. White, crystalline; very soluble in alcohol and in ether.

Sulphate of Menaphthylamine. Best obtained by neutralising the base with sulphuric acid. — White, perfectly amorphous substance, only moderately soluble in alcohol and in ether; on evaporating the solution it is reprecipitated as a white powder.

Bydriodate and Hydroh*omate of Menaphthylamine are crystalline and very soluble in alcohol and in ether.

Hydrochloraie of Menaphthylamine. White, amorphous compound turning slightly red in the air. Rather soluble in water, very soluble in alcohol and in ether. Decomposed by heat, hydrochlorate of naphthyl- amine subliming, and a black residue remaining in the retort.

Perkin.

C«H»7N« 311-0 .... 89-6

HCl 36*5 .... 10*4 10-44

C«HVN»,HC1 847-5 .... 100-0

NUrate of Menaphthylamine is the most beautiful of all the salts of menaphthylamine. It is prepared by dissolving the pure base in dilute

BICYANOMBNAPHTHYLAMINE. 1 27

boiling nitrio acid. It is deposited from this solution in small white prisms. Almost insoluble in cold water; dissolves abundantly in alcohol and in ether.

ChloroplcUincUe of Menaphthylamine is best obtained by mixing an alooholio solution of platinio chloride with warm alcoholic solution of hydrochlorate of menaphthylamine ; small, yellow, brilliant scales are then deposited. If aqueous solutions are employed, the compound is imme- diately precipitated as an amorphous powder, which is almost white but soon assumes a green colour. Perkin found 19'07 p. o. Pt.; the formula C«H"N«,HC1 + PtCP requires 19-08 p. c.

Teroklwide of Odd gives a blue precipitate with solution of menaph- thylamine.

Menaphthylamine dissolYCS in alcohol and in ether.

Bicyanomenaphthylamine.

C«H"N» = C*«Cy»Ad»H",H» .

W. H. Perkin. Chem. Soc. Qu. J. 9, 8 ; Ann. Pharm. dSy 236 ; J. pr, Chem. 68, 152 and 441 ; lAMg k Kopp's Jahretb. 1856, 538.

DieymenapMhylamine. (Perkin.) Bieyaimenaphtalidm,

Formation, Produced from menaphthylamine and gaseous cyanogen (comp. 126, 2).

Preparation. Gaseous cyanogen is passed through ether containing menaphthylamine in suspension. The whole is dissolved, and after a time, bicyanomenaphthylamine is deposited as a crystalline, dark-yellow substance, and is purified by washing with ether.

Propertiei. Pale yellow; crystallises with difficulty.

Perkin.

at 100^

46 C 276 .... 7600 76-00

17 H 17 .... 4-69 4-71

5 N 70 .... 19-31

C«>Cy«Ad»H",H2 .... 353 .... lOO'OO

Insoluble in VKXter.

Bicyanomenaphthylamine is a base, although a very unstable one; it dissolves with ease in dilute acids and may be reprecipitated by ammonia, if added immediately after dissolving the base; but, like cyan- aniline and bicyanomelaniline, it cannot remain longer in acid solution, without undergoing complete decomposition. If the solution of bicyano- menaphthylamine in acids be left to itself only a few seconds, it becomes turbid and deposits yellow menaphthoximide. (Perkin.)

C«H»7N» + 4HO + 2HC1 - C«(Cm02)CyNAdH",0» + 2NH*CL '

Bicyanomenaphthylamine is moderately soluble in alcohol and in ether.

128 GONJUGATED COMPOUNDS CONTAINING 2 AT. C»HN7.

Oxanaphthalide.

C«*ff«NH)* = C*»(C*HO«)NAdH«0».

Zdvin. Feimb. Aead. BuU, 16, 282; Ann. Pharm. 108, 228; J.pr. Ohem. 74, 379 ; Jiep. Chitiu pure. I, 148.

Fcnrmation. By the action of heat on oxalate of naphthylamine (oomp. 100« a and b).

Freparation. The residue which remains after fusing acid oxalate of naphthylamine, is treated with alcohol, whereby the formylnaphthalide (p. 117; is dissolyed out^ leaving insoluble oxanaphthalide.

Properiia, Small scales. Melts at about 200^. Zinin found 77'78 p. 0. G and 4*87 p. c. H ; by calculation, 77*64 p. c. G and 4*70 p. c H.

DeoomposiUans. Heated for a long time above its melting-point, or submitted to dry distillation, it decomposes for the most part, yielding almost pure carbonic oxide, and forming carbonaphthalide G^y NH"^ HH)'. — 2. It is but very slightly affected by dilute aqueous pciash or even by rather concentrated ocum f nitric acid exceptea) ; but if it be boiled with alcoholic potash or heatea with concentrated aaueous potash (1 pt. potash to 3 or 4 pts. water), it is resolved into naphtnylamine and oxalic acid.

Insoluble in water^ sparingly soluble in boiling akohoL

Menaphthoxiiiiide.

C«H"NK)* = G*»(C»HO>)CyNAdH»,0»(f).

W. H. Pbbkin. Chem. See. Qu. J. 9, 8 ; Ann. Fkarm. 98, 236 ; J. pr. Chem. 68, 162 and 441 ; Liebig & Eopp'a Jaki^. 1856« 538.

FommtUm. (Comp. p. 127.)

Freparation. Warm, alcoholic solution of bicyanomenaphthylamine is mixed with hydrochloric acid and allowed to stand, whereupon me- naphthoximide is deposited in small yellow spangles.

Fraperties. Small, yellow spangles.

Perkin. dried at 100**.

46 C 276 .... 75-66 75*6

15 H 15 .... 4-10 4-2

8N 42 .... 11-50

4 0 32 .... 8-74

C«H»NH)* .... 365 .... 100-00

DeeompaUums. 1 . When heated, it melts at 245^ and is decomposed at 260^ puffing out white vapours having a strong and most peculiar

ALIZARIN. 129

odour ; the substance hereby formed is probably naphthalocyanic acid (p. 118.), analogous to aailocyanic acid. — 2. Witb Kqueona potash it forms menaphthylamine and oxalic acid ; and hence may be regarded as acid oxalate of menaphthylamine mintu 4 At. water. (Perkin.) — 3. It is converted by acids, in a similar manner to melanoximide, into oxalic acid and menaphthylamine; a white neutral body being simul- taneously formed.

Insoluble in water; very sparingly soluble in alcohol and in ether (it may be obtained crystallised from the latter, though with difficulty).

Ternaphthylphosphamide,

H. ScHipp. Ann, Pha)^. 101, 299; J,pr. Chem. 70, 264 ; Cffiem. Gaz. 1857, 211 ; Chem. Cenir. 1857, 166 ; LiMg d: Eopp's Jahresb. 1857, 389.

M>rmatton and Preparation, Naphthylamine heated with oxy- chloride of phosphorus on a water-bath, yields a reddish nncrystallinc product, while the excess of liquid contains hydrochlorate of naphthyl- amine.

This, as SchiflT proved, is ternaphthylphosphamide^ since from ozychloride of phosphorus and ammonia or aniline, terphosphamide, N^PO^H^, or terphenylphos- phamide, C»H»8N»P0», is produced. (Schiff.)

The dried substance is readily decomposed by hot water, or by boiling alkalis or acids; melted with potash, it evolves naphthylamine, and yields phosphate of potash.

Primary nucleus, O^W^ ; Oxygen^nucUuSy C"H*0*.

Alizarin.

C»HW = C«»H«0*,0«.

Colin & RoBiQUBT. Ann. Chim, Phys. 34,225; J. Phai^i, 12, 407;

Berz. Jahresh. 7, 265; N. Tr, 14, 1, 174, KuBLMANN. J. Phwrm, 14, 354 ; Berz. Jaliresh, 8, 275. Zenneck. Pogg. 13, 261. Gaultieb db Claubry & Persoz. Ann. Chim. Phys. 48, 09 ; N. Tr.

25, 2, 186. F. F. RuMGB. Verhandl. dcs Vereins zur Brforderung des Gtwerhfieisses

in Preussen, 1835, Heft 2 ; J. pr. Chem. 5, 374 ; abstr. Ann. Chim,

Phys. 63, 282. Robiquet. J. Pharm. 21, 387 ; J. pr. Chem. 6, 130;— against Runge :

Ann. Chim. Phys. 63, 297; — against Decaisne : Ann. Chim. Phys,

73, 274. Decaisne. J. Pharm. 24, 424 ; J.pr. Chem. 15, 393. J. ScHiEL. Ann. Pharm. 60, 79.

VOL. XIV. K

130 PRIMARY NUCLEUS C«H»«: OXYGEN-NUCLEUS C»H«0*.

J. HioGiw. PkiL Mag. J. 33, 282 ; J. pr. Chem. 46, 1.

ScHUNGK. References given nnder Rnbian.

Debus. Ann. Pharm. 66, 351 j iV. Ann. Chim. Phys. 38, 498.

J. WoLPP <k Strecker. Ann. Pharm. 75, 20; Pharm. Centr, 1850,

593 ; Ohem. Soc. Qu. J. 3, 243. RocHLEDER. Wtm. AJcad. Bei\ 6, 433; J. pr. Ohem. 55, 388; Ann. Pharm. 80, 321 ; Wien. Akad. Per. 7, 804 ; Ann. Phaivi. 82, 205 ;

J. pr. Chem. 06, 85.

Ejctraciive or resinous Madder-red, Erythrodanum, Alizarine (Colin & Robiquet) ; Matidre colorante rouge (Gaaltier & Peraoz) ; Krapp-roth (Run^, Schiel) ; Lizaric acid (Debus). Constitates, together with purpurin (ziii, 325), the red colouring matter of the roots of Rubia tinctorum and R. peregrina. Discovered in 1826 by Colin & Robiquet, after Bocfahok {Tasekenb. 1811, 60) and Kuhlmann {Ann. Chim. Phys. 24, 225 ; N. Tr. %, 2, 111) had in vain sought to isolate the red colouring matter of madder.

Source. In madder root. According to Colin and Robiquet and others, it exists ready formed, bat according to Decaisne's microscopic researches, it is derived from a yellow substance disseminated unequally through the entire root. According to Schunck, the substance from which alizarin is derived is rubian ; according to Higgin, it is xanthin ; and according to Rochleder, ruberythric acid ; the two last-named bodies are regarded by Schunck as mixtures or decern position-prodncts of rubian. (See Rubian.) Part of the alizarin yielded by madder is fonnd ready formed in the dried root, and may be extracted therefrom by alcohol.

Formalion, 1. Schunck's rubian fields when heated a sublimate of alizarin ; by boiling acids or alkalis, or by contact with erythrozym, it is resolved into alizarin and other products (see Rubian). — 2. Schunck's ] ibianic acid is decomposed under the same circumstances as rubian, yielding alizarin and sugar (comp. Rubianic Acid). — 3. Rochleder s ruberythric acid, boiled with acids or alkalis, yields the same decompo- sition-products {we Ruberythric Acid).

4. In madder. Phenomena accompaiiying the foi'mation of alizarin in madder. Extract of madder, prepared with cold or luke-warm water, becomes after a time thick and gelatinous, and loses its bitter taste and yellow colour. (Higgin, Schunck.) — In this reaction, the erythrozym (see below) decomposes the rubian in the extract of madder in the same manner as pure rubian is decomposed (see Rubian), (Schunck.) — The xanthin and the greater part of the rubiacin disappear, giving rise to alizarin. (Higgin.) — Fresh cold-prepared extract of madder is reddish brown, has at first a sweet, then an unpleasantly bitter taste, and dyes cotton fabrics a pure yellow, like xanthin. After an hour or two, it becomes gelatinous, and, if sufficiently concentrated, deposits orange flakes of alizarin and rubiacin, more of which are precipitated by sul- phuric acid ; and after filtration, a perfectly sweet and no longer bitter liquid remains, which dyes calico pale red, and (tested by the method given under xanthin) contains no more xanthin. (Higgin.)

If the alizarin is precipitated from fresh extract of madder by acetate of lime, and the filtrate divided into three parts, whereof a is immediately examined, b diluted with water and allowed to stand for four hours, and c allowed to stand for three hours; hydrochloric acid precipitates from a, pure

ALIZARIN. 131

Tnbiacin, while xanthin remains in tlie filtrate j h on tlie contrary is no longer bitter, yields with hydrochloric acid a precipitate of rubiacin, but contains no xanthin j c has become lighter, has deposited flakes of alisarin, and contains mbiacin in solution. — Hence xanthin is converted into rubiaoin and this into alizarin. This change also takes place in Tacuo, and accordingly without the influence of oxygen (as Decaisne supposed), being in fact due to a nitrogenised constituent of madder (see BfT/throzym) of which good madder contains sufficient to decompose an addition of 20 p. c. of its weight of xanthin. The decomposition takes place most rapidly between 50"^ and 5o°, at which temperatnre all the xanthin in madder over which water has been poured, is converted in half an hour into rubiacin, and in 4j- hours almost all the rabtacin is converted into alizarin. By prolonged standing, the alizarin becomes fixed on the madder- fibres, and cannot then be extracted by water till the whole has been treated with acid. — This change is retarded by boiling the madder. Decoction of madder retains its bitter taste and deep yellow colour after long standing. A cold-prepared infusion deposits on boil* ing, flakes of a nitrogenised substance, and the filtrate then undergoes no further change. Acids precipitate from the cold infusion the same substance, together with rubiacin, alizarin, and pectin, leaving a filtrate which contains xanthin, and does not decompose. The nitrogenised sab- stance, together with pectin, is precipitated as a jelly from the cold infusion by alcohol, and the filtrate undergoes no further change ; but if the liquid be heated with the precipitate till all the alcohol is driven ofi^, it redissulves, and the clear solution suffers the usual decomposition. (Higgin.)

Preparation, A. From madder. 1. The operation is conducted as described at page 326, vol. xiii, and the alizarite of alumina thus obtained is decomposed by boiling dilute hydrochloric acid. The precipitated alizarin is dissolved in boiling alcohol, crystallised by slowly evaporating the solution, and purified by recrystallisation. (Debus.) — In the same way Schanck decomposes the alizarite of alumina obtained in the first method of preparing rubian (see below) ; whereupon, however, on cooling the alcoholic solution of alizarin and allowing it to stand, a brown pul- yerulent resin is generally deposited between the crystals, and must be removed by levigating with alcohol. — Wolff ^ Strecker boil the alizarite of alumina obtained by method 1 (xiii. 826,) repeatedly with concentrated aqueous carbonate of soda, as long as the liquid acquires a deep colour, whereby purpurin is extracted ; an admixture of resin is then removed by repeated washing with warm ether, and the residue is decomposed as above.

2. Madder washed as described (xiii, 326, 3), is boiled with solution of alum for four days ; whereupon the brownish red precipitate containing the alizarin which is deposited from the extracts, is repeatedly boiled with dilute hydrochloric acid, the residue washed and dissolved in alcohol. On evaporating down the alcoholic solution and allowing it to cool, it deposits crystals of alizarin, which is freed from the purpurin contained in it by dissolving in a small quantity of alcohol and repeatedly boiling with solution of alum, as long as the liquid becomes coloured ; whereupon the alizarin is precipitated and the purpurin passes into solution. The alizarin is obtained in crystals by washing the product, dissolving the ether, and abandoning the solution to spontaneous evaporation. (Runge.) Schiel adopts a similar method, boiling with alcoholic solution of alum,

k2

132 PRIMARY NUCLEUS C»H» : OXYGEN-NUCLEUS C^H«0<.

the precipitate, which is deposited on cooling from the madder-extract pro- pared with alum, whereupon the colouring matters form two strata on cooling. He removes the upper light red flocculent stratum ; again treats the lower dark-brown stratum with alcoholic alum ; boils ; and thus con- tinues the operation, till the upper flakes give a pure violet solution with potash, whereupon he separates the alizarin from the undissolved portion by boiling with hydrochloric acid, recrystallising from alcohol, and finally from ether.

3. Kochleder proceeds as described (xiii, 327)) or precipitates the alizarin and purpurin from the aqueous aecoction of madder by baryta- water, filters ofl* the violet precipitate, and decomposes it with moderately strong hydrochloric acid, whereby chloride of barium is dissolved out, leaving a residue of alizarin containing a little purpurin, which may be separated by recrystallisation.

4. Commercial garancin is warmed two or three times with ^ pt» ammonia-alum dissolved in water; the liquid evaporated with constant stirring; the residue dried, pulverised, treated with boiling bisulphide of carbon (or with absolute alcohol), and filtered from nndissolvea alum ; and the brilliant golden-yellow solution is allowed to cool ; whereupon alizarin crystallises out in silky needles. (L. Vilraorin, J, Chim, M6d. 1859, 255 ; Dingl. pol Joum. 152, 159 ; Cliem. Centr, 1859, 380.)

5. When the extract prepared from madder with wood-spirit is tritu- rated with 10 pts. water, and heated in closed vessels for 15 minutes at 250°, the water after cooling is found full of crystals of alizarin, which may readily be separated from the fused extract at the bottom of the vessel ; and by repeating the operation three times, the whole of the alizarin may be extracted. (Plessy & Schiitzenberger, Campt, Trend, 43, 167 ; ^. Pr. Chem. 70, 314.)

Older methods, Alsatian madder is softened with 3 or 4 pts. of cold water for 10 minutes, and the mass is pressed between linen. The brownish red liquid coagulates in a trembling jelly, which is gradually pressed through several folds of thick linen, then moistened with water and again pressed out. The fresidue may be sublimed ; or else it may be exhausted with alcohol ; the tincture reduced to \tSx of its volume ; the residue mixed with a little sulphuric acid and a large quantity of water ; and the resulting bulky, brownish yellow precipitate waf^hed by decantation with a large quantity of water, as long as the wash- water exhibits an acid reaction. It is then dried, and the alizarin is either sepa- rated by sublimation or extracted with ether. (Colin & Robiquet.) — Kuhlmann recommended to extract with boiling alcohol either the crude madder, or madder previously washed with cold water, then to evaporate the tincture, and when the residue has become almost thick, but still contains alcohol, to precipitate it with sulphuric acid and water, and either to sublime the precipitate or extract it with ether. {J, Flhaiifu 14,363.) — Zenneck washes madder with cold water, then with dilute sulphuric acid ; exhausts the dried residue with ether ; and sublimes the residue left by evaporating the ether. An oil obstinately adheres to sublimed alizarin, and may be removed by rincing the crystals with ether and pressing them hard between blotting paper. (Robiquet.)

Gaultier and Persoz prepared their matiire colwante rouge, which appears to be impure alizarin, by precipitating the alkaline decoction of madder obtained as described (xiii, 326, 2) with an acid, washing the precipitate, dissolving it in alcohol, and evaporating.

ALIZARIN. 133

Useful for comparing different hinds of Madder, 10 kilogr. madder are boiled for 80 minutes with 2 kilogr. alum and 20 kilogr. water^ then poured upon linen, and the residue is pressed and treated three times in the same manner. The united extracts are allowed to stand for a certain time, and after they are quite cold, decanted, and mixed, during constant stirring, with 025 grammes of sulphuric acid (previously diluted with twice its weight of water), whereupon thick reddish flakes are precipi- tated, which, after having been thoroughly washed, are dried in the air. Alizarin thus obtained still contains lime, xanthin, and purpurin. To remove these substances, it is dissolved in aqueous carbonate of potash and the filtrate is precipitated by sulphuric acid. Avignon- madder yields from 2 to 3 p. c. alizarin. (Meillet, Eev. scient. 1, 213.)

B. From Rubian, 1. By boiling with acids. Aqueous rnbian (or extract of madder prepared with boiling water) is boiled with a large quantity of dilute sulphuric acid as long as orange-coloured flakes con- tmue to deposit ; it is then allowed to cool, and the flakes are collected and washed (the filtrate from them sometimes yields an additional quantity when again boiled with fresh acid). They contain alizarin, rubiretin, verantin, and rubianin, and are submitted to the following treatment :

a. In case only Alizarin is required. The substance is dissolved in alcohol, precipated with hydrate of alumina, aud filtered ; tbe precipitate is treated with aqueous carbonate of potash or soda, as long as anything is dissolved ; tbe residue is collected and decomposed by an acid ; and the precipated alizarin is crystallised from alcohol. (Schunck.)

In case Rubiretin^ Verantin^ and Bttbianin are also required, — The substance is dissolved in boiling alcohol; the reddish yellow solution filtered boiling; and the residue boiled with fresh alcohol as long as the latter acquires a dark yellow colour. The yellow or brownish yellow crystalline mass left in the residue is chiefly rubianin, which, however, may also be dissolved by frequent treatment with boiling alcohol, whence it crystallises on cooling, as well as from the first extracts. The solutions are left to cool, and the crystals of rubianin containing verantin (see further treatment of this below) are separated from the mother-liquid (which, however, still contains a little rubianin). Acetate of alumina is now added to the liquid, whereby aJl the alizarin together with a small quantity of verantin is precipitated as a dark red powder, which is collected and washed with alcohol till the washings are colourless. The mother-liquid serves for the preparation of rubiretin, rubianin, and verantin. The precipitate is decomposed with hydrochloric acid; the flakes of alizarin and verantin thus separated are washed with water and dissolved in alcohol ; and all tho verantin is precipitated from the solution as a reddish brown copper-compound by acetate of copper, while the alizarite of copper remains dissolved in the dark purple filtrate, from which alizarin is prepared by precipitating with hydrochloric acid, thoroughly washing the precipitate, dissolving in alcohol, and roorystal- lising. (Schunck.)

The following method is adopted to purify the rubianin, rubiretin, and verantin, likewise obtained —

a, Rubianin, When an aqueous decoction of madder is employed instead of rubian, mbiacin is obtained in place of rubianin. — a. The crystals of rubianin containing verantin obtained as above are dissolved in

134 PRIMARY NUCLEUS C^H^o : OXYGEN-NUCLEUS 0»HW.

boiling alcohol ; tbe verantin is precipitated by acetate of lead as verantite of lead ; and tbe liquid is filtered and lefib to cool, wbereupon large lemon-yellow needles of rubianin are deposited. — /3. The mother-liqaid remaining after the precipitation of the alizarite of alumina, and still containing rubiretin, rubianin, and verantin, is evaporated to dryness, and the residue is mixed with hydrochloric acid and washed with water till all traces of acid and alumina have been removed. The residue is boiled with water, whereupon brown drops of resin are precipitated, and brownish yellow flakes float on the water. These are poured off with the liouid from the resinous drops (rubiretin and verantin), and this treat- ment IS repeated as long as flakes are obtained. The flakes consist of rubianin and verantin, the first of which dissolves by repeated decoction with water, and is deposited in orange^coloured flakes on cooling. These are dissolved in boiling alcohol, and ae the liquid cools, crystals of rubianin are obtained, while a small quantity of alisEarin and rubiretin remains in the mother-liquid. (Sohu&ck.)

b. Eubiretiiu When the resinous drops obtained above are treated with cold alcohol, they yield rubiretin, verantin remaining undissolved. (Scbnnok.)

c. Verantiai. Obtained in the preceding processes partly as verantite of lead, partly as verantite of copper, and partly as insoluble residue (a and b). The first two are decomposed with dilute sulphuric acid, and the verantin is extracted with boiling alcohol, then dissolved in a small quantity of boiling alcohol, and the dark reddish or yellowish brown powder deposited on cooling is purified by redissolving in alcohol. (Schunck.)

The madder-root exhausted with boiling water for the preparation of rubian, still contains alizarin, rubiacin, and verantin. It is boiled with hydrochloric acid, washed with water, and boiled with potash, whereby a dark red solution is formed, which being filtered and supersaturated with an acid, yields a dark, brownish red precipitate. This being boiled with water, yields alizarin and pectic acid, and leaves a residue of rubian and verantin. The alizarin is separated from the pectic acid by recrystal- lisation. The mixture of rubiacin and verantin boiled with ferric nitrate, yields a solution of rubiacio acid, which may be precipitated by hydro- chloric acid, while verantin remains undissolved. (Schunck.) See below, riijbiftciaic «cid.

2. By hmUng with alktdis. Rubian is boiled with an excess of caustic soda, till the colour of the liquid, which was at first blood-red, has turned purple-red, and the liquid having become more concentrated, deposits dark purpl^red alizarite of soda. The solution is now decomposed with excess of dilute sulphuric acid, whereupon it becomes colourless, depositing orange-coloured flakes, which, having been thoroughly washed with water, form a mixture of alizarin, verantin, rubiretin, and nibiadin. The flakes are treated with boiling alcohol, which dissolves them leaving a dark-brown substance (formed from sugar) ; the liquid is filtered, and the filtrate is precipitated with acetate of alumina, whereby alizarite of alumina, together with a small quantity of verantin, is precipitated, and is further treated as above described. (Schunck.) — For the farther treat- ment of the mother-liquid containing nibiadin, rubiretin, and verantin, see Bubiadin.

ALIZARIN. 135

3. By fermentation — Action of Erythrozym on Rubian — or by Ferment

tation of Madder, By thU method alizarin, mbiretin, and verantin are obtained in smaller quantity than by methods 1 and 2, and are more difficult to purify. Erythrozjm is added to aqueous rubiau, and the liquid is allowed to stand in a moderately warm place until it has become tasteless and colourless, owing to the deposition of a brown jell j. If this deposit should not take place in 24 hours, more erythroxym must be added. Or madder is stirred up with cold or warm water^ and left in a warm place till a jelly is formed. In both cases, the mass is mixed with a little water, and the jelly is collected on a filter and washed with a small quantity of water. It contains alizarin, rubiretin, verantin, rubiafin, rubiagiu, and rnbiadipin, which are separated as follows :-—

The mass is well boiled with alcohol as long as the liquid acquires a yellow colour, and acetate of alumina is added to the filtrate, whereby alizarin, verantin, and rubiafin are precipitated in combination with alumina, but only partially. The whole is then filtered (for the further treatment of the precipiute, see below), and sulphuric acid and a large quantity of water are added to the dark brownish-red filtrate, whereby the whole of the dissolved substances are precipitated as a yellow powder, which, having been thoroughly washed with water, is redissolved in boiling alcohol and mixed with excess of acetate of lead. The dark purple-red lead-precipitate, which is filtered boiling, contains alizarin, rubiretin, verantin, and rubiafin ; the dark yellow filtrate rubiagin and rnbiadipin. The lead-precipitate is decomposed with boiling hydrochloric acid, and the precipitated yellow flakes are washed and covered with cold alcohol, which extracts rubiretin, leaving alizarin, rubiafin, and verantin. On the other hand, the above-mentioned precipitate produced by acetate of alumina is decomposed with boiling hydrochloric acid ; the orange fiakes thereby separated are added to the residue of alizarin, rubiafin, and verantin, which was left undissolved by cold alcohol ; and the whole is dissolved in boiling alcohol and mixed with acetate of copper, which forms a purple precipitate (rubiafite, verantite with a small quantity of alizarite of copper). After filtering off the precipitate, alizarin alone remains in solution and is precipitated by hydrochloric acid and water, and purified by crystallisation. (Schunck.)

Treatment of tJie Verantite and BubiaJUe of oopper. The purple copper precipitate, decomposed by hydrochloric acid, deposits insoluble red flakes, which, after washing, are dissolved in boiling alcohol, and treated with hydrated stannous oxide, whereupon only iidnajln remains dissolved, and crystallises from the filtrate in brilliant needles and laminsD, while verantin, together with a small quantity of alizarin, is precipitated as a stannous oxide-lao. (Schunck.) See VermUm,

Higgin obtains his alizarin (rnbiacin and xanthin), the first of which is probably a mixture of alizarin and purpurin (see Wolff & Btrecker, Ann. Pharm, 75, 3), in the following manner : — Madder is exhausted in a digesting funnel with hot water, till the washings run off almost colourless ; the cold extract is precipitated with dilute sulphuric acid ; the precipitated flakes, containing alizarin, rnbiacin, and a small quantity of pectin, are collected; and the filtrate, containing xanthin, traces of alizarin, and a small quantity of sugar, is kept for the preparation of xanthin. The flakes are first washed with water acidulated with sul- phuric acid, then with pure water, afterwards mixed with an equal bulk of powdered chalk, and boiled with water, till the washings assame a

136 PRIMARY NUCLEUS C»HW: OXYGEN-NUCLEUS C»H60^:

bright red colour. This aqueous solution contains indnadn, which is separated bj acidulating the filtrate with sulphuric acid, collecting and washing the greenish yellow precipitate, and recrystallising from alcohol. The residual chalk contains His^gin's alizaHn, which is extracted by digesting with dilate hydrochloric acid, filtering, washing the residue, and recrystallising from alcohol.

Preparation of HiggirCs Xanthin, The filtrate obtained as above is neutralised with carbonate of soda ; the rubiacin and alizarin still in solution are precipitated by digesting the liquid for half an hour at bS^ with a small quantity of hydrate of alumina ; the phosphoric and sul- phuric acids are separated from the filtrate by means of baryta-water ; and the xanthin is precipitated from the filtrate as a red lac by subacetato of lead. This being washed with water, suspended in water, and decom- posed by sulphuretted hydrogen, deposits xanthin together with sul- phide of lead. The mixture is then washed with cold water and the xanthin extracted by boiling water ; the solutions are evaporated to a syrup (neutralised with baryta, if necessary), and then, to complete dryness; the residue is extracted with absolute alcohol; and the alcoholic solution is evaporated. (Higgin.)

The madder, after thorough washing with hot water, still contains the greater part of the alizarin (p. 135) together with only a small quantity of rubiacin. To separate the alizarin, the madder residue is boiled three or four times with a weak solution of alum, whereby the rubiacin is removed, and the residue is then boiled for a quarter of an hour with a saturated solution of alum and filtered, this treatment being repeated till the madder is exhausted and has become ash-grey. The united decoc- tions are cooled to 32^ and strongly acidified with dilute sulphuric acid, whereupon the alizarin is precipitated, the precipitation being promoted by rapidly stirring the liquid. The product is collected and purified as above, fliggin's alizarin difiers from that prepared by other chemists, by its property of dissolving with purple-red colour in boiling aqueous alum. Since this solution does not yield much deposit on cooling, it perhaps consists of purpurin (p. xiii, 325), or according to Schunck, of alizarin con- taining verantin (see below, Verantin)* When boiled with aqueous sul- phate of ammonia (or sulphate of potash) it is converted into a purple- red powder, without dissolving (the behaviour of pure alizarin is not known), and may thus be separated from Higgin's rubiacin.

Pwperiies, Hydrated alizarin (p. 138) parts with its water between 100° and 120°, becomes opaque, assumes a darker red colour, like native chromate of l^id, and is converted into anhydrous alizarin (Schunck), which melts at a higher temperature, solidifies in a reddish brown crystalline mass on cooling, and sublimes, according to Schunck, at 215°, according to Schiel, at 225°, in long, brilliant, golden yellow needles^ reflecting light with red colour. (Colin k Robiquet.) Sublimed alizarin forms foar-sided, flexible (Zenneck), brilliAiit, orange-ooloured (Range, Schiel), reddish yellow (Debus), red, trauBparent needles. (Robiquet.) It is brighter in colour than before sublimation, bright orange, transparent, and very brilliant. (Schunck.) In the first sublimation there always remains a residue of carbon, according to Colin & Robi-* quet, Runge & Shnnck, Wolff & Strecker, but not on resubliniation, according to Colin «c Robiquet & Range. Neutral (Clolin & Robiquet^. Reddens litmus. (Zenneck.) Heavier than water. Tastes bitter and acid. (Zenneck.)

ALIZARIN.

137

Wolff & Strecker's calculation. Schunck's calculation. Robiquet. ^ ^* *

^ mean.

20 C 120 .... 68-96 14 C 84 .... 69-42 .... 7009 .... 67*46

6 H 6 .... 3-45 5 H 5 .... 4-13 .... 3'73 .... 4-22

6 O 48 .... 27-59 4 O 32 .... 26-45 .... 26-18 .... 2832

C»H«0« .... 174 .... 100-00 C"H»0* .... 121 .... 100-00 .... 10000 .... 10000

Debus.

mean*

C 68-97

H 3-79

O 27-24

100-00

Wolff & Schnnck.

Strecker. earlier, mean,

dried. sublimed.

. 68-4 69-13 .... 69-61

4-01 .... 3-73

26-86 .... 26-66

100-00 .... 100-00

a.

c	69-37
H	4-07
O	26-56

Scbunck. later, b. e.

mean,

6907 .... 69-59

4-70 .... 415

26-23 .... 26-26

Rochleder. d. mean. at 100^

69-38 67-93

4-16 3-77

26-46 28-30

10000

100-00

10000

10000 10000

a was obtained from rubian by sulphuric acid; b by soda; c by erythrozym; d from rubianic acid by sulphuric acid and soda. (Schunck.)

Eariicr formulie of alizarin: C^K^Qi^^ (Robiquet); C»H>0» (Schiel); C^H^O* (Debus); C"HWO» « 3C»H*0« + Aq for the alizarin which Rochleder investigated. (Rochleder.) The formula C^H<0> given by Wolff & Strecker is most generally adopted ; this does not exactly correspond with Schunck's analyses, and according to him does not explain the connection of alizarin with rubian and rubianic acid, and especially of the formation of alizarin observed by Schunck in decomposing rubianic acid (see Rubianic Acid); Schunck's formulae are therefore likewise given in the followiog pages.

DecomposUions, 1. Alizarin heated on platinnm-foil, melts and burns

with flame. (Schunck.) When Schiel filled a glass bulb with alizarin, and passed a current of oxygen into it, an explosion took place as the substance was fused, and shattered the apparatus. 2. It is conrerted by boiling dilute nitric acid into oxalic acid and a peculiar acid (Schunck), into phthalio acid, (xiii, 10.) (Laurent & Gerhardt.)

C»H«0« + 2HO + 80 = am^O^ + C*H«08.

3. When alizarin is suspended in water and chlorine gas passed through the liquid, it turns yellow, f^iveB by heat a colourless sublimate, and dissolves in alkalis without much colour. (Schunck.) — It remains apparently unchanged by the action of chlorine, but if mixed with potash after the excess of chlorine has been removed, it gives a deep red solution like purpurin and a purple-red precipitate with baryta; hence it has probably been converted into purpurin :

0»H«0« + 40- CWH«0« + 2 C0«. (Wolff & Strecker.)

Aqueous alizarin is rapidly turned pale brown by chlorine. CZenneck.) 4. It 16 converted into phthalic acid hy ferric nitrate or chloride at the hoUing Jieat, (Schunck.) (For the behaviour of the alkaline solution with ferrous sulphate, see xiii, 329.) 6. It is decomposed by boiliug with chromate of potaik and sulphuric acid, (Debos, Schunck.) — 6. It reduces tei*chloride of gold on

138 PRIMARY NUCLEUS C»HW2 OXYGEN-NUCLEUS C»H60*.

addition of caustic potash. (Schunck.) — 7. According to Wolff & Strecker, alizarin is converted into purpurin by the fermentation of madder^ inasmuch as these chemists were able to obtain only parpurin, but no alizarin^ from fermented madder. This is denied by Schunck.

Combinations. With water, — a, Hydrated AlistaHn. Crystallised from alcohol: long, transparent, dark-yellow prisms of high lustre, resembling isatiu, without any shade of brownish yellow or red, which they have only when contaminated with verantin. (Wolff & Strecker.) Large, rose-coloured needles. (Debus.) Brownish yellow, crystalline powder (Runge); brownish red mass, having a brilliant fracture. (Gauliier & Persoz.) It parts with 18' 12 p. c. water at 100°, (C*»HH)« -h 4Aq = I714j C"H'^0* -I- 3Aq = 1824 p.c), without changing its form, and is converted into anhydrous alizarin. (Schunk.)

Wolff & Strecker'B calculation. Schunck's calculation. Schunck.

20 C 120 .... 57*14 14 C 84 .... 56-75 .... 56-98

10 H 10 .... 4-76 8 H 8 .... 5-40 .... 506

10 O 80.... 3810 7 0 56.... 37-85.... 3796

C»H«0«,4Aq .... 210 .... lOO'OO C"H«0*,3Aq .... 148 .... 10000 .... 100-00

h. Aqueous Alitarin. Alizarin is with difficulty moistened by cold water (Wolff <fc Strecker), and dissolves in it very slightly, but more readily in boiling water. (Colin & Robiquet.) It dissolves sparingly with yellow colour in boiling water, and is deposited in flakes on cooling. (Schunck.) The solution is rose-coloured (Colin &c Robiquet), only when the water contains alkali. (Schunck, Wolff & Strecker.) The solu- tion prepared with boiling water does not yield any deposit on cooling (Gaultier & Persoz); it is precipitated by acids. (Kuhlmaun.) The solu- bility of alizarin in water rapidly increases when the mixture is heated in a sealed tube above 200°. 100 pts. water dissolve at 200^^ 0*82, at 225% 1-70 and at 250% 3*16 parts. (Plessy & Schlitzenberger. Compt. rend, 43, 167; J. pr. chem, 60, 314.)

It is not affected by weak ckcids (Gaultier & Persoz), by hydrochloric acid, (Schunck.) Boiled with dilute acids, it dissolves with yellow colour^ and is deposited in orange -yellow flakes on cooling. /Runge.)

Dissolves in sulphuric add without evolution oi sulphurous acid, forming a blood-red solution from which it is precipitated by water unchanged. (Colin & Robiquet and others.) The colour of the solution in sulphuric acid is dark yellowish brown, and is not changed by heat. (Schunck.)

Dissolves in bisulphide of carbon, with reddish yellow colour. (Zenneck.) Alizarin combines with salifiable bases. These compounds, which are regarded by Debus as salts, Uzaraies, are red, violet (or blue), and are insoluble in water and in alcohol with the exception of the ammonia, soda, and potash-salts. They seldom, if ever, contain 1 At. metallic oxide to 1 At. alizarin.

When dry gaseous ammonia is passed over alizarin, the mass becomes warm and turns Tiolet, but parts by heat with all the ammonia it haji taken up and reassumes its yellow, colour. Heated in a stream of ammonia, alizarin sublimes unchanged, but acquires a violet colour. (Rochleder.)

Dissolves in aqueous atMnumia with orseille-colour, without any blue

ALIZARIN. 139

lustre OD tbe surface. (Wolff <Sb Strecker.) The ammonia-solution is purple-red (Range), violet-red (Colin & Robiquefc), red (Schiel) j it becomes turoid as the ammonia evaporates (Gaultier & Persoz); leaves a violet-brown film. (Scbunck.) Dissolves in nUphide of ammonium with beautiful reddish brown colour. (Gaultier & Persoz.)

Dissolves readily in aqueous caiutic alkalis ; at a eertain concentra- tion, the solution appears of a deep purple colour by transmitted light, and pure blue by reflected light; when more diluted, it appears uniformly violet. (Wolff & Strecker.) Tbe solution is pure blue (Colin & Robiquet); of a beautiful red, permanent in the air (Gaultier 6c Persoz); of a magnificent violet-blue, and, when saturated, purple (Runge); violet (Schiel); purple, and leaves on evaporation a purple uncrystalline mass. (Scbunck.)

Dissolves in aqueous alkaline carbonates as in ammonia (Wolff & Strecker), with magnificent purple colour. (Scbunck.) The solution is orange-red (Gaultier & Persoz); red. (Schiel.) Dissolves in arsenite, arseniate, and silicate of potash. (Gaultier & Persoz.) — It does not dissolve in cold bicarbonate of soda, till the solution is warmed, where- upon carbonic acid is evolved. (Zenneck.)

Alizarin is precipitated by acids from its alkaline solutions in deep orange-coloured flakes. (Scbunck.)

Alizai'iie of Soda, Alizarin is dissolved by heat in a oold-saturated solution of carbonate of soda, and the compound which is deposited on cooling is dried, then dissolved in absolute alcohol and precipitated by ether. Purple flakes, insoluble in concentrated solution of carbonate of soda and in cold concentrated saline solutions, but soluble in water and in alcohol with orseille colour, which is turned blue by caustic soda. (Wolff & Strecker.)

Alizariie ofBaiyta. Baryta produces a beautiful blue precipitate in the solation of alizarin in ammonia (Robiquet <& Colin); it precipitates and decolorises the potash solution. (Scbunck.) Alcoholic alizarin boiled with baryta, turns lilac, and deposits a lilac precipitate. (Zenneck.)

a, Sibasic. Alcoholic alizarin is precipitated with excess of baryta- water ; the precipitate is washed out of contact of air with water and warm alcohol, till the washings are no longer coloured by addition of potash ; and the residue is dried at 100''. (Wolff & Strecker.)

Wolff Sc Strecker.

C»H«0' 174 .... 50-43

2BaO 153 .... 44-35 440

2 HO 18 .... 5-22

C20H«O« + 2BaO,HO.... 345 .... 10000

b. Sesqinhasic, 1. Ammoniacal solution of alizarin yields with chloride of barium a magnificent purple (Schunck), almost pure blue precipitate, above which a colourless liquid remains. (Wolff & Strecker.) When dry, it forms a dark-brown, almost black mass, which acquires a yellow metallic lustre by trituration in ^n agate mortar. (Scbunck.) 2. It was once obtained by precipitating alcoholic alizarin with baryta- water as in the preparation of the bibasic salt, and contained, at 100"^^ 38-3, and at 120", 39-8 p. c. baryta. (Wolff <fe Strecker.)

140 PRIMARY NUCLEUS C^H": OXYGEN-NUCLEUS C»H«0\

c , ^ , Wolff & ai 100». Schunck. gtrecker.

2 C»H«0«,3H0 375 .... 6204

3BaO 229-6 .... 3796 38'03 .... 38*3

2C»H«0«, + 3BaO,HO .... 604-5 .... 100-00

At 120* « 2C»H«0«,3BaO (by calculation, 39*7 p. c. BaO). (Wolf & Strecker.) According to Schanck, the formula is C>^H«C^,BaO or G*^H<fiaO«,UO, which requires 38-78 p. c. BaO.

c, Sesqui-aeid, Alizarin is dissolyed in aqneous ammonia, and after tho excess of ammonia ha^ been evaporated off, the solution is precipitated with chloride of barium. After drying at 100^, the salt still loses weight at 120°. (Wolff & Strecker.)

Wolff & Strecker. at 120''. mtatu

60 C 360 .... 53-3 53-35

18 H 18 .... 2-7 2-85

18 O 144 .... 21-3 20-90

2 BaO 153 .... 22-7 22-90

3C»H«0«,2BaO 675 .... 1000 100-00

StTorUiorioaier produces a beautiful blue precipitate with ammoniaoal alizarin. (Colin h Robiquet.)

Alizarite of Lime. Lime-wcUer decolorizes alizarite of potash and precipitates alizarite of lime (Schunck) ; it behares with ammoniacal alizarin like baryta-water. (Colin k Robiqueti) Alcoholic alizarin boiled with hydrate of lime acquires a lilac colour and deposits a lilac precipitate. (Zenneck.) Carbonate '{tLnd phosphate) of lime take up the colouring matter from aqueous (but not from alcoholic) alizarin ; it is to this affinity between alizarin and phosphate of lime that the red colour of the bones of animals feeding on madder is owing. (Berzelius, A, Oehlen, 4, 124.) Alizarin dissolves in calcareous waters and forms a blue lac. (Runge.)

To prepare alizarite of lime an ammoniacal solution of alizarin is pre- cipitated with chloride of calcium. Magnificent purple precipitate, like the baryta compound. (Schunck.)

Schunck. 4it 100^ mean.

2 C»HW,3HO 375 .... 81-7

3 CaO 84 .... 18-3 18-44

2C»H«0« + 3CaO,HO .... 459 .... 100-0

The formula is thus given by Wolff & Strecker ; Schunck writes it CiKlaH^.O^.UO, which requires 10*03 p. c. CaO.

Ammoniacal alizarin produces a violet precipitate with chloride of magnesium (Zenneck), a purple precipitate. (Schunck.) Alcoholic alizarin boiled with magnesia^ behaves as with lime or baryta. (Zenneck.)

Alizarite of Alumina, Alizarin is scarcely soluble in alum-solution (Colin & Robiquet), insoluble. (Gaulticr &c Persoz and others.) When concentrated solution of alum is boiled with alizarin, it turns yellow, and on cooling becomes almost colourless, depositing what it had dissolved (Wolff & Strecker) ; it acquires a red iridescence, and on cooling deposits

ALIZARIN. 141

small crystals of alizarin^ none of whicb remains in solution. (Scbunck.) The solutions of alizarin in alcohol and in potash are decolorised by hydrate of alumina^ while the whole of the alizarin is precipitated, imparting a red or reddish purple colour to the alumina. (Scbunck.) Alizarin dissolves in aluminate of potash. (Gaultier & Persoz.) It forms the base of madder-lake.

Alcoholic or ethereal solution of alizarin is precipitated by oxide of zinc, (Debus.) Alizarin dissolves readily in stannotcs chloride, and in large quantity in stannous oxide mixed with potash (Gaultier & Persoz) ; it is thereby reduced. (Scbunck .) Ammoniacal alizarin forms a brown precipitate with tin-salts. (Zenneck.)

Alvzariie oj Lead, Ammoniacal alizarin produces a purple-red precipitate with acetate of lead. — a. Two- thirds ? Alcoholic alizarin is precipitated with alcoholic acetate of lead. Purple precipitate, becoming deep red on standing. (Scbunck.) b. Three-fourths ? Alco- holic alizarin feebly acidulated with acetic acid is precipitated with alcoholic acetate of lead, so that the first remains in excess ; whereupon a violet precipitate is formed, stable at 160'', insoluble in water, soluble in acetic acid and in potash. (Debus.)

According to Wolff & Strecker. According to Schunck.

Scfannck. mean.

40 C	240 .... 36-1 ....	.... 14 C	>....■ o4 ....	37-57 .... 37-23
10 H	•»•• 4 tx •••«••.. til		1-78 .... 1-64
10 O	80 .... 12-1 ....		24 ....	10-75 .... 11-67
3 PbO	336 .... 60'3 ....	PbO	112 ....	49-90 .... 49-46

2C»HH)«,3PbO .... 666 .... 1000 C"H*0»,PbO.... 224 .... 10000 .... 10000

Prepared with alizarin obtained by decomposing rubian, it gave 50-44 p. c. PbO. (Schunk.)

b. According to Wolff & Strecker. ^ ^^^t ^^^^^

60 C 360 .... 38-2 38-35

15 H 15 .... 1-6 1-97

15 O 120 .... 12-8 1206

4 PbO 448 .... 47-4 47*62

3C»H«0»,4PbO 943 .... 1000 10000

According to Debus, it is C»H»07,2Pb0.

Ammoniacal alizarin produces purple precipitates with ferrous and ferric-salts (Schunck); brown precipitates. (Zenneck.) Alcoholic and potash solutions of alizarin are precipitated dark purple by fenHc oxide, (Schunck.) Ammoniacal alizarin produces a purple precipitate with salts of copper (Schunck), a brown precipitate (Zenneck) ; and likewise with salts of mercury and gold. Silver-salts are precipitated bright violet (Zenneck)^ purple, and then reduced. (Schunck.)

Alizarin dissolves in cold and more abundantly in boiling alcohol, with yellow colour. (Schunck, Wolflf, & Strecker.) The solution turns red on the addition of a small quantity of ammonia. ^WolfF & Strecker.) It dissolves in alcohol in almost every proportion (Colin & Robiquet), at 12'' in 210 pts. of alcohol of sp. gr. 0-84. (Zenneck.) The hot-prepared

142 PRIMARY NUCLEUS C«H".

eolation does not deposit crystals on cooling, bat on dilation. (Schanck.) It is precipitated by water and by acids. (Kahlmann, Scbanck.)

Alizarin dissolves more readily in ether than in alcobol, with golden yellow colour (Colin & Robiquet, and others); at 12^ in 160 pts. ether of sp. gr. 0'73. (Zenneck.) The solution is not reddened by small quantities of alkalis^ since the compoand of alizarin with the alksui is precipitated. (Wolff &Strecker.)

Alizarin dissolves sparingly in boiling acetic acidy and imparts to it a yellow colour. (Schunck.) Dissolves slowly in cold, rapidly and more abundantly in hot glycerin, forming an intensely scarlet liquid, which deposits red flakes when mixed with water. (Arnodon, DingL pol. Joum. 147, 465.)

Alizarin dissolves in rock-oily oil of turpentiney and in fatly oiU, (Zenneck.) It produces on mordanted fabrics all the colours which can be produced by madder. (Colin, Robiquet, and others.)

Primary nucleus C*H".

Paranicene. C«»H".

St. Evre. N, Ann. Chim. Phys, 25, 503 j J.pr. Ckem. 46, 465.

Formation, (xi, 176.)

According to Gerbardt (JNT. Ann. Chim. Phys. 45, 101), Pisani & E. Kopp {Compt. Chim. 1847, 198) obtained only cblorobenzolc acid by the action of chlorine upon benzoic acid dissolved in potash, and not St. Evre's chloroniceic acid. If this opinion be correct, and St. Evre had described as chloroniceic acid a mixture of benzoic and chlorobenzoic acids, chloronicene may be identical with chlorobenzene or chloride of phenyl (xi, 173), and chloronicene with chloraniline. Nitrochloronicene would be the unknown niirochlorobenzene. It remains therefore to shew whether the formulse of paranicene, nitroparanicene, and paracinin are to be changed in a corresponding manner, and to indicate the origin of these bodies. (Kr.)

Passes over when chloroniceate of baryta or a mixture of chloroniceic acid with excess of baryta or lime, is submitted to dry distillation, after the chloronicene (C*C1*H"), and contaminated thereby, as a white sub- limate, which must be pressed between paper, carefully washed with cold ether, and passed in the state of vapour through a tube containing lime heated to redness.

Lemon-yellow, broad lamina?, of sp. gr. 1*24, and boiling at 265^ It has a penetrating taste aud smell. Vapour- density = 4-79.

			St. Evre.
			mean.
20 C 12 n	120 12	.... 90-90 . 910 .	90-77 9-04
C^H^ ..	132	.... 100*00 .	99-81
C-vapoar . H-gas		Vols. 20	Vapour-density. 8-3200
12	0-8316
Paranicene<	-vapour .	2	9-1516
		4-.5758

It is violently attacked by fuming nitrie acid and finally dissolves, depositing needles of paranicene on cooling. A small quantity of resin is formed at the same time.

Dissolves in alcohol and in ethei\

CUMINIC ALCOHOL. 143

Gmainic Alcohol.

Cr»ffH)» = C«>H",H«0».

Kraut. DistertcUum uher DerivaU de$ CuminoU und Cymens, Gott 1854; abstr. Ann. Pharm. 92, 66 ; J, pr, Chem. 64, 159 ; Pharm. Centr. 1855, 107 ; I^. Ann, Ckim. Phys. 43, 347.

Cymylic alcohol.

Formation. Prodnced by the action of alcobolic potash on cuminol at mean temperature, or more rapidly at the boiling heat.

Preparation, 1 vol. of cuminol is distilled upwards with 2 vol& of alcoholic potash for an hour ; a large quantity of water is then added, and the whole is distilled, as long as oil-drops float on the distillate. A mixture of cuminic alcohol and cymene then passes over together with alcohol and water. This is collected, shaken up with very dilute solution of alkaline bisulphite in order to remove any undecoroposed cuminol that may be present, then washed with water, dried over chloride of calcium, and distilled alone. The cymene which first passes over is collected apart, and thus separated from the cuminic alcohol which distils between 240^ and 250°. The product is purified by several fractional distillations, the first portion of the distillate being rejected.

Propeii^ies, Colourless oil, having a feeble and pleasant aromatic odour and a burning taste. Boils at 243°. Taking into accooat the correction necessary for ihe temperature of the column of mercury, it must boil at a higher tern, pcrature, probably at 270*. (H. Kopp. Ann, Pharm, 96, 23.)

Permanent in the air. Neutral.

20 C 14 H	120 14 16	.... 80*00 ... .... 9*U^ ...I .... 10*67 ....	Kraut. 79-58 9-36
•t x^ ••••••••••«••••■	1106
C?»H"02	150	.... 100*00 ...	100-00

Decompositions, 1. Cuminic alcohol is converted by nitric acid into cuminic acid. — 2. When cuminic alcohol is mixed with strong sulphuric acid, heat is developed and a brown resin is formed, which is brittle at ordinary temperatures but becomes semi-fluid in boiling water ; no con- jugated sulphuric acid is produced. — 3. It dissolves potassium with evolution of hydrogen, and on the application of heat is converted into a yellow granular mass, which is decomposed by water into hydrate of potash and cuminic alcohol. — 4. Boiled continuously for 10 or 12 hours with 5 or 6 vols, of alcoholic potash, it is almost completely converted into cymene and cuminate of potash :

3(C»H"02) + KO,HO « C»H»KO< + 2 C«HM + 4 HO. 5. Heated with chloride of benzoyl to 80% it evolves a large quantity

144 PRIMARY NUCLEUS C^U^.

of hydrochloric acid, and leaves a brown residue becomin/^ battery on cooling, probably benzoate of camyl.

Combinations. Caminic alcohol is insoluble in water. It does not unite with the alkaliuo bisulphites. It mixes with alcohol and ether in all proportions.

Cuminol.

GERnARDT & Cahours. (1841.) JV. Ann. Chim. Phyn, 1, 63; /. pr.

Chem. 23, 321 ; Ann. Phai^. 38, 67 : N. Br. ArcJi. 27, 155. Cahours. N. Ann. Chim. Pht/s. 23, 345 ; J. pr. Chein. 45, 143; abstr.

Ann. Pharm. 70, 44. Bertaonini. Ann. Pharm. 85, 275. Ghiozza. N. Ann. Chim. Phys. 39, 216. Kraut. Dissert, iiber Cuminol und Cym^n, Gott. 1854; abstr. Ann.

Pharm. 92, Q^ ; J. pr. Chem. 64, 159 ; N. Ann. Chim. Phys. 43,

347. SiEVEKiNO. DisseH. iiber Cuminol und Cymen, Gott. 1857 ; abstr. Ann,

Pharm. 106, 257; J.pr. Chem. 74, 505. J. Trapp. Pettrsb. Acad. Bull. 16, 298 ; J. pr. Chem. 74, 428 ; Ann.

Pharm. 108, 386.

Cumhuc aldehyde. Hydride qfcumyl.

Sources, Occurs together with cymene in Roman oil of cumin, the volatile oil of Cuminum cyminum. (Gerhardt & Cahours.) It exists ready formed in the seeds, and may be extracted by absolute alcohol, and, precipitated with water, after evaporation. (Gerhardt & Cahours.) Roman cumin seeds, distilled four times with water, yield 3*27 p. c. oil. (Noad, Ann. Pharm. 63, 286), 28 p. c. (Zeller, N. Jahrb. Pliarm. 1854, 1, 225.) The oil is bright golden-yellow, of sp. gr. 0*975, very mobile, and has a sharp, aromatic, and slightly bitter taste. (Bley, ^. Tr. 1 9, 1, 3.) Roman cumin oil is coloured pale yellow by a small quantity of resin, formed by the action of the air on cuminol ; hence its colour gradually deepens. It becomes acid on exposure to the air. It begins to boil at 170 , and the portion passing over at 175° contains 88*27 p. c. C, 10*83 p. c. H, and 0*88 p. c. 0 ; the portions which come over after- wards up to 230^, are progressively richer in oxygen, till at 255^ an oil passes over containing 85*88 p. c. C, 10*40 p. c. H, and 3*66 p. c. 0. (Gerhardt & Cahonrs.) Roman cumin oil is resinised by fuming nitric acid, and when treated with sulphuric acid, becomes viscid dark brownish red, and then milky on addition of water, owing to the deposition of resin. It turns greenish yellow with bromine, without undergoing further change, and dissolves iodine with brownish red colour, witbout evolving heat or detonating. It forms a liniment with caustic potash, also with ammonia. It dissolves abundantly (?) in water, and readily in alcohol and in ether. (Bley.)

Cuminol occurs also in the volatile oil of the seeds of the water- hemlock (CietUa virosa.) (J. Trapp.) Ten pounds of the seeds of this plant gave by distillation with water 2 oz. of a colourless, limpid oil, lighter than water, and possessing the odour and taste of Roman cumin seeds. When this oil is shaken with concentrated aqueous bisulphite of

CUMINOL. 145

Boda, it becomes milky and solidifies in 12 hours in a white crystalline mass of bisulphite of soda and caminol to which cymene still adheres. The cymene is removed by pressing the product between blotting paper (whereby the oil is absorbed^ and may be afterwards separated by distil- lation), and the mass is completely purified by recrystallisation from weak alcohol. (T. Trapp.)

Proration. From Roman Cumin oU. 1 . The oil is distilled in an oil-bath till the temperature has reached 200°, when all the cymene passes over together with a large quantity of cuminol j after prolonged neating, the residue consists of pure cuminol. This is distilled in a stream of carbonic acid, and preserved out of contact with the air. (Gerhardt & Cahonrs.) — 2. By submitting Roman cumin oil to repeated fractional distillation, it is divided into two parts, one boiling below lOO'' and containing almost all the cymene ; the other boiling above 190^, and containing cuminol together with small quantities of cymene and cuminic acid. When 1 vol. of the latter is shaken up with 2 or 3 vols, con- centrated aqueous bisulphite of soda, it forms a granular crystalline mass, which, after standing for 24 hours, during which time it becomes quite bard, is collected and pressed between blotting paper frequently renewed, and distilled with water and an alkaline carbonate or caustic alkali ; pure cuminol then passes over with the vapour of water.

The cymene which has passed over below 190** contains a little more cuminol, which may be sepaniited by shaking the liquid with dilute bisulphite of soda, removing the precipitate, and distilling the solution with aqueous carbonate of potash. (Bertagnini, Kraut.) — If the com- pound of cuminol with bisulphite of soda be decomposed with dilute sulphuric acid and submitted to distillation, an oil no longer capable of combining with bisulphite of soda, remains in the residue; it is therefore better to rectify alone the cuminol separated by sulphuric acid from the compound with bisulphite of soda. (Sieveking.)

Pi'operties, Colourless or yellowish oil. Boils at 220^ without decomposition, if air be excluded (Gerhardt & Cahours); from platinum, at 229*4 , or, taking into account the correction necessary for the mercury column of the thermometer, at 236-6», under 748 mm. pressure. Sp. gr. = 0"9727, at 13'4^ = 0-9832 at 0^ (H. Kopp, Ann. Pharm. 94, 317.) Vapour- density = 5' 24, but at the high temperature required for the determina- tion the cuminol decomposes slightly. (Gerhardt &c Cahours.) It has a strong smell of cumin, and a sharp, burning taste. (Gerhardt ds Cahours.)

Gerhardt & Cahoursi Jhied over chloride qf calcium, mean,

20 C 120 .... 81-08 80-89

12 H 12 .... 8-11 8-45

2 0 16 .... 10-81 10-66

C»H>20» 148 .... 10000 100-00

Vols. Vapour-density.

C-yapour 20 8-3200

H-gas 12 0-8316

O-gaa 1 1-1093

Caminol-vapoar 2 10*2609

1 5-13045

VOL. XIV.

I

146 PRIMARY NUCLEUS C^H".

DecomposUions. 1. Oxidises at mean temperature in the air,

especially iu moist air. It becomes resiniscd and acid by distillation in

vessels containing air. (Gerhardt & Cahours.) — 2. It is very slowly

decomposed by water at mean temperature^ without evolution of

hydrogen^ into cuminic acid and an oil richer in hydrogen (probably

cuminic alcohol, Kr.). (Gerhardt & Cahours.) — 3. It fuming nitric acid

be gradually dropped upon cuminol, avoiding all elevation of temperature,

till the brown colour of the mixture just disappears, the liquid on

standing deposits white crystals of cuminic acid. If he^t be applied, a

large quantity of resin and nitrocuminic acid are obtained, even if dilute

nitric acid be employed. (Gerhardt & Cahours.) — 4. Sulphuric acid

dissolves cuminol, if the liquid be kept cool, with dark red colour ; on

adding water, a brown tar is precipitated. (Gerhardt & Cahours.) —

5. It is converted by moi^t h.romine or chhrine, ip diffuse daylight, into

bromo- or chloro-cumiuol. In the sun, chlorine is taken up more freely,

probably because several atoms of hydrogen are replaced by chlorine.

(Gerhardt & Cahours.) — 6. Cuminol, evaporated with hydrochloric acid,

leaves a mixture of resin and cuminic acid. (Gerhardt & Cahours.) —

7. By pentachJoiide of phoaphojtis it is converted into chlorocuminol.

(Cahours.) — 8. Dry gateoiu ammonia converts it, after a while, into a product analogous to hydrobenzamide. (Gerhardt & Cahours.) Sieveking was unable to obtain this product. Even on prolonged contact with aqueous ammoma, it does not form crystals, but only a yellow mass, which cannot be obtained in crystals, even after solution in ether and CTaporation. (Sieveking.) Sieveking once obtained crystals by passing ammonia into alcoholic cuminol, but the quantity was too small for

analysis. — 9. Its alcoholic solution is converted by nUphide of ammonium into thiocumol, C'^H*'^^ (Cahours, Compt. rend. 25, 459.) — 10. Potas- sium acts but slightly in the cold on cuminol, becoming dull but not evolving any gas-oubbles. On gently warming the tube, a violent action ensues, hydrogen is evolved in large quantity, and cuminol -potassium formed. (Gerhardt & Cahours.) — II. Wbei) cuminol is dropped on fused hydrate of potash, each drop as it comes in contact ^ith the potash, turns first red, then white, and solidifies, forming cuminate of potash. (Gerhardt & Cahours.)

C»H"02 -t- KO,HO = C»H"KO^ + 2 H.

When a piece of hydrate of potash is covered with cuminol and a gentle heat applied, it becomes covered with a gelatinous cauliflower-like mass (witbout evolution of hydrogen), which, on being separated from the potassium and pressed between paper, deposits, in contact with water, cuminol (cuminic alcohol, according to Kraut), while cuminate of potash remains in solution. (Gerhardt & Cahours.) It is decomposed by aqueous potash (Gerhardt & Cahours), and more rapidly by alcoholic potash (Kraut), without evolution of hydrogen, into cuminate of potash and an oil (Gerhardt & Cahours) ; into cuminic alcohol. (Kraut.)

2C»H«0« + KO,HQ « C»H"0* + C»H"KO^

Decomposition with evolution of hydrogen also takes place when cuminol is acted upon by fused potash not too strongly heated. (Gerhardt & Cahours.) — In this reaction, cymene is liberated, the cuminol being first decomposed into cuminate of potash and cuminic alcohol, and the latter further decomposed into cuminate of potash and cymene. (Kraut.) — 12. By a mixture of bichromate of potash and sulphuric acid, it is con- verted into cuminic acid (Gerhardt & Cahours) ; if the action be prolonged.

I

CUMINOL. 147

insolinic acid is formed (xiii, 318). (Hofmann, Ann. Phann. 07, 207.)

By heating Roman cumin oil with chromate of potash and snlphnric add| Persoz obtained cyminic and cumino-cyminic acids, the first being identical with cnminic acid« the second with insolinie acid. {Compt, rend, 13, 431.) — ]3. By the action of cyanide qfpotaetmm on cuminol, Gerfaardt & Cahoars onoe obtained a product analogous to benzoin, which, however they were unable to produce again.-— 14. Heated with chloride qfcumyl, it forms cumyl. (Chiozza.)

CombincUions, With Potamum, Cuminolrpotauium. When camiool IS carefully heated with a slight excess of potawium, a yiolent reaction, accompanied by abundant evolation of hydrogen, takes place, and the whole of the cuminol is converted into gelatinous cuminol-potassium. (Gerhardt & Cahours.^ Chiozxa heats cuminol with potassium in a covered platinum crnciole, presses the product between blotting paper^ and places it in vacuo over sulphuric acid, which absorbs with avidity the adhering cuminol. — According to Gerhardt & Cahours, it is also produced by the action of fragments of caustic potash on cuminol at ordinary temperatures (p. 146).

It is decomposed by water into cuminol and hydrate of potash, and rapidly converted by moist air into cumin ate of potash. (Gerhardt & Cab ours.) With chloride of cumyl, it forms chloride of potassium and cumyl; with chloride of benzoyl a similar product, which is rapidly converted by aqueous potash into cumyl. (Chiozza.)

With Bisulphite of Ammonia* When Roman cumin oil (mixture of cymene and cuminol) is mixed and shaken up with aqueous bisulphite of ammonia of 29° B., it forms almost immediately a crystalline mass, which, when separated from the mother- liquid and dissolved in boiling alcohol, deposits after a time beautiful groups of needles. (Bertagnini.) If the compound is kept in a sealed glass tube in the dark, it remains unchanged for several months, and then turns yellowish, probably from spontaneous decomposition. (Bertagnini.)

With Bisulphite of Potash. When Roman cumin oil is gently warme with aqueous bisulphite of potash of between 28° and 80° B., a large part of it dissolves, and is deposited on cooling in brilliant lamince of the com- pound of bisulphite of potash and cuminol. The undissolved portion yields all its cuminol when shaken up with fresh quantities of bisulphite of potash^ so that only cymene remains. (Bertagnini.)

The compound is decomposed by water. Heated in a test tube, it evolves sulphurous acid and cuminol. It dissolves in water containing a small quantity of a bisulphite^ without decomposition, even when heat is applied. It is insoluble in concentrated solutions of the alkaline bisul- phites. (Bertagnini.)

With Bisulphite of Soda, Roman cumin oil, shaken up with aqueous bisulphite of soda of 27° B., forms a buttery mass, becoming hard m the course of a few hours. This is separated from the mother-liquid, and dissolved in very dilute boiling alcohol ; whereupon it crystallises from tho solution on cooling, in needles which may be purified by reorystal- lisation from dilute alcohol. (Bertagnini.)

Brilliant, white, inodorous needles (bulky, nacreous scales : Trapp), which turn yellow on prolonged exposure to the air (Bertagnini) ; they effloresce in the air. (Trapp.) When heated, it evolves sulphurous acid

L 2

148 PRIMARY NUCLEUS C»H".

and cuiniaol, and leaves sulphite of soda and charcoal (Bertagniui.) It is decompose<l by boiling water, depositing a white powder, and forming a tnrbid milky liquid. (Trapp.)

Tt is decomposed by (aqueous 1) ammonia ; after prolonged contact, a thick oil is precipitated, probably resembling the oil produced from cuminol by ammonia. (Sieveking.) Insoluble in cold water. (Trapp.) Dissolves in water containing a small quantity of a sulphite, especially with the aid of heat. The solution is decomposed by heating with bases or acids. It is decomposed by iodine or bromine, with formation of sulphuric acid and separation of cuminol ; an excess of bromine forms a crystalline, easily fusible substance, which combines with bisulphites and is probably bromide of cumyl (bromocuminol ?). (Bertagniui.)

It does not dissolve in concentrated solutions of the sulphites, or (slightly, Trapp) in cold alcohol or in ether. (Bertagniui.)

NaO 20 C ... 15 H ...

2 S

10 o ..

		Bertagnini.
		tnean.
31	.... 11-48 ..	11-84
120	.... 44-44 ..	44-71
15	.... 5-55 ...	...., 5-33
32	.... 11-85
80	.... 26-68

C»Hi202,NaO,2S02 + 3Aq 278 .... 10000

Cuminol prepared from the seeds of the water-hemlock contains 8*67 p. c. Na (calculation « 8-52 p. c). (Trapp.)

Guminic Acid.

C»°H»0* = C«>H» 0* '

Gerhabdt & Cahours (1841). N, Ann. CMm, Phys. 1, 70; J, pr.

Chem. 23, 329 ; A7in, Pharm. 38, 76. Persoz. Compt, rend. 13, 431 ; J, pr. Ckem. 25, 55 ; Ann. Pharm. 44,

311. Gbrhardt. Compt. chim, 1, 75 ; JN', Ann. Chim. Phys. 37, 404 j Ann,

Pharm. 87, 77. Cahours. Compt. rend^ 24, 554 ; iV. Ann, Chim. Phys. 25, 36 ; Ann.

Pharm. 69, 243; N. Ann. Chim. Phys. 23, 347; J. pr. Chem. 45,

144; abetr. Ann. Pharm. 70, 45; JV'. Ann. Chim. Phys. 52, 201. Fr. Field. Ann. Pharm. 65, 51 ; Mem. Chem. Soc. 3, 408 ; J. pr. Ckem.

44, 136. A. W. HoFMAi9N. Ann. Pharm^ 74, 344; farther, 97, 197. CiiiozzA. iV. Ann. Chim. Phys. 39, 219. Kraut. Dissert, uher Cuminol und Cym^n, G&tt. 1854 ; Ann. Pharm,

98, 366 ; N". Br. Arch. 96, 274.

Acide cunUnique. — Acide epminique (Persoz), CumtruHure. Discovered by Gerhardt 8c Cahours. The acid observed by Chevalier (z, 109) in Roman camin oil which had become add by exposure to the air was, doubtless cuminic and not saodnic acid. (Kr.)

Formation. Produced by the oxidation of Cuminol by air, moist bromine or chlorine^ nitric acid or chromic acid; \vith evolution of

CUMINIC ACID. 140

hydrogen, whon caminol is fused with hydrate of potash. (Gerhardi & Cahours.) With simultaneous formation of cuminic alcohol (Kraut) : by the actiott of water^ or of aqueous (Gerhardt & Cahours), or alcoholic potash on onminol. — From cuminic alcohol^ by oxidation with nitric acid ; hjr fusing it with hydrate of potash, hydrogen being evoWed ; by boiling it with alcoholic potash, cymene being simultaneously produced. (Kraut.)

Preparation. Hydrate of potash is fused in a retort, into the tnbulus of which a funnel-tube, drawn out to a fine point, has been fitted, and cuminol or Roman cumin oil is gradually dropped into the retort, each drop becoming solid and white as it comes in contact with the hydrate of potash, while (if Roman cumin oil be used) cymene distils over. When all the cumin oil is decomposed, the residue is dissolved- in water, and any unvolatilised cymene that may be present is removed with a pipette. Kitrio acid in slight excess is then added, whereby cuminic acid is precipi- tated in white or yellowish flakes ; these are collected on a filter, washed and fused in a dish ; the fused mass, which solidifies on cooling, is separated from adhering water and distilled per se ; and the distillate is crystallised from alcohol. — If it is not required to coUeet the cymene, the Roman cumin oil may be dropped on potash fused in a dish, whereby the operation may be more rapidly conducted. (Gerhardt & Cahours.)

When the hydrate of potash is fused in glass retorts, the vessels are rapidly corroded; and the use of an open dish occasions much loss from the volatilisation of cuminol; it is therefore preferable to decompose Roman cumin oil with alcoholic potash, so that the cuminic alcohol at first formed may be completely decomposed into cuminic acid and cymene (Kr.) — Persoz heats Roman cumin oil with a mixture of 5 pts. bichro- mate of potash, 11 pts. oil of vitriol, and 40 pts. water, whereby a distillate containing acetic acid and a mixture of cuminic and insolinic acids is obtained (xiii, 319), and is separated by alcohol, in which inso- linic acid is insoluble.

Properties. Beautiful, white, tabular prisms. (Gerhardt & Cahours.) (Rhombic, according to Persoz.) Melts at 1 15°. (Persoz, Gerhardt.) In the earlier inTestigations of Gerhardt and Cahours, its melting point was found to be 92°; but this add contained cymene. (Gerhardt, Compt, rtnd. 20, 1443.) — It floats on boiling water as a colourless oil, which solidifies on cooling. Boils above 250°, but volatilises with the vapour of water. Sublimes readily without decomposition in beAutiful long needles. The vapour has an acid sufibcating smell. Tastes strongly acid (it is tasteless, Persoz), and has a faint odour of bugs. (Gerhardt & Cahours.)

Gerhardt* Hofmann. Gerhardt. Cahours. Ory$tali. mean.

20 C 120 .... 73-17 73-12 .... ^2-66 .... 72-91

12 H 12 .... 7-32 7-53 .... 7*37 .... 7-38

4 O 32 .... 19-51 19'35 .... 19-97 .... 19-71

C»H"0^ 164 .... 100-00 100-00 .... lOO'OO .... 10000

Hofmann analysed cuminic acid which had passed unchanged through the system into the urine; Gerhardt the acid obtained from aceto .cuminic anliydride. It is isomeric with eugenic acid.

150 PRIMARY NUCLEUS C^WK

Decompositions. 1. Cuminic acid is converted by boiling faming jiitric acid (and bj cold nitrosalphario acid : Krant) into nitrocaminic acid j by beated nitrosidphuric acid, into binit1*ocuminio acid. (Cahours.) — - 2. By pentuchhride of phosphorus, into chloride of cumyl. (Cahours.) Its soda-salt mixed witn terchloride of phosphorus loriiis chloride 6{ cumyl and phosphite of soda. (Gerhardt.) Cklorophosphoric acid converts cuminate of soda into cuminic anhydride. (Gerhardt.) — 4. By boiling with bichromate of potash and sulphuric acid, it is con- verted into insolinic acid. (Hofmann.) — 5. By dry distillation with excess of caustic baryta^ it is decbmposed into carbonate of baryta and cymene. (Gerhardt Sc Cahours.) — 6. It t>asse8 through the system unchanged into the uHbe. (Hofmann.) — 7. The potash-salt heated with bromide of cyanogen yields cumonitHle and bromide of potassium. (Cahours.) — 8. The soda-salt heated with chloride of acetyl^ benzoyl, or cumyl, forms the corresponding cdtijugated anbydtide. (Gerfaatdt.)

Combinations, The acid is sesreely soluble in cold tMter, slightly in boiling water, from which it is deposited on cooling. (Gephardt & Cahours j Persoz.) — It is more soluble in acidulated water, hence it must not be precipitated with too much nitric acid. (Gerhardt and Cahours.)

Dissolves in strong sulphuric acid without coloration. If the acid has not been purified by sublimation and then by crystallisation from alcohol, it still contains an oil, and turns red with sulphurie acid. (Gerhardt A Cahours.)

Cuminic acid forms salts with bases : Guminates, They resemble the benzoates. (Persoz.) -« It deeomposeff the alkaline carbonates. (Ger- hardt & Cahours.)

Cuminate of Ammonia. Friable tufts, becoming dull in the air, probably from loss of ammonia. (Gerhardt & Cahours.) It is decom- posed by heat, partly into cuminic acid and ammonia, partly into cumin- amide and cumonitrile. Heated in a sealed tube, or heated almost to fusion for a long time in a retort, it is for the most part principally converted into cuminamide, and when rapidly distilled, into cumonitrile. (Field.)

Cuminate of Potash. lU-definedj deliquescent crystals. (Gerhardt & Cahours.)

CumincUe of Baryta, Carbonate of baryta is decomposed by cuminic acid. The concentrated solution, filtered hot, deposits immediately on cooling, nacreous scales, each of which at the moment of its formation exhibits the prismatic colours. Tastes very bitter; dissolves readily in alcohol and in ether. (Gerhardt & Cahours.)

Ba 20 C 11 H	Dried at 100-. 68-6 .... 29-61 120 .... 51-82 11 .... 4-76	Gerhardt & Cahoturs. 29-88 51-41 4-81
4 O	32 .... 13-82	13-90
C»H"BaO*	231-6 .... 10000	10000

CumincUe of Copper. Greenish powder, becoming stongly electric by pressure. Remains unchanged at 250^ Melts at 260", and swells

OXYCUMINIC ACID. 151

up slightly, without volatilising. The residue contains a small quantity of metallic copper, cuminic acid, cuprous cuminate, and a copper- salt, which, when decomposed by acids, deposits a semi-fluid oil. (Chiozza.) By dry distillation, it yields cuminic acid and cymene. (Kraut.)

OwminaJte of 8Uvei\ Nitrate of silver gives with cuminate of ammonia a white curdy precipitate which rapidly blackens in the light. Subjected to dry distillation, it yields carbonic acid and cuminic acid (part of which is decomposed into carbonic acid and cymene), and leaves a residue of charcoal and carbide of silver^ the latter remaining unchanged even when the salt is ignited in the air.

Gerhardt & Cahoars. Dried at \W. mean.

Ag 108-1 .... 39-87 40-06

20 C 120-0 .... 44-22 44-19

11 H 110 .... 405 411

4 0 32-0 .... 11-86 il-64

C«H"AgO< 271-0 .... 100-00 lOO'OO

When prepared with cuminic acid obtained by acting on cuminic alcohol with nitric acid^ it contains 39-69 p. c. Ag. (Kraut.)

Cuminic acid is readily soluble in alcohol and ether, and crystallises from the solutions by evaporation. (Gerhardt & Cahours, Persoz.) It dissolves in warm glacial acHic acid in all proportions, and crystallises therefrom on cooling. (Persoz.)

Ozycmninic Acid.

Cahours. N. Ann. Chim. Phys. 53, 838 ; Ann. Pharm. 109, 20. Acide o^ycuminique.

Formation and Preparation. Amidocuminic acid is dissolved in excess of moderately concentrated nitric acid, and nitric oxide is passed through the solution ; whereupon nitrogen gas is evolved, and, after pro- longed action, oxycuminic acia is obtained.

Properties, Small, yellowish brown prisms.

20 C 12 H	120 .... 12	.... 66-66 . 6-66 . .... 26-68 .	Cahours. 66-18 6-81
6 O	... 48	27-01
C20HUO« ....	.... 180	.... 100-00 ..	10000

It bears the same relation to cuminic acid aa glycolic (xii, 508) to acetic acid, Dissolves sparingly in cold, readily in boiling water.

152 PRIMARY NUCLEUS C»H".

Combines with salifiable bases, forming compounds some of whic crystallise well.

Oxycuminate of Silver. Yields on ignition 37 '41 p. c. Ag, corre- sponding to the formula C^AgH"0^ whicn requires 87*63 p. c. Ag.

Oxjonminic acid is more readily soluble in (dcohcl than in water.

Chlorocnmol.

C»H»C1« = C*>H» a*.

Cahours. (1848.) N. Ann. Chim. Fhys. 23, 345 ; J, pr. Chem, 45,

143 ; abstr. Ann, Pharm. 70, 44. J. P. SiBYEKiNO. Dissert, iiber Cuminol und Oymen, Qott. 1857 ; abstr.

Ann. Pharm. 106, 258 ; J. p7\ Chem. 74, 505. J. TUttschepp. Petersb. Acad. Bull. No. 392 ; J. p\ Chem. 75, 370;

abstr. Eep. Chim. pure. 1, 268.

ChloroewmnoL

Formation and Preparation. Pentachloride of phosphorus reacts

violently and rapidly on cuminol ; the mixture becomes hot, and yields

by distillation oxychloride of phosphorus boiling at 111", and chloro-

cumol, leaving bat a small residue. The portion distilling between

250° and 265° is collected apart, washed with water and dilute potash

till all traces of oxychloride of phosphorus have been destroyed; then

again with water ; afterwards dried over chloride of calcium and rectified.

(Cahours.) In tlie action of pentachloride of phosphoroa on cuminol, charcoal ia deposited. (TUttscheff.) If the product obtained from equal numbera of atoms of pentachloride of phosphorus and cuminol be heated to 150 , after the oxychloride of phosphorus has distilled OTcr, it blackena, cToWes large quantities of hydrochloric acid« and on being further heated to 250** or 260% yields scarcely any chlorocnmol. It is therefore preferable to place 5 pts. pentachloride of phosphorua in a tubulated retort, into the tubulus of which a glass tube is fitted by means of a perforated cork, and to connect with this a dropping burette, by which 2 pts. cuminol may be introduced by small portions. After the action has ceaaed, the whole is heated to 150% or till almost all the oxychloride of phosphorus has passed over, and the residue is mixed with water ; whereupon the chlorocumol is deposited at the bottom of the vessel. This is collected, carefully separated from adhering water, and distilled by itself. The portion distilling between 250** and 260% amounting to | ths of the cuminol employed, is collected apart. (Siereking.)

Properties. Limpid liquid, heavier than water. (Cahours.) Boils between 255° and 260° (Cahours) at 255"^, with slight decomposition, evolving hydrochloric acid and depositing charcoal. (Tiittscheff.) It smells like chloride of benzoyl (Cahours); penetrating, and not disagree- able. (Sieveking.)

Cahours.

20 C 120 .... 69-11 6001

12 H 12 .... 5-91 611

2 CI 71 .... 34-98 34-18

C="H'2Cl' 203 .... 10000 100-30

ACETATE OF CUMOGLYCOL, 153

Decompogitions. 1. Heated with alcobolio ammonia in a sealed tube, it forms chloride of ammonium and a thick yellow oil (Sieveking.) — 2. It does not appear to be decomposed by aqueous potash, (Cahours.) *— d. With hydrosulphate of potassium, it yields chloride of potassium, and a yiscid product of repulsive odour. (Cahours.) — The alcoholic solution, treated for some time with sulphide of ammonium, yields a dark red resin soluble in ether. (Sieveking.^ — 4. By freshly precipitated oxide of silver it is conyerted into cuminol. (TiittschefiN) — 5. When 2 At. ethylate of soda are heated with 1 At. chlorocnmol, chloride of sodium and a red liquid are obtained. When this product is distilled, first alcohol, and then, between 170° and 238% an oil passes over, which behayes with alkaline bisulphites like cuminol. ^Sieyeking.) — 6. With acetate ofsUver, it forms acetate of cumo-glycol (Sieyeking); with henzoate of silver, henzoate of cumofflycol. (TUttscheff.)

Insoluble in waier, (Cahours.) Readily soluble in alcohol and in ether. (Cahours.)

Conjugated compounds of the Primary Nucleus, C*°H^'.

Acetate of Gumoglycol.

C»H»K)» = 2C*HK)»,C»H"0«.

J. P. SiETBKiNa. (1857.) Dissert, uher Cuminol und Cym/en, Gott, 1867; Ann. Pharm. 106, 258 ; /. pr. Chem. 74, 505.

Acetate qf CumyUne. Bssigsdure Cumol-ather,

Preparation. Chloroeumol is mixed with excess of acetate of silyer, and the reaction, which immediately ensues^ is finally aided by a gentle lieat. The product is treated with ether ; the solution eyaporated ; and the residue washed with aqueous carbonate of soda, and crystallised from ether, whereby yellowish crystals, contaminated with an oil, are obtained.

Properties. Colourless crystals, resembling the swallow-tail crystals of gypsum. Melts at a moderate heat, and diffuses a powerful odour of acetic acid and cuminol.

28 C 18 H	168 .... 67-2 .. 18 .... 7*2 ..	Sieveking. titeofia 70-7 7-6
8 O	64 .... 25*6 ..	21-8

2C<H»0>,C»H»0* .... 250 .... 100-0 100*0

It gave too miiGh carbon in the analyds, owing to the presence of an oil.

154 CONJUGATED COMPOUNDS OF THB PRIMARY NUCLEUS C»H".

fienzoate of Cumoglycol.

C«H»o» = 2C**H»0',C^ri"0«.

J. TiJTTSCHRFP. Petersb. Acad. Bull. Ko. 392 ; J. pr. Chem. 75, 3t0. Bibenzoate qf Cumol; henzoate qf CUmplene,

Fo7*7nation and Preparation* Seven pts. chlorocuinol are mixed in a porcelain dish with 16 pts. benzoate of silver ; the. mass thereby formed is treated with ether, which leaves the chloride of silver undissolved ; and the resulting solution of benzoate of cumoglycol is left to evaporate spontaneously, whereupon a brownish yellow oil, solidifying in crystals in a few days^ is deposited. This is pressed between paper, washed with aqueous ammonia, and recrystallised alternately from ether-alcohol and absolute alcohol.

Properties. Brilliant, colourless needles, melting at 88°, and solidify- ing in crystals on cooling.

Tlittscheff. Needles, metm,

48 C 288 .... 77-01 76-94

22 H 22 .... 5-88 5-98

8 O 64 .... 1711 17-13

2C"H«0»,C»Hi202 374 .... lOO'OO 100-00

Decompositions, it cannot be volatilised without decompositioii. — 2. It is dissolved by cold sulphuric acid with dark redcoloiir ; the solution blackens by boiling. — 3. It is not attacked by boiling nitric add, — 4. It is not affected by ammonia or by concentrated baryta-water. — 5. Distilled with caustic potash, it yields benzoate of potash and cnminol.

Dissolves in alcohol, especially in warm strong alcohol, and is precipi- tated by water. Dissolves readily in ether, a^tene, and chloroform*

GumyL

Q40H»o* = C*°H"(C*'H"0')0».

Chiozza. (1852.) Compt. rend. 35, 225; Ann. Pharm. 84, 102; J. pr. Chem. 57 J 178 ; in detail, N'. Ann. Chim. Phys. 39, 216.

Cumyle.

FormaJtion. 1. By heating cuminol with chloride of cnmyl. The reaction takes place only at a high temperature, at which the hydro- chloric acid evolved further decomposes the cumyl and tarns it brown. — 2. Cuminol-potassium is heated with chloride of cumyl. — 3. Cuminol- potassium is acted upon by chloride of benzoyl, whereby an uncrystal- lisable oil is formed, which, when heated with aqueous potash, yields cumyl together with other products.

CUMINATE OF ETHYL. 155

Preparation, To freshly prepared caminol -potassium (p. 147), an eqniyalent quantity of chloride of cumyl is added ; whereupon the mixture liquifies^ and when gently heated, becomes pasty, and deposits chloride of potassium. The excess of chloride of cumyl and any cuminio anhydride that may hare been formed are removed by washiufi^ the product with weak potash ; the mixture is shaken with ether, which takes up the cumyl ; the ethereal stratum is decanted, and dried over chloride of calcium ; and the ether is evaporated over the water-bath.

Properties. Viscid oil. Cooled to— 18° in a freezing-mixture, it solidifies in a clear, uncrystalline mass. Heavier than water. It has a faint odour at ordinary temperatures^ and an agreeable odour of geraniums when heated.

40 C

22 H 40

		Chiozza.
		a, 6.
		mean.
240 ....	81-6 ....	.... 80-55 .... 81-5
22 ....	/ 9 ...a	• a.. i'ntj .... 7'0
VM ...a	10-9 ....	.... 11-48 .... 10-7

C«H»0* 294 .... 100-0 10000 .... 100-0

a was obtained by method 2, b by method 3.

Decompositions. 1. Cumyl takes fire with difficulty and burns with a smoky flame. — 2. Heaied above 800°, it decomposes with ebullition, into cuminic acid and other products poorer in oxygen, leaving a residue of charcoal. — 3. It is attacked by cold strong sulphuric acid, and on heating the mixture, it blackens and gives oflT sulphurous acid. — 4. Dis- solves in fuming nitric add without evolving red vapours, and on addition of water, a yellow, neutral, Roft resin is deposited, with which flakes of cuminic acid mix as the liquid cools. — 5. Gently warmed with fragments of caustic potash, it is decomposed into cuminol and cuminate of potash. Alcoholic potash exercises the same action. It is likewise attacked by aqueous potash, but more slowly, and when boiled with it, is converted into an oil containing 816 p. c. C & 8*6 p. c. H.

It is scarcely soluble in cold^ readily in boiling alcohol.

Cuminate of Ethyl.

C~H"0* = C*H»0,C«>H"0>.

Geruardt & Cahours. (1841.) N, Ann, Chim. Phys. 1, 77. Cahours. N, Ann. Chim. Phys. 28, 348.

Cuminic ether, Ether cuminique, Cuminvinester.

IbiTnation and Preparation, 1. A solution of cuminic acid in abso- lute alcohol is saturated with gaseous hydrochloric acid ; the chloride of ethyl and excess of alcohol are expelled by heating the liquid on a water bath; the ether is distilled ofi*; and the distillate is washed with carbonate of soda and rectified over oxide of lead. (Gerhardt & Cahours.) —

156 CONJUGATED COMPOUNDS OF THE PRIMARY NUCLEUS 0»H»,

2. When chloride of cum jl is aclcled to strong alcohol, the mixture becomes hot, and on addition of water, deposits cuminate of etbjl. (Cahours.)

Pi'operties, Colourless liquid. Lighter than water. Boils at 240°. Vapour density = 6*65. It has a yer^ agreeable odour of pippins.

24 0

16 H

40

		Gerhardt & Cahonrs.
144 ....	75-00	74-45
16	8-33	8-65
a ....	16-67	16-90

C^H«0,C»H"03 .... 192 .... 100-00 100-00

Vols. Density.

C-Tapoar 24 9*9840

H-gaa 16 M088

O-gaa 2 2-2186

Ether-yapour 2 13-3114

1 6-6567

Decompositions, The vapour is readilj inflammable, and bums with a blueish flame. — Heated with potash, it yields alcohol and cuminate of potash. (Gerhardt & Cahours.)

Insoluble in tvcUer. Dissolves in every proportion in aloohol and in ether, (Gerhardt k Cahours.)

Acetocuminic Anhydride.

C«*H"0* = C*H»0»,C«H"0».

Gerhardt. (1852.) Conipt* rend, 34, 904; Ann, Pharm, 83, 114; iu detail, N. Ann, Chim, Phys, 37, 304 ; Ann, Pharm, 87, 82.

Cuminate acitique. Acetate cuminique, Anhydrous Cuminacetie Acid,

Obtained in the same way as acetobenzoio anhydride (xii, 05), from cuminate of soda and chloride of acetyl.

Properties, Neutral oil having an agreeable odour of Spanish wine. Heavier than water.

Cahoari.

24 C 144 .... 69-90 70-14

14 H 14 .... 6-80 6-93

6 O 48 .... 28-30 22-93

C*H»C)»,C»H"08 .... 206 .... 100-00 100-00

Decompositions. 1. When moist, it rapidly becomes acid, depositing laminsB of cumin ic acid, and difiusing an odour of acetic acid. — 2. It is decomposed by distillation into acetic anhydride and cnminic anhydride. ^- 3. By alkalis it is converted into a mixture of cuminate and a<:etate.

CUMINATE OF PHENYL. 157

Cuminate of Phenyl,

C»H"0* = C»H»0,C?»H"0».

Williamson & Sorugham. Phil. Mag. 7, 870 ; Chem. Gag. 1854, 193 ;

Ann. Pharm. 92, 316 ; J. pr. Chem. 62, 365 ; Pharm. CerUr. 1854,

506 ; y. Ann. Chim. Phy%. 41, 491. Kraut. Dissertation, Gbtt. 1854 j N. Br. Arch. 96, 272.

Cuminsaure'CarbohoMrej CumyUphenyl,

Formation. By the action of chloride of cnmyl on phenylate of potash. (WilHamBon & Scrugham.) — By the dry distillation of cumo- salicylic acid, or of a mixture of chloride of cumyl and salicylate of soda in equal nomhers of atoms. (Kraut.)

Preparation. 16 pts. salicylate of soda are heated with 18j- pts. chloride of cumyl in a retort, at first gently, till the mixture has become pasty and the odour of chloride of cumyl has disappeared, then more strongly, as long as oil continues to pass over. The distillate is heated to boiling with dilute aqueous potash, whereupon cuminio and carbolic acids dissolve in the potash, and cuminate of phenyl is deposited on cooling as a crystalline mass which is purified by washing, freezing, and repeated recrystallisation from alcohol. (Kraut.)

Properties. Long, white needles, melting between 57° and 58^. Distils withont decomposition. It has an agreeable odonr, resembling that of benzoate of phenyl, especially when heated.

Kraut.

32 C	192 16 32	.... 80*00 .... 6'60 ... .... 13'40 ...	mean. 80*58
16 n. *..«^«.«**a«««*«*aafl*«**	6*87
4 O	12-55
C^«H»0,C»H"C ....	240	.... 100-00 ...,	100-00

Decompositions. 1. When a mixture of cuminate of phenyl and nitrate of soda is heated with strong sulphuric acid, binitrocuminic acid (and probably nitrocuminic acid) is formed. (Kraut.) — 2. It is resolved by strong sulphuric add into cuminic acid and sulpho-carbonic acid. (Rrant.)— '3. It is not decomposed by aqneous potash, but alcoholic potash decomposes it, yielding cuminate and pnenylate of potash. (Krant.)

It is insoluble in water. Dissolves readily in hot alcohol and in ether.

Benzo-cnmmic Anhydride.

C»*H"0« = C^H»0»,0»H"O».

Gerhardt. (1852.) Ann. Pharm. 82, 114; N. Ann. Chim. Phys. 37, 285 ; Ann. Phai-m. 87, 79.

Anhydrous Bensocutmnic acid, Cfummate qf benzoyl, Benmoats qf cumyl, Was* ser/reie Bemoes&ure-Cuminsdure.

Preparation. 20 pts. dried cuminate of soda are heated in a retort with 15 pts. chloride of benzoyl, till the odour has disappeared ; afteir

158 CONJUGATED COMPOUNDS OP THR PRIMARY NUCLEUS C«H«

which the whole is allowed to cool. A thick^ almost colourless syrnp is thus obtained, which is warmed with water to dissolye out the chloride of sodium ; whereupon the benzo-cuminic anhydride collects at the bottom of the vessel as an oil. This is washed first with aqueous carbonate of soda, then with water, and after pouring oflf the water, dissolved in ether and gently warmed till the ether and adhering water have evaporated.

Properties. Thick, almost colourless, and inodorous oil. Sp. gr. = l']]5at2d^ Heated in open vessels, it appears to volatilise without decomposition, and yields very pungent vapours.

34 0

16 H

60

		Gerbardt.
204 .... 76-12 ..	75-89
16 ..	5-97 ..	618
48 ..	.. 17-91 ..	17-93

C»H»0»,C»H"0* 268 .... 100-00 10000

Decompositions, 1. When kept vnoist, it turns acid. 2. It cannot be distilled without decomposition, but yields an acid, buttery distillate solidifying in the neck of the retort. 3. Ammonia converts it into bensamide, or benzoate of ammonia, aud cuminamide. 4. By alkalis it is converted into a mixture of benzoate and cuminate.

Gumosalicyl.

C^H^W = C"H»0>,C»°H"0'.

CAHOtTRS. Compt, rend, 44, 1252 ; Ann, Pharm, 104, 109; in detail, N, Ann. Ckim. Phys. 52, 197; Ann, Pharm. 108, 317.

Cumoialicyle.

Formation and Preparation. Chloride of cumyl does not act in the cold on salicylous acid ; but on applying heat, abundance of hydrochloric acid is evolved, and solid cumosalicyl is formed, which is purified by pressing between blotting paper, washing with warm aqueous potash and boiling water, and repeated recrystallisation from strong alcohol.

Properties. Brilliant, colourless, friable prisms> melting at a gentle heat to a clear oil, and solidifying on cooling.

Cahours.

34 C 204 .... 761 75-79

16 H 16 .... 5-9 5-97

6 0 48 .... 18-0 18-24

C"H»08,C»H"03 268 .... 1000 10000

It is attacked by chlorine, bromine, 2aidi fuming nitric acid, giving rise to cry stall isable products. It is not attacked by solid caustic pot^tsh or by aqueous potash, either in the cold or when heated.

Insoluble in cold, slightly soluble in boiling toaier.

Dissolves in alcohol^ especially in warm alcohol. Dissolves readily in ether.

CUMINIC ANHYDRIDE. 159

Guminate of Mefhyl-Balicyl.

C»H«0» = C»IPO,C«>H"0»,C"H*0*.

Oerhardt. (1854.) C(mpi, rend. 38, 32; Ann, Fharm. 89, 3G2j Chetn, Centr. 1854, 131; TraiU, 3, 327.

Cumintaure MethylsalicyUdure.

Wbea chloride of cumyl is heated with salicylate of methyl, a viscid oil is ohtained, which crystallises when mixed with ether, and eyapo- rated.

FropeHies. Crystallises from alcohol in very hrllliant laminae, and from ether, by spontaneous evaporation, in thick, oblique prisms. It is deposited from its hot saturated alcoholic solution as an oil which remains fluid for a long time.

Insoluble m vnUer^ slightly soluble in cold alcohol. Very soluble in rf/*er.

Oenantho-cmninic Anhydride.

C»*H»*0« = C"H"0«,C»H"0«.

Chiozza & Malerba. Ann. Pharm. 91, 102; Chem. Centr, 1854, 793; J, pr. CJiem, 64, 32.

Cumyi'Oenanthylal, Anhydrous Oenantho-cuminic acid, Oenanthylate qf Cumyl,

Obtained by the action of chloride of cumyl on oenanthylate of potash.

Colourless oil, smelling feebly of apples and slightly aromatic in the cold. Lighter than water. Heavier than water (Chiozza & Malerba). (Ger- hardt, Traits, 3, 601.) When heated, it yields vapours which attack the organs of respiration.

Chiossa 8c Malerba.

34 C 204 .... 73^91 74-0

24 H 24 .... 8-69 8-2

6 0 48 .... 17-40 17-8

C'nrW,C?»H"0» 276 .... 100-00 100-0

Cuipinic Anhydride. C*>H«0» = C«»H"0*,C»H"0».

GERnARDT. (1852.) Compf. rend, 34, 904; Ann. Pharm. 83, 114; more detailed, N, Ann, Chim. Phyi, 37, 304; Ann, Pharm, 87, 77.

Anhydrous cuminic acid, Cuminate cuminique.

Formation, 1. By the action of chloride of cumyl on cuminate of ^<lft* — 2. Py the action of oxychloride of phosphorus on cuminate of

160 CONJUGATED COMPOUNDS OP THE PRIMARY NUCLEUS CnV'K

soda, — 3. Aceto-cuminic anhydride is resolved by distillation into acetic anhydride and cuminic anhydride.

Preparation, Similar to that of benzo-caminic anhydride (p. 157). The ethereal solution is generally rendered milky by chloride of sodium ; This is removed by evaporating the solution and again treating the residue with ether.

Properties. Viscid, almost colourless oil, solidifying in crystals after a time. Tasteless. It has a faint odour like the ethers of the fatty acids. Neutral.

40 C

22 H

60

		Gerhafdt
		oil, aolidijied mvM.
240 ....	77-42 ....	.... 77-43 .... 77-35
22 ....	7-10 ....	.... 7-15 .... 7-17
48 ....	15-48 ....	.... 5-42 .... 15-48

C«H"0»,C»H»0» ,.. 310 .... 100-00 10000 .... 100-00

Decompositions. Exposed to moist air, it gradually becomes filled with brilliant laminae of cuminic acid, into which it is at last completely converted. — By aqueous ammonia it is gradually converted into solid cuminamide.

Cuminaric Acid.

C»*NH"0« = C«AdH"0«,0*. Cahours. N. Ann. Chim, Phys. 53, 356 ; Ann. P?tarm. 109, 31.

Formation and Preparation. When the compound of glycocol and oxide of silver is acted upon by chloride of cumyl, chloride of silver is formed, together with cuminuric acid, which is soluble in warm alcohol and crystallises on cooling or by slow evaporation, in yellowish brown prisms. The product is purified by pressure between blotting paper and recrystallisation .

Cahours.

24 C 144 .... 66-15 04-91

N 14 .... 6-33

15 H 15 .... 6-78 6-66

6 O 48 .... 21-74

C9*NH»0« 221 .... 100-00

It bears the same relation to cuminic acid, as hipparic to benzoic

acid.

Boiled with hydrochloric acid, it takes up water and is converted into cuminic acid and hydroohlorate of glycocol.

CuminuraU of silver contains 32-61 p. c. Ag (C'*AgNH"0« = 32-92

p. c).

Cuminuric acid dissolves in alcohol, especially when warm.

SASSAFRAS-CAMPHOR. 161

Sassafras-Camphor.

Binder. (1821.) Hepert. II ^ 3^6,

Saint-Evrb. y. Ann. Chim. Fhys. 12, 107; J. pr, Chem. 34, 372; abslr. Campt rend. 18, 735; N. J. Pkarm. 10, 314»

In oil of Sassafras. Rectified oil of sassafras is cooled by an artificial freezing mixtare, and the crystals, which are deposited after a few hours from the tnrbid liquid, are collected, pressed between paper, melted, and recrystallised by means of a freezing mixture. (St. Evre.)

Hard, white, oblique four-sided or irregular six-sided prisms, bevelled with two faces, and somewhat truncated on the bevelling edge.

It crackles when pressed together. Sp. gr. = 1*245 at 6°; 1-11 in the liquid state at 12° 5'. It remains liquid at 5°, but solidifies below 17'' ; solidifies at 7•5^ (Binder.) — Vapour-density = 5-85. (St. Evre.)

It has an odour of sassafras, and tsistes at first sweetish and warm, afterwards burning. (Binder.)

	10 H	120 10 32	....	74-07 .... 617 .... 19*76 ....	St. Evre.
	.... 73-86 .... 73-94 .... 6-61 .... 6-24 .... .... X9-53 .... 19-o2 ....	73-83 6-29
	4 0	19-83

C?»H»»0* 162 .... 100-00 100-00 .... 100-00 .... 10000

It becomes rapidly altered in the air. (St. Evre.) — When set on fire, it bums with a very smoky flame. — Mixed with niirie acid, it turns yellow, dissolves with reddish brown colour, and is partly converted into a brown viscid resin. — With fuming sulphuric acid it effervesces, evolving sulphurous acid and depositing spongy charcoal. (Binder.)

Appendix to Sassajroi-camphor*

Oil of Sassafras.

Binder. (1821.) Eepei-t. U, 3^6.

B0NA8TRB. J. Pharm. 14, 645; abstr. J. Chim. mid. 4, 484; N. Tr. 19,

1, 210. Satmt^Evrb. N. Ann. Chim. Phys. 12, 107 ; J> pr. Chem. 34, 372 ;

abstr. Compt. rend. 18, 735; N. J. Phaim. 10, 314. Zeller. Stud, uber aether. Ode., 1850.

Estenee ofMonqfroM.

Source and Preparation. Occurs in the wood and bark of the roots of Lauras sassajraa L. »- The wood is rasped and distilled with water, and the oil which sinks to the bottom of the aqueous distillate is collected. Commercial oil of sassafras is generally adulterated (a) with oil of

vol.. XIY. M

162 OXYGEN-NUCLEUS C»W»02.

lavender; it is then specifically lighter than the pure oil; (6.) with oil oftwpentine, which, when the oil is submitted to distillation, passes over and noats on the distillate; c with oil ofcloveSy the impurity remaining in the residue, when the oil is distilled with potash.

Properties. Yellow (St. Evre); varies between pale-brown and reddish yellow. (Zeller.) — Sp. gr. = 109 at 10° (St. Evre), between 1-07 and r09. (Zeller.) — Begins to boil at 115^^ the boiling point rising to 228", when it remains nearly constant. (St. Evre.) — It has an odour of fennel and a sharp (St. Evre)> fiery taste. (Bonastre.) — It is neutral. (Zeller.)

St. Evre.

C 72-19

H 6'40

O 21-41

100-00

The analysis corresponds to the formula C^H^^O',* but oil of sassafras is a mixture (St. Evre) of two oils, one heavier, the other lighter than water. (Bonastre.)

DecomponUons. 1. When kept for some time or cooled, it deposits crystalline sassafras-camphor. (Binder, St. Evre.) 2. On dMUation, it leaves a brownish yellow residue. (St. Evre.) — 3. Distilled through a tvbe healed to redness or over heated soda-lime, it yields naphthalin and phenylic alcohol. (St. Evre.) — 4. Saturated with chlorine, it becomes opaque, milky, and viscid. (Bonastre.) ; evolves hydrochloric acid and is converted into a viscid mass containing common camphor. (Faltin, Ann, Pharm, 87, 376.) — 5. It is violently attacked by bromine, being converted into bromide of oil of sassafras and evolving hydrobromic acid. (St. Evre.) — 6. With iodine, it turns yellowish brown without becoming viscid. — 7. Mixed with cold nitric acid, it gradually becomes flesh- coloured (Bonastre), reddish brown with slight elevation of temperature. (Zeller.) With hot nitric acid it turns red (Daryk) ; warmed with weak nitric acid, it yields oxalic acid (Daryk, St. Evre) ; with moderately con- centrated acid, a brittle resin. (Zeller.) It readily takes fire with fuming nitric acid (St. Evre), leaving a brown resin. (Hasse, Crell. Afin. 1785, 1,422.) — 8. Treated with strong sulphuric acid, it frequently takes fire, and is converted into a red, acid resin, mixed with charcoal. (St. Evre.) Mixed with \ pt. strong sulphuric acid, it turns greenish, yellow- ish-brown. (Zeller.) — 9. Saturated with sulphurous acid, it turns green, and afterwaras orange-coloured, deposits sulphur, becomes hot, and yields a mixture which on standing separates into two strata, the upper, consist- ing of undecomposed oil, the lower of an oil boiling at 235% and repre- sented by the formula C^^H^^'. If the action of sulphurous acid be con- tinued for a longer period, an oil containing sulphur is formed, corre- sponding in composition to the formula C^H'^0%. — 10. It is not altered by phosphoric anhydride. — 11. Distilled with pentachloride of phosphorous, it is converted into chloride of oil of sassafras, with violent evolution of hydrochloric acid. — 12. It is not attacked hy potassium, — 13. Saturated with ammonia it yields bulky prisms containing 73-17 p. c G, 6*18 p. c. H, and 20*65 0. (St. Evre.) Cooled oil of sassafras is rendered turbid by

• This is wrong, CWH»0O2 » BO-60 C, 7-46 H, 11-94 ; perhaps it is C«HWO* » 72-00 C ; 6'G6 H; and 21*340.

PYROXANTIIIN. 163

ammonia, and becomes viscid, but not crystalline. (Bonastre^ — 14. It is not altered bj bichromate of potash and sidphwnc acid (St. Evre) ; de- posits yellowish-brown, resinous flakes. (Zeller.) — 15. It is not affected by chloride of zinc. (St. Evre.)

ComhiTiations. Dissolves in 4 or 5 pts. alcohol of sp. gr. 0*85, and sparingly in aqueous alkalit* (Zeller, Bonastre.)

Oxygen-nudem C*H*0*.

Pyrozanthin.

ScANLAN. (1855.) FhU. Mag. J*., [8], 41, 395; also J. pr. Chem,

7,94. Apjohn & Greooby. Froc. of the Boy, Irish Acad, 1836, 33; J.pr.

Chem. 13, 70. ScHWEiZER. J. pr. Chem. 44, 129.

Eblanin. Discovered simultaneously by Pasch & Scaulan (1835), and named after the place of residence of the latter. (Dublin, laf. Eblana.)

Formation, 1. By heating the precipitate formed by lime in crade 'wood-spirit. — 2. By saturating the most volatile portion of crnde wood spirit with lime, and heating. — 3. By the action of potash on the pyroxanthogen contained in crude pyroligneous acid. (Schweizer.)

Preparation. 1. Crude wood spirit is distilled till 15 p. c. has passed over; the distillate containing acetic acid is saturated with lime and redistilled ; and from the dry, dark-coloured residue, consisting of acetate of lime, lime, brown resin, and pyroxanthin, the first two substances are -extracted with hydrochloric acid, after which it is repeatedly boiled with alcohol. The first extracts contain almost exclusively a brown resin, smelling like pitch ; the last contain principally pyroxanthin ; these are evaporated, and the crystals thereby deposited are recrystal- liscd from alcohol. (Apjohn & Gregory.) — 2. The most volatile part of crnde pyroligneous acid (from ash- wood) is distilled in a water-bath, till the distillate will scarcely take fire, and the residue is distilled alone over a naked flame, till nothing but water containing acetic acid passes over. This second distillate is supersaturated with potash, and the orange-yellow flakes thereupon deposited are washed on a filter, first with water, and then repeatedly with a small quantity of hot alcohol, to remove the resin^ which is especially deposited when the liquid has been nearly saturated. It is then dissolved in boiling alcohol, and the crystals deposited en cooling are recrystallised from alcohol. If the flocculent precipitate produced by potash is immediately crystallised from alcohol instead of being first washed with a small quantity of warm alcohol, in order to remove the greater part of the adhering resin, the crystals obtained are difficult to purify. (Schweizer.)

Properties, Long, yellow needles whicli begin to sublime in a current

M 2

164 OXYGEN-NUCLEUS C^HH)^.

of air at 134^, melt at 144% solidify in crystals on cooling. (Apjohn & Gregory.)

20 C 8H	120	.... 75-00 ... .... 6*00 ... .... 2000 ...	Apjohn. Gregory. 74-1 .... 74-3 6-1 .... 5-5
4 0	32	19-8 .... 20-2
c?mH>*	...... 160	.... 100-00 ...	..... 1000 .... 100*0

C>>H'CH, according to Gregorj, C^H^^O^, according to Gmdin.

Decompodtions. 1. It is decomposed by heat in closed vessels. 2. It is partly decomposed by dry gaseous ehlorine between 80° and 100° into a blackish brown resin, with evolution of hydrochloric acid. — 3. It is violently attacked by fuming iwlric acid, being converted into oxalic acid and a substance which explodes by heat. Dissolves in concentrated nitric acid without evolution of gas; the solution mixed with water deposits a brownish yellow substance, which explodes by heat when dried, dissolves in potash, and is not reprecipiiated from this solution by acetic acid. — 4. With cold strong sulphuric acid, it turns reddish brown, afterwards blackish brown, and finally deposits blackish brown flakes. Strong sulphuric acid, diluted with an equal bulk of water, dissolves pyroxanthin, even at a gentle heat, with fine purple-red colour ; the solution, after a few days, deposits blackish brown flakes, but as long as it remains purple red, it deposits unchanged pyroxanthin on addition of water. — 5. Dissolves in concentrated hydrochloric acid, forming a magnificent purple red solution. The freshly prepared solution deposits unchanged pyroxanthin on addition of water, but after a time loses its colour, especially in the air, and deposits blackish brown flakes. (Apjohn & Gregory.)

ComUnatums. P3rroxanthin is insoluble in water, slightly soluble in aqueous potcuh and in ammonia.

Dissolves in glacial acetic acid, and is precipitated therefrom by water.

Dissolves in alcohol and in etlier ; crystallises from the hot concen- trated solution on cooling, and is precipitated therefrom by water. (Apjohn St Gregory.)

Appendix to Pyroxantldn.

Pjnrozanthogen.

ScHWEiZER. (1848.) J,pr. Chem. 44, 129.

Source and JPi^aration, Occurs in crude pyroligneous acid. The wood-spirit is first distilled from this liquid, and the residue is then dis- tilled alone, as long as water containing acetic acid passes over. This second distillate is then mixed with ether and allowed to stand for 24 hours with frequent shaking ; the stratum of ether swimming on the surface of the liquid is poured off and distilled; the i-esidue is mixed with water ; and the heavy brownish oil thereby precipitated is repeatedly washed with water and distilled several times with water.

CIILOniDE OF CUMYL. 165

Properties, Transparent, colourless, or yellowisli oil, heavier than water. Solidifies at — 28° in a white, fatty^mass. It has a disagreeable odonr of smoked fish, and a strong pungent taste.

It is probably a mixture. (Schweizer.)

DecomposiHons. 1. It acquires a darker colour on exposure to atr and liglU, — 2. Yields a dark distillate by heat, and leaves a dark yellow and, finally, black resinous residue. — 3. Its aqueous or alcoholic solution is decomposed by potash, lime^ or baryta (also by carbonate ofpotaA and by ammonia with the aid of heat); yielding (1) a precipitate of pyrox- anthin; (2) a reddish-brown, easily fusible resin, insoluble in water, sparingly soluble in aqueous potash, and readily soluble in alcohol and in ether ; (d) a soft resin smelling of creosote, precipitated from the solution by sulphuric acid ; (4) a yellowish oil, which may be extracted from the solution by ether, resembles pyroxanthogen, but no longer yields pyroxanthin with potash; and (5) a peculiar acid. — 4. It reduces mercury from mercurous salts. — 5. Its alcoholic solution precipitates acetate of lead on addition of ammonia, in thick white flakes.

Comhinatums. Dissolves very sparingly in cold water, more readily in hot water; readily in wood- spirit, alcohol, and ether. (Schweizer.)

Bromirve-nvdeus C*BrH*^

Bromocuminol.

C«»BrH»0» = C»BrH",0».

Gebhardt & Cahours. (1841.) N, Ann, Chim. Phys. \, 86.

Hydrwre de bromoeumyle.

Dry bromine reacts on cuminol in the same manner as chlorine, and fonns bromocuminol as a heavy oil, which is readily resolved by water into cuminic acid and hydrobromic acid. The aqueous solution of bisul- phite of soda and cuminol is decomposed by bromine, with formation of sulphuric acid and separation of cuminol, which is converted by excess of bromine into a crystalline, readily fusible substance, which combines with the bisulphites and is probably bromide of cnmyl (bromocuminoU). (Bertagnini, Ann, Phat^n, 87, 277.)

ChXorine-nudeus C^KJllP*.

Chloride of Gumyl.

C»H"C10» = C»C1H",0«,

Cahours. (1841.) Compt, rend, 22, 846; Ann. Pharm, 60, 254; Compt rend. 25, 724. — iV. Ann. Chim, Phys, 23, 347 ; J* pr, Ohem. 45, 144 ; ©xtr. Ann. Pharm. 70, 45.

CMorj:U7nyI, CumylchlorHr,

Formation and Preparation. Pentachloride of phosphorus reacts on cuminic acid below 60^ evolving large quantities of hydrochloric acid,

166 CHLOKINE-NUCLEUS C»CIH».

and yields a mixture of oxyohloride of phosphorus and chloride of cnmyl. The product is rectified, and the portion distilling between 250° and 260^ is collected apart^ washed with cold water, dried over chloride of calcium and rectified. (Cahours.) — Ozychloride of phosphorus with 3 at. cuminate of soda yields chloride of cnmyl. — Terchloride of phosphorus reacts at common temperatures on the alkaline cuminateS; forming chloride of cumyl and an alkaline phosphite^ which readily attacks the chloride of cnmyl, so that the distillate is rendered impure oy substances containing phosphorus. (Gerhardt, Ann. Pharm, 87, 64.)

Properties. Colourless, very mobile liquid of sp. gr. 1'07 at 15°, Boils between 256'' and 258''.

9(i P	120 .... 65-79 ...	Cahours. 65-75
1 1 TT		6-17
CI 2 O	35-5 .... 19-41 ... 16 .... 8-77 ..	19-71 8-37
C»C1H»02	182-5 .... 100-00 ,..	100-00

Isomeric witb'chlorocuminol.

Decompositions, 1. It is decomposed by moist air into hydrochloric and cuminic acids. — 2. Boiled with aqueous potashy it quickly yields tho same products. — 3. By dry gaseous ammonia (Cahours) and by carbonate of ammonia (Gerhardt and Chiozza, p. 167)> it is converted into cumar mide. — 4. It becomes strongly heated with alcohol^ and, on adding water to the liquid, cuminate of ethyl is separated as a light oil With the silver-compound of glycoeol, it forms cuminuric acid (Cahours, p. 160); with pkenylate of potaskf cuminate pf phenyl (Williamson & Scrugham^ p. 157); with aniline, cumanilide (Cahours, p. 177); with stdpJiO' phenylamide, cumyl osulphophenylamide (p. 177), and at a higher tem- perature, eumonitrile and sulphophenylic acid; with henzoylsutphoplienyl' argentamide, cumylbenzoylsulphophenylamide (p. 179) (Gerhardt & Chiozza) ; with saUcylotis aevd^ cumosalicyl (Cahours, p. 158) ; with salicylate of soda, cumosalicylic anhydride, and on distillation, cuminate of phenvl (Kraut, p. 157); with salicylamide, cumosalicylamide (Gerhardt & Cniozza, p. 179); with oenanthylate of potash, oenanthocuminic anhydride (Chiozza & Malerba, p. 159) ; with nitranisidine, the com- pound corresponding to benzonitranisidide (xii, 269); "wiihnitrocumidine, a crystallisable product (Cahours, p. 352 ) ; with cumind-potassium, cumyl (Chiozza, p. 154); with cumincUe of potash, cuminic anhydride (Gerhardt^ p. 159) ; with eugenic aeidy cameneagenyl (Cahours) ; with piperidine, cumylopiperide. (Cahours.)

ChlorocuininoL

C»C1H»0» = C~CIH» 0». Gerhaudt & Cahours. (1841.) N, Ann. Okim, Fhys. 1, 82.

Ilydrure de chlorocumyle.

Preparatwn, Dry chlorine gas passed in daylight through cuminol previously dried over chloride |of calcium, is absorbed with evolution

CHLORONICENE. I67

of hjdroohloiio acid. The liquid becomes heated^ torns ired^ and ia then gradually decolorised^ and after a few hours becomes saturated with chlorine^ whereupon the excess of chlorine and the hjdrochlorio acid are expelled by a stream of carbonic acid^ and the product is kept so as to preserve it irom air and moisture.

Ft'opertiea. Yellowish liquid, heavier than water. It has a very powerful odour^ differing from that of euminol.

20 C 11 H	.... 120 .... «5-79 .... 11 .... 6*03	Gerhardt & Cahoars. 64-64 6-54
CI 2 0	... 35-5 .... 19-41 .... 16 .... 8-77	2218 6-64
C»H»C10« .. .	.... 182-5 .... 100-00	100-00

Isomeric wHh chloride of cnmyl.

According to Gerhardt & Cahoars, it had absorbed hydrochloric acid, and conse- quently gave too little C, and too mach H and CI.

Decompositions, 1. Decomposed by moist air into hydrochloric and cuminic acids. It does net keep well, even in stoppered bottles, but turns red, becomes turbid, and evolves fumes of hydrochloric acid; perhaps a spontaneous decomposition takes place without the interven- tion of moist air. — 2. It is decomposed by distillation into hydrochloric acid, carbon, and a peculiar volatile oil. — 3. It dissolves completely in a few moments in boiling aqueous potash, as chloride of potassium and cnminate of potash. — 4. Strong sulphuric acid dissolves chlorocuminol with evolution of hydrochloric acid, forming a crimson solution which in contact with moist air soon deposits crystals of cuminic acid. — 5. When dry gaseous ammonia is passed through chlorocuminol, it becomes thick and stops up the tube; if the chlorocuminol is dissolved in absoluto alcohol, a large quantity of chloride of ammonium is immediately deposited, and on adding water to the decanted liquid, a chlorinated oil is precipi- tated, which with potash yields cuminic acid, and when heated by itself, hydrochloric acid, charcoal, and a peculiar volatile oil. Hence ammonia appears merely to combine with the hydrochloric acid formed by the slow decomposition of the chlorocuminol, and not to act on the compound itself. --!- 6. It does not yield cuminate of ethyl with absolute alcohol.

Chlmnemucleus C«>CPH^^

Chloromcene.

C»C1*H«».

St. Evbe. (1849.) N, Ann. Ohim, Phys. 25, 495 ; also Ann. Phai^m, 70, 263 ; also J, pr. Chem. 46, 458.

Nichte monochlor^.

Formation and Preparation. By distilling chloroniceic acid (C"C1H»0*, xi, 176) with excess of lime or baryta :

2C»C1H»0* « C»CPH»« + 4C0».

168 OXYBROMINE-NUCLEUS C»Br8H=0».

ChloroDLcene then passes over first, as a brown-yellow liquid^ tlien para- nicene, C^°H' or C*H", in yellow crystals.

Impure cbloroniceic acid may be used for tbe preparation, in which case the distillate will contain benzene, C"H^ This may be distilled off at 90° in a stream of carbonic acid or hydrogen (air would decompose it), and if tbe receirer be then changed, chloronicene may be collected between 290° and 295°, and there remains a liquid mixture of chloro* nicene and a solid hydrocarbon which solidifies on cooling.

Propetim. Pale yellow oil, of sp, gr. 1*141 at 10°, boiling between 292° and 294°, and having a yapour-dansity of 7'52. In vessels con- taining air, it turns brown after some weeks.

St. Evre. mean. Vol. Density.

20 C 120'0 .... 5976 60'71 C-vapour 20 8-3200

2 CI 70-8.... 35-26 34-69 Cl-gas 2 4-9086

10 H 10-0 .... 4-98 5-52 H-gas 10 0*6930

C»CPHW .... 200-8 .... 100-00 100-92 Vapour 2 13-9216

1 6-9608

Thus according to Laurent & Gerhardt. {CompL cMm, 1849> 163). According ^ Evre, the atomic weight is only half as great. Gerh identical with chloride of phenyl, C^H^Cl (see page 142).

to St. Evre, the atomic weight is only half as great. Gerhardt afterwards regarded it as

nil

Fuming nitric acid attacks the compound with violence, converting it into nitrochloronicene and a resin.

Oxj/hromine-niLcleus C*^Br^H'0*.

Brom-sassafiras Oil.

C»H»Br«0* = C*»H'Br«0»,0«.

St. Evre. (1846.) iV. Ann. Chim. Phys. 12, 107 j also J. pr. Chem, 34, 372 ; abstr. Compt, rend, 18, 735 ; N. J. Pharm, 10, 314.

Formation and Preparation, When bromine is slowly dropped into sassafras oil, a lar^e quantity of bydrobromio acid is evolved, and tho oil becomes crystalline. The crystalline mass is pressed between paper, wasbed with tue smallest possible quantity of ether, which separates froe bromine and a fibrous substance resembling solid cbloride of carbon, and dried in vacuo at 130^

Propertiei, White needles united in tufts.

St. Evre.

20 C 120 .... 1512 14-64

2 H 2 .... 0-25 0-25

8 Br 640 .... 80*60 79-84

4 0 32 .... 4-03 5-27

C»Ii'Br80* .... 794 .... 100*00 lOOOO

NITROPARANICENE. 169

Decompositions. 1. By chlorine in sunshine, it is converted into a tough mass, free from hydrogen and resembling sesquichloride of carbon — 2. Heated with aqufoxis potash, it yields a brittle translucent resin still containing bromine.

It dissolvea in boiling ether.

Oxychlorine-nudeus C*^CPHO*.

Ghlor-sassafras Oil.

C«»HCPO* = C»«CPHO',0'.

St. Evre. (1846.) N. Ann. Chim. Phys. 12, 107; also J. pr, Chem. 34, 372 ; abstr. Compt. rend. 18, 735 ; xV. J. Fharm. 10, 314.

Foi'mation and Preparation. By distilling in the oil-bath a mixture of sassafras oil and pentachloride of phosphorus, washing the oily distillate with water to remove oxychloride of phosphorus and hydro- chloric acid, and rectifying it over oxide of lead in a stream of carbonic acid

Properties, Boils at 238^

Nitro-nudeus C»XH".

Nitroparanicene.

C»NH"0* = 0»oXH".

Paranichie nitrogine. (Compare page 142.)

Foimation and Preparation (p. 142.) Paraniceno is dissolved in fuming nitric acid, and the needles which separate on cooling are freed from resin by recrystallisation from alcohol and ether.

20 C K 11 H	120 14 11	.... 67-79 ... .... / 9L ••• .... 0 A 1 ...	St. Evre. mean. 67-63 8-12 5-87
4 O	32	18-38
C*XH»	177	.... 100-00 ..	...... 100-00

Hydrosulphate of Ammonia converts it into paraniccne (St. Evre^ N, Ann, Chim, Phys. 25, 506.)

170 NITRO-NUCLEUS C^^XH".

Nitrocmninic Acid.

C20NH"0«=C»XH",0*.

Cahours. (1848.) Compt, rend. 24^554; N, Ann. Chim. Phys. 25, 36 ; J. pr. Chem. 46, 346 ; Ann. Pharm. 69, 243. — N. Ann. Chim. Phys. 53, 334; Ann. Pharm. 109, 18.

First obsenred in 1841, bj Gerhardt & Cahonra {N. Ann. Chim. Phys. 1, 69.)

Formation. By the action of fuming nitric acid on cuminic acid. (Cahours.) — 2. If a solution of cuminic acid in cold nitro-sulphuric acid be mixed with water, nitro-cuminio acid separates from it after a short time. (Kraut, N. Br. Arch. 96, 274.)

Preparation. Cuminic acid is dissolved in warm concentrated nitric acid; tne solution is heated to the boiling point, whereupon red vapours are evolved, but no violent action takes place ; and after boiling for some minutes, it is precipitated with water. It then deposits a yellow, heavy, quickly solidifying oil, which must be washed two or three times with water and recrystallised from alcohol.

Propei'ties. Yellowish white crystalline scales.

			Cahoara.
			mean.
20 C	... 120	.... 57-41 ...	57-33
N	... 14	6-69 ...	6-79
11 H	... 11	.... 30-64 ...	• •••• V 0 #
8 O	... 64	30-51
C»XH"0*	... 209	.... 10000 ...	10000

Decompositions. 1. On treating the ammonia-salt with sulphuretted hydrogen (Cahours), or with iron-filings and acetic acid, (Boullay, Compt. rend. 43, 399), it is converted into amidocuminic acid. — 2. It is not altered by boiling with chromate of potash and sulphuric acid. (Hofmann, Ann. PJiarm, 97, 206.)

ComJbinations. The acid is insoluble in toater. It dissolves very readily in ammonia, potash and soda> forming crystallisable salts.

NUrocumvnate of Lime. Yellow needles grouped in stars. Becomes darker coloured by exposure to light. When dried at 100^, it contains 8'54 p. c. calcium, and is therefore C^CaXH^^O^ (calculation 8*77 p. c. Ca.) (Kraut, N. Br. Arch. 96, 274.)

Nitrocuminate of Silver. Obtained from the ammonia-salt by double decomposition. Beautifully white. Contains after drying in vacuo, 34-0 p. c. Ag. (C~AgXH»«0* «= 3417 p.c. Ag.)

Nitrocnminic acid dissolves readily in ak^l and ether.

BINITROCUMINIC ACID. 171

BinitFociimiiiic Acid.

C»H^«NH)« = C»X»IP,0*.

Gahouiul (1849.) i\r. Ann, Chim, Phys, 25, 36 ; J,pr, Cheat. 46, 346 ;

Ann. Fharm, 69, 243. BouLLEY. Compt. rend. 43, 309; Chem. Centr. 1856, 782. Kraut. ilT. Br. Arch. 96, 274 ; Chem. Centr. 1859, 85.

JFormation and Preparaticn, Foaed euminic acid dissolves wiihont orolotion of gas in niirosulpliaric acid ; and the solution on being heated to the boiling pointy gives off red raponrs, becomes turbid, and soon deposits crystalline laminae, which may be washed with water and recrjstallised from alcohol. (CahoarsL) The solution of cnminic acid in nitrosnlphoric acid is precipitated with water, after standing for 24 hours at a medium temperature; the precipitated brown powder is washed with water, and boiled with milk of lime; and the filtered solution is mixed with hydrochloric acid, which precipitates binitrocuminic acid, — to be purified by washing with water and recrystallisation from alcohol. (Kraut.)

Properties. LaminsD having a stronp^ lustre. (Cahonrs.) Light yellow crystals of the doubly oblique prismatic system. Henhcnohedrons {Fig. 121.) with the angles ii : y = 83° 321'; y : tr = 82° 50'; « : v = 87° 4*5'. The acute edge y v, is truncated by a dodecahedral face inclined to y at 118° 2*9', and to v at 154"^ 47*1'; there is also to the left in front an octohedral &oe making with u an angle of 133^ 2*1', and to the left behind an octohedral face making with u an angle of 133° 4'2^ Disregarding the slight inequality of these last two angles, the face u, the two octohedral faces, and the dodecahedral face form toother a rhombic prism with perpendicularly truncated edges, the faces y and v resting upon it in a doubly oblique direction. Cleavage parallel to «. (v. Dauber.)

Becomes darker in colour by exposure to light. (Kraut.)

Cahonrs. Kraut.

20 C 120

2N 28

10 H 10

12 O 96

	meam.	mean.
47-24 ....	.... 47-27 ..	.. 47-31
11-02 ....	.... 10-83
3-98 ....	... 3'"" .... %'AO
37-«l ....	.... 37-91

C»X«H»0* 254 .... 10000 100-00

Deeompoiitiom. I. Not acted npon by fuming nt^n'c ocuf, even at the boiling heat. (Cahonrs.) — 2. Treated with ironjilings and acetic acid, it forms biamidocuminic acid. (Bonllet.)

Combinations. According to Cahonrs, binitricuminic acid does not possess acid properties, being neither dissolved nor decomposed by warm ammonia, potash or soda-ley. According to Kraut, on the contrary, it does behave like an acid, and forms salts which acquire a darker yellowish red colour by exposure to light.

Binitroeuminate of Baryta, Obtained by dissolving the acid in baryta- water, precipitating the excess of baiyta with carbonic acid . boiling,

172 NITROCHLORINE-NUCLEUS C^X^CPHs.

and evaporatlDg the filtered solution. It first separates in films wliicb become crystalline under the mother-liquor. After drying over oil of vitriol, it does not diminish in weight at 1 20°. It contains 20*48 p. c. Ba. and is therefore 0»BaX»H'0*. (Calculation = 21-30 Ba.) (Kraut)

JBiniirocuminaie of Lime, — Prepared like the barjta-salt. Yellowish red crystalline needles, which dissolve easily in water, with deep wine -red colour, do not diminish in weight at 1 20° after drying over oil of vitriol, and contain 7*01 p. c. Ca. ; therefore = C^CaX'H'O* (calculation = 7-33 Ca.) (Kraut.)

BinUrocuminate of Silver* — Obtained by precipitating the aqueous solution of the lime-salt with nitrate of silver, and recrystallising from hot water. Light yellow needles, which are scarcely altered by expo- sure to light. After drying over oil of vitriol, they give off 5*26 p. c. water at lOO'' (2 At. = 4*74 p. c.) : and then contain 29*76 p. c. Ag. (C*»AgX»H»0* = 29-91 p. c.) (Kraut.)

Binitrocaminic acid is soluble in alcohol, and easily soluble in ether.

Binitrocuminate of EthyL

C»*N'H"0" = C*H«0,C«X»H»0>. Kraut. i\r. Br, Arch, 96, 278.

Obtained by repeatedly passing hydrochloric acid into alcoholic bini- trocuminic acid and precipitating by water, and purified by treatment with carbonate of soda, washing with water, and recrystallisation from alcohol.

Colourless^ aggregated needles. Melts at 77*5°

Kraut.

24 C 144 .... 51-07 50-44

2 N 28 .... 9-93

14 H 14 .... 4-97 5-56

12 O 9fi .... 34-03

C*H»0,C»XHPO».... 282 .... 100-00

Ammonia converts it into binitrocuminamide, which crystallises in thick yellow prisms soluble in alcohol. — Treated with iron filings and acetic acid, it forms biamidocuminate of ethyl. (Boullet, Compt, rend. 43, 399.)

Binitrocuminic ether is soluble in alcohol,

Nitrochlorine-nucUm C'^X'Cl'H^.

Nitrochloronicene.

c«nh:ji»H80* = c«>x«ci»m

St. Evrb. N, Ann* Chim, Phys, 25, 495 ; J, pr, Cheni, 46, 458 ; Ann, P/uxrm, 70, 263.

NiirotUcine monoehhrd ^ C^^^XCIH^ (St. Evre). See page 142.

FomuUion and- Freparaiion, (comp. p. 167.) Chlorouiceno is troafod with fuming nitric acid, and the] resulting mass is dissolved in alcohol

CUMINAMIDE. 173

of 36^. The less soluble resin is then first deposited, and afterwards nitro- chloronicene crystallises oat, which may be farther purified by recrystal- lisation from alcohol.

Long, amber-yellow, silky needles.

St. Evre. mean*

20 C 120-0 .... 41-26 40-92

2 N 28-0 .... 9-63 8.62

2 a 70-8 .... 24-34 2409

8 H 8-0 .... 2-75 2-83

8 O 640 .... 22-02 23-54

C?»X2CPH8 290-8 .... 100-00 100-00

An alcoholic solation of hydrosulpJiate of ammonia turns it brown, then dark violet, and yields chloronicin, with deposition of sulphur. Soluble in alcohol and in ether.

Amidogen-nudeus C'^AdH".

Guminamide.

C»NH'30« = C»AdH",0^

F. Field. (1847.) Ann, Fharm. 65, 45; Mem. CJiem. 8oc 8, 404;

Fhil, Mag. J. 31, 459 ; J. pr, CJiem. 44, 1 36. Gerhardt. Ann. Fharm. 87, 79. Gbrhardt <& Chiozza. Ann. Fharm. 87, 299 ; N. Ann. Chim. Fhys.

46, 135.

Formation. 1. By heating cuminate of ammonia. (Field.) — 2. By the action of ammonia on cnminate of ethyl. (Dumas, I^. Ann. Chim. Fhys. 23, 349.) — 3. By the action of dry amiiu/nia gas (Cahours, If. Ann. Chim. Fhys. 23, 249), or of carbonate of ammonia (Gerhardt & Chiozza) on chlorocumyl. — 4. Cuminic anhydride is gradually converted into cnminamide by the action of aqueous ammonia. — Benio-cuminic anhydride 18 converted by ammonia into a mixture of benzamide or benzoate of ammonia and eaminamide, to be separated by aqueous ammonia, which dissolves chiefly the benza- mide. (Gerhardt) — 5. Gumonitrile is slowly converted into cuminamide by alcoholic ammonia. (Field.)

Freparation, 1. Chloride of cnmyl is triturated in a mortar with carbonate of ammoni% and the mixture gently heated ; whereupon car- bonic acid is eyolred, and cnminamide is produced, to be separated from sal-ammoniac and excess of carbonate of ammonia by washing with water. (Gerhardt & Chiozza.) -^ 2. When cuminate of ammonia is heated in a sealed tube in the oil-bath to the boiling point of the oil, or continuously heated in a retort to incipient fusion, cuminamide is produced, and may be purified by recrystallisation from boiling dilute aqueous ammonia. (Field.)

Froperties. Crystallises by rapid separation from its concentrated aqueous solution, in tables; by slow separation from a dilute solution, in long opaque needles. (Field.)

174 AMIDOGEN-NUCLEUS C»AdH".

Field. Gerhardt.

20 C N 13 H	.... 120 .... 14	.... 73-68 ... .... 0*d<b ... .... /*7if ... .... 9*01 ...	mean. 73-66 .... 8-50 ■ .... o'lv .... .... 9-71	73-28 800
2 O	.... 16
C»NH»»0» ....	.... 163	.... 10000 ...	100-00

Field's caminamide was obtained by formation 1 and 5 ; Gerhardt's by 4.

Decomposition. Cuminamide withstands the action of strong acids and alkalis more obstinately than other amides, and is converted by them into ammonia and cuminic acid^ only after very long boiling. From sola- tion in aqueous potasb, it crystollises in large tables. (Field.) — When fused with potassinm it does not form cyanide of potassium. (Dumas^ Malaguti & Leblanc^ Compt. rend. 25, 600.)

Combinations. Cuminamide is insoluble in cold, but soluble in hot water. (Field.) It is insoluble in cold ammonia (Field), very sparingly soluble in boiling ammonia. (Gerhardt.) It dissolves in all proportions in alcohol and in ether, whether cold or hot. (Field.)

Amidocumiiiic Acid.

C*>NH«0* = C»AdH",0*.

CAnouns. Compt. rend. 44, 567 ; Ann. Pharm. 103, 87; J. pr. Cheni. 72, 112. — Compt. rtnd. 46, 1044; Ann. Fhai^m. 107, 147; J. pr. Chem. 74, 223. — In detail: iV. Ann. Chim. Fhys. 53, 322; Ann. Phaimfi. 109, 10; abstr. Rep. Chim. pure. 1, 29.

Cuminamic aeidf Cuminamingaiire.

Formation and Preparation. Nitrocuminate of ammonia is reduced by excess of hydrosulphuric acid; the liquid is evaporated at a gentle heat till all the ammonia is expelled and the excess of sulphur is sepa- rated ; the concentrated solution is precipitated by a slight excess of acetic acid ; and the resulting precipitate is collected, washed, dried, and recrystallised from alcohol. (Cahours.) — It is also obtained by treating nitrocuminic acid with iron filings and acetic acid (a brisk action then taking place attended with rise of temperature, after which the mixture must be heated for a while in the water-bath); digesting the mixture with aqueous carbonate of soda; filterin^^; neutralising the excess of carbonate of soda with acetic acid; precipitating with acetate of lead; and decom- posing the precipitate with hydrosulphuric acid. (Boullet, Compt. rend. 43, 39P.)

Properties. Colourless or light yellow crystals. By spontaneous evapo- ration of the solutions, it is obtained in tables.

Cahours.

20 C 120 .... 6704 66-80

N 14 .... 7-81

13 H 13 .... 7-20 7-13

O 32 .... 17-89

C-'ONir-'O' 179 .... 100-00

AMIDOCUMINIG ACID. 175

DecompofUtons, 1. In solution in nitrie acid, it is converted by nitric oxide gas into oxycaminic acid. — 2. By treating alcolwlic amidocuminic acid with nitrous acid, light yellow needles are obtained, consisting of a new bibasic acid =C«N»H»0» (P. Griess, Com^pt rend. 49-80);

2C»NH»0* + NO' - 3 HO + C^N'RaO^

3. Distilled with caustic baryta or lumps of potash, it yields an alka- line carbonate together with cnmidine.

Combinations. Dissolves sparingly in cold^ much more freely in boiling water.

Amidocuminic acid unites with acids, forming crystalline salts. It unites also with bases, (BouUet^ Compt. rend. 43, 399.)

Sulphate of Amidocuminic acid. — Amidocuminic acid is mixed in slight excess with oil of vitriol diluted with an equal bulk of water, and the mixture is dissolved in warm alcohol. On cooling, thin, white, silky needles are deposited. The compound has a slightly sweet taste, dis- solves sparingly in cold, easily in hot water.

Cahoon.

20 C 120 .... 52 64 53-01

N 14 .... 614

14 11 14 .... 614 6-22

5 O , 40 .... 17-54

S0» 40 .... 17-54 17-28

C»NH»0<,H0,S03 228 .... 10000

Ilydrochlorate of Amidocuminic acid. — Amidocuminic acid dissolves slightly in boiling hydrochloric acid, and the solution on cooling deposits thin needles. The compound may also be prepared by adding alcohol to a mixture of amidocuminic acid and hydrochloric acid, whereby a con- siderable quantity of amidocuminic acid is dissolved, and evaporating. Delicate shining prisms, which dissolve in water, and are partly precipi- tated on addition of hydrochloric acid.

Cahours.

20 C 120-0 .... 55-68 55-56

N 14-0 .... 6-49

14 H 140 .... 0-49 6-56

CI 35-5 .... 16-47 16-28

4 O 32-0 .... 14-87

C»NH"O^HCl 215-5 .... 100-00

Nitrate of Amidocuminic acid forms beautiful prisms.

Chloroplatinate of Amidocuminic acid. — Obtained by adding alcohol to the mixed solutions of concentrated bichloride of platinum and hydro- chlorate of amidocuminic acid, warming the mixture till it dissolves, then filtering and leaving the solution to evaporate.

Long reddish needles.

176 AMIDOGEN-NUCLEUS C»Ad3H».

Caliours.

20 C 120-0 .... 31-21 ....... 81-00

N 14-0 ^... 3-64

14 H 14-0 .... 3-64 3-79

3 C! 106-5 .... 27-69

Pt 980 .... 25-48 25-52

4 0 32-0 .... 8-34

C»NH»0*,HCl,PtCP .... 384-5 .... 100-00

Amidocuminio acid dissolres in alcohol and in ether more readily than in water.

Amidocuminate of Ethyl.

C*N H"0*= C*H»0,C«>AdH»^0».

Cahours. N, Ann, Chim, Phys, 53, 340; Ann. Pharm. 109, 21. Cuminamate Sihylique, Cuminamic ether, Amido^euminvineeter.

Formation and Preparation. By quickly redacing an alcoliolic sola- tion of nitrocuminate of ethyl with hydrosulphate of ammonia, or with iron filings and acetic acid. (Boullet, Compt, rend. 43, 399.) — On evaporating the solution, an ahundant separation of sulphur takes place ; and the concentrated filtrate deposits a dark heavy oil, which may be purified by repeated solution in alcohol and precipitation with water.

Cahours.

24 C 144 .... 69-56 6936

N 14 .... 6-76

17 H 17 .... 8-21 8-34

4 0 32 .... 15-47

C*H*0,C?»NH»0» .... 207 .... 10000

By ammonia, it is slowly converted into an amide, probably homolo* gous with phenyl-urea. It dissolves in sulphuric, hydrobromic, hydro* chloric and nitnc acids, forming crystal! isable compounds.

Amidogen-nucleus C"^Ad'H*^

Biamidocnminic Acid.

C»N«H"0* = C»Ad«H*«,0*. Boullet. (1856.) C(mpt. rend. 43, 399; Ohem. Centr. 185G, 782.

Produced from binitrocuminic acid by the action of iron filings and acetic acid in the same manner as amidocuminio acid from nitrocuminio acid (p. 174).

Crystallises. Combines with bases.

CUMYL-SULPHOPHEN YLAMIDE. 177

t

Conjugated Amides of the Cuminic series.

Cumanilide.

C»NH"0» = C»{NH.C»»H»)H"0« or C»(NH.(?»H"0«)H».

Cahofrs. (1848.) N. Ann. CJiim. Phys. 23, 349; J. pr. Ghent. 45. 129; abfitr. Ann. Fharm. 70, 46.

Phenyl- cuminamide^

Chloride of cumyl becomes heated in contact with aniline, and yields a prodact, which, after washing with aqneons potash and recrystallisatioa from alcohol, forms silky needles resembling benzoic acid.

*

Cahoun.

32 C 192 .... 80-28 8033

N 14 .... 5-92

17 H 17 .... 7-U 7-07

2 O 16 .... 6-69

C«NH»W 239 .... 100-00

When treated with phosphoric anhydride^ it does not yield cnmanil- nitrile. (Cahonrs, Ann. Fharm. 74, 40.) It diflsolres sparingly in alcohol.

Cumyl-sulphophenylamide.

C«NH"S*0« = C«(NH.C»H"0»)H»S»0*.

Gerhabdt k Chiozza. (1856.) iT. Ann. Chim. Phys. 46, 151.

Aioiure de tuffopMnyh et tThydrogine,

Preparation. Snlphophenylamide is treated with chloride of onmyl

in the oil-bath at a constant temperature ; it is then rapidly attacked,

and on cooling solidifies to an amorphous glassy mass, which may be

crystallised from alcohol. If the temperature were allowed to liae too high, cnmonitrile and sulphocarbolic acid would be produced.

Properties. Bectangalar prisms, with shining, well-developed ter- minal faces. Melts at 161^.

32 C N 17 H	... 192 ... 14 ... 17	.... 63-4 4-6 .... 5-6 .... 10*5 .... 15-9	Gerfaardt & Chiona. 63-3 4-7 5-7
2 S 6 O	... 32 ... 48
C»NHWS»0« ....	.... ,303	.... 100-0

XIY.

178 CONJUGATED AMIDBS OF THE CUMINIC SERIES.

When qaickly heated in a test-tnbe, it yields cnmonitrile. — Treated in a elightly ammoniacal solution with nitrate of silver^ it yields cnmyl- sulphophenylargent amide, and in presence of a larger quantity of am- monia, a sticky mass, prohably amidooumylsulphophenate of silYer."

It does not dissolve in boiling water. It dissolves readily in warm aqueous ammonia ; also in cold, and still more in hot alcohol.

Gmnyl-sulphophenylargentamide.

(?»NHWAgS»0« = C"(N.Ag.C~H"0*)H»S*0*.

Gerhardt & Chiozza. (1854.) Compt, rend, 88, 457 ; Ann, Pharm, 90, 107; fully, iV^. Ann, Chim,Phy8, 46, 153.

Azoture de su\fophinyle, de cumyU et d' argent.

Preparation. Cumyl-sulphophenylamide suspended in boiling water is dissolved by addition of a few drops of ammonia, and the solution is precipitated by nitrate of silver.

Properties, Very light, slender needles.

32 C

N 16 H

^« 28

60

		Gerhardt & Chiozza.
192	•••.	46-8	46-4
14	•■••	S-4	3-2
16	• •!•	8-9	3-9
108	«t«t	26-3
32	*»„	7-8
48	«•••	11-8

C»NHi«AgS«0« 410 .... 1000

It decomposes quietly when heated^ giving off cumonitrile. — It dis- solves readily in ammonia, and the solution when evaporated yields

cumyl-sulphophenyl-argent-hydrobiamide. Dcarcely soluble in boiling tvater.

Gmnyl-snlphophenyl-ai^ent-hydrobiainide.

C»N»H»»S»0« = C»(N.Ag.C»H"0»)H*S«0* + NH>.

Gerhardt & Chiozza. (1854.) Compt rend. 88, 457; Afm, Pharm, 90, 107; J.pr. Chem, 62, 49.— In detail, i\r. Ann. Chim. Phye, 46, 154.

Diazoiurt de iuffopMnylet de cumyle, d^argent, et d'hydrogene.

Preparation, By dissolving cumyl-sulphophenylargentamide in am- monia, and leaving the eolation to evaporate, if ,T.por.ted b, heat, it yidd.

an Oil.

Properties, Nacreous needles, grouped like a fan.

CUMYL-SALICYLAMIDB. 179

Gerhardt & Chiozsa*

32 C 192 .... 450 45-0

2N 28 .... 6-5 6-2

19 H 19 .... 4*5 .., 4-7

Ag 108 .... 25*3

2S 32 .... 7-5

6 O 48 .... 11-2

C»N«H»AgS«0» .... 427 .... 100-0

By continued boiling with wateVf it gives off a little ammonia. Disaolves very sparingly in boiling water. Soluble in alcohol.

Ctunyl-benzoyl-sulphophenylamide.

C«NH«SH)» = C»(N.C»H"0».C^*HK)*)H»S»0*.

Oebbardt & Ghiozza. (1863.) dympt, rend. 37, 86; Ann. Fharm, 87> 302. — In detail, iT. Ann. Chim. Phys. 46, 149.

Azoture de ntffoph^yle, de benxoUe et de cumyh.

Produced by the action of chloride of cumyl on benzoyl-sulphophenyl- argentamide, and obtained in confused prisms by dissolving the product in boiling ether and evaporating the ether.

Scarcely soluble in water. Dissolves with difficulty in afMnonia ; the solution is precipitated by acids and by the salts of Uad and silver.

Dissolves in alcohol more readily than benxoyl-salicylamide. Sparingly soluble in ether.

Gumyl-salicylamide.

0»*NH"0* = C~(N.C"H«0*)H»0«f

Oerhardt & Ghiozza. (1853.) Compt. rend. 37, 86; Ann. Pharm. 87, 301; /. pr. Chem, 60, 144. — In detail, N. Ann. Chem. Phy$. 46, 141.

Azoture de salieyle, de cttmyle et d^hydrogene.

Obtained by the action of chloride of cumyl on salicylamide (xii. 321), in a similar manner to beuzoylnsalicylamide.

Properties. Yerj light, shinine needles. Melts at about 200^^, be- eomes pasty at a stronger heat, and remains so on cooling.

34 C

N

17 H

60

			Gerliurdt & Ghioisa.
			mean.
204	• •••	72-0	I....... /I'od
14	• •••	4-9	610
17	• •••	60	6-10
48	■ •••	171	16-95

C«NH>70« 283 .... 100-0 10000

N 2

180 AZO-NUCLEUS Cr»NHn.

Az(hnucUu8 C«»NH".

Oumonitrile C«NH".

Fb. Field. (1847.) Ann. Pkarm, 65, 61; Afem, Chem. Soc S, 408; J. pr. Chem. 44, 136 ; Phil. Mag. J. 31, 459.

Formation. 1. By the dry distillation of caminate of ammonia, cuminamide being formed at the same time. — 2. By the action of bromide of cyanogen on cuminate of potash, carbonic acid being like- wise evolred. (Cahonrs, N. Ann. Chim. Phys. 52, 201; Ann. Pharm. 108, 320,

C»H"KO< + C?NBr = 2C0» + KBr + C*NH". 3. By the action of heat on cumyl-sulphophenylamide and on cnmyl-sulpho-

phenylargentamide. l^t in the preparation of cumyl-suIphophenyUmide, the mixtorB of chloride of cumyl and snlphophenylamide he too strongly heated, cnmonitrile and Bulphocarbolic add are produced. (Gerhardt & Chiozza, N. Ann. Chim Phys.

46, 157.)

Preparation. Cuminate of ammonia is heated in a retort to complete fusion and then maintained in violent ebullition, whereupon large drops of cumonitrile pass over together with water. As soon as the oil has completely passed over, it is separated with a pipette from the distillate^ and the watery liquid is poured back into the cooled retort, and redis- tilled five or SIX times. The whole of the oil thus obtained is freed by washing ^ith ammonia from traces of cuminic acid dissolred in the oil; it is then washed successively with hydrochloric acid and water, dried by leaving it for some days over chloride of calcium, and rectified. The portion which goes over last may contain water.

Properties. Transparent, colourless oil of sp. gr. 0*765 at 14^ Refracts light strongly. Boils constantly from platinum wire at 239*', under pressure of 0*7585 met Has a very strong, but agreeable odour, and a burning taste.

			Field.
			iRemi.
20 C	120	.... 82*76 ....	.... o£'oO
N	•••«• x^	•••• 9 DO ••••	.... 9*34
11 H	11	•••■ 7*do ....	7*77
C»NH"	145	.... 10000 ....	.... 99*94

Decompodttons. 1. The vapour of cumonitrile is inflammable and bums with a brilliant flame. — 2. Cumonitrile is but slightly altei^ by strong nitric acid in the cold, but on boiling, cuminic or nitrocuminio acid IS produced. — 3. Heated vriih potassium, it 'becomes darker and forms a large quantity of cyanide of potassium. — 4. Alcoholic potosA, does not alter it immediately, but converts it, after a few days, into a crystalline pulp consisting of the oil turned yellow and cuminamide.

Cumonitrile dissolves but slightly in water, and renders it milky.

PARANICINE. 181

Paranicine.

(P^NHw = C»NH",H*.

St. Eybe. JV. Ann. Chim. Phya. 25, 506; Ann. Phartn, 70, 266; J, pr. Chem. 46, 468.

Compare page 142.

Formation and Preparation (comp. p. 169.) Sulphuretted hydrogen is passed through alcoholic solution of nitroparanicine saturated with ammonia; the liquid is evaporated; the residue is dissolved in weak hydrochloric acid ; and the filtrate is left to crystallise, whereupon octo- hedrons of hydrochlorate of paranicine separate out From this salt ammonia precipitates paranicine in pale yellow flocks.

20 C N 13 H	120 14 18	.... 81*63 ... .... o*d4 ...	St. E^re. 81*34 ..... af'tfl 8*82
0»NH»	147	.... 100*00 ...	99*67

If paranicine be dissolyed in ether immediately after precipitation, and the ether then evaporated, there remains an amber^oloured oil, which dissolves in hydrochloric add, and is precipitated by ammonia in snow-white flocks. These flocks dissolve in cold ether, and on evaporating remain as a solid massy without passing throagh the liquid state.

Paranicine is insoluhle in water.

Its solutions in dilute nitric^ acetic and oxalic acids, yield crystallis- able salts soluble in water.

Hydrochlorate of Paranicine, Octohedrous which redden litmus. Decomposes readily by contact with the air. Insoluble in cold water.

St. Evre.

20 C 1200

N 140

14 H 14*0

CI 36*9

	mean.
65*57 ....	.... 65-69
7-65 ....	.... 7*86
7*65 ....	.... 7*73
1913

C~NH» HCl .... 183*6 .... 100*00

Chloroplatinate of Paranicine, Obtained by precipitating the hydro- chlorate with bichloride of platinum. Crystalline precipitate which becomes liquid after a while, and is altered by light and air.

St. Evre.

20 C 120-0 .„. 34-00 33-71

N 14*0 .... 3*97

14 H ., 14-0 .... 3*97 4-31

Pt 98*7 .... 27-96 27*77

3 CI 106-2 .... 30-10 2900

C*»NH",HCl,PtCl« 362-9 .... 10000

Paranicine is soluble in acetic add. and in ^/ter.

182 CHLORAZO-AMIDOGEN-NUCLEUS C»CPNAdIP,

CfklorassO'amidoffen'nudeus C'^l'NAdH^

Chloronicine.

C»N»C1«H» = C»Cl»NAdH«,H«

St. Eybe. (1 849.) N, Ann, Chim. Fhys. 25, 499; J. pr. Chem. 46, 463; Ann. Pharm, 70, 265.

Formation and Preparation (comp. p. 173.) Into an alcoliolio solution of nitrochloronicine, ammonia gaa and hydros alphnric acid are passed alter- nately, as long as snlphur continues to deposit; the liquid is lx>iled down ; the residue exhausted with dilute hydrochloric acid, and the gold-yellow filtrate evaporated to the crystallising point In this manner, hydro- chlorate of chloronicine is obtained, the concentrated aqueous solution of which, on being mixed with ammonia, deposits brown flocks of chloro- nicine, which dissolve on addition of more water and are therefore difficult to purify.

St. Evre.

20 C 1200 .... 61-99 5154

2 N 280 .... 1213 13-39

2 CI 70-8 .... 30-67 29*58

12 H 12-0 .... 5-21 5-61

C»N»CPH« .... 230-8 .... 100-00 100-12

St. Evre rappoiecl the atomic wdgbt to be half this amoimt. Laurent & Gerhardt doubled bis formula (Compt chim, 1849, 163).

According to Gerhardti the compound is perhaps identical with chloranfline (oomp. p. 142).

Decompositions. 1. The solution of hydrochl orate of chloronicitie neutralised with ammonia acquires an alkaline reaction after a while from decomposition. The solution of chloronicine in ether leaves on evaporation a pale brown oil which dissolves completely in cold hydro- chloric acid, forming a solution from which ammonia throws down para- nicine (p. 181.)

HydrocMorate cf Chloronicine. Light yellow, slender prisms, gene- rally united in stars by threes. Reddens litmus strongly. Turns brown on the surface when exposed to the air. — its concentrated solution mixed with a few drops of ammonia, immediately turns hyacinth-red and deposits chloronicine

in brown flocks. Dissolves very easily even in cold water.

St. Evre.

20 C 120-0 .... 39-52 4032

2 N 280 .... 9-22 9*91

4 CI 141-6 .... 46-62 45*52

14 H 14-0 .... 4-64 5-48

C»N2C1*H» 2HC1 303-6 .... 10000 101-23

Chloride qf mercury precipitates hydrochlorate of chloronicine.

CTMENB. 183

CMoroplatinate of Chloronicine. Prepared by mixbg aqueous hydro- clilorate of chloronicine with bichloride of platinum, evaporating^ and washing the deep yellow granular precipitate with ether.

St« ATTQ*

20 C 120'0 .... 18-67 18*83

2 N 28*0 .... 435 5-38

8 CI 283'2 .... 44-07 4364

14 H 14-0 .... 2-18 1-93

2 Pt 197-4 .... 30-73 3022

C»NK:1»H» 2HCl,2PtCl2 ... 642-6 .... 10000 100-00

Acetate of Chloronicine, Chloronicine recently prepared and dried in vacuo, is dissolved in dilute acetic acid, and the solution is evaporated in vacuo.

Pale yellow, four-sided prisms, easily decomposible by light and air. Has an acid reaction, even after repeated reorystallisation.

St. RVTBa

28 C 168-0 .... 47-88 47*66

2 N 28-0 .... 7-98 8-41

2 CI 70-8 .... 20-18 19-88

20 H 20-0 .... 5-70 632

8 0 64-0 .... 18-26 1783

C»N'CPH",2C<H<0<.... 350-8 .... 100-00 10000

Primary Nudeui C»H".

Cymone. C»H".

GERHARDT& Gahours. (1841.) N. Awn, Chim. Fhys. 1, 102; Ann.

Fharm. 38, 101. N. Ann. Chim. Fhys. 1, 372; Ann. Fharm. 38,

345. Z. Delalande. (1841.) N, Ann. Chim. Fhys. 1,368; Ann. Fharm.

38, 342. NoAD. Ann. Fharm. 63, 281; Mem. Chem. Soc 8, 421; Fhil. Mag. J.

32, 15; abstr. t/.^r. Chem. 44, 145. Mansfield. Ann. Fharm. 69, 162; Chem. Soc. Qu. J. 1, 244. Kraut. Denertation nber CuminoL und Cymjen. Gottingen, 1854;

abstr. Ann. Fharm. 92, 96; J. pr. Chem. 64, 159; I^. Ann. Chim.

Fhys. 43, 347. Church, i^. Fhil. Mag. J. 9, 256; J. pr. Chem. 65, 384.—^. FhxL.

Mag. J. 13, 415; J. pr. Chem. 72, 125; Ann. Fharm. 104, 111. A. W. HoFMANN. Ann. Fharm. 97, 206; N. Ann. Chim Fhys. 52, 104. Barlow. Ann. Fharm. 98, 245. Haines. C^em. Soc. Qu. J. 8, 289; J. pr. Chem. 68, 430; Chem. Centr.

1856, 593. Lallbmand. N. Ann. Chim. Fhys. 49, 156; abstr. Ann. Fharm. 102,

119. SiEYEKiNO. Dissfrtation iiber Cuminol und Cynien, Qott. 1857; abstr.

Ann. Fhat^. 1 06, 260.

184 PRIMARY NUCLEUS C»H",

J. Tbapp, Pder$b. Acad. BuU. 16, 296; Ann. Pharm. 108, 386; J. pr. Chem. 74, 428.

Cfymen, Cymol, Camphogen (Delalande). Camphene, Hydride qf Thymyl, ThymyU fDaiseritcff,

Sources. In Roman oil of cumin, the volatile oil of Cuminum Cyndnum (Gerhardt & Cahours. For the amount see p. 144.) — In the volatile oil of water-hemlock {Cicuta virasa), (Trapp, p. 145); in the volatile oil of Ftychotis Ajoioan, according to Haines; but according to Stenhouse, it does not occur in that oil (see Thymol.) — In volatile oil of thyme (Lallemand.) Mixed with thjmene, it forms the greater part of that which distils below 180", and may be obtained by agitation with oil of vitriol, which dissolves the thymene, while cymene floats on the surface (Lallemand).

Formation. 1 . In the dry distillation of coal, passing over into the lighter, but for the most part into the heavy oil of coal-tar (Mansfield.)

— 2. By distilling camphor with phosphoric anhydride (Delaland); with chloride of zinc (Gerhardt.) — 3. In the action of moist carbonic acid gas on oil of turpentine at a low red heat, there is produced, with evolu- tion of carbonic oxide, an oil having the composition of cymene (Deville Ann, Ohim^ Fhys. 75, QQ):

C»HW + 2C0« - C»HW + 2H0 + 2CO.

4. By boiling cuminic alcohol with alcoholic potash (Kraut.) — 5. When purined oil of wormwood is repeatedly distilled over phosphoric anhy- dride, and finally over potassium, a compound is obtained similar to or identical with cymene f Leblanc, N. Ann. Chim. Phys. 1 6, 334.) — 6. Oil of wormseed (the volatile oil of the officinal Semen Cynce) does not contain cymene ready formed; but from the cinsabene (C"H* or C*H") and cmcebene-carophor (C*°H'0 or C*H^®0*) contained in it, cymene is pro- duced, toother with other oils, by heating with iodine or with dilute nitric acid. a. By distilling wormseed oil with iodine, agitating the product with potash-ley, then with mercury and lumps of potash, a mixture of cymene, cinsBbene and ciusebene-camphor is obtained. — b. When wormseed oil is distilled with 2 vols, nitric acid of sp. gr. 1'16, nitrous fumes are evolved and volatile oils pass over. At the same time there is produced a resin, which, by continued boiling with an additional 2 vols, nitric acid, is converted into toluylic acid, nitrotoluylic acid and other products. Hence Hirzel supposes that cymene is first formed and immediately undergoes further alteration. (Hirzel, Zeitschr, Pharm. 1854, 23 and 67; 1855, 84 and 181; see also infra, Wormseed-oil.)

Preparation. From Eoman OU of Cumm. — 1. The portion which passes over in fractional distillation below 200^ is rectified over caustic potash, the whole of the cuminol then remaining behind as cuminate of potash. (Gerhardt & Cahours.) The cymene thus ohtained amoimta to 41—44 per cent, of the Roman oil of cumin. (Noad.) — 2. The cuminol is separated in the manner described at page 145, and the cymene is dried and rectified.

— 3. If it be not desired to obtain the cuminol, or only as cuminic acid, the Roman oil of cumin may be decomposed with alcoholic potash, as described at page 149. (Kraut.)

B. From Coal-tar Oil. (See xi, 135, 136.)

CTMBNE. 185

C. From Camphor. Camphor is repeatedly distilled with phosphoric anhydride (Delalande), or better with fused chloride of ziuc, a few pieces of chloride of zinc being heated in a capacious tubulated retort to inci- pient fusion, and camphor added by small portions, whereupon the mix- ture froths up and blackens, and a distillate passes over still containing a large quantity of camphor. This distillate must be purified by repeated rectification over chloride of zinc. This process yields a lar|e quantity of cymene with a compantiTely small quantity of chbride of sine. (Qerhardt, Traits, 3, 608.)

Properties. Colourless, strongly refracting oiL (Gerhardt & Cahours.) Boils at 170-7° (ChurchJ; 171° (Mansfield) ; 171-5^ (Noad); 175° (Ger- hardt & Cahours ; Delalande ; Lallemand) ; at 177 5°, correction being made for the lower temperatures of the column of mercury in the stem of the thermometer. (H. Kopp, Ann. Pharm. 94, 819.) Cymene prepared from Roman oil of cumin boils after rectification over sodium at 170*7**» but after treat- ment with oil of vitriol aided by heat, and separation with water, it boils at 175 — 176° like the camphor prepared with chloride of zinc. (Church.)

Sp. gr. = 0-845 at 267° (Haines) ; 0*857 at 16° (Noad) ; 0*860 at ia° (Delalande) j 0*860 at 15^ and 0861 at U^' (Gerhardt & Cahours) ; 0*8678 at 12*6° = 0*8778 at 0°. (Kopp.) — Has an agreeable odour of lemons (Gerhardt <& Cahours, Noad) ; when prepared from camphor it haj9 a different odour (Gerhardt & Cahours) like that of camphor (Noad) ; but cymene prepared from Roman cumin-oil, if treated with oil of vitriol, and separated by water, smells like that prepared from camphor. (Gerhardt.) Oyvene prepared from Ptychotis has a sweetish, smoky odour. (Haines.) Permanent in the air.

(Gerhardt & Cahours). Vapour-density = 4*64 (Gerhardt & Cahours) ; 4*69 (Delalande.)

Gerhardt & delalande. Leblanc Kraut. Haines. Cahours.

mean.

20 C «.. 120 .... 89*56 89-07 .... 88*75 .... 88*9 .... 8895 .... 89*87

14 H 14 .... 10-44 10-83 .... 10-38 .... 10-6 .... 10*81 .... 10*66

C*H*< 134 .... 100-00 99*90 .... 99*13 .... 99*5 .... 99*76 .... 100*53

Vol. Density.

C-yapour 20 8-3200

H>gas 14 0-9702

Vapour of Cymene 2 9-2902

1 4*6451

The cymene analysed by Gerhardt & Cahours, was prepared from Roman oil of cumin ; De]alande*s from camphor ; Leblanc's from oil of wormwood ; Haines's from oil of Ptychosis ; Krauts from cuminic alcohol.

DeeomposUions. 1. On passing air for several months through cymene prepared from oil of thyme and contaminated with thymene, it becomes viscid, assumes a dark red colour, and partly disappears ; the mixture then yields thymene to aqueous potash. (Lallemand.) — 2. Cold fundng siUphwic acid dissolves cymene with dark red colour, without evolution of sulphurous acid, and forms sulphocy- molic acid. (Gerhardt <fc Cahours ; Delalande.) Ordinary oil of vitriol has no action upon cymene. (Gerhardt & Cahours.) Cymene exposed to the vapour of anhydrous sulphuric acid assumes a red and ultimately a black colour, becomes viscid, and forms with water a slightly coloured

186 PRIMARY NUCLEUS C»H".

solution of fiulpbocymolic aoid— dark-oolonied if tlie solphurio acid is in excess or brought into the liquid too quickly —which on standing deposits a thick oil still containing a large quantity of cymene. No product analogous to sulphide of benzene is formed in this reaction. (Sieveking.) — 3. Bromine and cldorine^ in presence of water, unite with cymene directly and without evolution of hydrochloric or hydrobromic acid, and form bromide or chloride of cymene and hydrogen. (Sieveking.) Dry chlorine heats cjrmene, turns it brown and chars it. When cymene is repeatedly subjected to slow distillation in a stream of chlorine, a large quantity of hydrochloric acid is evolyed, and finally between 170"^ and 230*^, an oil passes over containing 10*7 per cent, of chlorine, similar to that which is produced by the action of alcoholic potash on chloride of hydrogen and cymene. (Sieveking.) — According to Gerhardt and Gahours, bromine or chlorine eliminates hydrobromic or hydrochloric acid gas, and forms a brominated or chlorinated product, which is decomposed by distillation. — Cymene does not absorb hydrochloric acid gas. — 4. Cymene carefully mixed with strongly cooled (fuming ?) nib'ic acid, forms nitrocymene. (Barlow.) Moderately dilute nitric acid does not act upon it at mean temperaturo, but converts it, at the boiling heat, into a peculiar acid (Gerhardt & Cahours), into toluylic (xiii, 8) and nitro- toluylic acids (xiii, 22.) (Noad.) — 5. NitrostUphuric acid, when strongly cooled, scarcely affects it, but at 50° converts it into an oil, from which after some time binitrocymene separates. (Kraut.) — 6. Cymene is not at all affected by caustic potash. (Gerhardt & Cahours.) — 7. Heated with bichromate of potash arid sulphuric add, it is converted into insolinic

acid (xiii, 31 8.) (Hofmann.) It U violently attacked thereby and converted into an oil which is not altered by canatic potash. (Gerhardt and Cahours. It is not de- composed by continued digestion with chromic acid. (Noad.) — . 8. It is not altered

by digestion with sulphuric acid and peroxide of manganese. (Noad.) -* With permanganic acid, it solidifies to a pulp of hydrated manganic oxide, without formation of a peculiar acid. (Noad.)

GombifMUions. Insoluble in unUer, Does not combine with alkaline bisulphites. (Bertagnini, Ann. Fharm. 85, 186.) Dissolves readily in alcohol, ether and/a< oils, (Gerhardt & Cahours.)

Appendix to Cymene,

a Cymene. cr»H".

Barlow. Ann. Pharm. 98, 245.

By treating nitrocymene with a pulp of acetic acid and iron filings, Barlow obtained, besides cymidine, an oil which was insoluble in hydro- chloric acid, boiled at 175° after repeated rectification, and contained 89*21 per cent. G and 10-67 H. It had therefore the composition of cymene, but when treated with fuming nitric acid, it yielded nitrocymene lighter than water ; hence Barlow distinguishes it as a-cymene.

CABYOPHYLLIN. 187

Garyophyllin.

C»H*K)* = CS»H",2H0?

LoDiBERT. (1825.) J, Pharm. 11, 101; N. Tr, 11,1, 108; abstr.

Kastn, Arch, 5, 463; Bepert, 22, 134. BoNASTRB. J. Pharm. 11, 103; N. Tr. 11, 1, 112; abstr. Kattn. Arch.

5, 463; Eepert. 25, 134; J. Pharm. 13, 519. Chazbrbau. X Pharm. 12, 258.

Dumas. Ann. Chim. Phy$. 53, 169 ; Ann. Pharm. 9, 73 ; Pogg. 29, 90. Mylius. J.pr. Chem. 22, 105. Jahn. Ann. Pharm. 19, 333. MuBPRATT. Pharm, J. Trans. 10, 343; Liebig & Kopp^a JahrcAer,

1850,510.

NelJtele(nnpker, Stearoptene qfoil qfelove$, DiscoTered by Lodibert & Baget.

Sources. Occurs abandantlj in East Indian cloves, in smaller qnan- iity in those from Boarbon, not in those from Cayenne. (Lodioert, Bonastre.) It is not decidedly known whether the camphor which, according to Bizio {Brvgn. Giam. 19, 360), is deposited from oil of cloves in the cold, is identical with caryophyllin.

Preparation. Cloves immersed in cold alcohol are left to stand for about a fortnight till the crystalline deposit of caryophyllin no longer increases ; the precipitate is then collected on a filter. (Lodibert.) The resin which adheres to them may be removed by washing with aqueous soda. (Bonastre.) Mylius washes the caryophyllin which separates spontaneously from oil of cloves with cold alcohol, and crystallises it from boiling alcohol. Muspratt exhausts cloves with ether, separates the caryophyllin by water, and purifies it by treatment with ammonia. The prodact amounts to about 3 per cent, of the cloves. (Bonastre.)

Pivperties. Spherules composed of radiating, white needles having a silky lustre, somewhat rough to the touch, not phosphorescent when rubbed. (Bonastre.) When heated it melts like a resin (Bonastre) sinters together somewhat at 320°, but does not melt till heated above 330% forming a glass of faint yellow colour, which on cooling solidifies in crystalline nodules, melts again on renewed and stronger application of heat, and then solidifies on cooling to a mass exhibiting numerous fissures. This glass if again heated, becomes white and turbid, as if from incipient crystallisation, but melts again to a clear liquid, and flies to pieces sud- denly on cooling. After stronger heating, it becomes much more easily soluble in alcohol, forming a yellow solution, and being at the same time converted into a bitter astringent substance. ^Mylius.) At 280° it begins to volatilise Twith an odour of resin aocordmg to Bonastre), with- out colouring or fusion, and may be completely sublimed in an air-bath between 280° and 290° (Mylius) ; at 285^ (Muspratt.) Tasteless and inodorous. Neutral. (Bonastre.)

20 C 16 H	120 >.... lo	.... 7o-"4 ... .... xU Oo ... .M. xU*9<j ..■	Dumas. mean. 78-13 10-48 11-39	Mylius. mean. .... 78-14 .... 10-65
2 O	16	.... 11-21
C»HWO* ...	162	.... 100-00 ...	10000	.... 10000

Ettling {Liebig, Org. Chem. 338) and Muspratt obtained numbers corresponding to the formula C^RWO^.

188 CONJUGATED COMPOUNDS OF THE PRIMARY NUCLEUS C«H".

Decompositions, Caryophyllin huriM with a bright, white faliginoiis flame. (Jahn.) — 2. It dissolves in oU of vUriol' wiiAi rose-colour, changing to blood-red (Bonastre) ; it assumes with oil of vitriol an orange- colour, changing to blood-red, and when heated, to carmine-red, and then to brown with evolution of sulphurous acid. From the cold-prepared solution in oil of vitriol water throws down unaltered caiyophyllin ; and the portion which has not been dissolved by the oil of vitriol, but con- verted into a blood-red mass, swells up by contact with water and changes to a white, loose, semicrystalline tissue. (Mylius.) — 3. It is not altered by cold nitric acid (or even by the warm acid, according to Mylius) ; but by the boiling acid it is converted into a resin (with the fuming acid, a slight evolution of nitrous gas takes place), without formation of oxalic acid. (Bonastre.)

Cornbinations, Insoluble in water, even at the boiling heat. (Mylius, Jahn.)

Insoluble in dilute mineral adds, (Mylius.) Aoeording to Chazerean, it diBsolTes in water acidulated with Bulphurio acid. Insoluble in amw^jwi and potcuhy whether caustic or carbonated. (Mylius.)

Sparingly solable in aqueona 9oda, and somewhat more in aqaeoua pota»k, (Bonastre.)

Sparingly soluble in strong acetic acid ; insoluble in cold, soluble in boiling alcohol ; easily soluble in ether ; in both these liquids, however, it dissolves less readily, in proportion as it is more free from resin. ^Bonastre.) The alcoholic solution becomes milky on addition of water. (Jahn.) — Soluble in rectified oil of turpentine^ less in rock-oil. (Jahn.)

ConjugaUd compounds of the Pt^vmary-nudeus, C*H".

Sulphocymenic Acid.

C»H"S»0» = C»H",2S0».

Oerhardt & Cahours. (1841.) N, Ann. Chim. Phys. 1, 106; «/. pr.

Chem. 23, 355; Artn. Pharm. 38, 101. Delalande. N. Ann, Chim. Phys, 1, 368; Ann. Pharm. 38, 342. Church. Phil. Mag, J. 9, 256; J. pr. Chem. 65, 384. SiEVEKUiG. Dissertation uher Cuminol und Cymen. Qbtt. 1857, 17;

abstr. Ann^ Pharm. 106, 257; J. pr. Chem. 74, 505.

SulpkoeymoHe aeid, dcide tuffO'Cymenique (Gerhardt & Oahoors). Aeide su^o^ eamphique (Delaland.) 8u{foeymyUawre (SieveldDg). Adde thymyl-auffureiuf (Ger- hardt). CyineichwrfeUdure.

Formation, (p. 185.) — It appears also to be produced by the action of fuming oil of vitriol on chloride of cymene and hydrogen (see below). (Sieveking )

Preparation. Cymene is dissolved in a slight excess of fuming sul- phuric acid (the mixture being cooled, according to Gerh%rdt & Cahours; heated in the water-bath* according to Delalande); the liquid is diluted with water, satu- rated with carbonate of lead, and filtered ; and the solution of sulpho- cymenate of lead is evaporated to the crystallising point. — The aqueous solution of the crystals decomposed by sulphuretted hydrogen, and eva- porated iu vacuo after filtration, yields sulphocymenic acid. (Delalande.)

SULPHOCYMENIC ACID. 189

As the solution of the lead-salt is apt to decompose daring evaporation, and leave a dark-brown mass, the solution of which is not decolorised by sulphuretted hydrogen, Sieveking decomposes the baryta-salt with dilute sulphuric acid, removes the excess of that acid by carbonate of lead, and the dissolved lead by sulphuretted hydrogen, and thus obtains aqueous Bulphocymenic acid.

Properties. Small deliquescent crystals. (Delalande.)

Decompositions. 1. With fuming nitric add, it easily forms nitro- sulphocymenic acid, the salts of whicn detonate when heated. (Church.) — 2. The dry baryta-salt brought in contact with pentachloride of phosphorus, yields a yellowish distillate, which, when mixed with water, deposits a heavy brown oil. (Sieveking.)

Comhinations. With metallic oxides it forms the sulphocymenaies. These salts are all soluble ; hence the solution of the baryta-salt does not precipitate metallic salts. (Gerhardt <& Cahours.)

Svlphocymenate of Soda. — Obtained by precipitating the solution of sulphocjrmenate of baryta with an exactly equivalent quantity of carbo- nate of soda, and evaporating the filtrate over the open fire.

Slender needles or laminze having a silky lustre. Dissolves very readily in water and alcohol. Contams 5 At. water of crystallisation^ which go off at 1 70°. (Sieveking.)

Sieveking.

TMOU.

C»H"S20« 213 .... 75-80

Na 23 .... 8-18 8*22

5 HO 45 .... 1602 1480

C»NaH"S20« + 5Aq 281 .... 10000

Stdphocymenate of Baryta. — The solution of cymene in fuming sul- phuric acid (gently heated, according to Gerhardt <& Cahours) is satu- rated with carbonate of baryta, and the filtrate is evaporated to the crystallising point.

The crystals heated to 100° (Gerhardt & Cahours), 130° (Trapp), 170° (Sieveking) yield the anhydrous salt.

Gerhardt & Cahours. Dry. mean.

20 C 120-0 .... 42-61 42-15

13 H 130 .... 4-62 4-70

Ba 68-6 .... 24-36 24-10

2 8 32-0 .... 11-.36 11-60

6 0 48-0 .... 17-05 17-45

C»BaH«S20« 281-6 .... 100-00 100-00

The salt prepared with cymene from cicata-oil, contains 24-75 p. c. Ba (Trapp).

Compounds with Water. Sulphocymenate of baryta crystallises with 2 At. water (Gerhardt & Cahours), 3 Ai (Sieveking) with 4 At. (Dela- lande).

190 CONJUGATED COMPOUNDS OF THE PRIMARY NUCLEUS C»H".

a. Birhydt'oUd, — CrystalliBCS bj cooling or evaporatioii in lainin» haying a strong pearly lastre. (Gerhardt & Cahours.)

Gerhardt &. Cahoan.

20 C 120.0 .... 4005 3990

15 H 15.0 .... 502 5-25

Ba 68-6 .... 22-88

2 S 32.0 .... 10-66

8 O 64.0 .... 21-39

C»BaH"S«0« + 2 Aq 2996 .... 100-00

/3. Ter-hydvated. — The solution eraporated till a crystalline film forms on its surface and cooled, yields the ter-hydrated salt in pearly laminsB having the form of Brookite. (Sieveking.)

Sieveking.

20 C 120-0 .... 38-9

13 H 13-0 .... 4-2

Ba 68-5 .... 22-2 2230

2S 320 .... 10-4 1003

6 0 480 .... 15-6

3 HO 27-0 .... 8-7 8-67

C»BaHWS»0« + 3Aq .... 3085 .... 1000

<y. Tetra-hydrated. — Laminsa obtained by evaporation and recry- stallisatiou.

DeUlande.

20 C 120-0 .... 37-78 35-41

17 H 17.0 .... 5-35 5-67

Ba 68-6 .... 21-59

2 8 32-0 .... 10-07

10 O 800 .... 25-21

C»BaH»S80« + 4Aq 317-6 .... 10000

• _

Contains, according to Delalande (in accordance with his incorrect calculation of the tetra-hydrated salt) 26-1 p. c. of baryta, which however would come nearer to the quantity of baryta in the bi-hydrated salt (calculation^ 25*5 BaO).

B, Aqueous SoltUum, The barvta-salt dissolves readily in water, alcohol and ether. The aqueous solution decomposes when boiled ; the hot-saturated solidifies on cooling. (Gerhardt & Cahours.) Tastes bitter, then disagreeably sweet ; saccharine.

Interpolation. StUphocymenate qf Baryta containing the acid C^H^S'O'.

Gerhardt & Cahours, by neutralising crude sulphocymenic add, m the cold, with carbonate of baryta, once obtained a confusedly crystalline mass, which dissolved in water much more readily than the ordinary (hot-prepared) salt, and contained 15*75 p. c. barium, whence they regarded it as C'*^H^BaS^O^ (calculation 16*4 Ba.) Sieveking did not succeed in preparing this salt.

SvlphocymencUe of Lime, Obtained by neutralising crude sulpho- cymenic acid with marble. Thin colourless laminao (having the taste of the baryta-salt, according to Delalande), very soluble in water and alcohol. Gives off 1 At. water (7*97 p. c.) at 150% then 2 At. more (13*4 p. c. in all) at 170°, and then contains 7*98 p. c. alcum (C*H»CaSK)* =s 8-5 Ca). (Sieveking.)

ANBTHOL OR ANISB-CAMPHOR. 191

Sidphoeymenate of Lead. — FreparatUm (p. 188). Pearly lamin® which, at 120°, give off 10-3 p. o. water (4 At. = 10*24 p. c.) without further alteration. (DelaJande.)

Lamitue. Delalande.

20 C 120-0 .... 34*02 33*75

PbO 111-8 .... 31-69 31-80

17 H 170 .... 4*82 4-60

2 S 320 .... 9'07 9-40

9 O 72-0 .... 20-40 20-45

C»PbH»S«0« + 4 Aq 352-8 .... 100-00 10000

When prepared with cymene obtained from oil of cicata, it containsy after drying at 123% 32-56 p. c. lead (C»HwpbS«0« « 32-74), Trapp.

Cupric StUphocymenate, Ohtained by decomposing the baryta-salt with sulphate of copper. Light green laminae with a silky lustre, easily soluble in water and alcohol. (Sieveking.)

StdphocymenaU of Silver, The solution of carbonate of silver in sulphocymenic acid becomes coloured when evaporated in vacuo or over the water-bath, and leaves a brown residue containing a few needle- shaped crystals. (Sieveking.)

Oxygen-nucleua C*H"0*.

Anethol or Anise-camphor.

GuNTHBR. Aim. 1783, 156.

Saussuri. N. Ann. Chim. Fhys, 13, 280.

J. BuMAS, Ann. Fharm. 6, 253.

Blanchbt & Sell. Ann, Pharm. 6, 2873 (?)

CAHOtrits. Rev. Bcient. 1840, 342; J. pr. Chem. 22, 58; in detail, i^T.

Ann. Chim. Fhya. 2, 274 ; J. pr. Cfiem. 24, 337; Ann. Fharm. 41,

56; Compt. rend. 19, 795; in detail, iV. Ann. Chim, Fhys. 14, 489;

J. pr, Chem,. 36, 421. Laurent. Compt. rend. 10, 531 ; 12, 764; Rev. acient, 10, 5 and 376 ;

J. pr. Chem. 27, 232. Gerhardt. Ann. Chim.Fhys. 72, 167; Compt. rend. 15, 498; N. Ann,

Chim. Fhys. 7, 292; Compt. chim. 1845, 65; J. pr, Chim. 36, 267;

abstr. Compt. rend. 20, 1440.

Investigated particularly by Cahonrs, Latirent and Gerhardt, the last of whom recognaised the chemical identity of oil of tarragon with oil of anise and oil of fennel. The chief constitaents, chemically similar bat physically different, of the oils of anise, star- anise, fennel, and tarragon, are here united under the name anethol, which was formerly used provisionally by Gerhardt for anisoin.

Sources. The volatile oils of anise {Fimpinella Anisum), fennel

192 OXYGEN-NUCLEUS C»H«0«.

(Anethum MgnunUnm), tarragon (Artemisia Dracuncului), and star-anise {Illicium anisatum), consist almost wholly of anetbol ; and with the same mode of preparation, the oils of anise, fennel, and star-anise consist in some cases of a solid crystallisable variety of anethol^ in other cases of liquid anethol ; in the latter case^ they generally contain also small quantities of a hydrocarbon isomeric with oil of turpentine. Anethol exists ready formed in the plants, and, according to Mohr, sometimes separates in the form of a flocculent wool, from bruised fennel seeds which have been left to themselves for a long time. (Comment, tur Fretus. Fharmakopoe, 2, 207.)

Separation : a. Of solid Aneiliol (Anise or Fennel Camphor) from Oil of Anise^ Fennel, or Star-anise (see p. 191). The commercial oil is left to solidify at 0°, and pressed between filtering paper (Saussure) as long as the paper takes anything up, then crystallised two or three times from alcohol of sp. gr. 0*85 (Cahours), from warm alcohol of 90 p. c, and freed from adhering alcohol by fusion. (Blanchet & Sell.) The water which passes oyer with oil of fennel, deposits anethol, on keeping, in broad white lamixue. (Btzio, Brugn, Giom, 19, 360.)

b. Of liquid Anethol from Oil of Fennel ar Oil of Tarragon. Oil of fennel is subjected to fractional distillation, and the portion collected which passes over at 225° (Cahours) ; or the same process is applied to oil of tarragon, and the portion collected which passes over at 206° (Laurent) ; the last portions of the distillate are collected and rectified till a product of constant boiling point is obtained. (Gerhardt.)

Properties. Anethol exhibits totally difiTerent properties^ according as it is obtained from one or other of the above-mentioned oib.

a. Solid Anethol from Anise, Fennel, or Star-^nise oil. Anise-camphor^ Stearoptene of Anise-<yU. — White, granular mass. (SanssureV White shining laminsd. (Cahours.) Hard as white sugar (Saussure) ; friable, especially at 0""; melts at 16° (Bbinchet & Sell), 18° (Cahours), 20° ^aussure) ; at 15^ in the fresh state; at 20'', after keeping for a year. (Bizio.) boils at 220° (Blanchet & Sell) j at 222°, almost without decomposition (Cahours), and without alteration of the melting point. (Blanchet & Sell.) Sp. gr. of solid anethol at 12° =: 1*044; in the liquid state at 25° = 0-9849 ; at 50° = 0"9669 ; at 94° = 0-9256, the sp. gr. of water at 1 2° being supposed = 1 . (Saussure.) Has a fainter and more agree- able odour than anise-oil. v apour-density =5*19 at 338°, greater at lower temperatures. (Cahours, Compt rend, 20, 51; Fogg. 65, 420;

comp. Tii, 54.) Permanent in the air. (Blanchet & Sell.) Less volatile at ordinary temperatures than common camphor.

h. Liquid Anethol from Oil of Fennel. Oil which does not solidify at 10°. Lighter than water. Boils at 225°. (Cahours, see p. 191.)

c. Liquid Anethol from Oil of Tarragon, Colourless mobile oil, having the taste and odour of oil of tarragon. (Laurent.) Smells like oil of anise. (Gerhardt.) Sp. gr. 0*945 at 15°. Boils at 206°. Vapour-density = 6*157 (Laurent), 5-34. (Gerhardt.) Permanent in the air. (Laurent.)

ANETHOL OR ANISB-CAMPHOR. 193

Dvmas. if^, & Sell.

20 C 120 .... 81*08 80-18 .... 80-71

12 H 12 .... 811 8-28 .... 8-13

2 0 16 .... 10-81 11-54 .... 11-16

C»H>H)» 148 .... 100-00 100-00 .... 100-00

Cah<mra. Laurent. Oerhardt.

20 C 80-96 .... 81-00 .... 80-81

12 H 8-12 .... 8-85 .... 8-46

2 0 10-92 .... 10-15 .... 10-73

C*HBO* 100-00 .... 10000 .... 10000

Vol. Densitj.

Cvapour 20 8*3200

H-gas 12 0-8316

0-ga« 1 1*1093

Vapour of anethol .... 2 10*2609

5-1305

Solid anethol from aniae-oil (Dumas); liquid from tarragon-oil (Laurent, Ger- hardt). Blancbet & Sdl examined solid anethol from anise and fennel oil; Cahours, solid anethol frt>m anise-oil, and liquid from fennel oil with lilce results. For the composition of tarragon-oil, Laurent formerly gaye the formulae CP*H**0' and CH'^O'.

Deeampoaitions. 1. Anethol exposed to the air in the liquid state

jpraduallj loses the capability of crystallising (Cahours), and finally

changes to a resin. (Saussure.) Melted anethol, hut not the solid substance, absorbs oxygen from the air and thickens. (Blancbet & Sell, comp. p. 192.)

2. Anethol is inflammable, and bums easily with red, smoky flame. (Giinther, Laurent.)

9. Hydrated phosphoric acid converts it into anisoin. When distilled with anhydr<ms phosphoric <icid, it does not give off any hydrocarbon, bnt is eonyerted into anisoTn, part of which is decomposed dnring the distillation. (Cahours.)

4. Oil of anise mixed with small quantities of oil of yitriol, becomes heated, acquires a fine blood-red colour, and is converted into anisoin. It dissolves completely in 3 or 4 pts. of oil of vitriol (even in the fumiuff acid^, and after 24 hours, water separates part of it as unaltered oil, while the other portion remains dissolved, probably as sulphanetholic acid. (Cahours.) Tarragon oil is tnmed brown and resinised by Aiming sulphuric add, and on adding water, anisoin is precipitated, while a portion remains ^ssolred in combination with sulphuric acid. (Laurent.)

5. Solid anethol in contact with sulphurous (or hydrochloric^ comp. p. 195) acid gas becomes liqnid, absorbs a quantity of eas increasing as the pressure is higher and temperature lower, then mdually gives off a small quantity of carbonic acid, and remains liquid even after the gas has been driven off, (Bineau, N. Ann. Chim Phys. 24, 835.)

^ 6. Anethol dissolves iodine quickly at mean temperature, becoming thick after a few hours, and changing in a few days into a brown brittle resin. (Guizot, J. Fhys. 6, 230). This is doubtless anisoin. (Kraut.) Anethol, dropped into aaueous iodide of potassium saturated with iodine^ solidifies to a hard friable mass of anisoin. (Will & Rhodium, Ann^ Pharm. 65, 230.) See page 197.

VOL. xiv. o

194 OXYGEN-KUCLEUS C«H»0«.

7. Bromine, dropped npon anifie-camphor, causes mncli de?elopmeiit of heat and evolation of Lydrobromic acid gas, at the same time losing its colour and forming crystal Usable terbromanethol. Oil of fennel forms a Tiscid liqaid product with bromine. (Cahoars.)

8. Dry chlorine gas is rapidly absorbed by oil of anise, with rise of temperature and evolution of hydrochloric acid gas. The resulting products, which are viscid and semifluid at mean temperature, are richer in chlorine in proportion as the action of that gas has been longer con- tinned, so that at first terchloranethyl is produced, then, if -the action be assisted by a gentle heat, the compound C*^C1^H^^0', into which, perhaps, it is still possible to introduce a farther quantity of chlorine.

(Cahours.) Tarragon oil immersed in chlorine gas, thickens, becomes hot, gives off acid Tapours, and forms Laurent's chlorure de dragonyle,

9. Tarragon oil and star-anise oil, distilled with 8 pts. of chloride of lime and 24 pts. water, yield chloroform. (Ghautard, Oompi. rend, 34, 485 ; J, pr. Chem. &Q, 238.)

Da. When anise oil is poured upon chlorate of pokuh and a few drops of oil of vitriol are added, inflammation takes place. (A. Vogel, jun., Ann. Fharm. 74, 114.)

10. Fentachloride of phosphorus acts violently on anethol, giving off hydrochloric acid, and forming oxychloride of phosphorus, together with a chlorinated oil which is precipitated by water, cannot be distilled with- out decomposition, and appears to be C^W^CW (Kraut.)

11. Nitric acid forms with anethol, according to the degree of con- centration, temperature, and duration of action, either anisoic acid, or, together with oxalic and carbonic acids, — ^anisylous acid, anisic acid, and — finally nitranisic acid. By the action of fuming nitric acid, binitranisoTn is produced.

When star-anise oil is heated with nitric acid of sp. gr. 1*2, till the oil begins to sink to the bottom, anisoic acid {vide n^.) is produce«l. (Limpricht & Ritter, Ann. Fharm. 97, 364.) When anise oil is heated with dilute nitric acid (with 3 vols, nitric acid of 14° Bm., according to Cannizaro & Bertagnini) it sinks to the bottom, and is converted into auisylous acid (xiii, 120). By continued heating with nitric acid of 23° to 24% it is converted, with violent action, into a brown resin (anisoln? Kr.) and anisic acid (Cahours, xiii, 123). Nitric acid of 34° to 36° acts with great violence, first producing auisylous acid in the form of a heavy oil, which disappears after the action has been continued for some time, and if water be then added, nitranisic acid (xiii, 1 37) is thrown down in yellow flocks. (Cahours.) Fuming nitric acid acts with extreme violence, giving rise to abundant evolution of red vapours and forming binitranisoin. (Cahours.) Nitric acid of ordinary strength does not act upon oil of tarragon in the cold, but on the application of heat, a violent evolution of gas takes place, and the oil thickens, swells up, and finally solidifies to a brown crjrstalline resin, a mixture of anisic acid, aniso-nitranisic acid (xiii, 140), nitranisic acid, and a brown resiD, which may be converted into these acids by further treatment with nitrio acid. (Laurent.)

1 2. Anethol is not at all altered by boiling with aqueous potash or hy fusion with hydrate of potash (Gerhardt) ; not even by alcoholic potash. (Kraut) Heated to 300"" in a sealed tube with soda^lime, it is attacked, apparently with evolution of hydrogen, and yields a small quantity of aa Aoid isomeric with cnminic acid. (Gerhardt.) When passed over sodar- Jime at a low red-heat, it is partly carbonised, partly volatilised without

OILS ALMOST WHOLLY COMPOSED OF ANETHOL. 195

alteratioti ; no acid was found either in tbe aqueous solution of heated mass or in the residue. (Kraut.)

13. A mixture of chronuUe of potash and ntlpkuric acid converts anethol, with violent intumescence, into anisic acid, acetic acid passing over at the same time. (Persoz, Hempel : oomp. xiii. 124.) Rochleder (Ann. Pharm, 37, 347) likewise observed the formation of a peculiar acid on heating fennel oil with sulphuric acid and bichromate of potash.

] 4. With bichloride of tin (or terchloride of antimony) anethol thickens to a stiff red mass in which a few needles are perceptible, and from which anisoin is separated by water, alcohol or ether. ( Gerhard t.)

By distillation over fused chlo7*ide of zinc, anethol is converted into a mixture of metanethol and metanethol-camphor. (Gerhard t.)

16. Anethol heated with cliloride of benzoyl in a sealed glass tube to 120^ — 1 40% becomes viscid and brown. On distilling the product, the

freater part of the chloride of benzoyl passes over without evolution of ydrochloric acid, and on further heating, a decomposible residue is left which appears to be anisoin. (Kraut.)

Combinations. Anethol dissolves slightly in watery the solid variety less easily than the liquid, imparting its smell and taste. The solid variety crystalliaes on cooling from the botling solution in long needles. (Ottnther.)

With Hydrochloric acid. — Obsarred by Hombeig (CVeff. N: CAem. Areh. 3, 242) and by Saossnre. — Anethol absorbs 19-83 per cent, of dry hydro- chloric acid gas, and forms the compound C*^H"0',HCI. (Cahours.) Calculation = 19*78 HCl. Solid anethol is converted thereby into a limpid liquid, which, after a few hours, spontaneously assumes a fine red colour, and after a few days, gives off a third of the absorbed gas. Water removes the red colour, and yields a thick, white, opaque mixture. (Saussnre.)

Anethol does not unite with alkaline bisulphites. (Bertagnini, Ann. JPharm. 85, 180.)

It dissolves m alcohol and in aU proportions in ether. Solid anethol is less soluble in alcohol than the liquid variety. The solution is not precipitated by water. (Giinther.) Anethol from tarragon oil dissolves in an eqnal volume of warm alcohol. (Laurent^ Solid anethol from anise oil dissolves at 10^ in 4 parts, and at 15 in 0'6 pt. alcohol of n>. gr. 0*806 (Saussnre), and crystallises by spontaneous evaporation of the alcohol at 5^. (Bizio.)

Anethol dissolves in 10 pts. of oil of turpentine and in an equal qnan- iity of oil of almonds on heating, and orystalliaes on cooling. (GiinUier.)

Appendix to Anethol.

lis almost wholly composed of AnefhoL

cu Oil of Anise. Prepared from the braised seeds of Pi'mipindla Anisium by distillation with a six-fold quantity of water. {Phairm. boruss. ed. 6.)— -It is generally obtained from anise chaff, 100 lbs. of which yield lO^os. of the oil. (Martius) ; 100 lbs. of anise seed yield 26^01. (Van Hees, N. Br. Areh. 61, 18); 32^ (Zeller, N. Jahresb. Fharm. 1,148) ; Sd^os. (Martius, BepeH. 39, 238.)

o 2

196 OXYGEN-NUCLEUS C»H>*0«.

Colourless or yellowish. (Saussure.) Yellow. (Blanehet k Sell.) Sp. gr. 0-977 to 0*98 at 20"" (Van Hees), 0'9857 at 25° (Sanssore), 0*991 at 17*5° (Tremlich), 1*075 at 25° (Chardin) ; of the recently prepared oil^ 0-979 ; of the old oil, 0*9835 at 25° (Martins) ; different also according to the quantity of anise-camphor contained in it. (Blanehet & Sell!) It consists of } liquid and ^ solid matter (Saussure, Blanehet & Sell) ; of f camphor which (not however, according to Blanehet & Sell, from every sample of the oil : comp. p. 192) crystallises out at 10° (Blanehet & Sell), at 12^ to 14° (Tremlich), sometimes however only on opening and shaking the vessel, and then instantly. (Bnchner.) Crystallises less easily the older it is. (Geoffroy, Buchner.) The oil obtained from the seeds is more fluid than that obtained from the chaff, which crystallises sooner, and contains more camphor. (Martins.) Melts at 17°. (Saus- sure.) When exposed to the air, it takes up oxygen and becomes viscid ^Blanehet & Sell) ; resinises but does not turn sour, acetic acid being formed only towards the end of the process. (Bizio.) It dissolves at 24"* in 2*4 pts. of alcohol of sp. gr. 0*84 and in all proportions in cold alcohol of sp. gr. 0*806. (Saussure.) It contains 80*25 p. c. carbon, 8'55 hydrogen, and 11'2 oxygen. (Blanehet & Sell.)

b. Oil of Fennd. Obtained from the seeds of Anethum Faeniculum in the same manner as oil of anise from anise seeds (p. 196). — 100 lbs. of the seeds yield 50 oz. of oil. (Van Hees, Zeller.) Colourless or yellowish. (Lewis.) Solidifies below 10° (Margueron, J. Phys. 45, 136), but often remains liquid even at lower temperatures. Sp. gr. 0*896 at 15° (Chardin), 0*968 at 20° (Van Hees), 0*997 (Lewis, Hasse). Smells like fennel seeds. (Blanehet & Sell.) Tastes mild, sweetish. Contains, according to Gobel, 75*4 per cent. C, 10*0 H, and 14*6 0 ; according to Blanehet & Sell, 76*14 p. c. C, 8*49 H, and 1437 0. It consists almost entirely of two oils, a light oil volatile between 185° and 190°, isomeric with oil of turpentinei and anethol (sometimes solid, sometimes liquid). (Cahours.)

The more volaHlepart of fennel oil contains 87*86 p. c. carbon, 11*37 hydrogen, and 0*77 oxygen (Cahours), but it is difficult to purify it com- pletely from anethoL It thickens and becomes turbid when nitric oxide gas is passed into it, and if alcohol of sp. gr. 0*8 be then added to the liquid, a peculiar white substance is deposited containing C^H^N^O^*. This substance forms delicate white silky needles which turn yellow at 1 00°, and are completely decomposed at a stronger heat. (It dissolves in strong potash-ley and is precipitated therefrom by acids. It dissolves in ether^ scarcely in alcohol of 0*80, and sparingly in absolute alcohol. [Cahours, N". Ann. Chim, Phys, 2, 303.]) Heated with hydrate of soda. It gives off ammonia, a gas which irritates the eyes, and an oil having the odour of rock-oil. It is not attacked by hyposulphite of soda. Treated at mean temperature with hydrosulphate of ammonia, and then with an acid, it yields a precipitate which detonates slightly when heated. Boiled with hydrosulphate of ammonia, it dissolves with brown colour^ deposits sulphur, and emits a strong odour of bitter almonds, (Chiozza^

Gerhardt'$ TraiU, 3, 357.)

Cahours. CalculaiUm according to CWAonrt. mean,

60 C 360 .... 55*55 55«41

48 H 48 .... 7*40 7«41

8N 112 .... 17*28 17-19

16 0 128 .... 19*77 19*99

'^' 3C»H",NO».... 648 .... lOO'OO 10000

ANISO[N« 197

e. OU of Star-aniie. From the seeds of lUieiuin anisdtum. 100 lbs. of the seeds yield 40 ox. of oil (Van Hees), 35 oz. (Zeller). Mobile oil, transparent and colourless at first, but turning yellow after a few weeks. Does not solidify at 2*5^ (Meissner.) Deposits a camphor, like anise« camphor. (Cahours.) Sp. gr. 0976 at 20°. (Van Heee.) Smells and tastes like anise. Dissolves readily in alcohol and ether. (Meissner, Alman. 1818, 68.)

d. OU of Tarragon. Obtained by distilling with water the leaves of Artemisia DracunctUus. — Sp. gr. 0*9356. (Ghardin.Hardanconrt.) According to Laurent, it consists wholly of anethol, and boils between 200° and 206°. According to Gerhardt, it contains, together with anethol, extremely small quantities of a more volatile hydrocarbon.

Gerhardt. (1839.) Ann, Chim. Phys. 72, 167; in detail, Compt, ehim, 1845, 65; J. pr. Chem. 36, 267; abstr. (hmpt rend. 20, 1440.

Cahours. Bev. sclent. 1840, 342; J. pr. Chem. 22, 59; in detail N. Ann. Chem. Fhys. 2, 284; J. pr. Chem. 24, 344.

Laurent. Rev. scient. 10, 5; J. pr. Chem. 27, 232.

Will <& Rhodius. Ann. Pharm. 65, 230; Pharm. Ocntr. 1848, 230.

Uelsmann & Kraut. J. pr. Chem. 77, 490.

JUrinotu variety qf anethol (Gerhardt).

First obserred in 1826, by Unyerdorben {Pogg. %, 484 )« afterwards re-discoTered and inrestigated by Gerhardt. Uelsmann & Kraut showed that tbe product which Will & Rhodius obtained by the action of iodine on anise oil, was aniso'in, as Gerhardt (N. J. Pharm. 14, 130) had previously suggested.

Formation. By the action of bichloride of tin or terchloride of anti- mony (Gerhardt), of phosphoric acid or oil of vitriol (Cahours), of iodine dissolved in iodide of potassinm (Will & Rhodius) on anethol.

Preparation. 1. Bichloride of tin is poured upon anethol (or upon crude oil of anise or tarragon) ; the thick red mass thus produced is pre- cipitated with water ; and the precipitated flakes are colleoted and puri- fied by solution in ether and evaporation. (Gerhardt) — 2. Anethol is treated with terchloride of antimony, till it turns red, and the mixture is diluted with water and boiled, whereupon the mass turns white and settles down. — The deposit is collectea and washed, then pressed be- tween bibulous paper, and purified by solution in a small quantity of ether and precipitation with weak alcohol ^Gerhardt.) — 3. Oil of vitriol is dropped upon oil of tarragon contained in a large basin, care being taken that the mass does not become too strongly heated. A hard, fissured mass is thereby formed, which must be well washed with hot water. (Gerhardt.) Cahours uses at most 1^ pt. oil of vitriol to 1 pt. anise oil, and distils carefully after washing with water, whereupon, according to his statement, a small quantity of anisoin passes over, the greater part being however converted into a heavy oil (see page 200, 2). — 4. A cold-

198 OXYGEN-NUCLBUS C»H»0«.

saturated solation of iodide of ^otassiam is saturated with iodine ; anise or fennel oil is then dropt into it, with strong agitation ; and the thick gelatinous magma is dilated with 6 or 8 vols, alcohol. Anisoin then separates as a white powder, which is to be washed with alcohol ; its onantity amounts to more than half that of the oil used ; in the ease of lennel oil to 54*8 p. c. (Will & RhodiusV

To obtain the anisoin pure, it must oe repeatedly dissolved in ether and precipitated by alcohol. — Or the brittle product obtained by the action of iodine upon anethol maybe pulverised ; ether then poured upon it; the solution shaken up with excess of soda-ley ; the decanted ethereal solution precipitated with alcohol ; and the precipitated anisoin washed repeatedly with water, then dried, pulverised, and purified by repeated solution in ether and precipitation by alcohol. (Kr.)

Properties. Yellow, transparent resin, or thin microscopic nodules. (GerhaHt) White powder (Will & Rhodius), which, by spontaneous evaporation of its ethereal solution, may be obtained in small needles. (Cahours.) Extremely electrical. (Will '& Rhodius.) Melts between 140° and 145° (Uelsmann & Kraut) ; at a heat considerably above 100^, and solidifies to a colourless glass. (Will & Rhodius.) At a higher temperature, it volatilises partly undecomposed. Heavier than water. Inodorous. (Cahours.)

20 C 22 H	120 .... 81-08 . 12 .... 8-11 .	Gerhardt Cdiimr., ^^ 80-75 .... 80-97 .... 77'84 8-20 .... 8-09 .... 8-34 1105 .... 10-94 .... 13-82	Uelfmann &Kraat. mean, .... 80-69 8-09
2 O	16 .... 10-81 .	.... 11-22
C»H»«0» ....	.... 148 .... 100-00 .	10000 .... 10000 .... 10000	.... 10000

Will & HhodiuB gave the formula C»HWO<.

Isomeric with anethol, metanethol, metanethol- camphor and cnminol.

Decompositions, 1. Anisoin when heated in the air, bums like a resin, emitting an aromatic odour. (Cahours.) — 2. By distillcUion, it is converted into methanethol and metanethol-camphor, into the last, espe- cially when pure anisoin is used. (Gerhard t^ comp. p. 199.)

3. In chlorine gas, at mean temperature, it turns violet, absorbs chlorine gives off hydrochloric acid, and becomes heated without melting. When chlorine gas is passed over anisoin at 100*^ as long as the substance continues to increatte in weight, and the excess of chlorine is displaced by dry air, a chlorinated pro<iuct is formed, without violet colouring, which contains 5V5 to 52*7 p. c. carbon, 4*5 to 4*8 hydrogen, and di-9 to -32-7 chlorine, and, according to Will <& Rhodius, is C*^C1*H**0*, more probably C=«Cl«H> 0» = Bichloranisoin. (Uelsmann & Kraut.) Calcu- lation 5'»*;J p. c. C, 4-6 N and 327 CI — 4. Anisoin is decomposed by strong nitric acid, only after continued boiling. (Will & Rhodius.) By fuming nitric acid, it is dissolved, with violent evolution of nitrons gas, and precipitated, on pouring the solution into water, as binitranisolTn. (Krant.) — 8. Fotask-lime attacks it at 300^ with evolution of hydrogen. Hydrochloric acid separates from the product yellow flakes which cake together to a brown resiu. (Gerbardt)

Ani8oin is insoluble in water. — It is not altered by dilute acids, or by potash or ammonia, even at the boiling heat.

MBTANETHOL. 199

It diflsolyes in oil of vitriol with red oolonr and is precipitated bj water. (Cahours.)

It does not dissolTe in alcohol, eyen with the aid of heat. It is soluble in ether, and is completely precipitated from the solution by alcohol : also in Yolatile oils.

Metanefhol-camphor.

C»H»0».

Gebhardt. (Ck>mp. page 197.)

Crytialliied variety qfAnetM (Gerhardt).

Formaiion and Preparation, •— 1 . Metanethol obtained by the dry distillation of anisoin (especially if pare), as above described, deposits in the neck of the retort crystals of meUinethol-camphor, which may be obtained in greater quantity by once rectifyiu^ the metanethol oyer chloride of sine, and separated from the oil by washing with alcohol. — 2. In the preparation of metanethol by dropping anethol on chloride of zinc in the meltod state (p. 200) crystals of metanethol-camphor are obtained, abundantly if oil of anise has been used, in small quantity if the preparation has been made with oil of tarragon.

Properties. Colourless crystals which do not melt at the heat of the water-bath after fusion, and distil without alteration at higher tem- perature& Solidifies to a radiated warty mass. Inodoroos.

Gerhardt. Cryttali. mean,

20 C 120 .... 81-08 81-45

12 H 12 .... 8-11 8-16

2 O 16 .... 10-81 ; 10*40

C»HnO» 148 .... 100-00 100-00

Itomeric with aniaoin, metanethol and cnminoL

By repeated rectification oyer chloride of tine, it is conyerted into metanethol, with separation of charcoaL With poUUhrUme it behayes like anisoin (p. 198).

Metanethol. (?*H"0».

Gerhardt. Ckmpt, chim. 1845, 65; J.pr. Ohem. 86, 872; abstr. Compt. rend. 20, 1440.

Liquid variety ^ e, of anethol (Gerhardt).

Formation. By distilling anethol oyer chloride of mnc. — 2. By the dry distillation of anisoin (p. 198). — 3. In the dry distillation of the sulphanethates, metanethol passes oyer and charcoal is separated.

200 OXTGEN-NUCLBUS C»H^»0».

Preparation, Anethol is dropped upon melted chloride of zino con- tained in a tabulated retort ; heat is applied as long as oil continues to pass over; and the metanethol-camphor produced at the same time is reconverted into metanethol by repeated rectification over chloride of

zinc. Oil of tarragon yields more metanethol and less of the camphor than oil of anise.

Properties. Colourless oil, having a vinous odour somewhat re- sembling that of anise. Sp. gr. 0*954 at 25^ Boils at 206°. Vapour- density = 5-75 at 247° ; 5-35 at 297°.

Vol. Density.

20 C 120 .... 81-08 .... 80-55 C-vapour 20 .... 8-3200

12 H 12 .... 8-11 .... 8-30 H-gas 12 .... 0-8316

2 O 16 .... 10-81 .... 11-15 O-gas 1 .... 11093

C»Hi303 .... 148 .... 10000 .... 10000 Vapour of Metanethol... 2 .... 102609

1 .... 5-1305

Isomeric with anethol, metanethol-camphor, anisoln and cnminol.

Sulphometaneihic Acid.

C»H"S»0« = C»H"0«,2S0».

Gerhardt. (1845.) Compt. ehim. 1845^ 65; J. pr. Ghem. 36, 375.

Stdphanethie ueidf Sulpkodracmuc acid, MetanethgckwrftUiSiure, MeianethoU sehwrfelsSure,

Known only in combination with bases.

Formation. — 1. By dissolving anethol in oil of vitriol. (Gerhardt.) — 2. The solution of anethol (from anise oil» according to Cahours, from tarngon oa, according to Laurent), in at least 3 or 4 pts. of oil of vitriol, if mixed with water after standing for 24 hours, deposits only part of the oil in the form of anisoin, the rest remaining dissolved in combination with the sulphuric acid, probably as sulphometanethic acid (p. 1 93). — 3. When thymol is heated with excess of oil of vitriol to 240°, sulphurous acid is evolved, and a viscid mixture perfectly soluble in water is obtained, which, after neutralisation with carbonate of baryta, yields a gummy very soluble salt, which behaves to ferric salts like sulphometanethate of baryta. (LaJlemand, N. Ann. Chim. Phys. 49, 150.)

On diluting with water the solutions obtained by 1 or 2, neutralising with carbonate of baryta, filtering and evaporating, 9iilpkometanethate of baryta is obtained aa a yellow, amorphous, gummy mass, which has a very bitter taste, dissolves readily in water and alcohol, does not precipi- tate the nitrates of calcium, lead, or silver, and produces with aqueous fei^ric salts, a deep violet colourings which is destroyed by ammonia and by acids. This, and the lead-salt of stUpkometanethic acid, which is like- wise amorphous, has the aspect of gum arabic, and is very soluble in water, yield by dry distillation, a distillate of metanethol with a residue of charcoal. (Gerhardt.)

BUGBNIN. 201

Baryta'Hiltf utU tii 100"*. Gerhardt.

20 C 120 .... 39-40 ^ 384

12 H 12 .... 8-94 4-3

BaSO* 116-5 .... 38-26 35-0

SO* 56 .... 18-40

C»H"Ba02,2S03+HO.... 3045 .... 10000

Lallemand found in snlphometanethate of baryta prepared from thymol, crystallised from weak alcohol and dried at 120'', 39*5 p. c. salphate of baryta (C»H»BaS30» ^ 39-4 p. c- BaO).

Gerhardt's analysis does not agree with his formula, for which he erroneously calculates the amount of salphate of baryta, at 34*6 p. c. (Kr.).

Eugenin. C»H»0* = C»H«0«,0» t

BoNASTBB. (1838.) J. Fharm. 20, 5e5'y Ann, Pharm, 13, 91. Dumas. Ann. Chtm, Phys, 58, 168; Ann. Fharm, 9, 71; Po^g. 29, 89.

Discovered by Bonastre* analysed by Dumas.

Separates after a while from the turbid water, loaded with rolatile oil, which is distilled from cIotos. (Booastre.)

Delicate, white, traosparent, pearly laminae, becoming yellowish after some time. Smells fainter than cloves. Tasteless.

20 C

12 H

40

	Dumas.
120 .... 73-17 ...	71-21
1^ .... /*d2 ...I	7-65
32 .... 19-51 ....	21-14

C»B}H>* 164 .... 100-00 10000

Isomeric with cuminic and eugenic adds, to the latter of which it is related in the same manner as benzoin to bitter almond oil.

With cold nitric acid, it acquires a bright blood-red colour as quickly as eugenic acid. (Bonastre.) Is but very slightly attacked by strong nitric add. (Muspratt, N. Phil. Mag, 2, 297.)

Soluble in all proportions jn cdcohol and ether. (Bonastre.)

Eugenic Acid.

CJ0H»O* = C»H"0»,0*.

BoNASTRB. (1827) J. Pharm. 13, 464 and 513; abstr. Atm. Ghim.

Phys. 85, 274; Pogg. 10, 611; Mag. Pharm. 20, 141. Dumas. Ann. Chim. Phya. 58, 165; Ann. Pharm. 9, 65; Pogg. 29, 87;

Ann. Pharm. 27, 151. Ettlimo. Ann. Pharm. 9, 68; Pogg. 31, 526. BocKMANN. Ann. Pharm. 27, 155.

Stbmhouse. Ann. Pharm. 95, 103; Pharm. Centr. 1855, 289. Calvi & Chiozza. Cimento 3, 419; Ann, Pharm, 99, 242; J, pr* Chem,

70, 125; Chem. Genir. 1856, 829.

202 OXYGEN-NUCLEUS C»H»OS.

A.BRUNINO. Ann, Phaimi, 104, 202; Jpr. Ghem. 73, 15^. C. Grey. Williams. Chem. Gca. 1858, 170 ; Ann, Pharm, 107^ 288 ; N. Ann. Ghim, Fhyt. 54, 433.

Eugenol, Nelkena&ure, Acid Oil ^f Cloves.

Bonastre discovered in 1827 the aoid nature of oil of oloyes, and investigated tbe remarkable oompoands with alkalis and other salt-bases, which bad already been observed bj Philipp (iT. Tr. 9, 1, 275) and Karls (Fog^, 10, 609).

Sources. Oconrs in oil of cIotob (Bonastre), together with a hydro* carbon isomeric with oil of turpentine (Ettling) ; in pimento-oil (Bo- nastre) ; in tbe so-oalled oil of cinnamon leaves from Ceylon (Stenhouse) ; in the oil of CaneUa dlha (W. Meyer & v. Reiche) ; and probably in the volatile oil of Brazilian clove-cinnamon. (Comp. p. 209.)

Separation of Eugenic Acid from Oil of Clows. The oil distilled from cloves which have beeu previously treated with alcohol to extract catyo* phyllin, consists solely of eugenic acid. (Dumas, Ann. Pharm. 27, 151.) 1. Crude commercial oil of cloves is mixed with strong potash-ley, and distilled as long as neutral oil of cloves passes over ; the residue is then mixed with phosphoric or sulphuric acid ; and the eugenic acid thus separated being distilled off, passes over as a clear colourless oil. (Ettling.) — 2. Oil of cloves is decomposed by hydrate of potash ; alcohol is added to the solidified mixture ; and the salt thereby separated is collected and frequently pressed. The potash -salt is decomposed with dilute sulphuric acid, and the liberated eugenic acid is dried over chloride of calcium and rectified. (Briining.) Dumas dehydrates eugenic acid by boiling and distilling, because, when treated with chloride of calcium, it readily becomes coloared or forms eugenate of lime.

Properties, Clear, colourless oil, having an unmistakeable odour and taste of clovea Sp. gr. = 10684 at 14° (Williams), 1*076 (Sten- house), 1*079 (Ettling). Boils at 242<> (Stenhouse), 243° (Ettling), 248" (Bnining), 251° (Williams), between 153° and 154° (253° I Wil- liams), (Dumas). Vapour-density = 5*858 (Williams), 6'4 ; (this number is probably too Idgh, since partial decomposition took place.) (Dumas, CalTi.)

Reddens litmus-paper. (Ettling.) It neither affects blue litmus or turmeric-paper, nor even the aqueous, alcoholic, or ethereal solutions of these substances. (Bonastre.)

20 C 12 H	. 120 12	.... 73*17 .... 7*32 .... 19-51	Damas. Ettling. BSckmamu mean, 69*01 .... 71*63 .... 71*7 7*40 .... 7*44 .... 7*4
4 O	32	23*59 .... 20*93 .... 20*9
C»H»0* .. 20 C 12 H	164	.... 10000 Stenhonse. mean. . 7213 .... ■ i'Ok .... . 20-56 ....	10000 .... 10000 .... 100*0 Calvi. Brttning. Williams. mean. mean. mean, 72*6 .... 72-61 .... 7310 7*1 .... 7'33 .... 7*65
4 O		20-3 .... 20*06 .... 19-25

C»H»0« 100*00 .... 100*0 .... 100*00 .... 10000

EUGBNIG ACID. 203

Tola. Vapour-density.

C-TBpoiir 20 8-3200

H-gas 12 0-8316

O-gas 2 2-2186

Eugenic acid-vapour 2 11*3702

1 5-6851

Stenhonse analysed eugenic acid from oil of cinnamon leaves ; Dumas gave tlie formula C^^W^Cfi, or the same doubled ; EtUing, C«iJ»Oi<^. The formula C^WH)*, which was previously proposed by Liebig {Orff, Chemie. 337) and by Geriiardt {Pricit 2, 171) was confirmed by Calvi> by Brllning, and finally by Williams.

Isomeric with cuminic acid and eugenin (p. 102).

DeeompasUioM, The decompositions of crude oil of cloves are here inserted, as far as they may with probability be attributed to eugenic add. — 1. Eugenic acid

soon acquires a brown colour, eyen in perfectly full and hermetically sealed yessels. (Williams.) — 2. It becomes coloured after boiliug for a certain time and leayes a brown residue ; hence the yapour-densitj is found too high in vessels containing air. (Dumas, Williams.) — 3. Oil of doves is turned dark-brown by oil of intriol (Gaultier de Claubry), first clov^red, then of the colour of wine-lees. (Bonastre.) Oomp. also

Brandes {N. TV. 21, 1, 37) 4. CJUorine^as causes cooled oil of cloves to

thicken, colours it green, imparts to it a balsamic odour, and becomes converted in a few days into hydrochloric acid. On submitting the whole to distillation, undeoomposed oil passes over, leaving a resin. (Bonastre.) Oil of cloves, gently heated with powdered ci>rrodve suhlir matey turns purple-red ; and, on application of stronger heat, a purple-red oil containing hydrochloric acid passes over, together with acid vapours, leaving a black residue. The same purple-red oil is likewise obtained by acting on oil of cloves with hydrocbloric acid gas or aqueous bydro- chloric acid. (J. Davy.) — Oil of cloves, in contact with cnloride of lime, becomes warm and emits vapours, without however taking fire. (R. Bdttger, «7. pr, Ch, 76, 241.) The less volatile oil of cloves is turned brown by small quantities of iodine, and in 24 hours acquires an olive* green colour ; while the more volatile oil is turned first brown, then blue, and finally greenish blue. (Jahn, If, Br. Arch. 66, 141.) 5. Fentor chloride ofphospkoTrus decomposes eugenic acid, and yields, amongst other products, a gas burning with green flame like chloride of methyl. — 6. With nitric add, eugenic acid forms oxalic acid and a brown resin.

giriining.) Oil of cloves readily takes fire with fuming nitric acid, eated with a large quantity of nitric acid, it yields oxalic acid (Karls, Crdl. Ann, 1785, 1, 302 ; Bonastre) ; with \ of its bulk of nitric acid, it immediately turns dark red, with evolution of nitrous fumes, and then dissolves in water with dark yeUow colour, which is rendered more intense by ammonia. (Bonastre.) — 7. Eugenic acid is converted by distillation over anhydrous baryta into a neutral oil, which is not affected by caustic potash, and, though possessing different properties^ has the same composition and vapour-density as eugenic acid. (Calvi.) Eugenic acid distilled with an excess of baryta yields the hydrocarbon C*^H" (xiii, 341) (Church, N.Phd, Mag. J, 9, 256). — 8. Oil of cloves is not affected by dry vermanganate of potash, (B5ttger.) — 9. With peroxide of lead it develops heat, and smokes, without however taking fire. — 10. Oil of cloves is not affected by mercuric oxide^ but it instantly takes fire, with emission of sparks and smoke, in contact with dry oxide of tUver, with peroxide o/n^v^ prepared by electrolysis^ or with oxide of gold.

204 OXYGEN-NUCLEUS C«H»0*.

the oxides being thereby reduced to the metallic state. (Bottger, J,pr. Ch. 76, 241.) — 11. In contact with dry nilropnuside of copper, oil of cloves acquires a violet colour, varying to cherry-red, and yields a slate-gray deposit ; T^nnr P^* nitroprusside of copper is sufficient to pro- duce a rose- red coloration. Oil of turpentine prevents the reaction. (Heppe, N. Br, Arch, 89, 57.) — 12. Eugenic acid in the form of potash- salt gives with iodide of ethyl, eugenate of ethyl ; with chloride of benzoyl {toluyl or aniiyl) it forms benzo-eugenic anhydride (or the corresponding anhydrides). — (Cahours, N, Ann. Chim, Phys, 52, 189.)

Combinations, Eugenic acid dissolves sparingly in water, imparting its taste and odour.

With bases it forms the eugenates, the formula of which is G^H^^MO' or C*H"MO*,C«H»0* ; according to Dumas, C»H"0*.MO. They are for the most part crystallisable, and, with the exception of the baryta- salt, readily decomposible by water and alcohol. The solutions of the eugenates of the alkalis become alkaline by evaporation. (Ettling.) By nitric acid they are coloured various shades between yellow and red ; they are decomposed by other acids (partially even by carbonic acid^ Ettling) with liberation of eugenic acid. (Bonaatre.)

Eugenate of Ammonia. Eugenic acid absorbs 9*73 p. c. of its weight of dry ammonia-gas (Dumas) ; when dry ammonia-gas is passed over it, it combines therewith, developing heat, but is not completely neutralized. (Ettling.) Oil of cloves in contact with ammonia-gas at 0^, thickens to a battery, granular-laminaceous, yellow mass, which ^^nally becomes dark, and with more ammonia acquires the consistence of tallow. (Bonastre.) Small, very brilliant crystals. (Dumas.) Fragile, white laminte (Bonastre, finining) ; heavier than water, of strong odour, and sharp, burning taste. (Bonastre.) In the air it immediately parts with ammonia (Dumas) ; melts a little above 0% and gives off ammonia. (Briining.) Though permanent below 12^ in sealed tubes, it is con- verted in the air into a volatile and rather darker oil, owing to loss of ammonia. (Bonastre.) Eugenic acid over which ammonia-gas has been passed to saturation, parts with ammonia when melted, and is converted into an acid salt ; and if ammonia be again passed over this product, it re-absorbs the gas to the amount of 4*14 p. c. of the weight of the acid. (Ettling.) — Dissolves in hot ammoniacal water, and on distilling the solution, passes over with the liquid, and crystallises from the cooled distillate as a white semi-solid mass, which gradually disappears even in stoppered bottles. (Bonastre.) Commercial oil of cloves yields with ammonia no crystals, but a pitch-like, buttery mass. (Dumas.)

DomaB.

C»H»0* 164 .... 90-61

NH« 17 .... 9-39 8-86

C»(NH*)H"0< 181 .... 10000

JSugenate of Potash. — Acidf — Oil of cloves is triturated with an equal weight of hydrate of potash, and the compound which is thus formed, with slight elevation of temperature, is dissolved in 5 pts. water (on boiling the solution a certain qnantitj of eugenic add is driven off: Bonastre, Cahri), then filtered and evaporated, so that the liquid, when left to stand in the cold for 24 hours, crystallises. (Bonastre.) An excess of concen- trated solution of caustic potash is added to eogenio acid, and, aoeording

EUGENIC ACID. 205

to Bruning, the solation is precipitoted with alcohol and the salt repeatedly pressed; according to Dumas^ the mass is stirred up, the excess of potash poured off, and the salt pressed between blotting paper, and crystallised from alcohol.

Brilliant, white, fragile laminsB, haying the bnming taste, and some- what of the odour of cloves. Reaction alkaline. (Bouastre.) Partly decomposed by recrystallisation from water. (Bonastre, Dumas.) According to Bonastre, it is also decomposed by alcohol and ether. Decomposes slightly at 100°, without perceptible alteration of weight* (Briining.)

Bonastre. Damaa. Briining.

At 100*" C, over oil qf

me€m» mean» triiroL

C^ROO' 319 .... 8708

KO 47-2 .... 12-92 11-69 .... 120 .... 12*22

C»H»KC)<,C»H«0* 366-2 .... 100-00

According to BrUning, tbe formula » O^HSBKO^, + 2Aq, which requires 12*2 p. c. KO.

Eugenate of Soda. When oil of cloves is poured over an equal

weight of hydrate of soda, it is gradually absorbed, forming a solid mass,

which, on addition of a little cold water, is converted, in 24 hours, into

fragile needles having a silky lustre. The excess of soda is removed by

pressing tbe crystals between blotting paper. It tastes like cloves

and strongly alkaline. On boiling the largely diluted aqueous solution,

a small quantity of oil is evolved, but the liquid again yields crystals on

evaporation. Dissolves in from 10 to 12 pts. cold, and in any quantity

of hot water. Dissolves in alcohol and ether with decomposition.

(Bonastre.)

Needlet, Bonastre.

C»H»C)» 155 .... 83-34 8145

NaO 31 .... 16-66 18*57

C»H"NaO* .... 186 .... lOO'OO

Eugenate of Baryta is precipitated in crystalline spherules wheu baryta-water is shaken up with eugenic acid (or with its aqueous or alcoholic solution : Briining), while only a small quantity remains in solution. The salt may be obtained in white nacreous needles by recrys- tallisation from hot water. (Bonastre.) The salt prepared from baryta- water and eugenic acid contains 27 p. c. BaO, but after recrystallisation from alcohol, it contains 32 p. c. BaO. (Ettling.) Smells and tastes of cloves. (Bonastre.) It is very stable, and may be recrystallised from water and from alcohol. (Williams.) When moist, ii absorbs carbonic acid from the air (Ettling), and turns brown. (Briining.) Dissolves sparingly in cold, and much more freely in hot water. (Bonastre.) For the decomposition of the baryta-salt by distillation, see page 203.

Briining. mean.

20 C 120 ... 51-82 5112

11 H 11 .... 4-75 4-89

3 O 24 .... 10-36 12-23

BaO 76-6 .... 3307 3176

C»H"BaO* .... 231-5 .... 100-00 tOOOO

Bonastre found 32-81, EUling 32*0, Calvi 32*8 (Gerkardi'e TraiUt 4, 1037), WiUiamSv in the salt dried at lOO^ 33*4 p. o. BaO,

206 OXTGBN-NUCLfiUS CP^WH^.

EugencUe of Strantia, Obtained by boiling or agitating oil of clorefl with strontia- water. White needles, less nacreoos than the barjta^salty with which thej agree in other properties. (Bonastre.)

EugencUe of Lime, Quicklime combines with oil of cloves, forming a solid, amorphous componnd, which is insoluble in cold and sparingly soluble in boiling water. — When oil of cloves is boiled with 2 pts of lime and water, the filtered solution deposits on evaporation yellowish crusts, which have a faint odour of cloves, a very repulsive taste, and are turned wine-red, with lively eflfervescence, by oil of vitriol. Dis- solves in 235 pts. water. (Bonastre.)

EtigencUe of Magnesia, Obtained by the action of oil of cloves on ealcined magnesia, as a very hard, white, non-crystalline compound, which is equally insoluble in cold and hot water. (Bonastre.)

Eugenate of Lead, Eugenic acid forms with oxide of lead, acid, basic, and hyperbasic salts. (Ettling.) By boiling oxide of lead with oil of cloves and water for three nours, a viscous, yellow, homogeneous mass, insoluble in water, is obtained. This when dried in the air becomes friable, and on addition of sulphuric acid, yields eugenic acid. Formed also by precipitating aqueous eugenate of potash (from oil of cloves, oomp. Schindlcr, N. Br. Arch. 41, 140) with subacetate of lead, as a thick, yellow deposit. (Bonastre.) Hyperbasic eugenate of lead contains 62-61 p. e. PbO. (Bonastre.)

Ferrous Eugenate. Boiling aqueous solution of eugenate of potash or soda gives immediately with ferrous sulphate, a magma which instantly turns blue. (Bonastre.) Aqueous ferrous sulphate gives no reaction with oil of cloves; but with eugenate of ammonia, baryta, or strontia, it acquires a light lilac-colour ; with eugenate of potash, from red to bice ; and with eugenate of soda, a violet or greenish-blue colour. (Bonastre.) By standing over iron filings for 24 hours, oil of cloves acquires a purple tint, without dissolving any of the iron (1 Kr.) — (Rattscher, Br. Arch. 14, 186.)

Cupric Eugenate. Solution of cupric sulphate precipitates aqueous eugenate of soda. The precipitate aggregates in a brown mass, which, when boiled for half an hour, changes from sky-blue to the colonr of verdigris. (Bonastre.)

Oil of cloves is completely soluble in concentrated acetic add, aloohtd, and ether. (Bonastre.) It is insoluble in acetic acid of sp. gr. 1*05. (Jahn, iT. Br. Arch, 66, 129.)

Appendix to Eugenic Add.

1. Fyrolivilic Acid.

C«H'H)» = C*H»H)* -h Aq(?).

SoBRBRO. Ann. Fharm. 54, 87.

Preparation. Pure dry oliyil (the crystalline resin of the wild oli tree) is slowly distilled in a retort, of which it occupies about one third.

PYROLIVILIC ACID. 207

till the residual black mass begins to swell up. Tbe pyrolirilic acid, which passes over as an oil together with water, is dissolved in ether, and the solution is distilled in a stream of dry carbonic acid, at a gradnallj increasing temperature. Ether, and all the water, first pass over, then tbe pure acid. (Chloride of calcium cannot be used for drying the acid, since it dissolves therein and cannot afterwards be separated.)

Properties. Colourless oil, heavier than water. Boils above 200°. It has an agreeable odour, and tastes and smells just like eugenic acid. Its aqueous solution reddens litmus.

				Sobrero.
				mean.
20 C	120	••••	69-36 ...	69-99
13 H	13	••••	7-51 ...	7-31
5 O	40	• • ••	2313 ...	22-70
C»H»0* ...	173	• ■••	10000 ...	100-00

Sobrero's analysis agrees very closely with Dumas's analysis of eugenic acid, but not with those of fidckmann and Ettling.

DecompogUions, I . Turns brown on exposure to the air, and after- wards acquires a reddish-brown colour. — 2. The poto^solution blackens and becomes opaque in the air, owing to deposition of carbon. — 3. If the solution be now decomposed with an acid, and the precipitated pyro- livilic acid distilled, a large quantity of charcoal remains in the residae and the distillate has the mean composition : 68*92 p. c. C, 7'64 H, and 23*440. — 3. It is converted by nitrie <teid into resin and picric acid. — 4. Reduces aqueous nitrate ofniver.

Pyrolivilic acid is very slightly soluble in water. It dissolves readily in solution of catutic potash^ without yielding a crystallisable salt. (This distinguishes it from eugenic acid.) — It dissolves chloride of calcium and cannot again be separated therefrom.

Lead-salt. Subacetate of lead gives with alcoholic pyrolivilic acid, white curdy flakes, which become soft at 100% and melt to a trans- parent, pnlverisable, resinous mass ; they dissolve in alcohol but not in water, and are precipitated from the alcoholic solution by evaporation or by dilution with water. The salt appears to vary greatly in composition. Prepared from the alcoholic solution by evaporation, it contains 57'30 p. c PbO ; precipitated from the same solution by water, 53* 16 p. c. PbO.

Obtained hy evaporation* Sobrero.

20 C 120 .... 30-99 30-59

12 H 12 .... 309 2-89

4 0 32 .... 8-29 8-89

2 PbO 224 .... 57-63 67 63

C»H>H>*,2PbO 388 .... 10000 10000

Pyrolivilic acid dissolves readily in aleohd and in ether. Water precipitates the alcoholic solution. The ethereal solution, when left to evaporate, deposits the acid in oily drops.

208 OXYOEN-NUCLBUS C»Hmo«.

2. Carmufellio Acid.

(?*H»0« (?).

MuspRATT & DAN80N. (1851.) N. FhU, Mag. J. 2, 293; J. pr. Chem. 55, 25.

Fotfnation and Preparation, About 20 lbs. of cloYes are digested in a copper vessel with 36 lbs. water, and the whole is boiled for an hoar. The dark-brown decoction is poured off, and the residue is repeatedly boiled with fresh quantities of water till the liauid is no longer coloured. The united extracts, amounting to about 270 lbs., are reduced bjr erapo- ration to 54 lbs., and divided into from 20 to 30 pts., each of which is mixed with cold nitric acid, and heated for several days in a covered vessel on a sand-bath. (If the extracts were evaporated to a syrup, a violent reaction would take place on treating them with nitric acid in the cold, and a blood-red liquid would be obtained.) A lively effervescence ensues, a suffocating gas which excites tears being eyolved, together with carbonic acid and a few nitrous fumes, while the liquid, which contains a large quantity of oxalic acid, becomes pale yellow and deposits abundant white flakes. All the gas is completely expelled; the liquid filtered (this requires a long time); the residue washed with boiling water; and the filtrate evaporated, till it deposits yellow micaceous laminae, which are dissolved in water and converted into a lead-salt by precipitation with acetate of lead. The washed lead-salt is decomposed by sulphuretted hydrogen, and the solution is decolorised with animal-charcoal and eva- porated^ whereupon dazzling white crystals of the acid are deposited. One pound of doves yields about 2 grains of crude acid.

Froperties. Brilliant, colourless, micaceous laminse.

24 C 20 H	Muspratt & Damon. At 100« (mean.) 144 .... 34*29 34*25 20 .... 4-76 4-81
32 O	266 .... 60-95 60-94

C^H»0» 420 .... 100-00 100-00

Deeompositums. 1. Heated in a test-tube, it melts, gives off vapours smelling like burnt sugar, and yields yellow drops of oil. — 2. It is not attacked by cold M of vitriol ; but chars on application of heat, with evolution of sulphurous acid.

Comhinatums. Insoluble in cold, sparingly soluble in boiling tvater. Combines with bases, forming taltt. Their formula, according to Muspratt and Danson, is C^H*0»,MO, and therefore probably C"*H"MO",HO. The acid dissolves in ammonia and in catutte potam. Its moderately dilute solution (in ammonia ? Kr.) produces with soluble salts of baryta, strontia, and Ume, transparent gelatinous precipitates which cause the solutions to solidify. It gives with salts of lead, a white, transparent, gelatinous precipitate ; with/errotM salts, white; with ferric salts, bright yellow ; with cupric salts, green ; and with silver salts, white flakes. The precipitates occupy an exceedingly small space after they

3. VOLATILE OILS CONTAININQ EUGBNIC ACID. 209

hare been dried, and then resemble laminse of mica. Tbey diBsolve with turbidity in dilute hydrochloric or nitric acid, except the lead-salt, which gives a clear liquid.

CarmufdUxte of Baryta, An equal number of atoms of carmufellio acid and acetate of baryta are dissolved in water ; the mixed solutions are evaporated to dryness ; and the residue is exhausted with water, and dried on a porous tile over oil of vitriol. — The precipitate obtained by throwing down nitrate of baryta with carmufellio acid, cannot after dry- ing be separated from the filter.

Barely soluble in water, abundantly in hydrochloric and nitric acid.

Calculation according to Mmpratt

^ Danton, Mnspratt & Danson.

C»*H»03« 420 .... 84-59

BaO 76-5 .... 15-41 15-80

C"H»0» BaO .... 496-5 .... 100 00

CarmufeUaU of Lead. Prepared like the baryta-salt. It is almost insoluble in water, but dissolves in nitric acid.

Calculation according to Muspratt

6c DansoH, Muspratt & Danson.

C«H»OM 420 .... 78-95

PbO 112 .... 2105 20-61

C«H»0»,PbO .... 532 .... 100-00 Carmufellic acid is insoluble in alcohol and in ether. .

3. Volatdle Oils containing Eugenic Acid.

a. Oil of Cloves. (GetciirznelJtenSl.) — From the buds or flower stalks of Eugenia caryophyUata, 100 pts. of cloves yield from 14*5 to 28 pts. of oil (Comp. Jahn, N. Br. Arch. 66, 129 j Zeller, N. Jahrb, Pharm. 1, 98) ; while the same quantity of stalks gives only 4 pts. (Van Hees, N. Br. Arch, 69, 41.) The oil does not pass over completely till the distillation has been continued for a long time. Colourless and trans- parent ; odour burning, peculiar ; taste sharp, biting and warm. Does not solidify at — 25^ (Bonastre) Deposits camphor in the cold. (Bizio.) Sp. gr. ^ 1*034 (Lewis) ; of the commercial oil, 1*055, of that prepared by Bonastre, 1 -061 (Bonastre) ; between 1*033 and 1-040 (Van Hees) ; between 1*046 and 1-058. The first portion of the distillate is lighter than the succeeding produKsts, so that by fractional distillation oils of sp. gr. 0*95 and 1*076 may be obtained. (Jahn.) Prepared from dove -stalks it has a difierent odour, and a sp. gr. 1*049 (Van Hees, Fhami. Centr. 1 847, 380) ; it then has a peculiar odour, like cabbage, and its sp. gr. is 1-051. (Jahn.) It is a mixture of neutral oil of cloves and eugenic acid (p. 202.) (Ettling), of the first of which the earlier portions of the distillate, as well as the oil from clove-stalks, contain a larger quantity. (Jahn.) Contains 73*6 p. c. C, 8*15 H, and 18*25 0. (Ettling.)

VOL. XIV. F

210 APPENDIX TO EUGENIC ACID.

b. OU of Cinnamof^leavea from Ceylon. Obtained according to Pereira^ by macerating cinnamon leaves in sea-water, and submitting the whole to distillation. Closely resembles oil of cloves. Brown oil having a penetrating, aromatic odour, strong, biting taste and sp. gr. 1*053. Reaction acid« Converted bj potash or ammonia into a buttery crystal* line mass. It is a mixture of benzoic acid, eugenic acid, and a hydro- carbon C^H^*. — (^Stenhouse, Ann. Fharm. 95, 103.)

By treating oil of cinnamon-leaves with excess of aqueous potash, decanting the undissolved oil, treating it with fragments of caustic potash, then with chloride of calcium, and finally rectifying it over potassium, the hydrocarbon is obtained as a colourless oil which strongly refracts light, has a specific gravity 0*862, boils between 160*^ and 165 , and smells like cymene. Contains 88*14 p. c. C, and 1 1*68 p. c. H, corre- sponding to the formula C^H^'. (By calculation, 88*24 p. c. C and 1 1 -76 B.) — (Stenhouse.)

c. Pimento-oil. (Nelkenjif^erdL) — Obtained from the fruit of Myrtue pimento. The pods yield 10 p. c, the seeds 5 p. c. oil. (Bonastre, J. Phami, 11, 187.) The whole frait yields 1*9 p. c. oil (Braconnot), 2*34 p. c. of sp. gr. 1*03. (Jahn, N, Br. Arch. QQ^ 155.) Colourless or pale-yellow \ it has a more agreeable smell and taste than oil of cloves (Voigtel), less agreeable (Bonastre), and slightly repulsive, recalling that of Myrttbs communis. It refracts light powerfully. When poured into water, it separates into two portions, one of which floats while the other sinks. (Jahn.) Becomes dark yellow by keeping. (Voigtel.) With ^th its bulk of nitric acid, it immediately turns dark red, with effervescence, and forms a yellowish red solution, the colour of which is rendered more intense by ammonia. (Bonastre.) With oil of vitriol, nitric acid, and iodine it behaves like oil of cloves. Freshly distilled, it will not mix with ammonia, but after standing in contact with it for eight days, it is converted into a colourless crystalline mass. (Jahn.) According to Bonastre, it forms with alkalis the same solid compounds as oil of cloves* (•/. Pharm. 13, 466.) It mixes with an equal quantity of caustic potash-ley, thereby developing heat and becoming turbid ; after- wards the liquid becomes quite clear and viscid, but on cooling it does not solidify m crystals, even on standing, and on addition of water is partly precipitated unchanged, while a resin remains in combination with the potash* (Jahn.) Dissolves completely in alcohol and ether. (Bonastre.)

d. Volatile oil of the Brazilian Clove-cinnamon, Obtained from Persea earyophyllata. (Martius.) Heavier than water, bright yellow, smells like oil of cloves, but less agreeably. Taste burning, like cloves. Bums with a bright flame, depositing much charcoal. It takes fire with fuming nitric acid. Forms with bases, compounds which are partly crystal- lisable, but can never be obtained neutral. Acids precipitate the oil unchanged. The compounds with ammonia, potash, and soda are crya- tallisable, but the lime-componnd is not. Readily soluble in alcohol, from which it is precipitated by water.

e. Volatile oil of Canella alba. By distilling white cinnamon, the bark of canella alba, with water and cohobating the distillate, 0*94 p. c. of oil are obtained. This in contact with aqueous potash parts with eugenic acid, and on being distilled after several days, yields first a lar^e

3ENZ0*fiU0ENIC ANHYDRIDE. 211

quantity of oil which floats on water (et and h), then a small qnantitj of oil heavier than water (c), while half resinised oil floats on the potash- ley which contains eugenate of potash in solution. The lighter oil has a strong aromatic odour, like oil of cajeput, and boils between 180^ and 245^; and by fractional distillation a first portion (d) is obtained at 180°, containing 75*25 p. c. C, 11-28 H, and 13-46 0. (If this be again fractionally and very slowly distilled, a portion boiling at 166'* (oa) is obtained, yielding 79'11 p. e. C, 10*64 H, and 9*25 O. On further distilling the lighter oil, an oil (6) is finally obtained of sp. gr. 0*941, and boiling at 245^ It contains 8054 p. c. C, 10 77 H, and 8-69 0. The oil (c) heavier than water does not combine with potash, and contains 73-7 p. c. C, 10-7 H, and 156 0. (W. Me^er & v. Reiche, Ann. Pharm. 47, 234.) Hence the oil of canella alba is a mixture of eugenic acid, cajeput oil, and an oxygenated oil. (Wdhler.)

Eugenate of Eihyl.

C^HiBQi ^ C*ffO,C«^H"0^

Cahours. (1858.) Compt rend. 46, 220; A7in. Pharm. 103, 265; J. pr, Ohtrn. 73, 259; more detailed, N. Ann. Ckim. Phys. 52, 189 ; Ann. Pharm. 108, 323.

Nelkenvinesier, EugenHthyl (Gm.). Nelkenaaures AethyL Eugenie ether.

Formation and Preparation. By acting on eugenate of potash with iodide of ethyl in a sealed tube. The product is washed with dilute aqueous alkali, dried over chloride of calcium, and rectified.

Properties, Colourless oil, boiling at about 240^ It has an aromatic odour, slightly resembling that of cloves. Neutral.

24 C	. .. 144 16	.... 75*00 ... .... B SA .... 16-67 ...	Cabonrs. 74*82
16 H	8 40
4 O	. ... 32	16*78
C*H«0,C»H"0»	.... 192	.... 10000 ...	10000

It is violently attacked by hrominej chlorine, or fuming nitric aeid, yielding a viscid product.

Insoluble in wcUer, Readily soluble in alcohol and ether.

Benzo-eugenic Anhydride.

Cahours. (1858.) ^'. Ann. Chim. Phys, 52, 189; Ann. Pharm. 108, 321.

Benzoate qf Eugenyl, Eugenate of Benzoyl, Benzeugenyl, Benzoe-Nelkentmure* Anhydrid.

Preparation. Chloride of benaoyl is heated with eugenic acid aa long as hydrochloric acid continues to be evolved, and until the masSi

p2

212 APPENDIX TO EUGENIC ACID.

which at finfe was risooiu and dark brown, has become bright brownish^ yellow. It is then left to cool in a stoppered vessel. The next dsj concentrated solution of potash is added to the mass (which sometimes is still fluid, sometimes solidified in crystals), wherenpon it solidifies, and is washed with water, pressed between blotting paper and crystallised from boiling alcohol.

Properties, Colourless needles, bright amber-coloured when not quite pure, melting between 50^ and 55°, and boiling above 360^

		Cahonn.
		mean.
34 C	204 .... 7612 ..	75-72
16 H	16 .... 5-97 ...	6-06
6 O	■ « •••••■•••■ «0 •••• A# w^	18-22

CMHHy.C^H"^ 268 .... 100 00 10000

It is yiolently attacked by bromine and by nUric acid. It is not affected by cold or boiling aqueous potash, but is resolved by solid hydrate of potash into benzoate and eugenate of potash.

Insoluble in cold and boiling water. Dissolves in boiling alookol and in ether.

Toluo-eugenic Anhydride.

Cahours. (1858.) N. Ann. Chim. Phys, 52, 189; Ann. Pharm, 108, 322.

Toluate qf Bv^enyl, Eugtnate qf Tbluyl, Tolveugenyl TolmyUNelketuawrt- Anhydrid,

Obtained and purified in the same way as benzo-eugenic acid, by the action of chloride of toluvl (C**C1H'0') on eugenic acid. Needles resembling those of benzo-eugenic anhydride.

Cahoun. mean.

86 C 216 .... 76-59 76-89

18 H 18 .... 6-38 6-48

6 0 48 .... 17-03 17-13

C»«H70»,C»H»()» 282 .... 100-00 100-00

Heated with fragments of caustic potash, it is resolved into toluate and eugenate of potash.

Insoluble in water. Dissolves somewhat readily in boiling alooltol, still more in ether.

CUMINO-SUGENJC ANHYDRIDE, 213

Aniso-engenic Anhydride.

C»H*W = C«H^O«,C*N"0».

Cahours. (1858.) If. Ann. C^im. Phys. 52, 189; Ann. Pharm. 108, 323.

Ani»aie qf Bugtnyl, Euffenaie qf Anuyl, AnUeugtnyl, AitU'Nelketudure' Anhydrid.

Chloride of anisjl acts on euffenio acid in the same way as chloride of benzoyl, and fields a ciystallisable product, insoluble in aqueous potash, and bearing the same relation to anisic acid, as benzo-eugenio anhydride to benzoic acid.

Gnmino^eugenic Anhydride.

C«H«o« = C~H"0*,C»H"0».

Cahours. Compt. rend. 46, 220; Ann. Pharm. 105, 263; more detaile JV: Ann, Chim. Phys. 52, 205; Ann. Pharm. 108, 323.

CwminaiB qf Bugenylf Euffemate qf Cfumyl, Cumeugenyl, CmtUn'Neikentaure, Anhydrid.

FarmeUion and Preparation Chloride of cumyl does not act upon eugenic acid in the cold, but on heating, abundant vapours of hydrochloric acid are evolved, while the mixture becomes coloured and thickens. When the evolution of hydrochloric acid has ceased, and the mixture has become light brown and liquid, it is left to cool, and the excess of eugenic acid or of chloride of cumyl is removed with concentrated potash-solution, whereupon the product solidifies in crystals. These are washed with water, pressed between blotting paper, and recrystallised from boiling alcohol.

Properties. Colourless, highly brilliant tablets, which melt at a gentle heat and volatilise when heated above 400^.

Cahonn.

40 C 240 .... 77-42 77*11

22 H 22 .... 7-09 7-14

6 O 48 .... 15-49 15-75

C»»H"0>,C»H»0> 310 .... 10000 100-00

Isomeric with caminic anhydride.

Decompositions. Decomposed by oil qf vitriol in the same way as by caustic potash {vid. inf.). — 2. Not affected by boiling AycfrocA/oric oHcL — 3. It is violently attacked hj fuming nitric acid, being converted into a viscid, reddish yellow resin and a crystalline body. — 4. It is not affected by boiling potash-solution, but caustic potash in fusion decom- poses it into cnminate and eugenate of potash.

214 CHLORINE-NUCLEUS Ca>ClH".

JBromine-micleiu C***BrH".

Hydrobromate of Bromo-cymene.

C*Br»H»* = C««BrH» HBr{1).

SiEVEKiNO. (1857,) Dissert iiber Cuminol and Cymen. Gott, 1857 ; abetr. Ann. Pkarm. 106, 261.

Bromide (^ Cymyl and Hydrogen, CfytnylbromUr, Formation Tp. 186).

Bromine is dropped into water, on which cymene floats, as long as the colour of the bromine continues to disappear, and the product is washed alternately with aqueous carbonate of soda and water, and then dried over oil of vitriol.

Colourless oil, heavier than water.

It cannot be distilled without decomposition. By prolonged boiling with alcoholic potash, it parts with all its bromine, being converted into an oil resembling cymene.

Chlartne-nucleus C"*C1H".

Hydrochlorate of Chlorocymene.

C«>CPH" = C«»C1H",HC1(?).

SiEYEKiNO. (1857.) Dissert, ilber Cnmincl and Cpmen. Gbtt. 1857; abstr. Ann, Fharm. 106, 261.

Chloride of Cymyl and Hydrogen^ CymylchlorUr.

Formation (p. 186).

Chlorine is passed into water, upon which cymene floats, till .the latter sinks. The product is washed with aqueous carbonate of soda and water and dried over oil of vitriol.

Limpid oil, containing 34, 41 p. c. CI (C"*H"C1» = 34-34 CI).

It turns yellow by keeping and evolves hydrochloric acid. It can- not be distilled without decomposition. It is not further acted on by chlorine. Becomes hot with fuming sulphuric acid, evolves hydrochloric acid, turns brownish-red and forms sulphocymenic acid. Heated with alcoholic ammonia, it deposits chloride of ammonium. Boiled with alco- holic potash, it turns red, deposits chloride of potassium, and is converted into an oil, which is separable by water, and when distilled passes over colourless at first, then coloured, evolves hydrochloric acid, and leaves a residue of charcoal. The distillate, after standing over hydrate of lime, distils between 170^ and 230°, still contains from 10 to 12*6 p. c. chlorine^ and has an aromatic odour.

Hydrochl6tate of chlorocymene does not dissolve in watery and but slightly in alcohol.

CHLORANISOL. 215

OwyhnminemucUua C»Br»H«0'.

Terbromanethol.

C^Br'H'O'.

Cahours. (1840.) Rev, sclent, 1840, 342; J, pr. Chem, 22, 58; more fully, N, Ann, Chim. Fhys. 2, 279 ; J. pr, Gkem, 24, 337 ; Ann, Pkarm, 41, 56.

BromanUol, Bromanisal, Formation (p. 194).

Preparation. Bromine is gradually dropped upon anise-oampLor, till a slight excess has been added, and the mixture is allowed to solidify. A brominated oil is then extracted by small quantities of ether, and the residue is dissolved in boiling ether, and left to crystallise. The crystals thus obtained are still contaminated with a small quantity of oil; they are therefore pressed between blotting-paper and recrystallised from ether.

Properties, Rather large, colourless, highly brilliant crystals, which crack between the teeth. Inodorous.

Cahoors. Crystals. mean.

20 C 120 .... 3M7 31*52

3 Br 240 .... 6238

9H 9 .... 2-34 2-66

2 0 16 .... 4-16

C»BrH»0« 385 .... lOO'OO

It is slightly decomposed by heat at 100°, and completely on distilla- tion, with evolution of hydrobromio acid. It is not further acted upon by bromine.

Insoluble in iKtter, slightly soluble in alcohol, more so in ether.

Oxyehlarine-nueleus C»*^C1»H»0*.

Terchloranethol.

Cahours. (1840.) JRev, acient. 1840, 342; J, pr, Chem, 22, 58. In detail. N, Ann. Chim, Phys. 2, 281 ; J. pr. Chem. 24, 337 j Ann, Pharm, 41, 5Q,

Chloranuol, ChioranUal, Formation (p. 194).

Only once obtained by the not too prolonged action of dry chlorine on anise-camphor.

In the cold it is a colourless syrup, which becomes more liquid when heated, and decomposes completely when distilled, evolving hydrochloric acid and leaving a residue of carbon.

216 KITRO-NUCLEUS CP^XW.

Cahonn. mean*

20 C 120-0 .... 47-71 47*72

3 a 106-5 .... 42-34 41-92

9 H 9-0 .... 3-67 3-66

2 O 16*0 .... 6-38 6-70

C»a*H»0» 251-5 .... 100-00 10000

jippendix to Terehloranethol.

Chloride of Draconyl.

Cahours. iT. Ann. Chim, Phys. 2, 282.

Laurent. Eev. sclent, 1842^ 5; /. pr. Ghem, 27^ 247.

Viertinhallffachgteklortu Anethol, (Gm.) Formation (p. 194).

JPreparaiion, Auise-camphor (oil of tarragoD, Laurent,) is acted apon at a moderate heat for a long time bj chlorine gas, till all action has ceased. rOahours.)

Colourless, semifluid, viscid and glutinous mass (Cahours) of the con- sistence of turpentine. (Laurent.)

Cahoara. Laurent.

20 C 120-0 .... 39-63 39-98 .... 39-90

44 a 159-7 .... 52-61 52-14

7iH 7-5 .... 2-47 2*75 .... 3-50

2 O 160 .... 5-29 5-18

C»CWH7*0« 303-2 .... 10000 100-OC

The compouDd from oil of tarragon ioTCstigated by Laurent, has according to him, the formula C«Cl7Hi<OS, according to Gerhardt, perhaps C»Cimi<0< {Traiti 3,356)).

Decomposes by distillation (Cahours), and (when prepared from oil of tarragon) erolves hydrochloric acid and vapours of a very thick oil, while a small quantity of carbon is left. (Laurent.) It is attacked by boiling alcoholic potash. The oil thus changed, which is still very thick, contains 42-5 p. c. C, and 3*4 H ; according to Laurent = C^CrH^CP; according to Gerhardt, it perhaps difl*ers from the preceding by containing less hydrochloric acid.

NUro-nudeui, C»XH»

Nitrocymene. C"NH»o* = C«>XH".

Barlow. (1855.) Ann. Pharm. 08, 247. Niiroejfmol, Nitrocyme. FbrmaHan (p. 186).

Preparation, Cymene which has been cooled by a freezing mixture is dropped into fuming nitric acid, likewise carefully cooled, till the

BINITROCYMENE. 217

whole has become green and thick ; it is then poared into cold water, and the nitrocymene, which is precipitated as a red oil, is washed first with water and then with aqneons carbonate of soda.

Properties. Reddish brown, transparent oil, heavier than water.

Permanent in the air. Prepared from cymene a (== nitrocyinene a) it is bright yeUow and lighter than water.

Decompositions, 1. It is decomposed by distillation with water ; on the water which distils oyer there floats a neatrai oil which has the pro- perties of cymene a, and is converted into a- nitrocymene by cooled faming nitric acid. — 2. When nitrocymene is added to a paste of iron filings and acetic acid, heat is developed. If the whole be distilled, after the reaction has terminated, a distillate is obtained which, by treat- ment with hydrochloric acid, is resolved into cymidiue, which dissolves, and an insolnble oil, a- cymene.

mtro-nucUus, C«X»H".

Binitrocymene.

Kraut. Ann, Fharm. 92, 70.

DinitrocymoL

Cymene is cautiously dropped into nitrosulphuric acid as long as it continues to dissolve ; the whole is then heated for some time to 50'', and, after standing for two days, is dilated with a large quantity of water, whereupon a brown, slowly solidifying oil is precipitated. On dissolving this oil in boiling alcohol, and leaving the solution to cool, drops of oil are first deposited, and on the removal of these, the liquid yields crystals of binitrocymene by evaporation.

Colourless, rhombic tables. Melts at 54°, and solidifies for the most part at 48°.

Kraut. mean,

20 C 120 .... 53-57 52-76

2N 28 .... 12-50

12 H 12 .... 5-36 5-66

8 0 64 .... 28-57

C»X«H>2 224 .... 100-00

Dissolves in alcohol and in ethery and is deposited from saturated solutions as an oil.

218 AZO-NUCLEUS 0«»NH«

Oxynitro-nudeus, (P^Xm^^.

Binitranisoin.

C»H»«N»0" =^C»X*H"0«.

Cahours. (1841.) K Ann. Chim. Phys. 2, 301. ^UranUide,

FomuUion and Preparation. 1. Formed when anise-campbor is heated with faming nitric acid, the reaction being attended with considerable development of heat, and evolution of nitrous fumes ; the product, how- ever, cannot be purified, since no solution of it can be made. — 2. Ani- soin is dissolved in fuming nitric acid, the solution is precipitated by pouring it into water, and the white pulverulent deposit is thoroughly washed. (Kraut.)

Snow-white, highly electric powder. (Kraut.) Yellow resin, melting at about 100°, and decomposing completely when distilled. Boiled with concentrated caustic alkali, it evolves a large quantity of ammonia, dissolves and forms a black, humus-like acid, viz., melanisic acid^ which remains combined with the alkali.

Cahours. Kraut.

20 C

2N

10 H

10 O

		mean.	at lOO*"
120	.... 50-35 ...	.... 52-38 ..	., 50-91
28	.... 11-87 ....	.... 11-25
10	4*19	.... 4-54 ..	4-49
80	• ••• «)o ov ••••	.... 31-83

C?ox2H»oO» 238 .... 100-00 100-00

It gave too much carboiii because it contaiaed anethol (Cahours).

Azo-nudeus, C"NH".

Cymidine,

C»*NH»» = C»NH» H«.

J. Barlow. (1855.) Ann. Pharm. 98, 253. — Notice of results : Phil. Mag. J. 10, 454; Chem. Gaz. 1855, 319; J. pr. Chan. 66, 341 ; Chem. Cewtr. 1856, 48 ; InttiU. 1856, 163.

Formaiion and Preparation. (Comp. p. 217.) Nitrocymene is added to a thick paste of acetic acid and iron filings, whereby heat is im- i

mediately developed. The whole is then distilled (after supersaturation with caustic soda, Kr. ?), and a very complicated product is obtained, from which the cymidine is extracted by hydrochloric acid. The cymi- dine, after the portion insoluble in hydrochloric acid has been removed, is precipitated from the solution by caustic soda, and extracted with ether. On distilling off the ether, the product remains in the retort as a brown oil, which is purified by distillation in a stream of hydrogen.

Properties. Vellow, inodorous oil, boiling about 250°. Neutral. Lighter than water.

p

NICOTINE. 219

DecompofUians. It is not affected by iodine^ and but very slightly by bromine. It is violently attacked and dissolyed by nUt^ acid ; soda separates from the solution a semi-solid substance. Becomes slightly warm with chloride of cyanogen, and forms a base, probably homo- logous with melaniline. This is precipitated by adding caustic soda to the solution obtained by boiling the mass with water. With chloride of benzoyl, it forms with evolution of heat, crystals, probably consisting of benzoyl cymidide .

Combinations, Cymidine dissolves sparingly in water^ and forms salts with acids.

Svlphate of Cymidine, White crystalline salt, soluble in water.

Hydrochlorojte of Cymidine. Strong hydrochloric acid forms with cymidine white clouds and an oil lighter than water, which solidifies in crystals by evaporation or agitation. Turns pine wood yellow. Its solution dyes the skin red. It is not coloured by chloride of lime. Contains 19 68 p. c. HCl, corresponding to the formula C"NH^,HCl (by calculation = 1972 p. a HCl.

With terchloride of gold, cymidine forms a yellow, crystalline salt, sparingly soluble in water.

Chloroplatinate of Cymidine, Aqueous solution of hydrochlorate of cymidine yields with platinic chloride a yellow precipitate which dis- solves sparingly in water, but abundantly in alcohol and especially in ether.

Barlow.

20 0 120-0 .... 33-78 33*77

N 140 .... 3-94

16 H 16-0 .... 4-51 4-67

Ft 98-7 .... 27-79 27*64

3 CI 106-5 .... 29-98

C»NH»«Cl,PtCl2 355-2 .... lOO'OO

Prepared from a- nitrocymene (» chloroplatiiiate of a- cymidine), it contains 27-66 p. c. Pt.

Oxalate of Cymidine. White, ciystalline salt^ insoluble in water. Cymidine dissolves readily in alcohol and in ether.

Jzo-nucleus C»N»H".

Nicotine.

C^'N^H" = C»N»H»,H^

PossELT & Rbiman^. Mag. Fharm, 24, 3138 ; further, 15, 2, 57 ;

presented as a prize essay to the Medical Faculty of Heidelberg,

in 1828. 0. Hbnry & Doutron-Charlard, J. Fharm. 22, 689; J. pr, Chem.

10, 208. LiEBiQ & Gaii^ Ann. Pharm, 18, 66.

220 AZO-KUCLEUS C»N»H«^

OuTiQOBA. Ann, Pharm. 41^ 114.

Barbal. Compt, rend, 14, 224; in detail, N. Ann. Chim. Phys.

ly 151; J. pr. Ckem. 26, 49; Ann. Pharm. 44, 281. — Compt. rendL 24,

218; J, pr. Ckem. 41, 466; more fully, N. Ann. Ckim. Phys, 20, 345. MELBSifB. N. Ann. Ckim. Phys. 9, 465; Ann. Pkarm. 49, 353; J. pr.

Ckem. 32, 372. T. Plahta-Reichekau. Dinert. uber dcu VerkaUen der wicktigden

AlkcUoide gegen RecLgeniien. Heidelberg, 1846. ScHLbssnfG. Ccmpt. rend. 23, 1142; J. pr. Cknn. 40, 184; more

folly, N. Ann. Ckim. Phys. 19, 230. Baswskt. jr. Ann. Chim. Pkys. 25, 322; J. pr. Ckem. 46, 470; abstr.

Ann. Pkarm. 70, 232. J. BoDEKEB. Ann. Pkarm. 73, 372. T. Planta & Kekul^ Ann. Pkarm. 87, 1. Stahlsohmidt. Ann. Pkarm. 90, 218 ; J. pr. C^em. 63, 89 ; Pkarm.

Centr. 1854, 680. Otto. AnleUung zur AutmitUung der Gijle. Brannachweig, 1856, 87.

Vaaqnelin {Ann. Ckim. 71, 139), in 1809, was the first to make experiments with the view of isolating the acrid principle of tobaooo ; he discoyered the volatility of the nicotme compounds and their behaTiour with potash, but did not succeed in isolating the alkaloKd. In this, Posselt and Reimann succeeded in 1828 ; Ortigosa, in 1842, analysed the compounds of nicotine, and Barral analysed nicotine itself. E. Davy

(Ann. Pkarm. 18, 63), described as aqueous nicotine the ammoniacal iquid obtained by the distillation of tobacco or tobacco-roots with solu- tion of potash, being unacquainted with pure nicotine ; his nicotine-salts were mixtures of these and ammonia-salts. {Instit. 1835, 137 ; Ann. Pkarm. 18, 63; J. pr. Ckem. 7, 90; J. Pkarm. 22, 18.)

FamuUian. The dried substance of rotten potatoes distilled with caustic lime yields nicotine, recognisable by its odour. (? Kr.) (Winkler, Jakrb. pr. Pkarm. 25, 82.)

Sources. In Nicotiana Tabacum, nutica, macropkylla and gkuinosa, in combination with malic acid. (Posselt & Reimann.) — As a salt. (Schlossing.) — Nicotine exists ready formed in tobacco, and is not formed in its preparation. (Henry & Boutron, Schlossing.) It can be as effectually separated by magnesia as by alkalis (Henry & Boutron), also by lime, baryta and ammonia. (Schlossing.) Acrid yapours are evolved from a boiling infusion of tobacco by carbonate or bicarbonate of potash ; the presence of nicotine in these vapours may be detected by mercuric chloride. Carbonate of lime produces the same effect, but to a less

extent. (Schlossing.) — Also when tobacco is distUled without alkali, nicotine passes over, though in smaller quantity. (Henry & Boutron.) When an aqueous or alcoholic infusion of tobacco is too rapidly evaporated down, strong vapours of nicotine are evolved. (SchWssing.) When unfermented tobacco is extracted with ether, the solution evaporated, and the residue heated, an odour of nicotine is perceived. (Only a small portion, however, of the nicotine is thus extracted.) Alcohol entirely removes the acrid qualities of tobacco ; the alcoholic extract precipitated with mercuric chloride eives the double salt of nicotine and mercury. (Schlossing.) If fresh tobacco-juice be preci- pitated with tannic acid, the precipitate decomposed at a gentle heat by

NICOTINE. 221

Excess of acetate of lead^ the liquid then filtered, the filtrate freed from lead by dilate sulphuric acid, evaporated to dryness, mixed with carbouate of lime and perfectly dried, a large quantity of nicotine may be extracted from the residue by ether. (Henry & 6outron.) Melsens supposed that nicotine was a product of the fermentation or of the imperfect com- bustion of tobacco. (iV. Ann. Ckim, Phys. 9, 471.)

The following are the percentages of nicotine in different sorts of dry tobacco leaves, deprived of their nbs. a, French tchciccos of the Depart^ ments: — Lot, 7*96 ; Lot et Garonne, 7*34 ; Nord, 6*58 ; He et ViUine, 6*29; Pas-de-Calais, 4*94; Alsace, 321 p. c. — b, American tobaccos: — Virginian, 6*87 ; Kentucky, 609 ; Maryland, 229 ; Havanna under 2 p. c. (Schlbssing.^ — Four kinds of Paraguay tobaccos contained 1'8; 2; 5*5 and 6 p. c. nicotine. (Lenoble, N, J. Phann. 22, 30; Lid>. Kopp, Jahresb, 1852, 531.) When tobacco leaves are prepared for snufi^, nicotine is lost in the fermentation (Henry & Boutron), to the amount of about frds, so that 100 pts. dry snuff still contain about 1*36 p. o. nicotine, chiefly as acetate which is soluble in ether. (Schlbssing, iv. Ann, Chim, Phys. 19, 246.) Tobacco-smoke contains nicotine which, when long porcelain pipes are smoked, is found in the juice collected in the bowl. (Melsens.) By the dry distillation of tobacco, Unverdorben obtained {Pogg. 8, 399), among other products, a base which, on being dissolved in water and boiled down with dilute sulphuric acid, was decomposed into ammonia, fuscine, and odorine (xi, 263). See also xiv, 234; Mntpyreumatic oil of tobacco.

Preparation. 1. Coarsely powdered tobacco is boiled with water; the liquid, after filtration through linen, is evaporated to the consistence of extract ; and before it has completely cooled, it is shaken up with 2 vols, alcohol of 36^. On standing, the semi-flaid mass divides into two strata, the lower, which is black and almost solid, consisting chiefly of malate of lime, while the upper forms a black solution containing all the nicotine. This is decanted ; the alcohol is distilled off; the residual extract again precipitated with alcohol ; the alcoholic solution again evaporated ; and the residue mixed, before it is quite cold, with concen* trated potash-ley, whereupon heat is developed. After cooling, the whole is shaken with ether, which takes up nicotine and other substances, thereby acquiring a deep yellow colour. On distilling the ethereal solu- tion, nicotine tolerably colourless passes over at 180°, but frequently contaminated with decomposition-products of the other substances ; hence it is more advantageous to proceed as follows : To the ethereal solution, powdered oxalic acid is gradually added, the whole being continually shaken, whereby, when the ether is not too aqueous, a white precipitate of oxalate of nicotine is immediately produced, which afterwards deli- quesces to a syrup at the bottom of the vessel. The liquid is decanted ; the precipitated syrup washed with ether, and decomposed by potash ; the liberated nicotine is taken up by ether ; the ethereal solution heated on a water-bath to expel ether, water, and ammonia; and the tem- perature then gradually raised, and kept for a whole day at 1 40°, while a stream of hydrogen is passed through the liquid. The product is now heated to 1 80", whereupon colourless nicotine passes over. 1 000 grammes of tobacco from Lot yield from 50 to GO grammes of nicotine. (Schlossing.) Posselt & Reimann adopted a similar process. (Vid, infra.)

2. Bad tobacco or tobacco-dust is macerated for 24 hours with water to which 1 p. c. of sulphuric or hydrochloric acid has been added ; and

222 AZO-NUCLEUS C»N»H'».

the expressed liquid is evaporated to the consistence of syrup, and distilled with about ^th of its bulk of strong potash-solution, water being added as long as an alkaline distillate, containing ammonia and nicotine, is obtained. This is subjected to either of the following treatments.

a. The distillate is saturated with fragments of caustic potash, wbich dissolves, developing considerable heat, and expelling most of the ammonia, while the nicotine is separated as an oily stratum. This is decanted and freed by a gentle heat from adhering ammonia. (Liebig & Gail.)

b. The distillate is neutralised with oxalic acid and eyaporated to dryness ; the oxalate of nicotine is extracted from the residue by boiling alcohol ; and the solution evaporated to the consistence of syrup, and shaken in stoppered bottles with fragments of potash and ether. By repeating this treatment, the whole of the nicotine is obtained dissolved in the ether. On distilling the ethereal solution in a water-bath, pure and aqueous ether, ether containing nicotine, and finally colourless oily nicotine (which is collected apart) pass over in succession. The nicotine still contains water. (Ortigosa.)

3. Finely cut Alsatian tobacco is digested with water containing sul- phuric acid, pressed out after three days, and the residue submitted to the same treatment till it has entirely lost its acrid taste. The liquid is evaporated to half its bulk, and distilled with lime ; the distillate is next shaken with ether, which tokes up most of the nicotine, then poured back into the retort and again distilled. The distillate is again treated with ether; poured back into the retort, after the ethereal layer has been decanted, and so on, till the residue no longer has any acrid taste. The brown ethereal solution is gradually heated to 140'^ within 14 days, whereby ether, water, and other bodies more volatile than nicotine are driven off, then mixed with slaked lime, and heated to 190° in a stream of hydrogen ; and the slightly coloured nicotine which passes over is collected as much as possible out of contact of air, and rectified. (Barral.)

4. From the so-called Tobcu^co mordant (Tabak^ize). The brown liquid, mixed with a slight excess of sulphuric acid, is evaporated to a syruDj and mixed with a slight excess of potash-^ley ; the liberated nicotine is taken up by ether ; the ethereal solution mixed with oxalic acid ; and the resulting precipitate of oxalate of nicotine decomposed by potash-ley. By shaking up the potash-solution with ether, the nicotine is again dissolved, and may be obtained pure by distilling off the ether, and recti^ fying perse.

Melseus purifies the nicotine thus obtained by placing it in contact with potassium till the metal is no longer attacked even on heating the liquid, and then distils the brown liquid over caustic baryta in a stream of hydrogen ; the purest portion passes over tovrards the middle of the distillation.

Older proceasifs. — Tobacco is distilled with water and -^ potash- hydrate (|- soda-hydrate and 12 pts. water, according to Henry & Boutron) ; the residue is mixed with thrice its bulk of water and redis- tilled; the united distillates containing tobacco-camphor (p. 232), nicotine, and carbonate of ammonia, are neutralised with sulphuric acid, and evapO'-^ rated nearly to dryness ; and the sulphate of nicotine is extracted from the residue by absolute alcohol. The alcoholic solution is evaporated ;

NICOTINE. 223

the residue is shaken up with aqueous potash j and the liberated nicotine is taken up hj ether; on distilling off the ether, the nicotine remains behind, amounting to -^^ of the tobacco. (Posselt & Reimann.) Heniy & Boutron distil the sulphate of nicotine with hydrate of soda, and free it from ammonia by leaving it in vacuo. — Posselt & Reimann likewise exhaust the decoction prepared with water containing sulphuric acid and evaporated with alcohol of 90 per cent. ; distil off the alcohol ; decom- pose the residue with hydrate of lime or magnesia; and separate the nicotine from it by distillation and agitation with ether, like Schlossing. They dehydrate the ether containing nicotine with chloride of calcium, and expel the ether in the water-bath. The nicotine thus prepared con- tains a trace of chloride of calcium.

JB^stimation of Nicotine in Tobacco. — 10 grammes of tobacco containing a known amount of water are introduced into a glass tube, the lower end of which, contracted and bent at right angles, is inserted into the lateral aperture of a flask holding {• of a litre ; the tobacco is moistened with a quantity of ammonia sufficient to liberate all the nicotine ; ether is poured into the flask ; and its neck is closed with a glass tube which conveys the vapours into a Liebig's condensing apparatus. The lower extremity of this condenser is bent, and fitted by means of a cork into the

flass tube containing the tobacco, so that the ether volatilised by the oilinfir^and again condensed by the cooling apparatus, passes through the tobacco, drops into the flask loaded with nicotine, is again volatilised, and again made available for exhausting the tobacco. The apparatus thus arranged is heated for 2 to 4 hours, or till a few drops of the ether which run off from the tobacco no longer leave any nicotine when evapo- rated at a gentle heat ; the tube containing the tobacco is then replaced by a receiver ; the lateral tabulus of the flask is closed ; and the liquid is distilled till the ethereal vapours, which at first are strongly ammo- niacal, no longer contain any ammonia, and are likewise free from nicotine. The remainder of the ether is left to evaporate in the air, and the quantity of nicotine remaining (from which resin separates) is esti- mated by the amount of sulphuric acid of known strength required to neutralise it. — 49 pts. of oil of vitriol (SO*H) correspond to 192 pts. of nicotine. (Schlossing.) Schiel {Ann, Pharm, 105, 257 ; /. pr. Ohem. 74, 127).

Processes for the detection of nicotine in cases of poisoning are given by Stag {Bull, de VAead. de MSdecine de Belgique, 9, 304 ; Jahrb, pr, Pharm, 24, 313; Ann. Pharm, 84, 379 j Liebig Sf Kopp*» Jahresber, IS."}!, 640) ; further : Orfila {J, Chim, mid. 21 J 399). See also Lehmann {Pharm, Cenir, ISbZ, 927) ; Melsens {BuU, de VAead, de MSdecine de Belgique [2], 1, No. 9 ; Rep, Chim, pure, 1, 232).

Properties, Colourless, transparent oil which remains liquid at — 6° (Posselt & Reimann), at — 10° (Barral), and when heated, even to tem- peratures short of 100°, gives off white vapours having an intolerable

odour, (Ortigosa.) — When nicotine is left in a yacaum for a few days, small crystals appear in it which resemble chlorate of potash, and deliquesce rapidlj in the

air. (Henry & Boutron.; It distils very slowly at 146°, begins to boil at 240° (towards 250°, according to Barral,) only a portion, however, dis- tilling colourless and undecomposed, in heavy white fumes (Posselt & Reimann, wVf.iV) — Sp. gr. 1048 (Henry k Boutron); 1033 at 4°; 1027 at 15° ; 1018 at 30° ; 10006 at 50^; 09424 at J01-5°. (Barral.) It has a sharp odour, slightly resembling that of tobacco (Barral), un-

224 AZO-NUCLEUS C»N2H".

pleasantly pungent, like tbat of dry tobacco, especially when heated (Posselt & Reimann) ; has a strong odour, unpleasantly like that of tobacco (Ortigosa) ; slightly ethereal. (Otto.) — Taste burning. (Barral.) Even when diluted, it has an extremely sharp and caustic taste, producing choking in the throat. (Henry & Boutron.) — It is poisonous, ^ of a drop being sufficient to kill a rabbit, and one drop being a fatal dose for a dog. (Posselt & Reimann.) — 5 milligrammes placed upon the tongue of a middle-sized dog kill it in 3 minutes, j- of a grain dropped into the eye of a full-grown cat produces contraction of the pupil and strong, narcotic symptoms, which, however, pass off in the course of an hour. (Gergis & Hesse, Ann. PhoLrnt, 7, 293.) Small birds are killed even by the approach of a glass rod moistened with nicotine. Very weak aqueous nicotine taken into the mouth, even for a second, produces heavy tur- pidity, lasting for 10 minutes, then a sensation of heaviness and head- acbe lasting for several hours. (Henry &c Boutron, comp. Melsens, Ann. Chim. Phys. 9, 468.)

Nicotine has a strong alkaline reaction. — Its vapour-density is 5*829 ; or, taking into account the 3 per cent, of residue left in the distillation, it is 5*607. (Barral.) It turns the plane of polarisation of a luminous ray strongly to the left. (Laurent, Compt. rend. 19, 926 ; Wilhelmy Fogg. 81, 527.) — Meat keeps for any length of time in nicotine vapour, merely assuming a brighter red colour. (Robin, Compt. rend. 32, 177)

			Barral.	MeUen8<	SchlOssing.
20 C	120	.... 74-08	. 73-69	.... 74-3	.... 73-59
2 N	28	.... 17-28	. 17-04	.... 17-3	.... 17*11
14 H	14	... 8-64	8-86	.... 8-8	.... 8-70
C»N»H" .	162	.... 100-00	. 99-59	.... 100-4	.... 99-4
		Vol.		Density.	•
	C-vaponr N-gas ...	20 .		8-3200
	2 .		1-9412 0-9702
	H-gM ...	14 .
	Nicotine-TaDoiir .... 2		11-2314
		r - 1 .		5-6157

Ortigosa, from his analysis of the platinum-salt, assigned to nicotine the formula QiO]^H8^ which was adopted by Barral. Melsens proposed the formula C^^H^ and Barral, after recalculating his own analysis, showed that this formula was in accordance with it; he, moreover, doubled it to agree with the vapour-density, a conclusion to which Schlttssing was also led by his determination of the saturating power of nicotine towards sulphuric add.

Decompositions. 1. Nicotine quickly assumes a brownish yellow colour when exposed to light. (Henry & Bonastre.) — 2. When distilled, even in an atmosphere of carbonic acid, it always leaves a small residue amounting to about 3 per cent., this effect being reproduced every time distillation is repeated. No gas is evolved; and the residue, which is insoluble in water, but easily soluble in alcohol, appears to be an isomeric modification of nicotine, (Barral.) Nicotine when distilled leaves a resin soluble in alcohol and precipitable therefrom by water. (Ortigosa.) The same residue remains when nicotine is left to €vaporate in the air. (Posselt & Reimann.) — 3. Nicotine exposed for some time to the at?*, turns brown, becomes more viscid, and is partly converted into a resin. (Posselt & Reimann, Burral and others.) 4. At ordinary tem- peratures, it is not set on fire by the approach of a flaming body, but burns

NICOTINE. 225

ID a wick with a bright smoky flame. (Posselt & ReimanD,) The vapour which rises from nicotine heated in a crucible may be set on fire. (Henry & Bontron.)

5. Warm oU of vitriol does not act immediately on nicotine, bnt gradually acquires a red>brown colour by contact with it; the solution supersaturated with hydrate of soda, yields nicotine free from ammonia. (Henry & Boutron.) Boiling oil of vitriol decomposes nicotine completely (leaving a black thick mass, according to Stahlschmidt), so that the liquid neutralised with ammonia tastes no longer sharp but only bitter. (Posselt & Reimann.)

6. Aqueous nicotine mixed with tincture of iodine, (or with aqneoos hydriodoua acid or hydriodite of potash mixed with chlorine), becomes turbid, and

yellowish at first, but afterwards crimson, even when diluted 1000 times (Posselt & Reimann); according to Planta, it produces with tincture of iodine, a kermes-brown precipitate. On mixing the ethereal solutions of iodine and nicotine, heat is evolved, and after a while the mixture soli- difies to a crystalline pulp of teriodonicotine. (Wertheim, Gerhardd Traits, 4, 193.)

7. When nicotine is dropped into a bottle filled with chlorine gas, a violent action takes place, sometimes attended with emission of light; hydrochloric acid gas is evolved; and the nicotine becomes blood-red, but loses its colour again by exposure to light for a few days, and then at a rather low temperature (below 8°) deposits long needles, which how- ever melt at a slightly elevated temperature. The liquid, which has become colourless by exposure to light, deposits when mixed with water, a white sediment, which may be recrystallised from alcohol, the super- natant very acid liquid becoming red-brown when evaporated at a gentle heat. (Barral.) — When chlorine is passed over nicotine, a dark brown solid substance is obtained, which dissolves readily in alcohol but does not separate in the crystalline form on evaporation. (Stahlschmidt.) — Chlorine-water does not act on nicotine in the cold ; if the liquid be heated at the same time, it turns yellow, without giving off nitrogen gas. (Henry Sc Boutron, BanaH) — Aqueous hypoMorous acid added to a concentrated aqueous solution of nicotine, produces a whitish turbidity, without evolu- tion of nitrogen gas, which however takes place immediately on adding a small quantity of ammonia. (Henry & Boutron.) Nicotine is quickly decomposed by aqueous perchloric acid. (Bodeker, Ann. Pharm. 71, 64.) By the action of chlorine on hydrochlorate of nicotine, a beautifully crystallised compound is formed, easily soluble in water, insoluble in alcohol. (Geuther & Ho&cker, Ann. Pharm, 108, 35.)

8. Nicotine heated with nitric acid, gives off copious red fumes, and if distilled with potash after the reaction is finished, yields a volatile base which appears to be ethylamine. (Anderson, Ann, Pharm. 75, 82.) — With hot nitric acid, it gives off nitrogen gas and yields a thick orange- coloured mass without any oxalic acid. (Henry & Boutron.) With nitric acid or acid chromate of potash and stdphurk acid, nicotine gives off a suffocating vapour and forms a brown liquid. (Stahlschmidt.) — Fuming nitric acid attacks it violently, even in the cold, but does not decompose it completely. (Posselt & Reimann.)

9. Hydrate of soda exerts a decomposing action upon nicotine, eliminating a small quantity of ammonia. (Henry & Boutron.) When nicotine containing water is left in contact with lumps of hydrate of potash, it dissolves potash, and yields by distillation a liquid which has an odour different from that of nicotine, contains 52 per cent, of carbon,

VOL. XIT. Q

226 AZO-NUCLEUS C»NSH«.

does not form ohloroplaiinate of nicotine when mixed with bichloride of platinum, but yields by evaporation of the mixed alcoholic solution, crystals easily soluble in alcohol. (Ortigosa, comp. p. 223.)

10. When cyanogen gas is passed oyer nicotine (Stahlschmidt), or into the alcoholic solution (Hofmann), a brown product is formed which does not crystallise from alcohol (Stahlschmidt) and does not exhibit basic properties. (Hofmann, Ann, Pharm, M, 145.)

11 . It acts upon cganate of ethyl less quickly than aniline, forming a compound which crystallises in beautiful taminse. (Wurtz, Oompt, rend. 22, 418; Ann. Fharm. 80, 349.)

12. In contact with iodide of methyl, it deposits a heavy brown oil, and solidifies on cooling as crystalline hydriodate of methyl-nicotine. (Stahlschmidt, Ann, Pharm. 90, 222.) — In contact with iodide of ethyl, it is converted, even at ordinary temperatures, more quickly at 100°, into hydriodate of ethyl-nicotine, (r. Planta & Kekul^, Ann. Pharm, 87, 3.) When iodide of amyl is heated for several days with nicotine in a seded tube, a brown syrup is obtained, which does not solidify, even when cooled and exposed to the air, or crystallise when its aqueous or alcoholic solu- tion is left to evaporate, but when treated with water deposits the excess of iodide of amyl and yields a solution of hydriodate of amyl-nicotine. (Stahlschmidt.)

Combinations, With Water, A. Hydrated Niootine. Nicotine ex- posed to moist air quickly takes up water, to the amount of 10 per cent, in a day, but gives it up again completely in a dry current of gas. (Schlossing.) In an air-space saturated with aqueous vapour, nicotine takes up, in the course of three weeks, 1*77 per cent, of water, which, however, is given off again when the hydrated nicotine is placed over hydrate of potash. Nicotine thus saturated with water solidifies com- pletely in a freezing mixture of ice and salt (Barral.)

B. Aqueous Nicotine. Nicotine dissolves in water in all proportions. (Posselt & Reimann, Barral and others.) With half its volume or less of water, it forms (when it contains resinous matter, according to Posselt & Reimann) a clear mixture which is rendered turbid by a larger addition of toater, (Ortigosa.) Hydrate of potash separates nicotine from its aqueous solution. (Liebig & Gail.)

Nicotine at 100° dissolves 10*53 p. c. stUphur, the greater part of which crystallises out on cooling, the nicotine returning a dark brown colour. — It does not dissolve phosphorus. (Barral.) It absorbs amm^mia gas but does not retain it more firmly than it retains water. (Schlossing.)

With Acids, Nicotine saturates acids completely. The salts of nicotine crystallise sometimes in laminar, sometimes in granular form. (Henry & Boutron.) The simple salt^ crystallise with difficulty, the double salts more easily. (Barral.) They have a very sharp taste. (Henry & Boutron.) Their aqueous solutions may be evaporated at a gentle heat without much loss of nicotine. (Posselt & Reimann.) They give off part of their nicotine when evaporated. (Henry & Boutron.) They emit the odour of nicotine when treated with potash-ley, and produce with iodine the kermes-colour of nicotine. (Posselt & Reimann.) They dissolve readily in alcohol of 40° (Henry & Boutron), but are iusoluble in ether, with the exception of tne acetate. (Schldssing.) Nicotine precipitates the salts of manganese, zinc, lead, iron, (vide inf^.) and tartar- emetio, like the alkalis. (Henry A; Boutron.) It precipitates the salts

NICOTINE. i27

6f manganese and iron in the cold, silyer-salts when heated. (Schl5s- sin^.) It likewise precipitates acetate of lead, acetate of copper, and chloride of cohalt. (Otto.) It does not precipitate barjta or lime-salts, bat when carbonic acid gas is passed into an aaaeons mixture of nicotine mixed with excess of nitrate of lime or chloride of barium, a precipitate of carbonate of lime or carbonate of baryta is formed in the proportion of 1 at. to 1 at. of the nicotine used. (Schlftssing.)

CaO.NO* + C»N«H" + HO,CO« = C»N«H",HO,NO» + CaO,CO».

Fhoiphate of Nicotine, The colourless ffjrrup obtained by neutralising nicotine with aqueous phosphoric acid, yiel<u by evaporation in sunshine, white crystals resembling cholesterin. (Posselt & Reimann.) — Nacreous laminae. (Henry & Boutron.)

Sulphate of Nicotine. — 100 parts of oil of vitriol neutralise on the average 329*7 pts. of nicotine, forming neutral sulphate of nicotine, C»N»H**,HO,SO». (Schlbssing.) (Calculation 330*6 pts.) The sulphate is a brown uncry^tallisable syrup. (Posselt & Reimann.) Nacreous laminae. (Henry & Boutron.)

Acid lodate of Nicotine is nearly insoluble in alcohol (Henry k Boutron.)

HydrochUyi^ate of Nicotine. — Nacreous Umine. (Henry & Boutron.) Obtained by saturating nicotine with dry hydrochloric acid gas, and leaving the product in vacuo, in long deliquescent white threads, which are more volatile than nicotine, and dissolve readily in water and alcohol, not in ether. (Barral.) When dry hydrochloric add gas is passed over gently heated nicotine, and the excess of hydrochloric acid is expelled by means of dry hydrogen gas, quantities of hydrochloric acid are taken up, varying from 1 to 2 At., but a considerable portion goes off on gentry heating the product. The alcoholic solution of the salt deflects the plane of polarisation of a ray of light to the left. {Pogg. 81, 527.)

C»N«H" 2 HCl	162 .... 68-94 73 .... 31*06 ....	Barral. .... 29*74
C»»N«HM2HC1	235 .... 100-00

Niirate of Nicotine crystallises with difficulty. (Henry & Boutron.) Aqueous nicotine forms with phosphate of magnesia a gelatinous pre- cipitate; with acid sulphate of alumina, needle-shaped crystals of a double salt. (Henry & Boutron.) With phospho-mclybdic add, it behaves like conine (xiii, 164; Sonnenschein, Ann. Fharm. 104, 47.) — Phosphantimonic acid (produced by dropping pentachloride of antimony into aqueous phosphoric acid) added to an aqueous solution containing 7^ pt. of nicotine, produces a slight turbidity. (F. Schulze, Ann. Pharm. 109, 179.)

Chloride of Cadmium with Hgdrochhrate of Nicotine. Nicotine forms with chloride of cadmium, a compound which is difficult to crystallise (G. Williams, Chem. Gaz. 1855, 450; Chem. CerUr. 1856, 47), ^solves

Q 2

228 AZO-NUCLEUS C»N«Hi«.

readily in water; does not give off any water at 100°, and corresponds to the formula C'»N»H",2HCl,5CdCl (Galetly, N, Edinb. n. PhU. J. 4, 94 ; Ckem, Centr. 1856, 606.)

By precipitating bichloride of tin with nicotine, a white double salt is obtained (Barral); with fennc chloride, a yellow-brown double salt (Barral) ; a brick-red precipitate (Henry & Bontron). With sulphate of copper, aqueous nicotine produces a greenish white precipitate, which is not turned blue or dissolyed by excess of nicotine. (Henry & Boutron.)

Nicotine with Mercuric Iodide. C*N'H",2HgI. Colourless laminas, obtained by triturating nicotine with mercuric iodide (whereby heat b evolved, and a portion of the nicotine consequently volatilised) and boiling the mass with water. (Wertheim^ Gerhardt^s Traits, 4, 192.)

lodomercurate of Nicotine. — A solution of mercuric iodide in hydriodio acid, is dropped into hydriodate of nicotine till the precipitate formed on each addition begins to be permanent ; the double salt then crystallises from the solution after standing for some time. The mother-liquor is decom- posed by evaporation. Small yellow prisms sparingly soluble in cold water and in alcohol. It is decomposed by hot water, depositing a reddish yellow resin insoluble in potash-ley. (Bbdeker.) Hydrochlorate of nicotine added to potassio-mercuric iodide, produces a yellowish white precipitate insoluble in hydrochloric acid. (v. Planta.)

Bddeker.

C»N»H« 164 .... 19'09

4 I 508 .... 57-84 58-33

2 Hg 200 .... 28-07 22-71

C»N«H",2HI + 2HgI 872 .... 10000

Nicotine with Mercuric Chloride, — Pure nicotine and acetate of nicotine form with solution of mercuric chloride, white flocks, easily soluble in hydrochloric acid^ insoluble in alcohol. (Posselt & Reimann.) Hydrochlorate of nicotine, throws down from corrosive sublimate, a white pulverulent precipitate eanly soluble in hydrochloric acid and in sal-ammoniac. (▼. Planta.)

a. With 2 at. Mercuric Chloride."^ By precipitating a solution of corrosive sublimate with aqueous nicotine. White crystalline precipitate which melts and turns yellowish below 100°.

Insoluble in water and ether, sparingly soluble in alcohol. (Ortigosa.)

Ortigosa.

20 C 120 .... 27-72 27-70

2 N 28 .... 6-46

14 H 14 .... 3-23 3-73

2 CI 71 .... 16-40 15-86

2 Hg 200 .... 4619 4553

C»N'H",2HgCl 433 .... 10000

6. With 6 At. Mercuric Chloride. A solution of nicotine in dilute hydrochloric acid is dropped into a saturated solution of mercuric chloride, as long as the precipitate at first produced redissolves, and the solution is set aside for a few days, whereupon, if it is sufficiently diluted, the com- pound separates in crystals. If the solution is too strong, an oil is pro-

NICOTINE. 229

duced, which dissolves in hydrochloric acid^ and may he converted into crystals hy addition of mercuric chloride. Clear, colourless, or pale yellow crystals^ sometimes an inch long. It crystallises in the right prismatic system. Comhination of two vertical prisms n and Ut and two pairs of hasal faces m, u, t, {Fig, 77); in addition, a horizontal prism I {Fiff, 78), u:t=i 148" 55' 17'; n:t— 129° 40' 33"; therefore m : m = 160'' 45' 16", ohservation gave 160"* 43' 28"; l:t = US° 57' 24". Cleav- age parallel to m, (Danher, Ann, Fharm. 74, 201.)

Dissolves sparingly in cold water and melts to a hrown resin in hot water. Dissolves in acidulated water, sparingly in cold alcohol. (Badeker.)

BQdeker.

C»N«H" 162 .... 16-9

6 CI 213 .... 21-7 21-6

6Hg 600 .... 61-4 61-9

C»N«HW,6HgCl 976 .... lOO-Q

ChloromercurcUe of Nicotine, With SAi. Mercuric Chloride, C»N»H",HCl,8HgCl. — Ohtained as a crystalline precipitate hy treating a cold neutral solution of hydrochlorate of nicotine with a larger excess of aqueous chloride of mercury. Crystallises from hot water in stellate groups of needles. (Th. Wertheim^ Gerhardt*8 Traite, 4, 191.)

Aqueous nicotine does not precipitate cyanide of mercury. (Henry & Boutron.)

Nicotine with Mercuric Cidoride and Cyanide, A neutral solution of hydrochlorate of nicotine is mixed with an equal quantity of a saturated solution of cyanide of mercury. Colourless silky prisms grouped in tufts^ dissolving easily and without decomposition m water and alcohol, both cold and hot. With hydrochloric acid, it evolves hydrocyanic acid Potash -ley does not precipitate the solution of the prisms, hut colours the solid salt reddish yellow. Contains 00*85 p. c. mercury, 17*76 chlorine, and 2-46 cyanogen, and is therefore probably C*N'H",5HgCl,HgCy or C»N«H",4HgCl,2HgCy. (Bodeker.)

Nicotine with Nitrate of Silver. — Aqueous nicotine does not pre- cipitate nitrate of silver. (Henry k Boutron.) a. With \ At. Nitrate of silver, 2C»N*H",AgO,NO*. When alcoholic nitrate of silver is mixed with excess of alcoholic nicotine, and the dilute solution left to evaporate, beautiful prisms are produced, which appear to belong to the oblique prismatic system. (Wertheim.)

b. With 1 At. Nitrate of Silver, C»N»H",AgO,NO». Obtained like a, but with excess of nitrate of silver. Colourless prisms.

Nicotine with Terchlofide of Gold — Aqueous nicotine forms with sodio-auric chloride a light orange-coloured precipitate. (Henry & Boutron.) Hydrochlorate of nicotine added to auric chloride, throws down light yellow flocks, insoluble or sparingly soluble in hydrochloric acid. (v. Planta.)

Chloroplattnite of Nicotine. — a. With 2 At. Hydrochloric add, L Nicotine is gradually added to a luke-warm solution of protochloride

830 AZO-NUCLBUS c»Nm«.

of platinam in hydrochloric acid, stirring constautly and cooling the iiqaid, because it is apt to get heated. There is then produced a crystal- line precipitate of orange-coloured chloroplatinite of nicotine w^ith 4 At. hydrochloric acid, the quantity increasing as the stirring is continued; and the mother-liquor filtered from this precipitate yields by evaporation or cooling, red-coloured right prisms of chloroplatinite of nicotine with 2 At. hydrochloric acid. — 2. This salt is obtained in larger crystals, when the orange-coloured salt is redissolyed in the mother-liquor by boiling, and the solution is left to cool and crystallise in vacuo. — 3. When the red prisms obtained by 1 or 2 are dissolved in a large quantity of hot water, the solution becomes turbid on cooling, from separation of yellow crystalline scales, isomeric with the red prisms obtained by ] or 2. (Raewsky.)

Leaves platinum when ignited on platinum-foil. With hot nitric acid it gives ofi* red vapours. It is turned brown by oil of vitriol, and when heated yields a brown precipitate and gives off sulphurous acid. It dis- solves sparingly in cold water, more easily in hot water (if heated with too little water, it becomes gelatinous on the surface and less soluble), and separates on

cooling in yellow crystalline scales, isomeric with the red prisms. It dissolves in cold nitric and hydrochloric acid, not in alcohol or in ether. (Raewsky.)

Red talt,

20 C 1200 ..

2 N 28-0 ..

16 H 160 ..

2 Pt 197-4 ..

4 CI 142-0 ..

C»N2HM 2HCl,2PtCl 503-4 ..

a. Red priBms. b. Yellow crystalline scales.

According to Raewsky, it is PtCl^O^'^NH^iHCl, that is to say, the hydroohlorate of a peculiar platinum base (the corresponding member to which among the ammoniacal platinum compounds (vi, 296) is not known ; a view which is opposed by Gerhardt with respect to this and the following compound {Compt, efum. 1849, 206), inasmuch as the latter gives off nicotine when treated with potash.

b. With 4 At Hydrochloric add. — {Preparation, vid. sup,). Orange- yellow crystalline powder (a); separates by spontaneous evaporation from its solution in hydrochloric acid, in very large, regular, orange- coloured rhombic prisms (6); from its solution in nitric acid in small yellow crystals (c). When dissolved in (an insufficient quantity of?) boiling water, it leaves an amorphous residue (d), whilst the salt a crys- tallises from the solution. (Raewsky.)

Heated on platinum-foil, it swells up, gives off hydrochlorate of nicotine^ burns like tinder, and leaves platinum. Cold oil of vitriol turns it white; hot oil of vitriol chars it, with evolution of sulphurous acid, and leaves a black residue of platinum. With potash, it evolves nico- tine. (Raewsky.)

Insoluble in cold water, {vide mp.) Insoluble in alcohol and ether. Dissolves in nicotine, forming a red liquid, miscible without turbidity with cold water; and on evaporating this solution in vacuo, there remains a thick, glutinous, very deliquescent mass, resembling treacle, which dissolves in water, hydrochloric acid, nitric acid, alcohol and ether.

		Raewsky.
		mean.
	a.	b.
23-8 ...	24-00	.... 241
5-6 ...	5-50	.... 61
3-2 ...	3-25	.... (5*^
39-2 ...	89-40	.... 39-1
28-2 ...	27-85	.... 27-5
100-0 ...	100-00	.... 100-0

NICOTINE. 231

and cannot in any way be made to crystallLse. (Baewsky.) Perhaps C«N^H",2HCl,PtCl or C»N»H^HCl,PtCl. (Gephardt, (?««©<. chim. 1849, 206.)

Raewsky.

a. b, c, d.

205

6-2

3-3

340

360

Orange'ifellttw salt. mean,

20 C 120-0 .... 20-8 20-5 .... 207 .... 204 .

2 N 28-0 .... 4-9 6-2 .... 4-9 .... 6*2 .

18 H 18-0 .... 31 3-2 .... 3-1 .... 3-4 .

2 Pt 197-4 .... 34-3 34-2 .... 34-3 .... 34-0 .

6 CI 2130 ... 36-9 35*9 .... 370 .... 362 .

C»N«HJ<,4HCl,2PtCl .... 576*4 .... 100-0 100-0 .... lOO'O .... 100*2 .... 100-0

Acoordiog to Raewsky, PtClC^NH^2HCl (oomp. p. 230.)

CJdoroplatlnate of Nicotine. — NicoHnplatmchlorid. -^ On mixing the solutions of hydrochlorate of nicotine and bichloride of platinum, a yellow crystalline precipitate is formed if the solutions are concentrated, and if they are dilute, there are deposited, after a while, oblique fonr-sided prisms belonging to the right prismatic system. (Ortigosa.) Barral <A>tains the same compound as a granular powder by precipitating bichloride of platinum with nicotine. Liebig & Gail precipitate with bichloride of platinum the distillate containing nicotine and ammonia obtained in the preparation of nicotine, as described at page 222, whereupon the liquid filtered from the precipitate of chloroplatinate of ammonium deposits, after three or four days, large ruby-red crystals. — The salt has a bitter and very sharp taste. (Posselt & Reimann.)

When exposed to the air, it becomes dull, and cannot be recrystallised without decomposition. Distilled with potash-ley, it yields pure nicotine. (Liebig & Gail.) It dissolves with difficulty in water. (Ortigosa.) Soluble in boiling water. (Barral.) It dissolves in hot dilute hydro- chloric acid (Ortigosa), somewhat in nitric acid. (Posselt & Reimann.) Insoluble in hydrochloric acid. (v. Planta.) Insoluble in alcohol and in ether (Ortigosa) ; very soluble in a slight excess of nicotine. (Barral.)

20 C 1200

2 N 28-0

16 H 16-0

2 Pt 197-4

6 CI 213-0

	Ortigosa.	BarraL
20-87 ...	20-98 ....	21-12
4-87 ...	4-74	4-81
2-78 ...	3-09 ....	3-16
34-36 ...	34-11 ....	34*25
37-12

C»N2HM 2HCl,2PtCl2 574-4 .... 100-00

Acetate of Nicotine, — Nicotine supersaturated with glacial acetic acid and exposed to the air, forms after 8 days a neutral syrup. (Posselt & Reimann.) Acetate of nicotine crystallises with difficulty. (Henry & Boutron.) Strong acetic acid forms with the ethereal solution of nicotine a clear mixture, from which water extracts the acetate of nicotine. (Posselt & Reimann.) According to Schlbssing also, acetate of nicotine is soluble in ether.

O^t^^o^ </ ilTtco^ine. -— Crystalline, easily soluble in water. (Posselt

232 AZO-NUCLEUS C»N2H'2.

& Reimann.) Insolable in ether. (Schlossing.) LaminaB having a pearly lustre. (Henry & Boutron.)

Nicotine forms a crystallisable salt with nicotic acid (x, 229).

Tartrate of Nicotine is obtained by evaporating its solution in the air, as a crystalline granular mass easily soluble in water. (Posselt & Reimann.)

Purpurate of NicoUne. — Aqueous alloxan, to which a few drops of nicotine are added, assumes in a few seconds a dark purple colour, and, subsequently, there are formed in the red liquid, colourless rhombic tables, very similar to those of uric acid when the latter have acquired their obtuse angles ; they may be freed from the mother-liquor by washing with a small quantity of water. The crystals dissolve in cold, moderately dilute potash-ley, with splendid purple blue-colour and the odour of nicotine. The purple mother-liquor may be evaporated over oil of vitriol to a blood-red viscid syrup, which dries up to an amorphous mass ; it is decolorised by absolute alcohol, with precipitation of brick-red flakes which dissolve in alkalis with carmine colour, emitting at the same time an odour of nicotine. (Schwarzenbach.) — Hence Schwarzenbach sup- poses that the mother-liquor contains acid purpurate of nicotine, and that the crystals contain the neutral purpurate. (WittsteirCi Vierteljahrsschr. 6, 424 and 8, 170.)

Picric acid added to hydrochlorate of nicotine throws down sulphur- yellow flocks, (v. Planta.)

Tincture of galls, added to aqueous nicotine, throws down a white curdy precipitate (Henry & Boutron) ; it forms, with hydrochlorate of nicotine, a whitish cloud, which disappears on addition of a few drops of hydrochloric acid, but is reproduced by a larger quantity, (v. Planta.)

Nicotine mixes in all proportions of alcohol. The mixture, when distilled, gives off first a comparatively pure alcohol, then spirit contain- ing nicotine. (Posselt & Reimann.)

It mixes in all proportions with ether, and the solution when distilled gives off pure ether, with only a little nicotine towards the end. It gives up all its nicotine to acids. (Posselt & Reimann.) Ether entirely removes nicotine from its aqueous solution.

Nicotine dissolves in about 40 pts. of oU of turpentine, easily in oil of almonds ; the latter solution has a very sharp taste, and gives up all its nicotine when shaken up with acetic acid. (Reimann.)

Appendix to Nicotine »

a. Nicotianine or. Tobacco-camphor.

Hermbstadt. Schw, 31, 442; abstr. Berz. Jakresber, 1823, 113. Posselt & Reimann. Mag. Pharm, 24, 138; Berz. Jahresbei-^ 1831, 193. LuNDERER. Repert., 53, 205. Barral. Compt. rend. 21, 1376.

Obtained by Hermbstadt, in 1823, from Nicotiana Tabacum. — According to Landerer, it is produced in the drying of the tobacco, inas- much as fresh tobacco- leaves do not yield it.

NICOTIANINE. 233

Preparation, The herb, either fresh or dry, is distilled with a small quantity of water, whereby a milky distillate is obtaiDed, on the sarfEUse of which nicotianine separates after a few days in laminar crystals.

The remaining portion of the distillate is mixed with subacetate of lead, the precipitate decomposed by a not qnite sufficient quantity of dilute sulphuric acid, and the liquid filtered from the sulphate of leaA is left to evaporate. ^Hermbstadt.) — According to Posselt & Reimann, this lead-precipitate is nothing but carbonate of lead, and does not yield any more nicotianine. These chemists pour 12 lbs. of water on 6 lbs. of tobacco-leaves ; distil off 6 lbs ; add to the residue 6 lbs. of fresh water ; distil again ; and repeat this treatment five times. The distillate deposits 11 grains of nicotianine, while nicotine remains in solution. Landerer extracts from the aqueous distillate of tobacco-leaves only a few drachms of water, from whicn the nicotianine separates on standing.

Properties, White, crystalline, laminar. Melts when heated, and then gradually evaporates ^Hermbstadt) ; in some weeks, when exposed to the air in open vessels. (Posselt & Reimann.) Smells like fine tobacco (Hermbstadt) ; like tobacco-smoke and lilac-blossoms^ more strongly when heated, but without exciting sneezing. (Hermbstadt.) On the tongue, or in the throat, it tastes like tobacco-vapour (Hermb- stadt) j not at all sharp, but warm and bitterly aromatic. (Posselt & Reimann.) When swallowed, it produces nausea and giddiness (Hermb- stadt) ; a dose of 2 grains produces no particular effect. (Posselt & Reimann.) Neutral.

Calculation accordii {Traite 4, 46 C 2 N	ig to Gerhardt. 193.) 276 .... 71-87 ... 28 .... 7-30 ... 48 .... 12-50 ....	Barral. 71-52 7-12
90 II		8-23
6 O		13*13
C46jpH»0«		384 .... 100-00 ....	100-00

According to Buchner (Report, 53, 209) it is, perhaps, a compound of nicotine with a volatile vegetable acid.

Decompositions. Nicotianine turns brown when exposed to the air. (Hermbstadt.) — It is insoluble in nitric acid when cold, but dissolves in it when hot, giving off nitrous gas. (Posselt & Reimann.) — It dissolves in potash-ley (Posselt & Reimann)^ and gives off nicotine when distilled therewith. (Barral.)

It is soluble in water. (Hermbstadt.) — It is not sensibly soluble in aqueous hydrochloric acid, and remains unaltered when evaporated by contact with it. — According to Hermbstadt, it precipitates lead and mercuric salts ; but, according to Posselt k Reimann, these precipi- tations do not take place. — It forms a white precipitate with tincture of galls. (Hermbstadt)

It dissolves in alcohol and io ether, — The alcoholic solution becomes milky on addition of vrater (Posselt & Reimann) ; according to Hermb- stadt, it does not.

284 AZO-NUCLEUS C»1<PU".

b. Empyreumatic Oil of Tobacco.

Zeisb. J. pr, Chem, 29, 888; Ann. Pharm. 47, 127; Pogg^ 60, 278. Comp«re p. 221.

Preparation, Diy tobacco is distiUed, and the resultiDg tar is recti- fied. The oil thus obtained is several times shaken up with water ; then dried orer chloride of calcium, filtered, twice rectified, a certain quantity of tar remaining behind each time, bnt only a small quantity the second time, and the first half of the distillate is collected.

Slightly pale yellow, transparent. Sp. gr. 0*87. Boils at about 195°.

Calculaiion according to Zei$e. Zeise.

11 C 66 „ 71-00 71-26

11 H 11 11-79 1201

2 O 16 O and N... 17-21 16 73

C"H"Oa 93 10000 10000

The oil contained about 3 per cent, of nitrogen which was not inclnded in Zeise'a calculation. Aa Melsens found nicotine in tobacco-smoke, which nicotine was not separated in Zeise's mode of preparation, the nitrogen of the nicotine appears to have been present in the oil, which would make the calculation altogether wrong. (Kr.)

The oil turns brown in contact with the air. — Bums with a strongly luminous, sooty flame. — Potassium acts on it slowly in the cold, and attacks it strongly when heated, converting it into a brown-red, viscid mass which yields by distiJlation a light yellow, somewhat viscid oil, having a strong aromatic odour, while a pitchy mass remains behind. — When the oil is boiled for five or six hours in a long-necked flask with lumps of potash-hydrate f and a little water, ammonia is evolved, and a yellow oil passes over, which boils at 220°, has a less unpleasant odour than the original oil, and does not act upon fused potassium. This oil contains 79*90 p. c. C, 10*01 H and 1009 O. The alkaline residue dis- solved in water, filtered from the separated charcoal, neutralised with sulphuric acid, and evaporated, giyes up butjrrate of potash to alcohol.

The oil is nearly insoluble in water. — It dissolves iodine quickly, and with brown colour. — It absorbs a small quantity of dry hydrochloric acid gas^ becoming thereby more viscid and brown-red, and recovering its pale yellow colour on addition of ammonia.

It mixes in all proportions with alcohol and ether.

By slow combustion of tobacco in the pipe. Melsens (N. Ann, Chim. Phys. 9, 471) obtained nicotine (p. 221) and tar. The latter, distilled with water, yielded a brown oil having a sharp and peculiar empyreu- matic odour, while a black, viscid mass was left soluble in alcohol. The oil is lighter than water; begins to boil at 140°, after drying over chloride of calcium, the temperature soon, however, rising to 200% and ultimately to 300^; and passes over, light brown at first, bat afterwards of darker colour.

METHYL-NICOTINE. 235

Methyl-nicotine.

C"NH» = C^«(C*H»)NHSH».

Stahlschmidt. Ann, Pharm. 90^ 222 ; «/. pr. Chem. 63, 89 ; Pharm, Centr, 1854, 680.

FormenicottH. Known only as a hydrate and in salts.

Formation, p. 226*.

Preparation, — Nicotine is mixed with iodide of methyl ; the aotioD, which soon begins, is allowed to come to an end; the dark-KSoloured hydriodate of methyl-nicotine, which solidifies in a crystalline mass on cooling (syrnpy, if the quantity of iodide of methyl is insufficient, bat becoming crystalline on the addition of a larger quantity), is washed with alcohol, crystallised from water, and the concentrated aqueous solution is decomposed with recently precipitated silver-oxide, whereby iodide of silver and an aqueous eolation of methyl-nicotine are obtained. This solution, evaporated over oil of vitriol at 100°, leaves a dark, viscid, new crystalline residue, probably consisting of hydrate of methyl- nicotine.

Its aqueous solution has a bitter taste. It is inodorous, has a strong alkaline reaction, and dissolves the cuticle like caustic potash.

It remains unaltered, when the solution of its hydriodate is heated with iodide of methyl.

Methyl-nicotine is a strong base. It saturates acids completely, and forms salts, of which the sulphate, hydrochlorcUe, nitrate, and hydrocyanate crystallise with difficulty; the hydrqfiuate, acetate, oxalate, and tartate not at all. Aqueous methyl-nicotine precipitates other oxides from copper and iron salts. It dissolves recently precipitated hydrate of alumina,

Hydriodate of Methyl-nicotine. Soluble in water, less soluble in alcohol, and nearly insoluble in ether.

12 C	720	.... 32-28 . .... 6-27 .... 4-48 . .... 66-97 .	Stablschmidt. 32-86
N 10 H	140 10-0	4-60
M •••■•«••«••••••	127-1	56-92
CWNH»HI	2231	.... 100-00

Chloromereurate of Methyl-nicotine. — Prepared on mixing mercuric chloride with aqueous hydrochlorate of methyl-nicotine, and may be crystallised in nodules from hot water. Contams 59*47 p. c. mercury, and is therefore C"NH',HCl,4HgCl. {Calculation, 58-39 p. c Hg.)

Chloro-auraie of Methyl-nicotine — Light yellow precipitate, produced by mixing the solutions of terchloride of gold and hydrochlorate of methyl-nicotine. It is nearly insoluble in cold water and alcohol. Dried at 100% it contains 45-23 p. o. of gold, C"NH»,HCl,AuCP = 45'28 p. c Au.

236 AZO-NUCLEUS C»N*H».

ChhroplcUinaUo/Methpl'nieotine. — Hydrochlorate of methyl-nicotine 18 precipitated with bichloride of platinum, and the precipitate is crystal- lised from boiling water. Ciystalline product^ sparingly soluble in cold water, insoluble m alcohol.

Stahbchmidt.

12 C 72-0.... 23-92 23-85

N 14-0 .... 4-64

10 H 100 .... 3-32 3-44

3 CI 106-5 .... 35-35

Pt 98-7 .... 32-77 3303

C»«NH»,HCl,PtCl» 301-2 .... 100-00

Hydrochlorate of methyl-nicotine mixed with chloride of palladium^ leaves on evaporation^ a syrup which may be obtained on crystallisation from alcohol.

Ethyl-nicotine.

C"NH" = C"(C*H»)NH*,H».

T. Planta & Kbkul£ Ami, Phai-m, 87, 2 ; J. pr. Chem, 60, 237; Fharm, Centr. 1853, 890; iV. Ann. Chim. Fhys. 40, 230.

Aethyl'tiieoiin, Vinemcotin, — First observed by Hofmann (Ann, Pharm, 79, 31.) — Known only in combination with water and acids.

Ftfrmaiion. (Comp. p. 22G.)

Preparation. Nicotine is mixed with excess of iodide of ethyl in a sealed tnbe, and heated for an hour in the water-bath, or till the mass solidifies in yellow crystals on cooling ; the product is dissolved in water ; the red resm which separates (it forms especially when the heat is too long continued) is removed by filtration, and the solution is left to evaporate ; it then yields radiating crystals of hydriodate of ethyl-nicotine. On digesting the aqueous solution of these crystals with recently precipitated oxide of silver, iodide of silver is precipitated, and an aqueous solution of ethyl-nicotine is obtained, which is colourless (or slightly reddish yellow, if prepared with crude hydriodate of ethyl-nicotine), inodorous, has a very bitter taste, a strong alkaline reaction, and dissolves the cuticle like caustic potash.

Ethyl-nicotine U G^^NH" (which, by addition of IHO, becomes Ci^NH^^O, corresponding to NH*0), if nicotine = CWNH?; or has the double formula, C»N«H2», if nicotine is C^N^H^^. (v. Planta & Kekul6.) In the formation of ethyl-nicotine, the molecule of nicotine (C^N^H*^) is split up in such a manner, that from 1 At. nicotine and 2 At. iodide of ethyl, 2 At. hydriodate of ethyl-nicotine are produced. (Gerhardt's Traits 4, 186.) — Ethylnicotine, witli addition of 1 H bears to nicotine the same relation that tetrethyl-ammonium bears to triethylamine.

Decompositions. 1. Aqueous ethyl-nicotine becomes turbid when heated, deposits a dark rea-brown oil, and gives off when distilled, a brown oil and a strongly alkaline liquid, which exhibits a deep red colour by transmitted light, and a green iridescence by reflected light ;

ETHYL-NICOTINE. 237

both these liquids colour the skin yellow, and have a pungent odour of stinking fish. Aqueous ethyl -nicotine undergoes a similar decomposition when left to stand in the air or in vacuo. — 2. Hydriodate and hydro- bromate of ethyl- nicotine are not altered by potash-ley in the cold ; but when heated with it, they yield the same products that are formed by the simple action of heat on aqueous ethyl-nicotine. — 3. Hydriodate of ethyl- nicotine melts when heated, turning slightly brown^ and yields a distillate of nicotine and iodide of ethyl, which partly recombine in the receiver, forming hydriodate of ethyl-nicotine. — 4. A concentrated aqueous solution of ethvl-nicotine, heated with iodide of ethyl, is con- verted into hydriodate of ethyl-nicotinOi without forming a base containing a larger proportion of ethyl.

OombiruUions. Ethyl-nicotine unites with acids, formine crystallis- able and very soluble salts. It is a strong base, which expels ammonia from its salts, and behaves with saline solutions like the fixed alkalis, throwing down the heavy metallic oxides and the alkaline earths.

Aqueous ethyl-nicotine absorbs ca9*6onic acid from the air. — Sulphate of ethyl-nicotine is a viscid syrup containing a few crystalline particles.

Hydtiodaie of Bthyl-nicotine, — Obtained by the action of alcoholic nicotine on iodide of ethyl, or by recrystallising from boiling alcohol the product prepared as described at page 236, in nodular groups of beautiful colourless prisms, which may be separated with some loss from the reddish yellow mother-liquor by absolute alcohol. It decomposes partially when its aqueous solution is evaporated, forming a red iodated resin. When heated, it decomposes in the manner above described (8). It is very soluble in water, sparingly soluble in alcohol and ether.

▼. Planta & Kekal^. t^mm oU of vitriol. mean,

C»<NH» 1100 .... 46-39

I 127-1 .... 5361 58-55

CMNH»,HI 237-1 .... 10000

Hydrohr&maU of Ethyl-nicotine, — When bromide of ethyl is brought in contact with nicotine, even in the cold, an oil is produced, which increases on heating the mixture in the water-bath, and finally solidifies in a crystalline masa It is even more deliquescent than the hydriodate. It dissolves with moderate facility in absolute alcohol.

Hydrochlorate of Ethyl^iootine is obtained as a radiated crystalline mass by evaporating its solution in vacuo.

Nitrate of Ethyl-nicotine. — Viscid syrup, containing a few crystalline particles.

ChioromurcujxUe of Ethyl-nicotine. — Mercuric chloride throws down from hydrochlorate of ethyl-nicotine, white flocks, sometimes caked together like a resin, which melt when heated, dissolve in boiling water, and separate in crystalline nodules on cooling. They may be washed with cold water.

288 AZO-NUCLBUS C«N*H«.

14 C ....			.... 15-22 .... 2-54 .... 2-17 .... 25-72 .... 54-35	▼. PlAiita & ICeknltf. 15-39
N.... 12 H ....		. ... 14 12	2-25
4 CI.... 3Hg		142 300	25-71 54-14
C"NH"	,HCi,3HgCl	.... 552	.... 10000

Chloroaurate of Ethyl-nicotine. — Terchloride of gold added to bydrochlorate of ethyl-nicotine, throws down a sulphur-yellow precipi- tate, which crystallises from its hot aqueous solution on cooling in splen- did gold-yellow needles.

T. PUnta 5c Keknl^.

M60fl.

C"NHWCH 252 .... 56-13

Au 197 .... 43-87 43-93

C"NH",HCl,AttCl* .... 449 .... 100-00

Chloroplatinate of Fthyt-nicoUne. — Hydrochlorate of ethyl-nicotine mixed with hichloride of platinum, throws down yellow flocks, which soon become orange .yellow and crystalline, and separate from boiling water in orange-red prisms, ^nerally acuminated It is nearly insoluble in boiling alcohol, insoluble m ether.

J^Hm oil of vitriol, or at 100^ ▼. Planta & Kekol^.

14 C 84-0 .... 26-65 26-61

N 140 .... 4-44

12 H 12-0 .... 3-81 3-24

3 01 106'6 .... 33-79

Pt 98-7 .... 31-31 31-29

C"NH",HCl,PtCP 315-2 .... 10000

Chloride of PaUadium is not precipitated by hydrochlorate of ethyl- nicotine, but on OTaporating the mixed solutions, a brown gum is obtained which, when its alcoholic solution is left to evaporate, leaves large brown rhombic tables.

With oxalic and acetic acid, ethyl-nicotine forms uncry stall isable salts.

Tannic acid does not precipitate aqueous ethyl-nieotine ; pieric add produces sulphur-yellow flocks.

Amyl-nicotine-

C»NH" = C»<'(CWH")NH*,H«.

Stahischmidt. Ann, Pharm, 90, 226.

Mylinicotin, — Known only in aqueous solution and as a platinum •salt.

Formation (p. 226). — Nicotine is heated with iodide of amyl in a sealed tube to 100° for several days; the product is dissolved in water; the separated iodide of amyl is removed ; and the solution is digested with

OIL OF TURPENTINE. 239

recently precipitated oxide of silver, whereby iodide of silver is separated, and an aq aeons solution of amyl-nicotine is obtained.

This compound bebaves with saline solutions like ethyl-niootine ; it saturates acids and forms salts, which cannot be obtained in the solid state, even by slow evaporation. The solution of amyl -nicotine, mixed with bichloride of platinum, throws down light yellow flocks, which, when dried at 100°, contain 28*25 p. o. platinnm, and are therefore C«»NH",HCl,PtCl« (calc. 2763 p. o. platinum).

Primary Nudeut G"H".

Oil of Turpentme.

Saussurb. a. GehL 4, 682; N. Ann. Chim, Phys, 13, 271; Schw, 29, 165; N. Tr, 5, 2, 112; Pogg, 25, 370; Ann. Chim. Phys. 49, 225; Ann. Pharm. 3, 157.

Gehlen. a. GeM. 6, 471.

Urb. Phil. Trans. (1818), 2, 338; Sohw. 28, 329.

HoiITON-LABILLARDli:RE. J. Phai'm. 4, 5.

Unverdorben. Pogg. 8, 485; further, 9, 516; further, 11, 34. BoiasBNOT & Persot. J. Pharm. 12, 214; Ann, Chim. Phys, 31, 442;

If. Tr. 13, 1, 225. Hermann. Pogg> 18, 368. Oppermann. Pogg. 22, 193.

WiNCKLBR. Repert. 32, 371; further, 33, 185; further, 34, 378. Blanchbt <& Sell. Ann. Pharm. 6, 259; Pogg. 29, 133. Dumas. Ann. Chim. Phys. 50, 229; Ann. Pharm. 6, 250. MuLLBR. N. Br. Arch. 1 1, 52. Br ANDES. N. Br. Arch. 11, 54. Zeller. Repert. 67> 265; Siudien iiber atherische Dele, Landau, 1850;

N. Jahrb. Pharm. 2, 292. PoLEX. N. Br. Arch. 1 8, 280. BoDTiONY. J. Chim. m^d. 10, 385. GuYOT. J. Chim. med. 12, 487; J. Phys. 5, 230. BiOT. Ann. Chim. Phys. 69, 22; N. Ann. Chim. Phys. 10, 11; Compt.

rend, 21, 1. AuBEROiER. J. Pharm. 27, 278. SouBEiRAN & Capitaine. J. Pharm. 26, 2; Ann. Pharm. 87, 311; N.

Br. Arch. 22, 171; further, 24, 17. Deyillb. Ann. Chim. Phys. 75, 37; J* Pharm. 26, 652; J. pr. Chem.

22, 81 and 158; Ann. Pharm. 37, 176; Compt. rend. 12, 394; If. Ann.

Chim. Phys. 27, 80; Compt. rend. 28, 424; abstr. Ann. Pharm. 71,

349; J. pr. Chem. 48, 62. Weppen. Ann. Pharm. 34, 235; further, 41, 294. WbLHER. Ann. Phajnn. 47, 237. Babourdin. i\r. J. Pharm. 6, 185.

GvfBouRT & BoucHARDAT. N". J. Pharm. 8, 18; J", pr. Chem. 36, 316. Bouchardat. Compt. rend. 20, 1836; N'. J. Pharm. 8, 87; «/. pr. ahem. 36,311.

240 PRIMARY NUCLEUS C»H»«.

Haobn. Pogg. 63, 574.

Cailliot. N. Ann, Chim. Phys. 21, 27; Ann, Pharm. 64, 376; J. pr,

Chem, 42, 233. ScHARLiNQ. Chem, Gaz. 1849, 417; Ami, Pharm. 74, 235. Schneider. Ann, Pharm, 75, 101; Pharm, Centr. 1850, 845. Chautard. Compt, rend. 33, 671; Compt. rend. 34, 485. ScHONBEiN. J. pr. Chem, 52, 135 and 185; further, 53, 65; further, 54,

74; further, 68, 272; further, 75, 80 and 98; Pogg. 106, 337. Berthelot. N. Ann. Chim, Phi/s, 38, 55; J. pr. Chem. 5Q, 463; abstr.

Compt. rend. 34, 789; N, J. Pharm, 22, 31; N. Ann. Chim. Phys.

39, 5; iV. Ann, Chim, Phys, 40, 5; abstr. Compt rend. 36, 425; Ann.

Phai-m. 88, 342; J. pr. Chem, 59, 137; Jf^. J. Pharm, 29, 40. Fluckioer. Bemer Mittheilungen, June, 1854; N. J, Pharm. 29, 40. Williams. Chem, Qaz. 1853, 365; J, pr, Chem, 61, 18; Chem. Gaz.

1854, 432; J.pr. Chem, 64, 440; N. Phil. Mag. J.y 5, 536. Knop. Pharm, Centralbl. 1854, 321, 409 and 498.

Memoirs specially relating to Turpentine-camphor and Terpinol.

BucHNER. Bepert. 9, 276; further, 22, 419.

Geiger. Mag. Pharm. 16, 64.

Bernhardi & Trommsdorff. N. Tr. 16, 2, 46.

Brandes. N, Br. Arch. 11, 285.

VoGET. N. Br. Arch, 23, 291.

Dumas & Peligot. Ann, Chim, Phys. 57, 334 ; Ann. Pharm. 14, 75 ;

J. pr. Chem, 4, 386. Hertz. Pogg, 44, 190.

WiOGERS. Ann. Pharm. 33, 358; further, 57, 247. Rammblsberg. Pogg, 63, 570. List. Ann. Pharm. 67, 362. Bbrthblot. N. J. Pharm. 29, 28.

Memoirs specially relating to Artificial Camphor.

Kindt. (1803.) A, Tr, 11, 2, 132. Trommsdorff. A. Tr, 11, 2, 135. Cluzel, Chomet & Boullat. Ann. Chvm. 51, 270. Gehlen. a. Gehl. 6, 458. Thenard. MSm, de la Soc. d^Arc, 2, 26. Offermann. Pogg. 22, 199.

Dumas. Ann. Chim. Phys. 52, 400; Ann. Pharm. 9, 56; Pogg. 29, 125. Berthelot. iT. J. Pharm. 28, 450; H, Ann, Chim. Phys, 40, 5, and 31.

Cdmphene (Deville); Baenee de tirkbenthine ; Bnenee of turpeniine: Terpen^ thindh Described in the 8th century by Marcus Graecus.

Sources, In the root, stem, branches, leaves, and pericarps of several trees belonging to the coniferous family, and to the genera Pimis, Picea, AbieSy Lartx ; hence also in turpentine, the resinous juice which exudes fr«)m incisions made for the purpose in the stems of these trees.

Dili OF TURPENTINB. 241

Satraetian. 1 . By distilling variotis kinds of tnrpentine either aJone or with water. — Steam or air, heated to 107°, is passed either directly through turpentine or through a spiral tube coiled up in the turpentine covered with water, and serving to convey to it the heat required for the distillation of the volatile oil. (Kates, Lond. J. Sept. 1854, 172 ; Aug. 1 85d, 86.)

When turpentine is distilled per se, the oil passes over first, and towards the end of the distillation, succinic acid sublimes. (Lecanu & Serbat, J. Pharm, 8, 451 .)

When Venice turpentine is distilled with water, the succinic acid remains dissolved in the water which passes over with the oil. Venice turpentine, distilled alone, yields first a more volatile, and afterwards a less volatile oil. (Unverdorben.)

Pine-redny subjected to dry distillation, yields, together with the oil, a brown or yellowish, seldom colourless, turpentine-water, amounting to 1 — r5 per cent, of the resin, and containing acetic acid. (Grimm, Ann. PluDfru 107, 255.)

2. By distilling various parts of coniferous plants with water. — In this manner, oil of turpentine may be obtained : From the cones of the silver fir (Abies pectinata, Dec.) (Zeller, Fliickiger), which contain the Tolatile oil in the pericarps, and a fixed oil in the seeds (Zeller) ; from the branches of the spruce fir (Pinus aJbies, L.) Gottschalk, Ann, Phatmu 47, 237); from the cones of the dwarf- pine {Pinus Mughw^ Scop.) (Blanchet & Sell) ; from the cones of the Scotch nr (Pinru sylvedru, L.), which serve for the preparation of forest-wool. (Uagen.)

Purification, 1. By distilling crude oil of turpentine : (a.) bf itself; (6.) with toater. The oil which fioats on the surface of the water in the distillate is skimmed ofi*, and dehydrated by agitation with chloride of

calcium. — When oil of turpentiDe ia rectified with water, the oil at first passes over alone, and is not accompanied by water till towards the end of the distillation, probably becanse the formation of vapour of water requires 550® of heat, whereas, according to Desprets, that of oil of turpentine vapour requires only 76° (? 6m.) Anberg;ier. — (c.) With aqueous alkalis or alkaline earihs* Oil of turpentine is distilled with milk of potash and lime (lOO pts. of the oil with 100 pts. water, 1 pt. carbonate of potash, and 1 pt quicklime. Berl, Indtuiriebl. 1841), the resin

dissolved in the oil then remaining with the lime. (Guthrie, Sill, Am* J. 21, 291.)

2. By agitation with ail of vitrioL — The oil of turpentine is shaken np with oil of vitriol diluted with an equal bulk of water, and then left at rest, whereupon the liquid separates into two layers, the lower of which takes up the brown resin ; the supernatant oil may be further purified from resin by renewed agitation with the acid, till the latter no longer becomes coloured, and at last completely freed from it by water. (Guthrie.)

3. By treating crude oil of turpentine with a quantity of alcohol less than sufficient to dissolve it. — When 8 pts. of oil of turpentine are shaken up with 1 pt. of the strongest spirit (with slightly rectified spirit, according to Schultze, N. Br. Arch. 74, 114), and the mixture is left at rest, two layers of liquids are formed, the upper of which is a solution of the resin originally contained in the oil, while the lower consists of the purer oil, which may be completely purified by repeated agitation with fresh quantities of alcohol. (Nimmo, 8chw. 36, 245 ; /. of Science, 13, 441.)

▼OL. XIY. R

242 PRIMARY NUCLEUS C»H><.

ModificatWM of Oil of Turpentine. — The volatile oil obtained from oooifersB (Dumas), even when prepared by distillation from one and the same species (Berthelot) is by no means a simple oil, bat a mixture of isomeric oils, which, though identical in chemical composition, differ in boiling point, specific gravity, and optical properties, according to their origin and mode of preparation, and, according to Bouchardat, are probably formed from the oil originally contained in the turpentine by the aciion of the air at the moment of its separation, or, according to Berthelot, partly exist in the turpentine ready formed. Accordingly we have to distinguish —

1. French oU of turpetUine, obtained from Bordeaux turpentine, the produce of Finus Maritima, — When French oil of turpentine is mixed with carbonate of potash and carbonate of lime, the mixture left at rest for a day, and then distilled in vacuo, first on the water-bath, and then on the oil-bath, the receiver being cooled with ice, the oil distils between 80° and 1 80°, while the residual turpentine becomes thicker. The oil which distils between 80°and 180°, appear to consist of only one substance ; but the latter portion of the distillate is a mixture of isomeric hydrocarbons and oxygenated oils, whose specific gravity, boiling point, and rotatory power vary between such narrow limits^ that the isolation of a single definite product from them is impossible. Even the oil obtained by repeated fractional distillation, yields, when again distilled, a distillate of different properties, though identical in chemical composition. — The portions of the oil, which, when it is shaken up with a quantity of alcohol insufficient to dissolve it, either remain below the alcoholic solution, or are separated therefrom by water, likewise exhibit different properties, the alcohol dissolving especially those oils which have comparatively little rotatory power. (Berthelot. )

2. English oil of turpentine (Camphene ^irit). from the Carolina turpentine of Finns tceda, L. (Gnibourt & Bouchardat), or that of Finxis AiutixdiSt Mich. (Berthelot.) — Turpentine from Finus Attstralis, fractionally distilled four times in vacuo, yielded distillates of like com- position but different rotatory power. (Berthelot.)

3. German oil of turpentine, from the turpentine of Pinus sylveslris, L, P. nigra, Link, F, rotundata, Link, F, abies, L.

4. Templin oil, from the cones of Finns Mughua (Blanchet & Sell) ; from the cones of Abies pectinata, Dec., especially that obtained in the Emmenthal, Canton Bern, and in Aargau. (Fliickiger.)

5. Venetian oil of turpentine, from the turpentine of Larix JEuropcea, Dec.

Fropeiiies, Colourless, mobile, transparent oil. Commercial oil of turpentine is yellowish, templin oil slightly coloured (Blanchet & Sell), the oil from the needles of the Scotch fir, yellowish-green (Hagen) ; templin oil becomes yellowish -green after some time. (Fliickiger.) — Sp. gr. 0-86 at 22° (Saussure), 0-872 at 10° (Despretz), 086 at 31^ (Brisson), 0879 (Aubergier), 0867 at 14° (Brix, Fogg, 55, 380), 0872 (Biot), 0-86 (Soubeiran & Capitaine), 0-8902 at 0° (Fraukenheim, Fogg. 72, 422).

French oil of turpentine has a density of 0*865 at 13" (Caillot, /. Fham. 16, 440) ; 0*8806 ; — after rectification with water, 08736 to

OIL OF TURPKNTINS. 213

0-8890 ; —after distillation without water^ 0*8780 ; — oil ten years old distilled over potash, 0*87 ; — Strasburg oil of turpentine distilled with water, 0*863 (Guibourt & Boachardat) ; — 0*8654 at Id'' ; — after distillation in vacno between 80° and 100^ it is 0*864 at 15° ; — when purified by shaking up with alcohol, 0-8616 to 0'86d0| while the oil which distils between 280° and 280° has a density of 0*9203 at 16°. (Berthelot) — English oil of turpentine : 0*863 (Guibourt & Bouohardat) ; 0*8665 &tl5° ; after fractional distillation, 0*886 to- 0*878. (Berthelot.) — Oil of turpentine from the silver fir, 0*850 to 0*856 at 13° (Caillot), 0*85 (Zeller) ; templin-oil (Fliiokiger), 0*856 at 6^ and 0*842 at 80°. (Berthelot.) — Oil from the Scotch fir, 0865 at IS"" (Caulliot) ; crude oil 0*8859 at 12°, rectified, 0*868 at 12^ (Hagen.) Oil from the spruce fir^ 0*880 at 15° (Blanchet & Sell), oil from the branches treated with potassium (vid infX 0*856 at 20"". (Wohler.) Oil from Mies Oanadensia and Venetian oil of turpentine, 0*863 at 13°.

Boiling point, 156*8° (Despretz) ; recently rectified, 152°, old, 158** (Ure), 150° (Blanchet & Sell), 157° (Aubergier), 159*2° (Brix, Pos^^. 65, 380), 156^ (Frankenheim, Fogg. 72, 422). — Oil from the spruce fir boils at 155° (Blanchet k Sell), that from the branches, after treatment with potassium, at 167° (Wohler) ; templin-oil from Pintie Mughta at IQ5°, templin-oil (Fliiokiger) at 172°. (Berthelot.) — The first products of the distillation of French oil of turpentine, purified with alconol, boil at 159*5° to 160"* under a pressure of 750°^ ; the later products between 161° and 162'', ^^ of the oil above 200°. (Berthelot.) -— It does not solidify at - 20° (Cailliot), not even at - 110° (Faraday, Pogg Ergan- zungsband, 2, 216). At — 27^ it deposits camphor, which melts at — 7^ (Margueron, J. Phys. 45, 136). — Expansion at sp. gr. 0*879 from 0° to 100^ = 0*106927 ; of oil boiled for 10 minutes and distilled = 0*103087 (Aubergier) ; at 0° and sp. gr. 0*8902, = 1 + 0*00O874< -f 0000001248^ between 11 and 145°, or from 0 to 100° = 0*09722 (Frankenheim, Pogg. 72, 4*25); of templin-oil (Fliickiger) from 30° to 130° = 01 12. (Ber- thelot)— Compressibility for one atmosphere at 12*6° = 0 0000657. (Aim6, Pogg. Erganz. Bd. 2, 237.) — Refracting power =: 1*471 (Becquerel & A. Cahours, Compt. rend. 6*867 ; also Pogg. 51,427) ; 1*472, of the thickened oil = 1*4938, after being liquefied at 40° = 1*4938 (Deville, Gompt rend. 11*865 ; also Pogg. 51, 433) ; of templin* oil (Fliickiger) = 1*467 (Berthelot).

The optical rotatory power of oil of turpentine is independent of that of the turpentine from which it has been prepared. French oil of tur- pentine rotates to the left like turpentine itself, but with diflerent strength ; English oil of turpentine to the right, whereas the turpentine (from Pintu tceda) used in its preparation rotates to the left ; Venetian oil of turpentine rotates, aoooruing to Soubeiran, to the left, but Venice turpentine rotates to the right. (Guibourt & Bouchardat, Biot) The French turpentine oil of commerce consists chiefly of IsBvo-rotatory oils, and contains but a small proportion of the dextro-rotatory. (Berthelot)

LsBvo-rotatory power of : French oil of turpentine, 39*95° (Biot), 43*38°, calculated for a sp. gr. of 1 (Soubeiran & Gapitaine), 28*82° (Guibourt & Bouchardat), 35*4'' (Berthelot). After rectification with water : first distillate, 31 '657^, second distillate 22*327°; distilled without water, 33'2d~' ; oil ten years old rectified over carbonate of potash, 33*95; Strasburg turpentine-oil distilled with water, 1 1 '69° (Guibourt & Bou- chardat) ; distilled between 80° and lOO'' in vacuo, 32*4° ; fractionally distilled, between 33*7° and 32*25° ; purified with water, 35*6° to 33*7 ;

R 2

244 PRIMARY NUCLEUS O^W^.

that which distils from 240'' to 280°, e'S"". (Berthelot.) By distQlation over the open fire, oil of tarpentine gains in rotatory power from 28*33° to 33-23° (BoDchardat). — Of Swiss oil of turpentine, 11*2 ; of templin oil (Fluokiger), 76*9° (Berthelot); of Venetian oil of turpentine, 5*24. (Gaihonrt & Bouchardat.)

Dextro-rotatory power of : English oil of turpentine from Pinus tcedaj 18'6° (Guibourt A Bouchardat) ; from Pinus Australts, 18*6^ (Ber- thelot) After fractional distillation: 1 =18*9° j 2 = 18 8''; 3 = 16-4 ; 4 = 17*2. (Berthelot.)

Specific heat = 0*462 (Despretz), 0*488 (De la Rive & Marcet), 0-42593 (Regnault), 0*41 ^Brix, Pogg, 55, 380), 0*416 at 2°. (Person, Pogg, 74, 422.) Heat ot combustion evolved in the combination of 1 gramme of oil of turpentine with oxygen = 10496 ; of 1 litre of tur- pentine-oil vapour = 68349 heat- unite. (Grassi, N. J. Pharm. 81,

177.)

Vapour-density = 501 (Despretz), 5013 (Gay-Lussac), 4763, (Dumas.) Latent heat of vapour = 768 (Despretz), 59*23 or 62*25 (Brix, Pogg. 55, 381) ; 687 (Frankenheim, Pogg. 72, 422). Specific heat of vapour 17787. (Ure.)

The vapour, mixed with a large quantity of atmospheric air, pro- duces a peculiar intoxicating effect when inhaled (Letellier, Compt. rend. 39, 243) ; in rooms recently painted with turpentine colours^ it produces poisonous effects. (Favrat, Compt rend. 45, 886.) It prevents the germination of seeds. (Ville, Compt, rend, 41, 757.) The smell of turpentine oil may be removed from vessels by shaking them up with a mixture of mustard and cold water. (Jourdan, J. Chim, msd, 22, 727.)

Oil of turpentine is neutral to vegetable colours. The oil from the needles of the Scotch fir reddens litmns, because it contains formic add. (Hagen.) Its taste and odour are strong and peculiar, like that of turpentine.

Strasburg oil of turpentine (Guibourt <b Bouchardat), that from the spruce fir (Blanchet & Sell), has an agreeable odour like that of lemons. The oil from the branches of the spruce fir smells like fir-branches and fixed oil of laurel, but after treatment with potassium, it has an odour of lemons and sweet oranges (Wbhler) ; templin oil has a balsamic odour (Fliickiger) ; templin oil from Pinus Mughus smells like orange- flowers (Blanchet h Sell); oil from the silver fir smells aromatic (Cailliat) ; like cumin, and has an aromatic, warming, slightly burning taste (Zeller) ; oil from the Scotch fir, has an aromatic odour liko that of lavender. (Hagen.) The smell and taste of oil of turpentine depend upon the amount of ozone which it contains ; strongly ozonised oil has a strong odour and taste of peppermint, and a few drops placed upon the tongue produce a peculiar persistent pain ; the newly rectified oil does not produce this effect, and nas a fainter odour. (Schonbein.)

1. Honton Labillardi^re. 2. Sanssnre. 3. Oppermann. 4. Hermann.

20 C 120 .... 88*23 87*6 87-788 84*59 88-88

16 H .... 16.... 11*77 12-3 11646 11*73 11*12

C^H" .... 136 .... 100*00 99 9 99*434 96*32 100*00

5. Blanchet

& Sell. 6. Damas. 7. W6hler. 8. Hagen. 9. Berthelot.

a, h,

88-56 88*4 88*38 88*21 88*0 87-1

11*52 11*6 11-78 11-61 12-3 11*9

10008 100*0 100*16 99-82 100*3 99^0

OIL OF TURPENTINE. 245

Vol. Density.

C-Taponr 20 8-3200

H-gas 16 1*1088

Vapoar of turpentine-oil 2 9*4288

1 4-7144

2, according to Saussure, still contained 0*566 nitrogen ; 4, according to Opper- mann, contained 3*6728 oxygen; 5, oil from the spmce fir; 7t from the branches of the spmce fir> after treatment with potassium ; 8^ from the needles of the Scotch fir ; 9, a. French; 6. English oil of turpentine.

Oil of turpentine is a hydrocarbon, since its Taponr passed, together with sulphur- vapour, through a red-hot tube, yields nothing bat bisulphide of carbon and sulphu- retted hydrogen. It contains 10 vols, carbon to 8 Tols. hydrogen, and the condensa- tion of 4 vols, hydrocarbon (hydrog&ne percarbur^) with 2 vols, carbon-vapour, produces 1 yol. yapour of oil of turpentine. (Houton-Labillardidre.) — Saussure found nitrogen in oil of turpentine, as well as carbon and hydrogen. Hermann found no nitrogen, but carbon and hydrogen in the ratio of 4 : 3. Oppermann found 4 per cent, of oxygen, together with carbon and hydrogen, and assigned to oil of turpentine the formula, C^i^H^'O. Dumas concluded, from Oppermann's analysis, that oil of turpentine was a compound analogous to ether, and containing the radical camphogea (supposed by him to exist in camphor), in combination with ^ At. water ; but from his own analysis he inferred that it is a compound corresponding to the formula C*^H^, and that the oxygen found by Oppermann proceeded from impurities. The suggestion advanced by Th^nard, that oil of turpentine is a mixture of several hydrocarbons, was thought by Blanchet & Sell to be corroborated by its behaviour with hydrochloric acid, these chemists supposing that oil of turpentine is a mixture of two isomeric oils of the formula C*H^, one of which, dadyl, forms a solid, the other, peueyli a liquid compound with hydrochloric acid, and that the variations in the properties of oil of turpentine depend upon the relative quantities of these two compounds. Since, however, oil of turpentine has a constant boiling pomt, and its rotatory power remains unaltered in the solid hydrochlorate, whereas in the liquid compound it is very weak, Soubeiran & Capitaine suppose that it is a simple compound, but is resolved into two isomeric compounds under the influence of hydrochloric acid. The dadyl of Blanchet & Sell is identical with the camphene of Soubeiran & Capitaine and with the turpentine oil of Deville. The peueyl of Blanchet & Sell is identical with the peucylene of Soubeiran & Capitaine, and the terebene of Deville. According to Soubeiran & Capitaine, both these compounds are products of the decomposition of oil of turpentine; but according to Deville, this is the case with terebene only.

Decompositions. Oil of turpentine exposed to the air gradually becomes yellowish and yisoid^ resinises completely after a short time (Unverdorben> Blanchet & Sell, Zeller, Wohler), and ultimately forms acetic acid (Boissenot & Persot; Bizio, Brugn, Gtom, 19, 360), formic acid (Laurent, Eev. scient. 1842, 119, Weppen), resins (Unverdorben, Weppen), and, in presence of water, it forms hydrate of turpentine-oil or turpentine-camphor. (Boissenot ^ Persot.) Oil of turpentine which has become thick by exposure to the air, contains a large quantity of resin partly soluble in potash, partly insoluble (this portion, however, being soluble in alcohol), and a compound of pyrocolophonic acid with a volatile oil, which latter is not soluble in potash, except in presence of the pyro-acid just mentioned, and can be distilled only with excess of potash and water. (Unverdorben). In oil of turpentine which had been long exposed to the air, hard crystals were found to have formed ; on distilling it, aqueous acetic acid finally passed over, and from this distillate, after standing for some time at 7^ crystals again separated. (Boissenot So Persot.) On the covers of zinc boxes in which oil of turpentine had been kept, Laurent found white, granular crystals of formiate of zinc. The presence of formic acid in oil of turpentine may be recognized by the acid reaction of the oil and of the water which

246 PRIMARY NUCLEUS €»H»^

passes oyer on distilling it It is produced by absorption of oxygen. (Weppen.)

c»H'« + 40O = 4Co« + scm^o*.

Oil of tarpentine, when exposed to the air^ likewise forms an acid resin, which may be extracted by agitation with water and carbonate of magnesia. From the aqneons solution of the magnesia-compound, acids throw down a white precipitate, whose alcoholic solution precipitates most metallic salts, even in the cold, but corrosive sublimate only when heated. From the precipitate obtained with acetate of lead, and decom- posed by sulphuretted hydrogen, alcohol extracts an acid resin, which remains when the solution is evaporated, partly as a brown viscid mass, partly in white crystalline scales. The lead-compouud contains 4599 p. c. carbon, 6*47 hydrogen, 18*36 oxygen, and 29'60 PbO; whence it is C»H«0*,PbO.

2. Electric gparks passing between the terminal wires of a battery immersed in oil of turpentine and placed very close together but not quite in contact, excite luminosity on the oil in contact with the ends of the wires, and give rise to the evolution of a permanent gas. (Pog^ gendorff, Pogg, 71, 227.)

8. Oil of turpentine is converted by heat into a less volatile oil* When heated in close vessels under a pressure of several atmospheres, it is partly converted into isomeric compounds of high boiling point (vid. Iwterebene and Meiaterebene.) (Berthelot.) Heating over the open fire increases its power of dissolving caoutchouc and likewise its rotatory power. When it is distilled with brick-dust over the open fire, it turns yellowish, acquires the odour of thyme and rock-oil, boils at 154% decreases in density from 0*8736 to 0*842, and likewise in rotatory power, which, in three experiments was found to diminish from 28' 83° to the left to 8*68'', 13*82'' and 1903° to the left; but, its power of dis- solving caoutchouc is augmented. (Bouchardat) In general, the rota* tory power of oil of turpentine is diminished by heating above its boiling point under pressure; that of the dextro-rotatory English oil is first diminished, and afterwards changed in direction, becoming lievo-rotatory. Its specific gravity is increased and its chemical properties are altered to a certain extent, according to the degree and duration of the heating. (Berthelot.)

From oil of turpentine which had been heated to 150^ for three days, crystals sublimed, which likewise collected in the neck of the retort when the oil was distilled in the water-bath, and emitted a resinous odour when thrown on red-hot coals. (Cluzel, Chomet & BouUay, Ann, Chim, 51, 270.) — Oil of turpentine sealed up in thermometer-tubes, becomes suddenly coloured and contracts when heated above 200°. (Aubergier.) — The rotatory power of oil of turpentine is not altered by heating it in an atmosphere of carbonic acid, even for 60 hours ; but French oil of turpentine, having a density of 0*8654 at 15® and a rotatory power of 35*4 to the left, after being heated in sealed tubes to 360° for ^ye hours, exhibits a density of 0*9154 at 11°. Oil of turpentine dissolved in alcohol exhibited after heating for an hour and a-half to 360% a rotatory power of 1 2° to the left. — English oil of turpentine of sp. gr. 0*8665 at 15% and 18*6° dextro-rotatory power, exhibits after four hours heating to 250% a density of 0*8657 at 15% and dextro-rotatory power = 15*3®; after sixty hours heating to 250"— 260% a laevo-rotatory power = 8*55; after two hours heating to 300% Isevo-rotatory power = 9*0*

, OIL OF TURPENTINE. 247

(isoterebentfaene); and after fire honrs heating to 860*", a density of 0-907o at 11°, and a laevo-rotatory power = 5*6, gas being also given off from it. Swiss oil of turpentine of sp. gr. 0*8618 at 15° and IsBvo-rota- torj = 1 1 -2°, exhibits after 74 hours heating to 300°, a sp. gr. = 0'8906 at 14°, a Isevo-rotatory power = 1*55°, and gives off gas.

The prod nets obtained by overheating oil of turpentine, exhibit in particular an increased power of absorbing oxygen. They are mix- tures of several hydrocarbons isomerio and polymeric with oil of turpen- tine, some of them having boiling points near that of the original oil, while some boil at higher temperatures. (Berthelot) In the same interval of time, 100 vols. French oil of turpentine absorbed 8*4 vol. oxygen, English 4-7, Swiss 4*9 vol.; after being heated to 300° for 42 hours, the French oil absorbed 5 vols, the English 9*7, and the Swiss 1-64 vol. oxygen. (Berthelot.)

4. By a red-heat. When oil of turpentine mixed with air is passed through a red-hot iron tube filled with coiled copper-foil, the products collected in the receiver are a large Quantity of water, needle-shaped cnrstals, and yellow tar, which gradually unites with the crystals, an odour of oil of amber being at the same time evolved. (Richter, Ann. Fharm, 32, 125.)

5. Oil of turpentine is inflammable, and bums with a bright smoky flame. When crystals of anhydrous chromic acid are pk^d on an asbestos- wick moistened with oil of turpentine, and projecting j- of an inch from a spirit-lamp filled with oil of turpentine, the oil takes fire and reduces the chromic acid to chromic oxide, which continues to glow if the flame be carefully blown out, and forms a peculiar-smelling transparent liquid, not containing naphthalin. (R. B5ttger, Ann, Fharm, 57, 134.)

Rectified oil of turpentine is used for illumination, either alone or mixed with other illuminating materials. A mixture of 4 vols, spirit of wine of 95 per cent., and 1 vol. oil of turpentine bums very clearly in lamps of peculiar construction; the illumiuating power of the mixture is not increased by distillation. (Auduard, J. Chim. mid, 19, 717.) — A mixture prepared by heating together 5 pts. of alcohol, 10 pts. oil of turpentine, and 1 pt. oleic acid, burns with a white light, without smoke or odour of turpentine. (Rousseau, J, Chim mid, 22, 300.) — 4 pts. of rectified wood-spirit and 1 pt. of oil of turpentine rectified over lime bum in lamps of peculiar construction, without smoke and with a bright white flame. (Fabre, Compt, rend, 21, 161.)

6. Oxygen gas is abundantly absorbed by oil of turpentine. The oil in the course of fourteen days' exposure to the air, absorbs its own volume of oxygen, and does not subsequently give it off on boiling. (Brandos.) 1 vol. oil of turpentine takes up in four months, 20 vok. oxygen, and if previously saturated with carbonic acid, gives off 16 vols, of that gas; in eight months, it absorbs 24*3 vols, oxygen; in nine months more, 27*2 vols.; in the tenth month, at a temperature of 18° to 20°, somewhat more than 1 vol. daily; but in the following thirty-three months only 9 vols, more; making the quantity of oxygen absorbed in the whole 43 months, 128 volumes. It acquires at the same time a dark yellow- brown colour, deposits a few volatile crystals, but remains liquid, and, after it has absorbed 50 vols, oxygen, gives off car- bonic acid and hydrogen ; but after evaporation, or after exposure to the sun, it deposits a very acid watery liquid, so that the evolution of hydrogen is perhaps a consequence of the decomposition of this water

248 PRIMARY NUCLEUS C»H>«.

produced by the oxidation of the oil of turpentine. (Saussnre, oom|t,

p. 256.)

7. Oil of turpentine absorbs chlorine gas, with rise of temperature and eyolution of hydrochloric acid. If the chlorine be passed into it, slowly at firstf and in excess only at the end of the process, the oil of turpentine is converted into a viscid, colourless liquid, which smells like camphor, has a bitter-sweet taste, turns the plane of the polarization to the right, and is a mixture of chlorinated oil of turpentine and chlorotere- bene. (Deville.) Oil of turpentine is turned deep yellow by chlorine gas, becoming at the same time, thicker, but not opaque, and not forming any artificial camphor. (Cluzel.) When 6 pts. of oil of turpentine are heated to boiling with 25 pts. peroxide of manganese and 100 pts. hydrochloric acid, with frequent agitation at the beginning, acid water passes oyer, together with a viscid yellow liquid, which is heavier than water, has an aromatic odour, does not contain free chlorine, boils between 240° and 270°, giving off a large quantity of hydrochloric acid, and leaving a residue, which is yellow, green, blue, ultimately black and thick, and solidifies on cooling. This distillate is perhaps identical with the product formed by the direct action of chlorine upon oil of turpen- tine. (Chautard.)

8. Bromine decomposes oil of turpentine, eliminating hydrochloric acid and forming brominated oil of turpentine. (Deville.) On mixing oil of turpentine with a few drops of bromine, hydrobromic add is evolved, the oil becomes heated, and is converted into a yellow viscid resin. (Balard, Ann. Chim. Phyt, 32, 377.) Fresh oil of turpentine mixed with \ of its bulk of water, becomes heated when bromine is gradually added to it, destroys the colour of the bromine till that liquid has been added in the proportion of 228 pts. of bromine (4 At.) to 100 pts. of oil of turpentine, and is converted into a colourless aromatic oil. (G. Williams.) — When oil of turpentine is mixed with aqueous hydrobromic and dilute sulphuric acid, a large quantity of water and aqueous bromate of potash added to the mixture as long as the solution retains a slight orange colour after agitation, and the excess of bromine then removed by means of aqueous hyposulphite of soda, the oil of turpentine is found to have taken up a quantity of bromine, varying with the age and origin of the oil, viz., French oil of turpentine 260*2 p. c. ; American 260*2 p. c. ; German 227*1 p. c. once however in earlier experiments (probably with impure or peculiar oil 38*7 p. c. (Knop.)

9. Iodine dissolves in cold oil of turpentine, with dark green colour at first (Deville); but a violent explosion soon takes place (Walker's, Pogg. 6, 126; Blanchet & Sell; Guizot), yellow or violet vapours are evolved, and an acid resin is left behind. The vapours of iodine and oil of turpentine act on one another with great violenee, forming a large quantity of hydriodic acid (Guizot); they decompose each other only after condensation, and without heat or explosion. Vapour of oil of tur- pentine is absorbed by iodine. (Winckler.)

When 1 pt. of iodine and 8 pts. of oil of turpentine are placed together under a bell-jar, the iodine is converted in the course of three days into a dark red resin, having a balsamic odour and an odour of iodine, ana hydrio- dous acid which floats upon the resin ; and after a week, if the glass be filled with the turpentine-oil, a brownish liquid having a balsamic odour sepasates from it. The resin thus obtained froths up when shaken with aqueons carbonate of potash, sinks to the bottom, and after washing with alcohol.

OIL OP TURPENTINE. 249

yields bv dry distillation, vapours of iodine and a thick oil like oil of inace, while charcoal and a small quantity of iodide of potassium remain behind. Its solution in ether gives with corrosive sublimate, red iodide of mercury, and with subacetate of lead, it yields after a few hours, iodide of lead. — After digestion with caustic potash, washing with alcohol, solution in 4 parts of ether, and evaporation of the solution at a moderate heat, it remains as a black, dry mass which has a balsamic and iodine-like odour, — burns when set on fire, with sparkling and a very smoky flame, — gives off, when heated, iodine and hydriodous acid in yellow needles, — is insoluble in water, and dissolves slowly with dark yellow colour in alcohol of 80 per cent., readily in ether. The dark brown ethereal solution is decolorised by agitation with potash-ley, and the decanted ether yields by evaporation a yellowish red, inodorous and tasteless resin not containing iodine, while the potash-ley takes up a quantity of iodine equal to 42*56 per cent, of the weight of the resin. (Winckler.)

When iodine is distilled with oil of turpentine, hydriodic acid is pro- duced, toother with a blackish viscid oil which is decolorised by agitation with aqueous potash (Deville) ; charcoal remains behind, and the distillate containing hydriodic acid deposits white flocks when shaken up with potash. (Guizot.) The brown solution of iodine in an equal quantity of oil of turpentine, the formation of which is attended with evolution of heat, gives off, when distilled to dryness, a large quantity of hydriodic acid, then a brown oil, and lastly a balsam which sinks to the bottom, while charcoal remains behind. The distillate when exposed to the air, gives off yellowish vapours, having a pungent odour like that of hydriodic acid, tastes very sour, gives off part of its hydriodic acid on exposure to the air, and the whole when placed near ammonia (the ammonia at the same time entering into the oil, Gm,), and then appears colourless, has a disagreeable taste and empyreumatic odour, and deposits the brown balsam which passed over with it, together with a small quantity of dis- solved iodine. Oil of turpentine distilled with rather less than an equal quantity of iodine passes over nearly unaltered. (Guizot.) *

10. Nitric acid acts on oil of turpentine in various ways, according to its strength and quantity and the duration of the action. Strong nitric acid acts on oil of turpentine with great violence, and often sets it on fire (Blanchet & Sell) ; an excess of the acid, diluted with an equal weight of water, forms, after continued boiling, carbonic acid, hydro- cyanic acid, terephthalic acid (xiii, 18), terebenzic acid, acid resins, terebilic acid (xii, 467), oxalic acid, terechrysic acid (xi, 424) (Cailliot), together with acetic, propionic and butyric acids. (Schneider.) By the action of moderately dilute nitric acid, acetic acid is produced ; by long continued boiling with very dilute nitric acid, nitrogen, carbonic acid, and carbonic oxide are evolved, whilst a resin remains, insoluble in water, and smelling of formic acid. (Deville.) — Nitric acid, mixed with ^ pt. alcohol, partially converts oil of turpentine into turpentine-camphor. (Wiggers, Anti. Fharm, 57, 247.)

Oil of turpentine, from turpentine produced in northern countries, is scarcely heated by nitric, acid. CBonsLBtre, J. Pharm. 11, 529). When a small quantity of oil of turpentine is heated with excess of nitric acid diluted with an equal weight of water, as long as red vapours continue to escape, carbonic and hydrocyanic acids are evolved, and a quarter of the oil passes over with somewhat diminished rotatory power, while resins and an acid liquid remain behind. The resins consist of tere- phthalic acid, insoluble in alcohol, and three resins soluble therein

250 PRIMARY NUCLEUS C»H".

(according to Cbantard, N, J, Pharm, 24, 166, they consist of two substances containing bjponitric aci<i, one of which dissolves in ammonia with red colour, and is precipitated therefrom in yellow flocks hy acids, while the other is insoluble in ammonia and in the fixed alkalis ; both, however, yield toluidine when boiled with potash). The acid liquid mixed with water, after evaporation, deposits a yellow pitchy mass, consisting of resin, terephthalic acid and terebensic acid (according to Svanberg & Ekman, J, pr. Chem. 66, 219. of an acid different from terephthalic add), while Uie mother-liquor retains oxalic acid (qnadroxalate of potash, according to Rabourdin), together with terebilic acid and a small quantity of tere- ohrysic acid. (Cailiiot.) — It is only chlorinated nitric acid that produces oxalic acid with oil of turpentine, and, on the other hand, less terebilic acid than is produced by pure nitric acid. (E. Kopp, Compt, Chim. 1849, 153.)

When 5 or 6 pts. of strong nitric acid diluted with an equal weight of water, are very gradually dropt into oil of turpentine very gently heated in a large tubulated retort, the portion which distils over being well cooled, a violent action soon takes place, the first portions of acid turning the oil brown, while the latter portions produce heating, ebuUi- tiun and emission of red fumes. If the mixture be boiled for 24 hours after the action is over, the resin adhering to the sides of the retort disappears, a viscid scum forms for a while on the surface, and the nitrio acid, on cooling, deposits a brown, bitter, acid resin. If the clear liquid in the retort be distilled down to one -third, and afterwards distilled oft several times, with addition of water, a greenish yellow liquid, rendered turbid by drops of oil, passes over first, then a clear distillate, containing (besides nitric acid), acetic, propionic, and butyric acids. (Schneider.)

1 1 . When oil of turpentine, saturated with nitrous acid, is distilled, a black resin is obtained, together with a red volatile oil, smelling like oil of turpentine and bitter almond oil. (Deville.)

\2, Oil of vitriol decomposes oil of turpentine with rise of tempera- ture, evolution of sulphurous acid, and formation of terebene and colophene. (Deville.) The mixture becomes heat-ed, gives off sul- phurous acid, and becomes brown and viscid. (Hatcbett.) On gently heating the mixture, a viscid mass is formed, partly soluble in water, partly sinking therein, sparingly soluble also in alcohol (Link) ; an oil, smelling like strawberries, a slightly volatile acid, a large quantity of light brown resin, mobile at 100°, insoluble in potash, also extractive matters. (Unverdorben.) Oil of turpentine distilled with i pt of strong sulphuric acid, yields a red brown oil, which when freed from sulphuric acid by potash, has an aromatic odour like that of anise- oil (Perse), like rock-oil, oil of turpentine, and oil of rosemary. (Heidt- roanii, JRep. 14, 48S.) When oil of turpentine is poured upon strong sulphuric acid, so that the two may not mix, the oil of turpentine floating on the top becomes thick alter 6 or 8 days, dissolves readily in strong sulphuric acid, and may be separated therefrom by water. Oil of turpentine, poured in like manner upon sulpbovinic acid, dissolves sparingly, gives ofi* sulphurous acid when distilled, and yields a mobile oil containing sulphuric acid, whilst a thick oil, likewise containing that acid remains behind. By rectifying the distillate over antimonide of potassium, it becomes mobile, free from sulphuric acid, acquires an odour nearly the same as that of oil of turpentine, and resinises easily when jexposed to the air. The viscid oil remaining in the residue may be extracted by ether, has an odour of camphor, and does not resinise in

. OIL OF TURPENTINE. 251

the air. (Ricbter, Arm, FhatTn. B2, 125.) When equal parte of oil of tarpentine and strong sulphDric acid are distilled together, two volatile oils (terebene and colophene) pass over, while a tarry and a solid residue are left behind. The distillate yields sulphuric acid to water ; the tarry residue is black, tasteless, difficult to bum, appears to volatilise undecom- posed when heated ; dissolves readily and in all proportions in ether and in oil of turpentine, partially only in nitric acid, the insoluble portion be- coming hard, not at all soluble in weak acetic acid or in alcohol of 85 p. c. ; sparingly in absolute alcohol ; by dry distillation, it yields sulphuretted hydrogen, sulphur, and a volatile oil, which does not act upon potassium. The solid black residue possesses the same properties, excepting that it is richer in carbon and sulphur and less soluble. The distillate consists of two layers, the upper of which smells like peppermint, is very acid, and deposits sulphur after a while ; after washing with soda, it is colourless, smells like thyme, is tasteless and neutral, bums like oil of turpentine, dissolves in all proportions in absolute alcohol, ether, and oil of turpen- tine, is not altered by nitric acid, turns greenish yellow, and gives off nitrous acid when heated with oil of vitriol and nitric acid, and is turned red by oil of vitriol. The lower layer of the distillate contains a very small quantity of a substance having an intolerable odour. (Boutigny.) When oil of turpentine is mixed by drops with a very large quantity of strong sulphuric acid, a red-brown solution is formed which deposits terebene when mixed with water ; if, on the other band, a very small quantity of sulphuric acid be poured into a larger quantity of oil of turpentine, the mixture becomes sensibly heated, blackens, and gives off a large quantity of sulphurous acid. (Gerhardt, Compt. rend, 17, 314.)

13. Oil of turpentine distilled with photphoric anhydride y is resolved into terebene and colophene. Glacial phosphoric acid turns the oil red. (Deville.)

14. Baracic add, heated with oil of turpentine to 100^, alters its rotatory power. French oil of turpentine, having a lavo-rotatory power of 35*4, exhibits, after being heated with boracic acid to 100° for 130 hours, a Isevo-rotatory power of 23'0. (Berthelot.)

1 5. Carbonic acid does not decompose oil of turpentine in the cold ; but when a mixture of the vapour with moist carbonic acid gas is passed through a tube heated nearly to redness, carbonic oxide and water are formed, together with a thm liquid, resembling acetone and isomeric with cymene. (Deville.)

C»Hi« + 2C0a = 2C0 + 2H0 + C»HW.

16. Oxalic, tartaric, citric, and acetic acid do not act upon oil of tur- pentine at ordinary temperatures, but, at 100°, they alter its specific gravity, rotatory power, odour, and boiling point, and some of its chemical properties, in various degrees, according to the duration of the action. (Berthelot.) French oil of turpentine of 1 re vo- rotatory power 35*4°, exhibits, after being heated to 100° for 73 hours, with crystals of oxalic acid, a IsBvo-rotatory power of 15*2° ; with crystals of tartaric acid, Isevo-rota- tory power=28'6° ; with aqueous acetic acid, Isevo-rotatory power=3r3°. English oil of turpentine, of Isevo-rotatory power 18' 6°, exhibits, after heating to 100° for 30 hours with crystals of oxalic acid, dextro-rotatory power = 162°; with glacial acetic acid, dextro-rotatory power = 147 . (Berthelot.) Berthelot, by heating oil of turpentine to 100° for 63 hours with oxalic acid, and subsequent distillation, obtained undecomposed oil of turpentine, a distillate smelling of terebene and exhibiting lasvo-

252 PRIMARY NUCLEUS C»W\

rotatory power of IS'B'^ to 35'4*', and^ lastly, a vieoid, yellow, non- iridescent distiUate, together with a solid residae. Oil of tarpentine, altered by acetic acid at a high temperature, exhibits the boiling point of the original oil. (Berthelot.) When oil of turpentine is distilled with strong sulphuric acid and acetate of potash, the distillate consists of aqueous sulphurous acid, terebene, and oolophene. (Deville.)

17. Anhydnms hydrojluoric acid imparts but a faint yellowish colour to oil of turpentine, even after long continued action, but throws down a greyish white tallowy substance, amounting to about T^th of the oil, and imparts to the oil a very acid pungent odour, which is quickly destroyed by exposure to the air, the oil then becoming decolorised and depositing orown flocks. (Gehlen.) The rotatory power remains unaltered, and the product contains but little fluorine (3*05 p. c.), so that it cannot be regarded as a fluorated oil of turpentine. 1 pt. of oil of turpentine placed in the cooled leaden vessel rapidly absorbs the hydrofluoric acid evolved from 1^ pts. fluor-spar by 8 pts. oil of vitriol, becoming brown and viscid, and separating when left at rest into two layers, the upper of which is brown and fuming, while the lower is oily, and, after washing with water, dissolves in ether and in oil of turpentine completely, but m rock-oil, with separation of white flocks which quickly disappear. The solution in aosolute alcohol, which is formed with difficulty, deposits on cooling, yellowish flocks which are not obtained from the other solutions, even after concentration and cooling to — 1 9°, On distilling the unaltered oil from leaden retorts, a fuming oil is obtained, which smells like camphor, while, by distillation from glass retorts, a thick, white, crystalline sublimate is obtained, having an aromatic sour taste, and consisting of a mixture of fluoride of silicium formed in the distillation, with the camphor-smelling oil just mentioned, which dissolves in ether, and remains, after evaporation of the ether, as a thick yellow resin free from fluorine. (Reinsch, J, pr. Chem. 19, 316.)

18. OU ofturperUine absorbs in the cold, 6*8 p. c. oigcueotu fluoride qf boron, and is thereby converted into an isomeric, iridescent, viscid liquid, which boils almost constantly at 300°, and has no rotatory power. — Oil of turpentine, sealed up in a glass tube with 2 vols, {-^zz) ^^ gaseous fluoride of boron, absorbs the gas, turns red, and becomes heated to the boiling point without evolution of gas; the heat thus developed is stronger than can be produced by the union of the oil with the fluoride of boron. Alcohol enclosed in the same tube is not converted into ether. (Berthelot.)

19. Gaseous fluM%de of silicium does not act perceptibly on oil of turpentine. (Deville.)

20. Hydrochloric acid gas converts oil of turpentine partly into hydrochlorate of terebene, partly into artificial camphor. (Deville.) — Oil of turpentine is converted by hydrochloric acid into camphene and peucylene» which then unite with the hydrochloric acid. (Soubeiran & Capitaine.) According to Blanchet & Sell, hydrochloric acid gas does not decompose oil of turpentine, but unites with the dadyl and peucyl already contained in it.

21. Eydrobromic and hydriodic add act in the same manner as hydrochloric acid gas. (Deville.)

22. An intimate mixture of 600 pts. water, 200 pts. chloride of lime, and 25 pts. oil of turpentine, emits, when distilled, a pleasant ethereal odour, gives off a large quantity of carbonic acid, froths up, and yields, even after the fire has been removed, a distillate which separates into

w^-

OIL OF TURPENTINB. 253

tbree layers, the nppermoat of which is undecomposed oil of tarpentino, the middle, an aqueous solution of chloroform, while the lowest consists of chloroform. (Ghautard.) — Bypohromous acid distilled with oil of tar- peutine, yields bromoform. When bromine is dropped into a thin paste of lime, as long as it is thereby decolorised, the mass becomes heated and thickened. If it be then brought back to its original consistence by addition of water, carefully mixed, during agitation, with a quantity of oil of turpentine equal in weight to half of the lime employed, and heated, a brisk action begins, though less violent than with chloride of lime, carbonic acid escaping and aqueous bromoform distilling over.

23. Liquid sidphide of phosph(ytnis converts oil of turpentine, after some months* contact, into a viscid, yellowish red resin which surrounds the sulphide of phosphorus, rendered very limpid and somewhat more mobile by the action. Sulphide of phosphorus takes fire under boiling oil of turpentine. (Bottger, J^ pr. Chem, 12, 359.)

24. Chlorochromic acid sets fire to oil of turpentine. (Thomson, FhU. Trans. 1827; Po(^g. 31, 607.)

25. Potassium does not act upon oil of turpentine in the cold.

(Blanchet & Sell ; Dumas.) It colours the oil brown and separates brown flocks without evolation of gas. (Deville, Hagen.) Potassium oxidises in oil of turpentine, gives off gas, and becomes surrounded with a thick resin. (Oppermann.) The oil of of the branches of the spruce fir, evolved hydrogen in a few minutes when treated with potassium, formed a light brown jelly, and was itself coloured brown because it con- tained an oxygenated oil. (W5hler.)

26. Ftued hydrate of potash colours ordinary oil of turpentine (with separation of brown fiocks, according to Devil le), but not Venetian oil of turpentine. (Scharling.) To the oil from tne branches of the spruce-fir, it imparts, on distillation, the odour of ordinary oil of turpen- tine. (Wohler.) — Common oil of turpentine is coloured by hydrate of potash, the more strongly the older it is, and may become heated to 60'' at the same time. — Both ordinary and Venetian oil of turpentine, when shaken up with bisulphide of carbon and fused hydrate of potash, yield after a while, a white saline mass which behaves like xanthate of potash. (Scharling.)

Strong potash-ley does not alter oil of turpentine from the spruce-fir or Scotch fir (Wohler, Hagen), or Venetian oil of turpentine, when dis- tilled therewith, inasmuch as the distillate exhibits the same behaviour as before towards hydrate of potash and bisulphide of carbon. (Scharling.) It colours the common oil yellow and gradually brown. (Blanchet & Sell.) — A mixture of strong potash -ley and oil of turpentine separates into three layers; the uppermost of which is an oil, the lowest, potash-ley, while the middle layer is brown, thick, and soluble in potash-ley if weaker than the ley originally used From this milky solution, acids throw down a viscid resin which fioats on the surface, and another which falls to the bottom in lumps and flakes, both being soluble in alcohol and having an acid reaction. The liquid resin becomes yellow and brittle after the adhering oil has evaporated. (Polex.)

27. Oil of turpentine absorbs 7i vols, ammonia gas at 16° (Saussure), acquiring a yellowish colour, but retaining its mobility. (Gehlen.) It forms a tallowy mass. (Saussure.) The milky liquid produced by agitating oil of turpentine with an equal quantity of aqueous ammonia separates, when left at rest, into three layers, the uppermost which is an oil, the lowest, a solution of sal-ammoniac, and the middle, a jelly like opodeldoc, which last, when separated from the liquid and pressed

254 PRIMARY NUCLEUS C^U>*.

between bibulous paper, forms a mass which melts between the fingers or when heated a few degrees abore 0^.

28. Oil of turpentine takes fire with chlarate of potcuh and a few drops of oil of vitriol, burning with a tremulous, very smoky flame and leaving charcoal. (A. Vogel Jun., Ann. Pharm, 74, 114 )

29. Quick lime kept in contact for some time with crude oil of tur- pentine, deprives it of its unpleasant odour. ^Blanchet &, Sell.)

30. Chloride of calcium, Jlitoride of calcium, chloride of barium^ cfdoride of strontium, iodide of ammonium and chloride of ammonium alter at 240^^—250^, the rotatory power of oil of turpentine, and accelerate the very slow transformation which takes place at this temperature. (Ber- thelot.) — French oil of turpentine of lievo-rotatory power 35*4% after being heated for 7 or 8 hours to 240°— 250° with chloride of calcium, rotates 22 1° to the left; with fluoride of calcium, 5*9^ to the left; with chloride of barium, 32*85° to the left; with chloride of strontium 18*4^ to the left ; — after being heated to 250'' for two hours with chloride of calcium, 15*2° to the left; to 270^ for two hours with chloride of calcium, 15*2° to the left; this last product is colourless and boils at 161°. English oil of turpentine, which rotates 18*6° to the right, exhibits after 7 or 8 hours heating to 240°— 250°, with fluoride of calcium, a rotatoiy power of 7'4° also to the right (Berthelot)

31. Chloride of Zinc does not act upon oil of turpentine at ordinary temperatures ; but at 1 00^, it alters the rotatory power, retards the forma- tion of turpentine-camphor, ultimately forms an oil containing C^H^^ and gives off hydrogen, increasing in quantity with the duration of the action, so that in 130 hours, from 15 to 30 volumes are evolved : — (C**H" = C*°H** -h 2H). (Berthelot.) — French oil of turpentine having a Ibbvo- rotatory power = 35*4°, exhibits, after 130 hours heating to 100° with chloride of zinc, a laevo-rotatory power of 15*5^; English oil of turpentine of dextro-rotatory power 1 8*6°, heated for four hours to 100° with chloride of zinc, exhibits dextro-rotatory power = 17*85°. Oil of turpentine heated to 270° with chloride of zinc, becomes coloured, smells of terebene, and increases in density from 0*8613 to 0*8698 at 11°. French oil of tur- pentine heated to between 100^ and 270° with chloride of zinc, yields when distilled at 160°, at first a distillate of apparently unaltered oil of turpentine, of Ifldvo-rotatory power 24*9'' to 35-4"^, then reddish coloured, and ultimately viscid oil having the boiling-point of colophene. (Berthelot.)

32. NUroprumde qf copper boiled with oil of turpentine produces a green or bluish green precipitate. By this reaction, oil of turpentine may be recognised in oxygenated oils, which colour nitroprusside of copper black-brown or green and themselves acquire a darker colour. (Heppe, N, Br, Arch 89, 57.)

33. Litharge or minium does not alter cold oil of turpentine (Brandes, Miiller), but, at a gentle heat, gives up oxygen to it, and converts it into terebentic and formic acids. (Weppen.) Hydrated oxide of lead colours an equal weight of oil of turpentine dark red after a short time ; with a smaller quantity of the hydrated oxide of lead, it turns yellowish after some days, the lead-compound itself remaining white. (Brandes.) Batic ^ acetate of lead, shaken up with an equal quantity of oil of turpentine, forms, after a few minutes, a thick mixture, whicn varies in colour from orange-yellow to wine- red, is insoluble in water, but dissolves partially in alcohol, leaving a yellowish, viscid, acid mass, containing lead ; with

OIL OF TURPENTINB. 255

excess of subaoetate of lead, the colouring takes place more slowly and is weaker. (Brandos, Miiller ; comp. also Oz(me with Oil of Turpentine, p. 275.) The altered oil is a mixture of acid resin with oxide of lead, adhering subaoetate, and oil of turpentine ; the latter separates trans- parent and colourless, only the subjacent basic acetate of lead exhibiting a red colour ; a yellow solid body separates between the two layers of liquid. The colouring is not due to an acid resin contained in the oil of turpentine, inasmuch as it is likewise produced by oil, which has been purified with potash-ley. (Polex.) A concentrated solution of bibasio acetate of lead imparts a dark red colour in a few minutes to oil of turpentine four years old ; with fresher oil, the same effect is produced in two hours ; the same oil acquires the same colour by boiling with lead- solution for a quarter of an hour. (Schindler^ N'. Br, Arch, 41, 40.) Bassic acetate of lead is coloured reddish after a while by crude oil of turpentine, but not by the rectified oil or by the vapour ; the crude oil loses these properties by boiling and distillation ; the rectified oil acquires them by three months exposure to the air. When oil of turpentine is shaken up with basic acetate of lead in a bottle containing air, it takes up oxygen, which does not escape when the oil is boiled alone or with water, but if previously red, it becomes decolorised and deposits yellow flocks and white hydrated oxide of lead. (Brandos.) The erode mixture of 1 pt. alcoholic sal-ammoniac, 8 pts spirit of camphor, and 8 pts. oil of turpentine, mixed with 2 pts. basic acetate of lead, acquires a kermes- brown colour in a few minutes, and solidifies to a jelly after some days. (Buchner, Br, Arch. 8, 133.)

Interpolation,

Terebentic Acid, cwh»^ow ?

Wkppen. Ann, Pharm, 41> 294.

Adde tiribentinigue. TerebentiniiiMre.

Pormaiion. 1. By heating oil of turpentine with litharge. 2. By the action of the air on oil of turpentine mixed with oxide of lead, formic acid being produced at the same time :

C»|ii6 + 14 0 « CWH»<0«> + (?WO*.

Preparation, Oil of turpentine gently heated with oxide of lead, becomes coloured* absorbs oxygen with avidity, then again gradually loses its colour and deposits a copious yellow precipitate. This precipitate is boiled and washed with alcohol as long as the water runs off turbid, then decomposed by sulphuretted hydrogen, the terebentic acid dissolved out by alcohol, and the solution evaporated till it crystallises.

Properties, By slow evaporation it forms delicate white crystals ; by quick evaporation, a brown tenacious mass. Its alcoholic solution reddens Utmus.

18 C 14 H	... 108 .... 14	53*46 .... .... 0 uO •••. .... 39*61 ....	Kolbe. a. b, .... 65-14 ... 64-00 6*97 .... 6*93
10 O	... 80	.... 37-89 .... 3907
C"H"0»o ....	... 202	.... 100-00 ....	.... 100-00 .... 10000

The acid used for the first analysis contained resin, formed in consequence of the temperature rising too high.

256 PRIMARY NUCLEUS C^H^^.

Combinatimu, The alcoholic aolutioii of terebentic acid precipitates moat metallio salts ; the precipitates are soluble in alcohol.

T^eientate qf Lead, Obtained, together with formiate of lead, as above described, in the form of a yellow precipitate, which may be purified by washing with boiling water. If it be heated somewhat above 100", while still moist from adhering alcohol, it bums away with a bright glimmering light, leaving a residue of metallic lead.

Terebentic acid dissolves in alcohol, and the solution is rendered turbid by water.

34. When oil of tarpentine is distilled with chromate of lead and dilute sulpharic acid, carbonic acid escapes, a small quantity of aqueous fonnic acid distils over, and sulphate of chromium remains behind.

85. Oil of turpentine, mixed with bichloride of tin^ thickens, and may become heated till it takes fire. (J. Dayj.)

ComlinaUons, 1. With Oxygen, — a. Oxide of Turpentine-oil. Hydivied Oxide of Turpentine. Laurent's Oxide de eamphine hydrati, — C"H"0*,2H0. — When a layer of oil of turpentine \ centim. thick is introduced into a elass bell-jar filled to f with oxygen, and closed at bottom with water, the yessel then placed in sunshine and the oxygen- j^ renewed as it is absorbed, the sides of the yessel below the oil become coyered with small prisms, which may be collected, and puri- fied by washing with water and oil of turpentine, and recrystallisation from alcohol.

Inodorous. Crystallises from boiling water in stellate groups of needles, which, when boiled with water containing sulphuric acid, yield a product smelling of oil of turpentine and camphor. It is soluble in water, alcohol, and ether, and crystallises from the hot solutions on cooling. (Sobrero^ Compt. rend. 83, 66; Ann. Pharm. 80, 106.)

20 C

18 H

40

	Sobrero.
120 .... 70-58 ...	.... 70-58
18 .... 10*58 ...	10-58
32 .... 18'84 ...	18-84

C»H»«0»,2H0 170 .... 10000 10000

h. Oil of turpentine absorbs oxygen gas, acquiring new properties, and being conyerted into ozonised oU of turpentine. In this compound part of the absorbed oxygen appears to be more intimately, a second portion (amounting to 5*2 per cent, of the turpentine oil) less intimately combinea, inasmuch as the latter may bo transferred to other bodies, and still exhibits the properties of free ozone. (Schonbein.) — The formation of ozonised oil of turpentine takes place on agitating the oil with cold air in presence of light, the action going on the more quickly, the more numerous the points of contact of the oil and the air, the brighter the light, and the lower the temperature When, therefore, oil of turpentine is left for four months in a bottle i filled with air, and exposed to aifi*used daylight, the air being renewed as it is used up, a mobile, acid, oxidising oil is obtained.

Ozonised oil of turpentine exerts an oxidising action on the following substances. It decolorises indigo-solution when agitated with it, espe- cially if the solution be warmed (hence if a portion of the ozonised oil be introduced into a bottle, together with a strip of linen dyed blue with indigo-solution, the linen is bleached in a few hours). It conyerts

OIL OP TURPENTINE. 257

aqueous sulphurous acid, with rise of temperature, into sulphuric acid ; colours solution of iodide of potassium immediately yellow, the oil at the same time becoming reddish, and, when heated, brownish yellow from separation of iodine (hence, when it is placed upon paper soaked in a mixture of iodide of potassium and starch, the paper turns brown, or, if moistened with water, blue). It converts a hot solution of ferrous sul- phate into ferric sulphate, which partly separates (basic salt) and partly remains in solution. Ozonised oil of turpentine colours white ferrous cyanide containing potassium, blue ; yellow aqueous solution of ferro- cyanide of potassium, deep yellow, especially on boiling ; converts arsenic spots on a porcelain plate into arsenic acid, and causes them to disappear completely in the course of 10 or 15 minutes (it does not affect antimony spots, even after a long time) ; decolorises sulphide of arsenic suspended in water, when heated and agitated with it ; likewise sulphide of lead and strips of paper coloured therewith, if these papers are suspended in a bottle containing the ozonised oil. (Sch5nbein.) — This property affords the means of detecting oil of turpentine in other oils which do not ozonise the air. (Williams, Overbeck, N. Br, Arch, 90, 138.) — Ozonised oil of turpentine boiled with phosphorus, not in contact with the air, forms phosphorous acid. Shaken up with finely divided silver and a small quantity of acetic acid, it forms acetate of silver. It dissolves guajac resin, forming a solution which is colourless at first, but afterwards turns blue, especially wheu heated, the ozone combining with the guajacum under the infiuence of beat. The oxidising action of ozonised oil of turpentine is intensified by the presence of blood- corpuscles and ferrous salts, the blood-corpuscles being thereby completely oxidised, and the protoxide of iron converted into sesquioxide. •— A mixture of oil of turpentine, containing 2 per cent, of ozone with a solu- tion of snbacetate of lead, acquires, when shaken up at mean temperature, a lemon-yellow to red-yellow colour, and forms protoxide and bioxide of lead, the greater portion of these oxides separatinc at once, while a smaller portion remains and separates from the filtered oil after 24 hours, so that the oil is but slightly coloured by the peroxide of lead, but never- theless continues to exert an oxidising action. The strongest colouring takes place in a mixture of 1 vol. solution of subacetate of lead (lead- vinegar, viii, 314,) and 2 vols, ozonised oil of turpentine ; but peroxide of lead containing protoxide is likewise formed with every other proportion of the mixture.

Ozonised oil of turpentine sometimes also exerts a reducing action. -— It abstracts part of the oxygen from peroxide of lead (oil of turpentine free from ozone has no action on that compound), losing its ozone at the same time, and giving off a gas not yet examined. It decolorises tincture of guajacum which has been coloured by peroxide of lead; also the aqueous solutions of permanganate of potash and of chromic acid mixed with sulphuric acid. — Hence even strongly ozonised oil of turpentine does not become coloured when shaken up with a few drops of lead- vinecar, inasmuch as the peroxide of lead formed in the first instance is quickly decomposed by the excess of ozone present.

Ozonised oil of turpentine is partially deprived of its peculiar pro- perties by boiling. (Schonbein.) It recovers them again when exposed to the air, and the yellowish residue possesses twice as much bleaching power as the distillate, though no oxygen is given off. (Williams.)

Sch&nbein explains the simultaneous oxidising and reducing powers of ozonised oil of turpentine, by assuming that peroxide of lead contains

VOL. XIV. s

258 PRIMARY-NUCLEUS C»HW.

a positire, and ozonised oil of tnrpentine a negative ozone, and that the union of these produces ordinary oxygen.

2. With Water, — Oil of tnrpentine forms with water three different compounds.

A. Turpentine-camphor. C»H»0*.

Hydrate of Oil of Turpentine. Pyroeamphorhtm (Trantwem), Ttrpen» ihinsalz (Buchner), Terpentinoleamphorid (Trommsdorff), Terpin (Benelius. List), Trihydrate d* essence de iSribenihine. (Devillc.) First observed in 1727, by GeofTroy, who, however, did not recognise it as a distinct compound ; examined by Buchner, who regarded it as a salt formed by the union of succinic acid with a volatile base ; recognised as hydrate of turpen- tine-oil by Dumas & Peligot, and by Wiggers.

Fo7*mation, I. The compound forms after a considerable time in mixtures of oil of turpentine and water. (Hertz, Deville.) In the follow- ing cases, also, the formation of turpentine-camphor appears to depend upon the presence of water in the materials, or else the camphor existed ready formed in the oil of turpentine, and afterwards separated. (Kr.): — When oil of turpentine is left to itself for a considerable time (Dumas, Brandos), even in closed vessels (Hafner, Geign) ; when it is heated for some time to 50° (Cluzel ; Blanchet A Sell) ; or distilled (Bnchner) ; by distillation of oil of turpentine which has been previously exposed to the air. (Boissenot & Persot.) — Turpentine-camphor passes over, together with acetic acid, in the distillation of old oil of turpentine which has been long exposed to the air, and separates in the crystalline form from the aqueous distillate, not by evaporation, but by continued cooling to —T*. (Boissenot & Persot); — when oil of turpentine is left in contact with ether. (Trommsdorff.) — 2. By the action of alcoholic nitric acid on oil of turpentine, oil of lemons, oil of bergamot, oil of copaiba, Stc, (Wiggers, Deville, Berth elot) ; on terpinol and isoterebenthene. (Ber- thelot.) — The alcohol serves merely as a solvent, and may be replaced by any substance that will dissolve both the oil and the acid, such as wood- spirit, acetone, ether, acetate of ethyl, butyric acid, or by such as dissolve only the oil, e.g., benzene or fusel-oil ; it may even be dispensed with altogether, but then the action is slower. The nitric acid, on the other hand, is essential to the formation of the turpeutine-camphor, although it does not itself suffer decomposition, and retains for some time its power of saturating bases, and of forming turpentine-camphor with fresh quantities of oil of turpentine, losing this power only after it has given rise to the formation of secondary products ; it cannot be replaced by any other substance except nitrous ether. — The formation of tur- pentine-camphor requires intimate contact of the acid with the oil. (Berthelot) — 3. By the action of oil of vitriol, hydrochloric acid, or acetic acid on alcoholic oil of turpentine, but in smaller quantity and less quickly than when nitric acid is used (^^iggers) ; acetic acid does not -woduce it. (Deville.) — Glacial acetic acid does not dissolve oil of tnr- p^^e, or convert it into turpentine-camphor, even after several years' contact 9 ^^^ ^^ ^ ^^^ drops of nitric acid be added, turpentine-camphor

TURPENTINE-CAMPHOR. 259

crystallises out in a few days. Neither does alcohol convert oil of turpentine into the camphor. (Deville.) — A mixture of oil of turpentine with hydrochloric acid, spirit of horde-radish, or spirit of caraway, deposits turpentine-camphor. (Rammelsberg, Pogg* 68, 570.) — When the liquid which remains after passing hydrochloric acid gas for some time throngh oil of turpentine, and separating the resulting crystalline compound, is mixed with water, turpentine-camphor separates from it. (Hertz.)

Prepcn^atton, 8 pts. of oil of turpentine are left in contact for 2 or 3 days with 2 pts. of nitric acid of sp. gr. 1*25 to I'S, and 1 pt. of alcohol of 80 per cent., the mixture being frequently agitated, then for a con- siderable time without agitation at 20° to 25°, whereupon two layers of liquid form, the lower consisting of nitric acid and alcohol, and the upper containing oil of turpentine, which in time becomes darker, and ultimately brown and opaque, and smells like hyacinths. After a few days, crystals appear at the surface of contact of the two liquids, increasing very quickly during the first fourteen days, then uniting in crystalline crusts, finally sinking to the bottom, and attaining to a larger size the more the mixture is kept at rest. The yellowish brown crystalline crusts (contaminated with a brown substance), are collected, left for a few days on bibulous paper, then pressed and dissolved in hot water ; the solution is boiled with animal charcoal and filtered ; and the crystals, which separate on cooling, are left to dry in the air. ( Wiggers.) — As a portion of the turpentine-camphor is very apt to be lost by volatilisation during the solution of the crystals in hot water and the boiling of the liquid, or by the decomposing action of the adhering acid, it is better to press the crystalline crusts between paper, pulverise them, and dissolve them in warm alcohol ; the turpentine-camphor then separates on cooling, while the oil and acid remain in the mother-liquor. By repeated crystal- lisation, they may be obtained quite pure, and hy spontaneous eyaporation of the cold-saturated alcoholic solution, in well developed crystals. (List.)

2. A mixture of 4 yols. oil of turpentine, 3 vols, alcohol of 85 p. c, and 1 vol. nitric acid is left to itself tor several months at mean tempera- ture (Beville), in shallow vessels. (Bertheloi) — In deep vessels, the formation of the camphor is not completed for several years, whereas, if shallow vessels are used, crystals appear after an interval varying from 48 hours to a week, and in a few weeks their formation is completed. (Berthelot.)

3. Hydrochloric acid gas is passed into oil of turpentine till the solid hydrochlorate begins to separate ; the passage of the gas is continued for some time j the liquid then cooled and left to stand for a night ; sufii- cient water is then added to make it cover the bottom of the vessel about an inch deep ; the mixture, after being shaken, is left to itself for a while ; and the crystals, which separate after some time on the sides of the vessel, or float upon the oil, are collected and purified. (Hertz.)

4. Oil of turpentine, in quantities of about 10 grammes, is left in contact for some time with nitric acid and acetone or butyric acid. (Berthelot^) Under these circumstances, the oil is sometimes wholly con- verted into turpentine-camphor. (Berthelot.)

The quantity of torpentine-camplior obtdned by these several methods varies with the constitutioii of the oil of turpentine used. Those kinds of tnrpentine-oil which yield much artificial camphor when treated with hydrochloric acid, likewise

8 2

260 PRIMARY-NUCLEUS C«HW.

yield the largest amoant of turpentine-camphor. (Wign^en.) By Wiggen* method, tarpentioe-oil yields 8*3 p. c. of tarpentme-camphor; Flackiger'a tempUii'Oil 15 p. c. (Plackiger). By Derille's method, turpentine-oil yields in 4 to 6 weeks, 6*25 p. c, after longer standing, 25 p. c. (Deville); French oil of turpentine in 3 months, 27 p. c. ; in two years 40 p. c. ; American oil of turpentine in two months yields quantities which may amount to 45*4 p. c. (Berthelot)

Vogel considered the presence of oil of amber as necessary to the formation of turpentine-camphor, and accordingly prepared it by mixing 1 pt. oil of turpentine with I pt. oil of amber and ^ pt. nitric acid of sp. gr. 1*25, and adding after 4 weeks ^ pt. alcohol, whereby he obtained in 18 weeks 12*5 p. c. tnrpentine-camphor ; by using equal parts of oil of turpentine, oil of amber, and nitric acid, and ^ pt. alcohol, he obtained 5*8 p. c; and with equal parts of oil of turpentine and nitric acid and j^ pt. alcohol, 0*42 p. c. turpentine-camphor.

Cryatallised tarpentiDe-cainplior is converted, by loss of water, into anhydrous turpentine-camphor. — Bihydrate of oil of turpentine (Deville), Tetrahydrate of oil of turpentine. (Berthelot.)

Properties, Milk-white, indistinctly crystalline mass (Wiggers), which volatilises nndecomposed at 150° (103", List), at IdO"" — Idd"* (Blanchet & Sell), and snblimes in acurahiated crystals like benzoic acid

SBuchner, Voget, Geiger), in slender needles having a silky lustre Brandos), as a woolly mass (Trommsdorff.) — It sublimes only in a current of air, not when the air is excluded ; when heated in a test-tube, it creeps up the sides. (List.) It is only when heated in considerable quantity, that it melts before subliming. (Brandes.) — Fused turpentine-camphor, suddenly cooled without access of moisturo, remains for several days tough and amorphous, but solidifies in the crystalline form on being touched by a sharp body, or heated to 36", or breathed upon, or brought in contact with water, alcohol, or ether. (List.)

Vapour-density 6*257. (Deville.) — Neutral. Inodorous. In the impure state it smells like turpentine. (Buchner, Trommsdorff.) The vapour smells like resin (H afner); like old oil of turpentine. ( Buchner.) — Tasteless. Its aqueous

solution does not act on polarised light. (Deville, Berthelot.)

Anhydroui Turpentine -eamphor, ^& g^^f* Wiggers. Deville.

20 C 120 .... 69*7 70*91 .... 69*59 .... 69*4

20 H 20 .... 11*6 1205 .... 11*68 .... 11*8

4 0 32 .... 18-7 17*04 .... 18*73 .... 18*3

C»HW0< 172 .... 100*0 100*00 .... 100*00 .... 100*0

Vol. Density.

C-vapour 20 8*3200

H.gas 20 0*1386

O-gas 2 2-2186

Vapour of Turpentine-camphor 2 10*6772

1 5*3386

Decompositwns, 1. Turpentine-camphor volatilises on red-hot coals without taking fire. ^Blanchet & Sell.) The vaponr may be set on fire in the flame of a candle, and continues to bum (Geiger) with a very smoky flame (Trommsdorff) ; according to Buchner, the combustion does not continue. It leaves a small quantity of easily combustible charcoal. (Geiger.) — 2. Distilled with anhydrous phosphoric acid, it yields terebene and colophene. (Deville.) — The solution obtained by heating

TURPENTINE-CAMPHOR. 26 1

turpentine-camphor with an equal weight of deliquesced glacial phosphoric acid, yields by distillation an aqueous distillate probably containing acetic acid, on which a light yellow aromatic oil floats^ and leaves a brown tumefied residue.

3. OU of vitriol dissolves turpentine-camphor with red colour (Boissenot & Persot), without heating (Trommsdorff), water beine sepa- rated and terpinol produced, which forms a yellowish red mass with the oil of vitriol. (List.) The solution has a balsamic odour, like that of artificial musk ; gives ofi* acid vapours (Buchner) ; becomes limpid after a few hours, and yields pointed crystals (Voget) ; and deposits resin on being mixed with water. (Boissenot & Persot.)

By boiling turpentine-camphor with dilute sulphuric acid, or with {iqueous bisulphite of potash, or with aqueous sulphurous add, terpinol is produced ^List) ; likewise, though more slowly, by the action of aqueous oxalic acia, tartaric acid, bitartrate of soda, or benzoic acid. (List)

4. HydroMorio acid gas converts turpentine-camphor, with separation of water, into solid bihydrochlorate of turpentine-oil (Deville) ; into a liquid compound of hydrochloric acid and oil of turpentine, isomeric with hydrochlorate of terebene (Wiggers), which, however, according to List, is a solution of artificial camphor in terpinol. — Pulverised turpentine- camphor absorbs hydrochloric acid rapidly; deliquesces, with rise of temperature, to a brown liquid in which heavy drops first separate, and afterwards crystallise, so that it solidifies and must be wanned in order to pass hydrochloric acid gas through it; the liquid, after saturation, solidifies in the crystalline form, leaving only a small quantity of hydro- chloric acid. (List.) — The solution of turpentine-cauiphor saturated while warm with hydrochloric acid gas, separates into two colourless layers, the lower of which is concentrated hydrochloric acid, and the upper a compound of oil of turpentine with hydrochloric acid. (Wiggers.) — Bihydrochlorate of turpentine-oil likewise forms in a mixture of turpentine-camphor and moderately strong hydrochloric acid. (List.)

5. Hydriodic acid, either gaseous or aqueous, converts turpentine- camphor into terpinol. The first product of the action is an iodated oil which, however, is completely decomposed by distillation, either alone or with water. (List.)

6. Turpentine-camphor dissolves without decomposition in cold nitric acid, the solution often beginning suddenly to boil (Tromnisdorif) ; it gradually turns yellow when heated and gives ofi* nitrous gas. (List.) — It deposits a yellow resin, and ultimately small yellowish crystals. (Trommsdorfi*) ; it smells like anise or fennel oil and rock-oil, and at higher temperatures, like camphor (Brandos) ; it emits an odour like that which is produced when a mixture of oil of turpentine and nitric acid takes fire. (Boissenot ^ Persot.)

7. When the vapours of fused turpentine-camphor are passed over sodcu-lime heated above 400^, terebentilic acid (xiii, 118) is obtained, together with marsh-gas and hydrogen :

C»H»0* « C«H»0^ + 2C«H< + 2H.

(Person ne^ Compt rend. 43, 553 ; Ann. Pharm. 100, 253.)

262 PRIMARY-NUCLEUS C^H"

8. When tarpentine-camplior ici heated to 250^ with iodide of ammonium, and the mixture is left at rest, two layers are formed, the lower consisting of aqueous iodide of ammonium with a few products of decomposition, and the upper of a hrown oil which smells like terpinol and prohably contains a hydrocarbon together with terpinol. (Ber- thelot.)

9. Turpentine- camphor is conyerted into terpinol by continued heating with chloride of zinc to 100^, or with chloride of calcium, fluoride of ccdcium, chloride of strontium, or chloride of ammonium to 160° — 180^ Chloride of barium and common salt do not act upon turpentine-camphor at thia temperature. (Berthelot.)

Combinations. With Water. — a. Crystallised Turpentine-Camphor,

— Anhydrous turpentine-camphor is hygroscopic, and, when exposed to moist air, swells up and is converted into crystallised turpentine-camphor. (List.)

Transparent, colourless, shining rhombic prisms belonging to the oblique prismatic system. Fig. 73, without pyU, m; u : u = 102° 23' ; u : u behind = 77° 37' ; < : « = 133° 48*5' ; < : t = 116° 15*5' ; i : 0 (the octohedral face) = 152° 3-5' ; o : it = 126° 58' ; o : o on the non-truncated edges = 135° 43'. The crystals are rhombic prisms with perpendicular truncation of the acute edges, and terminated by four-sided summits belonging to a rhombic octohedron, whose acute terminal edges are sometimes truncated by a pair of faces set upon the acute lateral edges of the prism (Rammelsberg, Fogg. 63, 570; see abo Wiggers, Ann, Fharm. 57, 249 ; Hertz, Fogg. 44, 190 ; List, Ann. Fharm, 67, 364.)

— The crystals obtained from a mixture of turpentine-oil with acetic acid and a small quantity of nitric acid, or of turpentine-oil and water, are different in form from those just described. (Deville.) The com-' pound is therefore perhaps dimorphous, a supposition which is corrobo- rated by Bernhardi's description. Crystallisation, augitio. Fig, 85 with t- and A- faces ; o : o = 75° 25' ; a : i = 127° 42^' ; o : t* = 136° 12J' ; ♦ : m behind = 75° 57f ; «i : tt = 126° 52^' ; « : ii = 106° 15f j t* : h = 151° 13'. Lamination parallel tot; deayage parallel to i. (Bem- hardi, N, Tr. 16, 2, 46.)

The crystals are half an inch long and 1 line hroad (1 to 2'" long and 4/"' broad, according to Buchner) united in tufts of fiye or six (Geiger, Boissenot & Persot) ; the lateral faces are longitudinally striated. (Buchner.) Harder than gypsum. (Trommsdorff.) — Sp. gr. 1*0994. (Trommsdorff.) In yacuo over oil of yitriol, they become dull, opaque, and give off 2 At. water (Deville); 9*423 p. c. Aq. (List.) (Calcu- lation, C'^oH»0* + 2 Aq. « 947 Aq.), also when heated to 100°. (Deville.^ This compound melts when heated, and gives off water above 75 (Hafner), below 100° (List), at 103°— 105° (Deville), (according to List, the dehydrated turpentine-camphor does not melt till heated to 103°), forming a

thin colourless oil, and solidifies on cooling to a milk-white, indis- tinctly crystalline mass of anhydrous turpentine-camphor. (Wiggers.)

— Crystallised turpentine-camphor dissolves readily in heated oils, whether ^«i or volatile (Trommsdorff, Buchner) ; from a warm solution in turpentine-oil, it does not separate on cooling (Hafner, Brandes), but from a solution in poppy-oil the separation takes place. (Hafner.) — According to Voget^ it is insoluble in oil of turpentine and in oil of almonds.

i

THE SO-CALLED LIQUID TURPENTINE-CAMPHOR. 263

& P r t diggers. Deyille. Rammels.

20 C 120 .... 63-16 63*8 .... 6331 .... 63*2 .... 64-05

22 H 22 .... 11-58 11-4 .... 11-55 .... 11-7 .... 10-61

6 0 48 .... 25-26 248 .... 2514 .... 251 .... 25-34

C»H»0* + 2Aq.... 190 .... lOO'OO 100-0 .... 100*00 .... 1000 .... 10000

The turpentine-camphor analysed by RammeUberg had not been recrystallised. According to BerzetiuSi it ii the hydrated oxide of a radical C^H^^

h. Aqtieous Twpentine-camphor. Crystallised tarpen tine-camphor dis- solves in 200 pts. of cold water (250 pts. according to Voget) and in 22 pts. of boiling water (24 pta., Trommsdorff; 30to 36 pts., Voget), and separates in the crystalline form from the hot solution on cooling. (Buchner, List.) Commercial turpentine-oils form turpentine-camphors of yarious degrees of solubility in water. (Bertbelot, N. Ann. Chim. Phy$, 40, 40.)

Torpen tine-camphor dissolves in hot aqneous ammonia (Brandos) ; it dissolves in dilnte aqueous alkalis, but when heated in concentrated aqueous alkalis, it melts without dissolving. (Trommsdorff.)

It dissolves in 8 — 10 pts. of ether. (Voget.)

It dissolves at 10° in 7 pts. of alcohol of 85 per cent.^ in 10 to 12 pts. of 86 p. c. alcohol, and in 5 — 6 pts. of boiling alcohol. The solution of anhydrous turpentine-camphor in alcohol yields crystals of the hydrated

compound. (Deville.) According to some statements, the solution becomes turbid when mixed with water; according to others, it does not.

Turpentine-camphor dissolves in acetic acid. (Boissenoi & Persot.) The solution is not rendered turbid by water (Brandes); wheq mixed with water, it deposits unaltered turpentine-camphor. (Trommsdorff.)

B. The so-called Liquid Turpentine-camphor.

C*»H»K)« = C»H",2H0.

MonohydraU d*i9senee de tir€bentAine, (Deyille.) BihySrate d*esitnc€ de Urt' ienlhine. (Berthelot.)

A mixture of oil of turpentine and alcoholic nitric acid for the pre- paration of solid turpentine-camphor having been kept for three months excluded from the air, and then exposed to the air, did not deposit any solid turpentine-camphor, but on addition of water, yielded liquid tur- pentine-camphor in the form of an oil, which, after being distilled, was found to be C^H^^O'. (Berthelot.) The same liquid turpentine-camphor is constantly produced in the preparation of the solid camphor, as described at page 259, 2, the mother-liquor which remains after the sepa- ration of the solid compound^ yielding by distillation, between 200° and 220^, a liquid product which turns the plane of polarisation to the left, and appears by analysis to be a solution of solid in liquid turpentine-camphor. (Berthelot.)

The liquid compound acts on polarised liffht like oil of turpentine. Rotatory power to the left = 42*4^. (Berthelot.)

264 PRIMARY-NUCLEUS C»HW.

Deville. Berthdot.

20 C 120 .... 77-9 76-4 .... 782

18 H 18 ..., 11-7 11-6 .... 12-1

2 0 16 .... 10-4 12-0 .... 9-7

C»HMO» 154 .... 1000 1000 .... lOO'O

In presence of water, it appears to be capable of passing, under cir- cumstances not precisely understood, into solid turpentine-camphor. Hydrochloric acid gas converts it into bihydrochlorate of turpentine- oil.

C. TerpinoL

C»H",HO or C*»H»,2H0.

M<mokydrat0 tTeuenee de iiribenthine, (Bertbelot, Gerhardt.) First prepared by WiggerSi ezunined and named by list.

^Bbrmatian, 1 . From turpentine-camphor (p. 258). a. By the action of hydriodic acid. (Wiggers.) — b. By continued boiling of the aqneoas solution with the stronger acids, in smaller quantity also by the weaker acids, e, g., tartaric, oxalic, benzoic, or sulphurous acid, acid sulphate of potash, or acid tartrate of soda. (List.) — c. By heating the camphor with chloride of zinc to 100**, with chloride of ccUciunij fluoride of calcium, chloride of strontium, or chloride of ammonium, to 160 — ISO**, or with iodide of ammonium to 250°. (Berthelot.) — 2. From bihydro- chlorate of turpentine-oil by boiling with water and alcohol (List), with alcoholic potash. (Berthelot.)

Freparation, Turpentine-camphor is heated for some time with con- centrated hydriodic acid nearly to the boiling point ; the supernatant oil which forms at 100° is distilled, washed and rectified with water^ and dehydrated by agitation with chloride of calcium. (Wiggers.) — 2. A hot aqueous solution of turpentine-camphor is treated with a small quantity of hydrochloric acid (or with a drop of oil of vitriol to 11*5 grm. of the turpentine-camphor) ; the turbid mixture is distilled, and rectified with water containing hydrochloric acid if it contains unaltered oil of turpentine ; the oil which has passed orer is dehydrated with chloride of calcium ; and the portion which in the rectification goes over at 168'', is decanted and collected. (List.)

Properties, Colourless, strongly refracting oil. (Wiggers.) Sp. gr. 0'852. Boiling point 168^ (List.) Has an agreeable odour of hyacinths, especially when much diluted. (List.)

Wiggers. List. Berthelot

20 C 120 .... 82-7 82-95 .... 82-98 .... 82-5

17 H 17 .... 11-7 11-64 .... 1176 .... 11*9

O 8 .... 5-6 5-41 .... 5-26 .... 6-6

C^W^O 145 .... 100-0 100-00 .... 10000 .... lOO'O

According to Berzelios, it is the oxide of a radical C^H^^

ARTIFICIAL CAMPHOR. 265

Decompositions. 1. Distilled with dcid chromaU of potash aud sul- phuric acidj it yields acetic acid. 2. With hydrochloric add gas, it assumes an amethyst-red colour, ultimately becoming darker; on con- tinuing the passage of the gas, crystals of bihydrochlorate of turpentine- oil separate in such quantity that the liquid becomes nearly solid. The same reaction is proauced by moderately concentrated a<^ueous hydro* chloric acid. (List.)

8. With Hydrochloric Acid, Oil of turpentine absorbs, with rise of tempera- ture, 50 per cent, of hydrochloric acid gas (Thenard), 363 toIs, at 22^, aud 0*724 met.

atmospheric prenmre.

A, Monohydrochlorate of Tnrpentine-oil. Artificial

Oamplior. C«>H«Ha.

Sahiouret Terpenthindl ; fetter kUnttlieher Chhreampher ; talzsaures Dadyl (Blanchet & Sell); sahtauree Canqthen (Sonbeiran & Capitaine, and Derille); Hydrochh' rate de ean^hine (Laurent); Monohydroehhraie eolide d'eseence de t^rSbenihene, (Gerbardt.) Disoorered in 1803 by Kindt, first described by Trommsdorff, inYestigated by Cluelj Chomet & Boullay^ afterwards by Damas and others.

Formation. 1 . By the action of hydrochloric acid gas an oil of tur- pentine (Kindty Trommsdorff), or, on a solution of 1 vol. oil of turpentine in 2 vols, bisulphide of carbon. (Berthelot.) Hydrochlorate of terebene is formed at the same time. (Soubeiran St Capitaine.) — 2. When 1 pt. of the liquid product obtained by saturating with hydrochloric acid gas a mixture of 1 vol. oil of turpentine and 2 vols, chloroform or acetone, creosote, acetic acid, butyric acid, butylate of ethyl, olein, oleic acid, or fusel-oil (or by saturating with hydrQchloric acid gas, oil of turpentine altered by oil of vitriol), is treated with 5 pts. of nitric acid, a violent action takes place, sometimes giving rise to explosion ; and when it is ended, artificial camphor is found as a sublimate in the neck of the retort. (Berthelot) — 3. By heating chlorinated oil of turpentine. (Deville.)

Preparation. 1. The gas evolved from 1 pt. of decrepitated common salt ana j- pt. oil of vitriol, is passed through 1 pt of oil of turpentine, which thereby becomes yellow and transiently turbid, deposits red drops of liquid, then becomes very hot (without rise of temperatare, according to Kindt), acquiring a darker and ultimately a red-brown colour ; it is to be set aside cold for 24 hours, and the resulting crystals separated from the acid mother-liquor. (Trommsdorff.) The oil must be well cooled; it increases in bulk by ^tb. (Olnzel.^— 2. Dry hydrochloric acid gas is passed to saturation into rectified oil of turpentine cooled from without, and the crystalline masses which separate [^after some hours are collected. (Oppermann.)

The portion of the oil which remains liquid is not converted into artificial camphor on continuing the passaffe of the gas (Trommsdorff, Oppermann), but deposits a small additional quantity of it when cooled to —10^ (Soubeiran & Capitaine.) The crystalline mass formed by the hydrochloric acid gas is dissolved or converted into a viscid oil by the portion which remains liquid, even at — 5^ ; the liquid must, therefore,

266 PRIMARY-NUCLEUS C»HW.

be quickly decanted from the crystalline mass, and the latter left to drain at a low temperature. (Hertz.) The most abundant formation of artificial camphor by the action of hydrochloric acid gas, takes place between — 30° and 4- 35**; within these limits, the crystals, proauced are always the same, thongh they vary in quantity; below — 30^, and at + 60° and + 100°, no crystals are produced. (Berthelot.)

Purification, 1. Artificial camphor is freed from adhering mother- liquor, first by draining, then by pressure (Trommsdorff ), or it is exposed to the air (Th6nard), or washed with water or aqueous potash (Cluzel) ; washed with alcohol and dried by exposure to the air. (Dumas.) — 2. It is sublimed : either alone, or repeatedly with 2 pts. of carbonate of lime (Trommsdorff), three times with hydrate of lime (Gehlen), or with an equal quantity of dry ash or porcelain clay, or charcoal powder (Glutei) ; with chalH and chloride of calcium at 30 — 40. (Oppermann.) — It decomjsoset when sublimed either alone or mixed with chalk or qaicklime. (Dumas.) — 3. By recrystallisation from alcohol. (Gehlen.) By drying the washed crystalline mass in the water-bath, and subliming it at 100"* mixed with burnt lime (Blanchet & Sell), by melting the expressed crystalline mass in the oil-bath. (Dumas.) — 4. By precipitating its alcoholic solution with water, washing the precipitate and drying it in the oil-bath till it melts, or in vacuo. (Dumas.) — 5. By boiling its solution with oxide of silver till the adhering hydrochloric acid \b removed, cooling the concentrated and filtered solution, and drying the separated crystals in vacuo. (Dumas.)

Artificial camphor is a mixture of isomeric bodies which differ only in their optical characters, and correspond to the different isomeric com- pounds used in their preparation, each of which produces only one artificial camphor distinguished by peculiar optical properties. (Ber- thelot.)

The quantity of artificial camphor obtained varies according to the origin of the turpentine-oil used in its preparation. — Oil from the Scotch fir yields but slowly a small quantity of artificial camphor (Hagen) ; that from the branches of the spruce fir, after treatment with potassium, yields none, even at 0°. (Wbhler.) Oil of turpentine heated with oxalic acid to 100^ for 130 hours, still yields artificial camphor; but the last pro- ducts of distillation of a French oil of turpentine which passed over between 240° and 280°, yielded none. (Berthelot.) — Trommsdorff obtained 26'5 p. c. artificial camphor; Cluzel 47 ; Oppermann more than 50; Berthelot obtained 51 p.c. at 0°, 67 at 35, Dumas 100'; Thenard, 110 per cent.

Properties, White, semi-transparent flocks (Trommsdorff), without crystalline form (Blanchet <& Sell) ; when obtained by sublimation, it forms needles united in tufts (Cluzel), bright feathery, shining ]amin», which may be kneaded like wax. (Oppermann.) — Melts at 115°, boils at 165°, but not without decomposition. (Blanchet & Sell.) — Rotatory power right or left and of various strength, depending upon that of the oil of turpentine from which it has been prepared. (Berthelot.) The rotatory power calculated for a specific gravity s 1 jg 34*07° to the left. (Soabeiran & Capitaine.) Prepared from a >ample of Freoch oil of turpentine distilled between 80** to 100" in Tacno, it had a rotatory power = 23'9'' to the left ; from the distillate of the tame oil which passed over above 100**, it rotated 23*9^ to the left; from the last dis- tillate of the same ofl, 22*3" to the left. The artificial camphor prepared from the

ARTIFICUL CAMPHOR. 267

most volatile portion of a sample of English oil of turpentine, had a rotatory power — 9'9*to the right; from the less volatile — 42 to the right; prepared from American oil of turpentine, 9** to the right. (Berthelot.) It smells like conmion camphor^ sometimes also like tarpontine ; its odour is generally less powerful than that of camphor. Its taste is aromatic, but not so pungent and bitter as that of camphor. — It does not redden litmus.

Dnmas.

Blanchet & SelL

20 C 120 .... 69-6 70-35 .... 70*2

17 H 17 .... 9-9 9-95 .... 100

CI 35-5 .... 20-5 19-85 .... 19*5

C»H",HC1 172-6 .... 1000 10015 .... 997

The hydrocarbon which, in combination with hydrochloric acid, forms artificial camphor^ is a peculiar constituent (called dadyl by filanchet 8t Sell,) existing ready formed in the oil of turpentine (Th^nard), having a composition different from that of common oil of turpentine (Oppermann), richer in hydrogen. (Gehlen.) Under the influence of hydrochloric acid upon oil of turpentine, camphene is produced, which unites with the hydrochloric acid to form artificial camphor. (Soubeiran & Capitaine. ) Oil of turpentine unites with hydrochloric acid without previous alteration. (Deville.y Artificial camphor is C^H^C1,H', the hydrogen-compound of chlorinated oil of turpentine. (Gm.)

Decompositions. 1. Artificial camphor when A^o/ed, partly sublimes unaltered, and is partly decomposed, with evolution of hydrochloric acid gas. (Gehlen, Th^nard, Damas ) It may be set on fire in a candle- flame (Saussure) ; it bums, even floating on water, with a green- edged flame, giving ofi* hydrochloric acid. (Trommsdorff.) — When it is distiued, or when its vapour is passed through red-hot tubes, a large Quantity of hydrochloric acid gas is evolved. (Gehlen, Th6nard.) — 2. It decomposes but slightly with water or absolute alcohol at 170^, completely with a larger quantity of aqueous alcohol at 135°, or when repeatedly heated with 60 p. c. alcohol to 150 — 160^, forming hydrochloric acid, a small quantity of gas which bums with a greenish flame, and an oil precipi table by water. TButtlerow, Chem.Centr. 1856, 406.) — 3. Heated with oil of vitriol, it is dissolved, with evolution of sulphurous acid. (Blanchet & Sell.) — 4. Chlorine gas converts it slowly, and with slight evolution of hydrochloric acid, into a liquid which is coloured yellow by chlorine, and easily decomposes, often with explosion, into hydrochloric acid and crys- tallised chlorinated oil of turpentine. (Deville.) — 5. Ordinary nitric acid neither dissolves nor decomposes artificial camphor (Cluzel) j con- centrated nitric acid dissolves it, forming a red-brown solution which gives ofl nitrous gas (Oppermann, Blanchet & Sell), as well as chlorine. (Thlnard.) It is rendered turbid by water. (Cluzel.) — 6. Heated with alcoholic potash to 150 — 160°, it decon^oses slightly, with formation of chloride of potassium. (Buttlerow.) Potash abstracts from its alcoholic solution a small quantity of hydrochloric acid. (Thenard, Oppermann.) — 7. When the vapour of artificial camphor, mixed with amrnonia gas, is passed through red-hot tubes, a volatile oil is formed, together with charcoal. (Blanchet <& Sell.) — 8. When it is distilled 5 or 6 times with liine, or when its vapour is passed over red-hot lime, the products are chlo- ride of calcium, water, and volatile camphilene. (Oppermann, Dumas.) — Sublimed with chalk or white bole, it yields an oil smelling of turpentine, a brown acid water, and hydrochloric acid gas; when sublimed with hydrate of lime, it yields a limpid oil which crystallises on cooling, and an add limpid liquid. (Gehlen.)

268 PRIMARY-NUCLEUS C^W\

9. Alooholio sulphocyanide of potassium, when repeatedly heated with the alcoholic solution of artificial camphor to 150 — 160"^, converts it into a liqaid, which, on addition of water^ deposits an oil having a disagree- ahle alliaceous odoar, and coutaining sulphur and nitrogen. Svlphocyanide of silver appears to act in like manner. (Buttlerow.) — 10. Chloride of tine decomposes it at 100°, with evolution of a gas containing hydro- chloric acid. (Berthelot.) — 11. Its aqueous solution is not altered by nvtraie of silver,

12. Heated for 30 — 40 hours in sealed tubes with 8 — 10 pts. of dry soap, or 2 pts. henaoate of soda, to 240 — 250^ it yields camphene. (Ber- thelot, CompL rend, 47> 26 ; abstr. Ann, Pharm. 110, 367 ; InttH. 1858, 52 j Cim<f»/o, 7, .161.)

Combinations, Artificial camphor imparts its taste to water. (Clnzel.) — It dissolves in 3 pts. of alcohol of sp. gr. 0*806 at 14° (Saussure) ; the solntion is rendered milky by water. (Trommsdorff. — It dissolves readily in oil of turpentine and oil of almonds. (Trommsdorfif.)

B. Bihydrochlorate of Turpentine-Gil. C^H'«,2HQ.

atroneneamphor (Deville), Bihydroekloraie d^ essence de iSrSbenihine (Berthelot), BihydrocMorfUe tolide d* essence de tfy^benthine, (Gerhardt.)

Formation, 1. By the action of fuming hydrochloric acid on oil of turpentine. (Berthelot.) — 2. By the action of hydrochloric acid gas or fuming hydrochloric acid upon crystallised or fused turpentine-camphor or terpinol. (Deville, List.)

Freparalion, 1. A thin lajrer of oil of turpentine is poured upon fuming hydrochloric acid, the liquid left to stand, at first with frequeut agitation, and the small crystals which separate after about a month are collected. The solution again exposed to the air deposits more crystals, and often likewise contains artificial camphor, which may be separated from it by nitric acid. (Berthelot.) — 2. A solution of oil of turpentine in alcohol, ether, or glacial acetic acid, is saturated with hydrochloric acid gas, mixed with water, and left to itself in a dish exposed to the air ; and the crystals which separate after a few hours are collected and dried. — Another mode of preparation is to saturate with hydrochloric acid gas a solution of 1 vol. turpentine-oil in 6 vols, wood-spirit, or 2 vols, acetone chloroform, creosote, or butyric acid, and leave it to evaporate at the temperature of the air. (Berthelot.)

Properties, Bihydrochlorate of turpentine-oil possesses all the pro- perties of the isomeric compound, lemon-camphor (Deville, Berthelot), excepting that the latter crystallises in small, rather elongated tables, and is less soluble in alcohol than bihydrochlorate of turpentine-oil, which crystallises in rhombic tables and dissolves with great facility in alcohol. (List.)

OIL OF TURPENTINE. 269

20 C	.... 120	.... 57-4 . 8-6 . .... 340 .	1. Deville. 2. List. 57-5 .... 67-0 8-8 .... 8-8 34-4 .... 34-4	3. Berthelot. .... 55-8
18 H		.... 9-0
2 CI	.... 71	.... oo'o
C»HW 2HCI ....	.... 209	.... 100-0 .	100-7 .... 100-2	.... 98-1

1 and 2 prepared from turpentine-camphor; 3, from tarpentine-oil, by the action of hydrochloric acid gas.

Decompositions, Tlie compound gives ofi hydrochloric acid when heated, (Deville.) — Boiled with water or alcohol (List), with alcoholic potash (Berthelot), it is resolved into hydrochloric acid and oil of turpen- tine. — When treated with potassium, it yields an oil haying the odonr of lemons. (Deville.)

With Jffydrobromie Acid, — Ht/drohromate of Turpentine-oil,

C**H*',HBr. Bromwatsersioff-saures Terpenthinol, Fester Bromcampher, Bront' hydrate de eamphene, (Deville.) Monobromhydrate solide d'estenee de tMbenthine,. (Gerhardt)

Formation. When oil of turpentine is acted upon by hydrobromic acid, this compound separates in the crystalline form, while hydrochlorate of terebene remains in solution.

Preparation, Oil of turpentine is saturated with hydrobromic acid^ and the mixture is exposed to the air so that the excess of acid may evaporate, and then cooled some degrees below 0°. The crystals which separate are collected, their quantity often exceeding that of the oil of turpentine used ; the mother-liquor is left to drain at a low temperature, and the crystals are pressed between bibulous paper, recrystallised from alcohol, and again strongly pressed.

Properties, This compound exactly resembles artificial camphor in appearance, crystalline form, and odour.

20 C 17H. Br.

	Deville.
	fneon.
120 .... 56-24 ...	66-06
1/ .... 7*ol ...	•t... 7*95
80 .... 35-95 ...	35-95

C»HW HBr 217 .... 100-00 9996

It dissolves in alcohol^ the solution, when exposed to the air, turning rod from liberation of bromine. (Deville.)

With Hydriodic Add, — Hydriodate of Turpentine-oil, C*®H",HI. — JodwoMseretofMtturee Terpenthinol, (LQwig.) lodhydrate de Camphkne, (Deville.) Monoiodhydrate d' essence de iiribenthine, (Gerhardt.)

Preparation, Hydriodic acid gas is passed into oil of turpentine, and the dark red, fuming, heavy liquid is freed from excess of acid by chalk, from excess of iodine by potash.ley, weak alcohol, or mercury, and from adhering water by chloride of calcium. (Deville.)

270 PRIMARY-NUCLEUS C»H»«.

Properties. Colourless oil, which does not solidify even at several degrees below 0°, has a sp. gr. of 1*5097 at 15°, and turns the plane of polarisation to the left. The rotatory power cannot be exactly deter- mined because the compound very soon loses its transparency. (Deville.)

Derille.

20 C 120 .... 46-0 ....... 45-99 .... 46-36

17 H .^., 17 .... 6-4 6-35 .... 6-56

I 127 .... 47-6 47-66 .... 47-80

C»H",HI 264 .... 1000 10000 .... 10072

It is a mixture of hydriodate of turpentine-oil and hydriodate of terebene, both of which are liquid. (Deville.)

Decompontioju, It decomposes quickly when exposed to the air, depositing iodine, absorbing oxygen, and turning black. When heated, it yields a heavy liquid distillate, together with iodine and hydriodic acid. (Deville.)

With hydrocyanic acid, oil of turpentine forms a heavy oil which sinks to the bottom, smells of hydrocyanic acid and camphor, may be freed from the excess of acid by washing with potash-ley, but not by washing with water, and afterwards recovers its original odour. (Ittner, Beitr. z. G. d. Blausaure, 1809.)

Phosphorus dissolves in warm oil of turpentine, and the solution solidi- fies completely to a spermaceti-like mass, consisting of a loose compound of phosphorus and oil of turpentine, which easily resinises on exposure to the air. (Jonas.) The smallest quantity of phosphorus in oil of turpentine may be easily recognized by the phosphorescence produced on adding oil of vitriol. (Jonas, Ann. Pharm, 34, 239.) Phosphorus does not shine in vapour of oil of turpentine, and may be boiled with the oil without taking fire. (J. Davy, Phil. Mag. J. 1833, July, 48 ; Echw. ^%,

387.J

Oil of turpentine dissolves 5*87 p. c. o{ sidphur at 75**, about 1*35 p.c. remaining dissolved on cooling. (Payen, Compt rend. 34, 456.) It readily dissolves iodide of cyanogen (Van Dyk, Repert. 21, 223), chloride of arsenic, cJdoride of phosphorus, and chloride of sulphur, with evolution of heat and formation of a colourless liquid ; with cupric oxide, cupric hydrate, or cupric acetate^ it forms at mean temperatures a green distillate, which is resolved by heat into a brown viscid oil and a precipitate of cuprous oxide. (A. Vogel.)

Sulphurous acid is absorbed by oil of turpentine with great rise of temperature, the oil turning light yellow, remaining mobile, and acquiring the odour of the acid. (Gehlen.) It absorbs 0-16 — 02 vols, carbonic oxide gas, TT to 1-9 carbonic acid, 2-5 to 2*7 nitrous oxidt (Saussure), 2-1 to 2-6 olefiant gas (Saussure, Faraday, N, BibL Univ. 59, 144), 5 vols, cyanogen gas (Gay-Lussac), 3*25 vols, phosphuretted hydrogen. (Graham,)

Oil of turpentine dissolves but a small quantity of succinic acid, even with aid of heat; but of benzoic acid, 100 pts. of oil of turpentine dis- solve 0*4 pts., and at 100°, more than their own weight, the acid separating in the crystalline form on cooling. (Lecann & Serbut, J. P/Mrm. 9, 89.) Suberic acid dissolves at d"* in 19 pts. of oil of turpen- tine, at 20° in 16 pts., at 44-5° in 11*5 pts., at 120^ in 2*1 pts., and at

COMPOUNDS ISOMERIC WITH OIL OF TURPENTINE. 271

170° in Ipt. ; tbe last-mentioned solution becomes, on cooling, tough, glutinous, and waxy. (Brandes, Ann Pkai^m, 9, 300.)

Oil of turpentine dissolves rmns and most volatile oils. Tt dissolves -^ of stearic acid (Braconnot), and, when mixed with alcohol, it dissolves almost any quantity of oleic and other faitr/ acids (Rousseau, <7. Chim. mid, 22, 310) j it mixes with bisulphide of carbon (Lampadins), and with chloroform. (Hnraut & Larocqne, Compt, rend, 26, 1 03.)

It dissolves in 7'4 pts. of alcohol, of sp. gr. 0*84, at 22° (Saussnre) ; (according to Bouillon-Lagraugfi and Voget, the solution reddens litmus) ; in 12 pts; of alcohol, of 33° B. (sp. gr. 0*858), at 10°; in absolute alcohol it dis- solves in all proportions (Blanchet & Sell) ; in 4 vols, alcohol of sp. gr. 0*83; in 5 vols, alcohol. (Auduard, J, Chim. mid. 19, 717). — 5 vols, oil of turpentine mix with 1 vol. alcohol; the mixture is not clouded by water, and is but slowly deprived of its alcohol when water is poured upon the mixture. (Vauquelln, BerzeL Jahresbr. 1824, 3, 181.) — It dissolves in acetone more readily than in aqueous alcohol. Wood-spirit or alcohol, diluted with so much water as to render it incapable of dissolving oil of turpentine, dissolves it after addition of a small quantity of benzene. (Mansfield, Cliem. Soc. Qu. J. i, 263.) — Oil of turpentine dissolves in wood-spirit in all proportions, and water added to the solution throws down the oil with milky turbidity. (Gmelin.)

Oils isomeric with Oil of Turpentine.

A. Products of the transformation of Oil of Twpeniine.

1. Camphene.

Berthelot. (1858.) Compt. rend. 47, 266; abstr. -4wn. Pharm. 110, 367. — Inst. 1858,52; Cimento, 7, 161; Liebig ds Kopp's Jahresber, 1858, 441.

Pormation and Preparation. — Monohydrochlorate of tnrpen tine-oil 18 heated with 8-10 parts of dry soap or 2 pts. benzoate of soda in sealed tubes to 240^—250° for 30 or 40 hours ; and the product is distilled till white vapours appear, then rectified, the portion which passes over from 160° to 180° being collected and pressed between bibulous paper after solidification.

Properties. Crystalline, camphor-like mass, which melts at 46^ and boils at about 160°.

Platinum-black converts it into camphor (or a substance very much like it). With hydrochloric acid, it forms a crystalline compound (mono- hydrochlorate of turpentine-oil ?) (Berthelot.)

2. Isoterebenthene*

Berthelot. (1853.) iV. Ann. Chim. Phys. 39, 16 ; abstr. Compi. rend* 26, 428; Ann. Phaim. 88, 347; J. pr. Chem. 59, 141.

Fm^mation. By continued heating of oil of turpentine under pres- sure.

272 PRIMARY-NUCLEUS C»ir«,

Preparation. Englisli oil of tarpentine (from Pinus Australts) is heated for three hours to 300° in a sealed tube ; the portion which goes over below 250^ is redistilled and rectified ; and the distillate obtained between 176*" and 178" is rectified.

Pi^opertuB. Thin^ colourless, strongly refracting liquid, of sp. gr. 0*8432 at 22°, boiling between 176° and 178°, and having a IsBvo-rotatorj power = 10° (Tarying however with the duration and intensity of the heating, and the nature of the oil of tarpentine used in the preparation). It smells like stale

lemon-peel.

Berthelot.

20 C 120 .... 88-23 88-1

16 H 16 .... 11-77 11-7

C»HW 136 .... 10000 99-8

The laevo-Totatory power of isoterebenthene is reduced from 8*8° to 7*0°, by heating the liquid to 100° for 30 hours with aqueous oxalic acid. •^- In 33 days it absorbs 16*8 p. c. oxygen, and gives off 1 p. c. carbonic acid.

Combinations. With Water. — When a mixture of 4 pts. isotere- benthene, 3 pts. alcohol, and 1 pt. nitric acid is left to evaporate in a shallow basin exposed to the air, crystals are formed in the course of a week, resembling turpentine-camphor in all their properties, while the mixture acquires the odour emitted in the formation of turpentine- camphor.

With fft/drochlonc acid. — Isoterebenthene absorbs 34 p. c. hydro- chloric acid gas at 24°, and forms a liquid mixture of hydrochlorate of terebene and bi-hydrochlorate of turpentme-oil :

3C«H« + 4HC1 = 2(C»HWHCI) + C»H»«,2Ha.

In contact with fuming hydrochloric acid for four weeks, it forms crystals of bi-hydrochlorate of turpentine oil.

Isoterebenthene absorbs 143 p. c. gaseom fluoride of boron at 23% assuming a darker colour and becoming tenacious. (Bert helot.)

3. Metaterebenthene.

Bbbthblot. (1853.) i\r. Ann. Chim, Phys. 39, 19.

Formation. By the prolonged action of heat on Englisli oil of tur- pentine under pressure, the first product of the action being chiefly isoterebenthene.

Preparation. When the product obtained in the preparation of isoterebenthene, as above described, is distilled, and the liquid remaining after the portion which distils below 250° has passed off, is

TEREBENE. 273

heated for several hours to 360°, and the portiou which volatilises below 360° is distilled off, the residue consists of metaterebenthene, the quantity of it being greater ia proportion to the time during which the oil of turpentine was heated.

Properties. Yellow, viscid oil, of sp. gr. 0-913 at 20^ and volatilising without decomposition above 360°. Has a strong and unpleasant odour^ especially when heated.

ComhincUions. It absorbs in 33 days, 9*7 p. c. oxygen, gives off 0*3 p. c. carbonic acid, and assumes the consistence of colophony. — It absorbs only half as much hydroddoric add ga» as isoterebenthene, viz., 17*7 p. c. at 24® corresponding to the compound 3C**H",2HC1.

4. Terebene.

Blanciiet & Sell. (1833.) Ann. PJiarm. 6, 259.

Deville. Ann, Clam, Fhys. 75, 37; J.pr, C/tem. 22, 82 j Ann, Pharm,

37, 176; J. Pharm. 26, ^55^ abstr. Compt. rend. 12, 394; N. Ann.

Chim. Phys. 21 y 85. SouBEiRAN & Capitaine. J. Pha)*m. 26, 1. Bertuelot. i\r. Ann. Chim. Phys. 88. 42; further 39, 14 and 21;

further 40, 5.

JPormation. — 1. By distilling oil of turpentine with oil of vitriol or anhydrous phosphoric acid ; also, together with colophene, by distilling cnrstallised or fused turpentine-camphor with anhydrous phosphoric acid. (Deville.) — 2. By the action of hydrochloric acid gas, hydrobromic acid gas, chlorine, bromine, or iodine, upon oil of turpentine, uniting however immediately with the acids or salt-radicals. (Deville.) — Only a portion of the oil of torpentine is oonyerted into terebene, which moreover cannot be separated without alteration from the componnds produced by the reaction. (DevUle.) — No terebene is formed by the action of hydrochloric acid ; for the hydrochlorate, which is formed in addition to the artificial camphor, possesses a rather strong rotatory power which pure terebene does not. (Berthelot.) This rotatory power is due to artificial camphor, which is always mixed with it. (Deville.)

Preparation. Oil of turpentine is mixed slowly and by drops with «f\f of oil of vitriol contained in a cooled vessel ; the red viscid mixture Is stirred and left to settle ; the liquid is decanted, after 24 hours, from the black sediment produced at the same time by the acid, and distilled at a temperature not above 210'^, whereupon sulphurous acid is evolved, and the colophene produced at the same time remains behind. To convert the still unaltered turpentine-oil in the distillate into terebene, it is repeatedly distilled with fresh quantities of oil of vitriol till the product has quite lost its rotatory power; and the distillate is washed with aqueous carbonate of soda, then with water, and dehydrated by chloride of calcium. (Deville.)

Properties. Colourless oil, resembling oil of turpentine, without rota- tory power, and having a rather agreeable odour of thyme. (Deville.)

vol. XIV. T

274 PRIMARY-NUCLEUS (^W^

Sp. gr. 0-864 at 8°. Boiling point 156°. (Prankenheim, Fogg. 72, 422.) Latent heat for the unit of weight 67*2. (Frankenheim.) Refracting power 1-474 (Derille, Fogg. 51, 433), V479 (Becquerel & Cahours, Fogg. 51, 427). Vapour-density = 4-812 (by calculation 47144 oomp. page ).

Deville. 1. 2.

20 C 120 .... 88-24 88-49 .... 88*1

16 H 16 .... 11-76 11-49 .... 11-9

C»H« 136 .... 100-00 99-98 .... 100-0

1. Prepared from oil of turpentine with oil of ntriol. — 2. From turpentine- camphor with anhydroaa phosphoric add.

Decompositions. The compound remains unaltered after two hours' heating to 300°. (Berthelot.) By chlorine it is converted, with evolution of hydrochloric acid, into chl&ivterehene ; by bromine, with evolution of hydrobromic acid, into hromoterd>en€. ^Deville.) — With a small quantity of iodine, it turns dark green, becomes heated, and loses its transparency, but does not deposit charcoal or give off hydriodic acid. When terebene is distilled with excess of iodine, hydriodic acid escapes, and an iodated viscid liquid distils over, which is easily decolorised by potash, and probably consists of iodoterebene. (Deville.) — When heated with oil of vitriol y it is converted into snlphoterebic acid. (Gerhardt, Gompt, rend. 17, 314.)

Combinations. Terebene does not form a hydrate, even after half a year's contact with water. (Deville.) — It absorbs gcueoiu Jliumde of boron without alteration. (Berthelot.)

With Hydrochloric acid. — a. Bihasic Hydrocklorate of Terebene. Sou9-chlorhydrate de i6r€bene (Gerhardt) ; Monochhrhydrate de t4r€b^»e, (Deville.) — 2C^H^',HC1. — Produced when hydrochloric acid gas is passed into terebene. — Mobile oil of sp. gr. 0*902 at 20% without rotatory power ; smelling strongly of terebene, and slightly of hy4rochlorate of terebene. (Deville.)

Devine. mean.

40 C 240-0 .... 78*16 78-28

33 H 33-0 .... 10-53 10-68

CI 35-5 .... 11-31 11-04

2C"HW,HC1 308-5 .... 100-00 100-00

b. Hydrocklorate of Ter^>ene. — PlUstiger kUtutlieher Camphor i saktmatt Peueylen (Sonbeiran & Capitaine); Mlztaures Peucyl (Blanchet & Sell); Biehhr^ hydrate de T€r&>hi€. (Deville.) Manochhrhpdrate Uauide d' essence ds tirSbeniMne, C»H^HCl.

Freparation. From the liquid which remains in the treatment of oil of turpentine with hydrochloric acid gas, after the separation of the artificial camphor. — 1. By distillation per se (Blanchet & Sell), where- upon hydrochloric acid and a dark-coloured oil pass over, and charcoal remains. (Trommsdorff, A. Tr. 1, 2, 132,) — 2. The liquid is heated for

TEREBEN£. 275

a short time in the water-bath ; the artificial camphor which separates on cooling is removed ; the liquid is neutralised with chalk and cooled to — 10", wherenpon an additional quantity of artificial camphor separates, but not all. The liquid, which is 83rrup7 in the cold, but very mobile at 15 — 18°, is decanted, mixed with 2 vol. alcohol, decolorised by boiling with animal charcoal, precipitated by water, and the oil which falls to the bottom is dehydrated by chloride of calcium. (Soubeiran & Capi- taine.)

Properties, Colourless oil, of sp. gr. 1*017, boiling at 19*92" (Soubeiran & Capitaine), at 28^ (Berthelot.) Turns the plane of polarisation to the left Refracting power = 1*4848. (Deville, Pogg, 51, 433.)

20 C	... 120*0 ... 17-0	.... 69*6 .... 20-5	Soubeiran & Capitaine. 70*3
17 H	9-9
CI	••• Wv*d	19-8
(PHWHCl	... 172-5	.... 100-0	100-0

Isomeric witb mono-hydrochlorate of turpentine-oil.

Decompositions, 1. When set on Jlre, it bums with a green-edged flame and an odour like that of benzoic acid. (Blanchet & Sell.) — 2. When chlorine gas is passed into it, it gives off vapours of hydrochloric acid, and thickens like oil of turpentine treated with chlorine, but without depositing crystals like the latter. (Blanchet & Sell.) — 3. Hydrochloric acid gas does not convert it into artificial camphor. (Cluzel, Ann. Chim, 51, 270.) — 4. When hydrochlorate of terebene is distilled with hydrate of limey hydrochloric acid and terebene are produced (Soubeiran & Capi- taine); the product is a thin, aromatic oil. (Geblen,.^. Gehl, 6,458.) No terebene is produced in this reaction, inasmnch as hydrochlorate of terebene cannot be freed from artificial camphor, even by repeated distillation and cooling ; and moreover, the lime used in the reaction, or the temperature which it requires, exerts at the same time a decomposing action on the separated terebene. (Deville.) — 5. .^/co/to^ decomposes hydrochlorate of terebene, especially when heated with it^ forming an acid product and an oil which is precipitated by water. (Blanchet & SeU.)

c. Hpdroehhraie if TVreimt with Bihydrochloraie iff TurpenHne^oil. C»H» 2Ha -i- 2 (C^HiSHCl.) The liquid whieh remains after the separation of hi- hydrocMorate of turpentiiieH)il» firom a solution of the oil in alcohol or glacial acetic acid saturated with hydrochloric acid gas (p. 268), and that which is produced by the action of hydrochloric add gas on isoterebenthene (p. 271)f contains 24*3 to 25-7 p. c. chlorine, and may accordingly be regarded as a compound of 2 At. hydrochlorate of terebene with 1 At bihydrochlorate of turpentine-oil; or as a compound of bihydrochlorate of turpentine-oil with artificial camphor, inasmuch as the former separates when the liquid is exposed to the air, perhaps after the Tolatilisation of the latter, and moreover artificial camphor and bihydrochlorate of turpentine-oil liquefy on being miied. But the liquid produced from French oil of turpentine and glacial acetic acid yields, when treated with nitric acid» a large quantity of turpentine-camphor, and is therefore not identical with a mixture of artificial camphor and bihydrochlorate of turpentine-oil, which under these circumstances does not produce artificial camphor. (Berthelot.)

Hydrochlorate of terebene dissolres in alcohol and ether, and is preci* pitated by water. (CluzeL)

T 2

276 PRIMARY-NUCLEUS C»H".

With Hydrchromic acid. — a. Bihasic HydrobromaU of TerAene. Soui' bromhydraie de Uridine (Gerhardfc); Monobrwaihydraie de tfyrlhene. (Deyille.) — 2C?*H",HBr. — Formed by the action of hydrobromio acid upon terebene. •— Terebene satarated with hydrobromic acid is shaken up with chalk to remoye free acid, then decolorised with animal charcoal, and precipitated by chloride of calcium. — Colourless oil of sp. gr. 1-021 at 24°, without rotatory power, smellint^ like terebene, somewhat like camphor, and becoming coloured after a while by exposure to the air. (DeviUe.)

40 C	... 240 ... 33 ... 80	•••• 9*0d ... .... 22-66	Deville. 68-63
33 H	9-53
2C»H^HBr.....	... 353	.... 10000

h. Monohydrdlyi'Omate of Terebene. — MonohnmhpdraU Uquide d*euence de UrSbenthene (Gerhardt) ; Bibromhydrate de UMine. (DeviUe.) C**H",HBr.

Formation (p. 252). The mother-liquor, alterable by exposure to the air. which remains in the preparation of hydrobromate of turpentine-oil, as described at page 26«0, is a solution of hydrobromate of turpentine-oil in hydrobromate of terebene, and likewise contains bromoterebene, pro- duced by the simultaneous liberation of bromine. The hydrobromate of terebene has not hitherto been separated from either of these liquids. — Oil of sp. gr. 1'279 at 21°, and solidifying completely at —5°. Rotatory power to the left, probably dae only to hydrobromate of turpentine-oil dissohed in it. (DeviUe.)

Deville.

20 C 120 .... 66-15 5404

17 H 17 .... 7-78 7-53

Br 80 .... 36-07 38-43

C»H",HBr 217 .... 100-00 lOO'OO

Witit Hydriodlc acid. — a. Bibasic Hydriodaie of Terebene. — Saui^

iodhydrate de UrSbene. (Gerhardt) Mono^iodhydryate de UHbine. (Deville.) — 2G*H",HI. — Formed by the action of hydriodic acid on oil of turpentine. — Hydriodic acid is absorbed by oil of turpentine with rise of temperature. The free acid is remoyed from the oil, which is dark-red after saturation, b^ shaking it up with chalk; dissolyed iodine is remoyed by agita- tion with dilute potash-ley, weak spirit, or mercury; and admixed water by chloride of calcium. — Transparent, colourless liquid of ap. gr. 1*084 at 21 ; without rotatory power. — Has an agreeable camphorous odour, and quickly acquires a dark red colour by exposure to the air. (Deyille.)

Deville. mean.

40 C 240 .... 60-59 60-87

33 H 33 .... 8-14 814

I 127 .... 31-27 30-49

* - — — — I — , _■ _ — _ _ - —

2C20HW HI 400 .... 100-00 99-50

CAMPHILENB. 277

b. Mcmchhydriodaie of Terthene. Monoiodhydraie UqtUde ffetnnei de OrS^ benihine, (Gerhardt.) Bi-iodhydraU de tMbkne. (DeyiUe.) C30H» HI. Pro-

dnced, togetber with hydriodate of turpentine-oil^ by the action of hydriodic acid upon that oil, but cannot be separated therefrom, inas^ much as both compounds are liquid* (DeriUe.)

Appendix to Terebene,

Sulphoterebic Acid.

C»H"SK)«1

TerebeniehiDrfelsUiire, prpenthnuchwrfeUaure. Formed by gently heating terebene with fuming oil of vitriol, or by dropping oil of turpentine, cubebs, pepper, lemons, or copaiba into a large quantity of oil of vitriol, but not so easily as terebene. (Gerhardt, Compt rend. 17, 313; Compt, ckim. 1845, 173.)

SidphoterebaU of Baryta. Prepared by heating terebene with oil of vitriol, saturating with carbonate of baryta^ filtering, and leaving the solution to evaporate. (Gerhardt.)

Gerhardt.

OA P	120-0 15'0	.... 42-8 .... 9*3 .... 28*8
IK TT
Ba	68*5	.... 24*2
£ DV^^.... «••...••••<	800
C»H»BaSH)« ..	.„... 283'5	.... 100-0

5. Camphilene.

Oppsbmann. (iSdl.) Poffg. 22, 199.

Dumas. Ann. Chim. Phys. 52, 400 ; Pc^^. 20, 125 ; Ann. Pliarm.

9, 56. Blanchbt k Sell. Ann. Pharm. 6« 276 ; Pogg. 29, 133. SouBEiRAN & Gapitaime. J, Pharm. 26, 1 ; Ann. Pharm. 34, 311. Laurent. Ann. Chim. Phys. (i6, 209. Dbville. Ann. Chim. Phys. 75, 74 ; J. Pharm. 26, 688.

Camphene (Damas); Dadyl (Blanchet & Sell); TSribine (Soabeiran); Camphilene (Deyille). — First prepared by Oppermann. — According to Dnmas and Blanchet & Sell, it is the base of solid artificial camphor ; according to Soabeiran & Capitaine and Devilie, it is contained therein in combination with hydrochloric acid, but without alteration.

Formation and Preparation, 1. Artificial camphor mixed with 2 — 3 pts. of qnicklime is distilled in the oil-bath ; the distillate is again mixed with quicklime ; the distillation is repeated five or six times in like manner (ten times, according to Oppermann, and Blanchet & Se]], or till the distillate no longer yields chlorine to potassium ) ; and tiie resulting oil, amounting to |ths of the weight of the artificial camphor, is freed from adhering hydrochloric acid by rectification over antimonide of potassium, which, however, is apt to eliminate hydrogen (Dnmas) and

278 PRIMARY NUCLEUS C»HK

form colophene. (Deville.) — 2. Vapour of artificial camphor is passed through a tube heated in the oil-bath to 190° — 195°, and filled with fragments of recently burnt lime ; the same operation is repeated with the distillate as long as it retains hydrochloric acid ; and the product is dried oyer chloride of ealcium. (Soubeiran & Capitaine.)

Properties. Transparent, colourless, or slightly yellowish oil (Blanchet & Sell); somewhat viscid (Oppermann). Bp. gr. 0*87 at 15"^ (Blanchet in Sell), 0*86 (Soubeiran & Capitaine); boils at 1 45'' (Blanchet & Sell), 156 (Dumas), 155° (Soubeiran & Capitaine). According to Opper- mann, it solidifies below 12^ to a transparent mass, which liquefies at the heat of the hand. (Oppermann.) — Vapour-density = 4*83. (Dumas.) It has no rotatory power. (Soubeiran & Capitaine, Deville.) Biot found that it had a Isero-rotatory power seTen dmei less than that of oil of tarpentinei bat, according to Soubeiran & Capitaine^ the camphilene which he examined contained undecomposed artificial camphor. It has a mild aromatic taste and odour. It resembles oil of turpentine in all its properties, but has a difierent odour, not however arising from decomposition by heat, since the vapour of oil of turpentine retains its odour after passing through a tube heated to 200°. (Soubeiran & Capitaine.)

Oppermann. Dumas. ^ ^^ '

20 C 120 .... 88'24 8848 .... 88*44 .... 88-61

16 H 16 .... 11*76 11-52 .... 11-56 .... 11-56

CSORW 136 .... 10000 100-00 .... lOO'OO .... 10017

Decompontions. Chlorine converts it, without evolution of hydro- chloric acid, into hydrochlorate of chlorocamphilene :

C»Hw + aCl = C»H«C1,HC1.

which, when treated with alcoholic potash, yields chloride of potassium and chlorocamphilene. The latter, if again treated with chlorine gas, yields hydrochlorate of bichlorocamphilene, which may again be decom- posed by alcoholic potash in the same manner as hydrochlorate of chloro- camphilene, yielding bichlorocamphilene, in which a further number of hydrogen-atoms may in like manner be replaced by chlorine. (Laurent) — Camphilene, treated with bromine^ becomes solid, and is probably con- verted into bromocarophilene. (Deville.) With iodine, it comports itself like oil of turpentine. (Blanchet & Sell.) By oil of vitriol and by heating with potassium in contact with the air, it is decomposed, with formation of a brown resin. (Oppermann.)

Combinations. Camphilene is not dissolved or altered by fuming nitric acid (Oppermann) ; alcoholic nitric acid converts it into a crystal- line hydrate. (Gerhardt, Traitd 3, 625.) It absorbs hydrochloric add gas rapidly, especially when heated, forming a solid (Oppermann), and a somewhat liquid compound, both destitute of rotatory power. (Sou- beiran & Capitaine.) — Fuming hydrochloric add, in contact with camphilene, forms many solid and a few liquid compounds. With hydriodic add, it forms a liquid compound. (Deville.)

Camphilene dissolves in alcohol^ etiier, and bisulphide of carbon, not in acetic acid, (Oppermann.)

COLOPHENB. 279

Appendix to Camphilene.

a. Colophene. C*oH«.

Deyillb. Ann. Chim. Fhys, 75, 66; J. pi\ Chem. 22, 158; J, Pharm. 26, 681; Ann. Pharm. 36, 102; abstr. Ctrnpt. rend. 12, 395. — N. Ann. Chim. Phys. 27, 85.

Formation. 1. In the distillation of oil of turpentine with oil of vitriol or anhjdroas phosphoric acid, also of crystallised or fused turpen- tine-camphor with anhydrous phosphoric acid, terebene being formed at the same time. — 2. Goes off, together with water, in the rapid distil- lation of colophony, charcoal being separated at the same time.

«

Preparation. 1. By collecting apart the viscid yellow oil, which, in the preparation of terebene from oil of turpentine with oil of vitriol (p. 273), passes over after the terebene has been distilled off and the heat is raised, and repeatedly rectifying it, at last over antimonide of potas- sium, whereby it is freed from an impurity resembling colophony, and from sulphur. — 2. Colophony is distilled over a brisk fire, and the yellowish distillate is purified like that obtained by the first process. Colophene thus prepared is contaminated with a body richer in carbon, which is produced by the action of the antimonide of potassium, and cannot be separated from the colophene by distillation.

Properties. Oil, colourless by transmitted light, and exhibiting by reflected light a dark indigo-blue iridescence. Sp. gr. 0*940 at 9"", 0-9394 at 25°. Boiling point between 310^ and 315°. Vapour-density = 11*13 (probably only twice as great as that of oil of turpentine, therefore = 9*526). Refracting power = 1*517 (Becquerel & Cahours, Poffg. 51, 427), 1*5212. (Deville, Poffff. 51, 433.) Without rotatory power. Smells like camphilene.

Deville. a. b.

40 C 210 .... 88-24 88*43 .... 88-1

82 H 32 .... 11*76 11*59 .... 11-9

C«H» „ 272 .... 100-00 100*02 .... 100*0

a. Prepared from oil of tnrpentiiie bj oil of vitriol ; b. from tarpentine-camphor by anhydrous phoq>horic add.

Colophene absorbs clUorine gae, without evolution of hydrochloric acid, becoming hot, and changing to a resin like colophony, which separates in yellow spherules from its solution in absolute alcohol. If, when the absorption of chlorine has ceased, the product be heated to fusion in the stream of chlorine, a large quantity of hydrochloric acid is evolved, and Deville's cJUorocolophene = C^^Cl^H** is formed, which how- ever still contains a resin removable by alcohol, and when distilled, gives off hydrochloric acid, yields a distillate of colophene and hydrochlorate of colophene, and leaves charcoal.

280 PRIMARY NUCLEUS C»H".

Hydrochlcn^ate of Colophene. Golophene absorbs hydrochloric acid gas, with rise of temperature, and acquires an indigo-colour. Hydro- chlorate of colophene gives up nearly all its hydrochloric acid when treated with chalk, and when distilled with baryta, yields Deville's colophiiene = C^^H^, which does not exhibit the dichroism of colophene, and has a refracting power for light = 1*5175. (Derille; Becquerel & Cahours, Fogg, 5 J, 433 and 427.)

b. Colophene from Camphor.

Glaus. J. pr, Chem, 25, 266.

Preparation. Camphor is distilled with an equal weight of iodine, whereupon hydriodic acid is evolved, camphine passes over at 180% and charcoal, iodine, campho-creosote and colophene remain behind. On increasing the heat, the two latter substances distil over as a bluish-greon oil, which is deprived of its creosote odour by agitation with potash, but cannot be obtained quite pure, even by distillation over lime^ and finally over potassium.

Properties, Thick, yellowish oil, with violet iridescence^ having ~a high boiling point, a mild taste, and an odour of violets.

Perhaps identical with colophene from oil of turpentine or from colophony.

Burns with a bright, very smoky flame.

Combinations. It is not soluble in vKiter or in weak alcohol, but dissolves in strong alcohol, in ether, oU of turpentine, rock-oil, and oamphine* When 2 drops of it are dissolved in 2 drachms of alcohol, the solution, after agitation with animal charcoal, exhibits a fine dark blue colour by reflected light.

6. Terebilene.

Blanchet & Sell. Ann. Fharm. 6, 250.

SuBEiRAN & Capitainb. J. Fharm, 2, 61; Ann. Pharm. 34, 311.

Deville. Ann. Chim. Phys. 75, 74; .7. PJutrm, 26, 689.

Peueyl (Blanchet & SelH; Tfy-ibilhie (Soubeiran & Capitaine ; Derille). ThU according to Blancbet & Sell, is one of the isomeric hydrocarbons which those chemists discovered in oil of turpentine. According to Soubeiran & Capitaine, it is a decomposition-product of peucylene, a body which they suppose to be formed from oil of turpentine under the influence of hydrochloric acid; according to DeTille, it is a product of the decomposition of terebene {tee page 245).

Formation and Preparation, By distilling hydrocblorate of terebene over quicklime (Soubeiran & Capitaine), and finally over potaasium (Blanchet & Sell), or by heating bydriodate of terebene witb hydrate of potasb, and rectifying tbe resulting oil over antimonido of potassium, in order to free it from iodine. (Deville.)

OIL OF BERGAMOT, 281

Propei'ties. Colonrlees mobile oil (Blanchet & Sell)^ of sp. gr. 0*86 (Blanchet & Sell, Soabeiran & Oapitaine), 0*843 at 21^ (Deville.) Boiling point 134^ (Blancbet k Sell.) Vapour-density = 4-707 (Soubeirau & Capitaine; Deville), by calculation 4-7144 (p. 245). Refracting power = 1*479 (Becquerel & Caboure, Pogg, 51, 427) j 1*4735. (Deville, Pogg, 51, 433.) Without rotatory power. Smells like tere* bene. (Soubeiran & Capitaine.)

Deville.

20 C ..^ 120 .... 88'24 88*42

16 H 16 .... 11-76 11-60

C»HW 136 .... 100-00 100-02

With hydrochloric acid, it forms a brown liquid compound. (Soubeiran & Capitaine.)

B. Natural Oih, or others related to them, (Arranged for the most part in alphabetical order.)

1. Oil of Bergamot

Vauquelin. (1817.) J. Pharm. 3, 241. Ohme. Ann. Pharm. 31, 316.

Soubeiran & Capitaine. J. Phaim. 26, 68; abstr. Ann. Phai'm, 34, 321. — •7. Pharm, 26, 509 j Ann. Pharm. 35, 313.

EMence de Bergamot.

Source. In peculiar cells in the rind of Citrus Bergamia.

Preparation. The cellular tissue of the fresh rind is torn to pieces in a funnel having its inner surface like a rasp, or on a board covered with teeth, and the oil which exudes from the lacerated cells is collected.

Properties. Yellowish, or pale greenish to dark yellow : after recti- fication with water, it becomes transparent, colourless, and mobile. (Ohme ; Zeller, Studien iiber dtherische Oele, Landan, 1 850.) — Sp. gr. 0*87 — 0*888 (Lewis, Zeller), 0*S56 (Ohme) ; after distillation with water, 0 869. (Soubeiran & Capitaine.) The first portion obtained by distillation with water, has a sp. gr. ^ 0*850, the last, 0*877. (Soabeiran & Capitaine.) Boiling point 183° (Ohme); of the first distillate obtained with water, 195^ t (Soubeiran & Capitaine.) It solidifies at a few degrees below 0°. (Lewis.) Refracting power 1*468. (Dey'iUe, Compt. rend. 11, 865.) — Rotatory power of the oil rectified with water. 25° to the right (of the first distillate, 45' right ; of the second, 38** right ; of the third, 2V right ; of the fourth, O" ; of the mixed distillate, 26'' right). (Soubeiran & Capitaine.) Of the first distil- late, 49*-396 right; of the last, 6*575 left. (Biot, Compt. rend, 11, 371 Has au

agreeable odour, less after distillation, and a bitter taste. (Ohme.) The oil IS neutral. (Zeller.) Sour from admixed acetic acid; neutral after distilla- tion withwater. (Ohme.) The Taponr of the acid-reacting oil has also a strong add reaction. (Ohme.)

282 NATUBAL OILS, ISOMERIC WITH OIL OP TURPENTINE.

Ohme. Soabeiran & Capitaine. Wohler.

a. b, c. d,

C 81'36 .... 84.98 .... 84*92 .... 73.03 .... 85*7

H 11-32 .... 10-12 .... 11-44 .... 10-83 .... 11-7

0 7-32 .... 4-90 .... 3*64 .... 16-14 .... 2-6

100-00 .... 10000 .... 10000 .... 100-00 .... 100-0

a. First disiillate: h. first distillate from a; e, last distillate; d. first distiUate of the bergamot-oil with water.

Bergamot-oil is a hydrate of oil of lemon, 3C^Hi^ + 4HO (Ohme); a mixtore of seTerai oils (Soabeiran & Capitaine ; Wohler, Ann, PAarm. 37, 137); it contains one or two oils of the formnla C^H^*, a hydrate of the same, and an oxygenated oil prodnced by the action of the air. (Sonbeiran & Capitaine.) It deposits bergaptene (p. 345) by keeping.

Decompositions. Bergamotroil burns with a luminoas flame. — 2. It dissolves iodine with effervescence and evolution of vapours, varying in colour from yellowish-red to violet, and is converted into a soft mass. (Zeller.) — 3. Miming nitric dcid colours it brown-yellow (Zeller) ; boiling nitric acid, bright green (Bonastre), and ultimately converts it into a brittle resin. (Zeller.) — 4. Oil of vitriol turns it yellow without thickening it ; afterwards, dark red to black, according to the quantity of the acid, and gives off sulphurous acid. (Brandos, Mag, Fharm, 32, 79.) — 5. With anhydrous pliosphoric add^ it becomes coloured and heated, and when distilled therewith, yields a colourless oil which smells like oil of turpentine,— rotates polarised light 4^ to the right (40° to the right before distillation), combines with hydrochloric acid, contains 88-93 p. c. C and 11-52 H, and is isomeric with citrene. The phosphoric acid is at the same time partly converted into phosphobergamic acid. (SouWiran

& Capitaine.) — 6. Bergamot-oil absorbs hydrochloric add gas with evolution of heat, acquiring a brown colour and emitting fumes in the air, and if subsequently distilled with water, yields hydrochlorate of bergamot-oil. (Ohme.) — 7. By distillation over hydrate of potash, it loses its agreeable odour. — 8. Mixed with aqueous a^iid chromate of potash and sulphuric acid, it turns brown. (Zeller.) — 9. VVith iodide of potasnum, it turns brown, the salt at the same time acquiring a yellow colour. (Hiibschmann, N. Br. Arch. 46,250.) — 10. With chlorate of potash, and a few drops of oil of vitriol, it bums with a smouldering very smoky flame, and leaves charcoal. (Vogel, Jun., Ann. Fharm. 74, 114.) 11. Distilled with 24 pts. water ana 8 pes. chloride of lime, it sives off carbonic acid with effervescence and yields chloroform. — 12. Distilled with hypobromite of lim>e, it yields bromoform. (Ghautard, Compt rend. 34, 485.) — 13. With an equal quantity of concentrated aqueous solution of bibasic acetate of lead, it turns lemon-yellow, and yields a light-coloured precipitate, (Schindler, N. Br. Arch. 41, 140.) — 14. NUroprusside of copper colours it darker and forms a grey precipitate. (Heppe, N. Br. Ardi. 89, 57.)

Combinations. 1. With Water. — Hydraied Oil of Bergamot. — C*H*0*. — The crystals which separate after four or six weeks, when 4 pts. oil of bergamot are set aside with 3 pts. alcohol of sp. gr. 0*84 and 1 pt. of nitric acid, are identical with the turpentine-camphor (p. 265) produced by like treatment of oil of turpentine. (Deville, iT. Ann. Chim. Phys. 27, 81 ; abstr. Ann. Fharm. 71, 348.)

CARVENE. 283

Aqueom Oil of Bergamot. — Oil of bergamot does not t&ke up water, even when boiled with it for a considerable time. (Soubeiran & Gapi- taine.)

2. With Hydrochloric acid, — Hydroehloraie of Bergamot -oil. — Produced by passing hydrochloric acid gas into bergamot-oil, and distilling the^ saturated oil with water, and passes over as a colourless, neutral, optically inactive oil, which smells like hydrochlorate of terebene. Sp. gr. 0-896. Boiling point 185°.

Ohme. ^?^Y^ & Capitaine.

C 78-91 .... 6300

H 10-87 .... 9-19

CI 8-34 .... 27-81

O 1-88

10000 .... 100-00

According to Ohmei it is 3C^H'^,HC1 + HO; according to Sonbciran & Capitaine, it is isomeric with hydrochlorate of dtrene.

The hydrochlorate when heated hums with a green- edged, smoky dame. — When repeatedly distilled over hydrate of potashf or burnt maj'blet it is converted into an oil having an odour of cajeput and still containing chlorine. Passed in the state of vapour over red-hot lime, it yields naphthalin, benzene, and charcoal. The alcoholic solution, added to aqueous nitrate of silver, throws down chloride of silver. (Ohme.)

Bergamot-oil dissolves in all proportions in ahsoluie alcohol; in ^ pt. alcohol of sp. gr. 0*85 (Zeller), in 2 pts. of sp. gr. 0 951 j ond in 28 pts. of sp. gr. 0*966 ; it takes up 8 p. c. alcohol of sp. gr. 0*966. (Vauquelin.)

2. Carvene.

VoLKEL. (1843.) Ann. Pharm. 35, 308. — -iww. Pharm. 85, 246;

abstr. J. pr, Chem. 60, 120. ScuwEiZER. J, pp. Chem. 24, 267; Ann, Pharm, 40, 329; abstr. Reperi.

80, 172.

Source. In oil of caraway, together with carvol. (Schweizer.)

Preparation. 1. The portion of oil of caraway, which passes over between 175'' and 178", is separated by repeated ^-actional distillation. ( Vblkel.) — Carvene caonot be separated from carvol by mere distiUation of oil of caraway, either /7er w or with potash-ley. (Schweizer.) — 2. Oil of caraway is boiled with pulverised hydrate of potash, as long as it smells of caraway, then distilled with water, till all the oil has passed over, and rectified over hydrate of potash, till the potash is no longer coloured by it. (Schweizer.) — 3. Oil of caraway is boiled with fused glacial phosphoric acid in a flask, the liquid, which distils over, being constantly poured back, until the distillate no longer smells of oil of caraway; and to purify the distillate completely from nndecomposed oil of caraway and from carva-

284 NATURAL OILS, ISOMERIC WITH OIL OP TURPENTINE.

crol produced at the same time, it is rectified over hydrate of potash^ till that substance is no longer coloured by it. Oil of caraway thus treated yields more than a third of its weight of caryene. (Schweizer.) — 4. Oil of caraway is boiled with iodine, and the distillate continually poured back, as long as hydriodio acid continues to escape, and the oil which passes oyer is rectified, the first portion of the distillate being collected apart. (Schweizer.)

Properties, Transparent, colourless, mobile liquid. (Schweizer.) — Sp. gr. 0-861 at 15^ (VSlkel.) — Boiling point 173^ — Vapour-density = 5*175 (by calcnlatioD, 4*7144, see page). — It has a faint, but agreeable taste and odour.

VSlkel. Schwetier.

20 C 120 .... 88-23 88-08 .... 8652 .... 87-03

16 H 16 .... 11-77 11-81 .... ll-;7 .... 11-74

C»H" 186 .... 10000 99-89 ..•, 98-29 .... 98-77

According to Ytflkel, its formula is C^H>«.

Decompositiana. 1. Caryene resinises when exposed in small quan- tities to the air. — 2. When set onjlre, it bums with a bright-bordered smoky flame. — 3. With chlorine^ it gives off hydrochloric acid, assumes a transient red-brown colour, and solidifies to impure chlorocaryene. — 4. Nitric acid conyerts it, with yiolent eyolution of nitrous acid, into a reddish-yellow, bitter, easily fusible resin, somewhat soluble in hot water, easily soluble in hot alcohol, in ether, in potash, and in acids, insoluble in cold alcohoL — 5. By oil of vitriol, it is immediately resinised, with rise of temperature and evolution of sulphurous acid. (Schweizer.)

Combinations. — Wiih Hydrochloric acid, Hydrochloraie of Carvene. G*'H^^2HCL — Anhydrous carvene absorbs dry hydrochloric acid gas, at first with rise of temperature, acquiring a transient red colour, and after two days deposits solid crystalline masses. It is saturated completely with hydrochloric acid gas; the crystalline mass which separates is pressed between paper and dissolved in warm alcohol ; and the crystals which separate as the solution cools, are again pressed.

Snow-white, shining scales, which molt at 50' 5\ solidify again at 41 '25°, and. have a faint taste and odour.

£\J \j ................ 18 H	.... 120 18	.... 07-4 ... .... 34-0 ..	Schweizer. 57-72 8-60
2 CI	.... 71	33-78
C»HW 2HCI ...	209	.... 100-0 ..	100-00

It decomposes when heated per se. Heated with water, it is yery quickly resolved into hydrochloric acid, and an oil which is probably carvene. Heated with potasli, it yields carvene, chloride of calcium, and water. ^- It dissolves readily in water, with some difficulty in cold alcohol, easily in hot alcohol. (Schweizer.)

Carvene dissolves slowly in water, easily in alcohol and ether. It does not dissolye chloride of calcium. (Schwei7.er.)

INDIFFERENT OIL OF CLOVES. 285

Appendix io Carvene.

Chlorocarvene c»«H'*Ci* (l)

ScHWEiZEn. (1841.) J. pr. Chem. 24, 270.

Preparation, Garvene is completely saturated with dry cblorine; the oil, which assnmes for a while a red-brown colour, and afterwards changes to a yellow greasy mass, is heated ; and the viscid, yellow trans- parent mass which separates therefrom, is washed with water, then with potash-sol ation, digested with alcohol, and dried orer oil of vitriol or hydrate of potash.

FrapeHies, Yellowish, transparent, semiflnid mass, which sinks in water, has a peculiar, but not unpleasant odour, and a sweetish taste.

Decompositions and Combinations. When heated, it gives off hydro- chloric acid and a viscid volatile oil, and leaves a carbonaceous residue. — It bums with difficulty when heated in a glass tube. Exposed to the air, it quickly becomes moist, white and opaque.

3. Indifferent Oil of Gloves.

EmiKG. (1834.) Ann. Pliarm. 9, 68; Pogg. 31, 52G. Erdmann k Marchand. J. pr. Chem. 23, 176. BniiNiNO. Ann. Phai^. 104, 204; J.pr. Chem. 73, 156, C. G. Williams. C/*«». Gat. 1858, 170; Ann. Phamu 107, 242; N. Ann. Chim. Phys. 54, 433.

Camphene of Oil pf Cloves,

Source. In oil of doves. It is found chiefly in the first portions of liquid which pass over on distilling cloves with water, while the last portions consist almost wholly of eugenic acid.

Separation from OU of Cloves. The oil which passes over on distilling oil of cloves, mixed with excess of potash, is again shaken up with aqueous potash, washed, dehydrated with chloride of calcium and rectified. (Briining.)

Properties. Colourless, strongly refracting oil. (Ettling.) Sp. gr. 0-918 at 8° (Ettling) ; 0*9016 at 14^ (Williams.) Boils at 142''—] 43^ (Ettling); at 251° (Williams); 255° (Briining). — Smells like oil of turpentine, different from oil of cloves. (Briining.) It is more viscid than oil of turpentine. (Williams.)

20 C 120 .... 88-24 87-17 .... 88-16 .... 87-38 .... 87-7

10 H 16 .... 11-76 11-76 .... 11-77 .... 11-90 .... 11-8

C»n»» 136 .... 10000 OS-93 .... 99-93 .... 99 28 .... 99-5

286 NATURAL OILS, ISOMERIC WITH OIL OP TURPENTINE.

It is not altered by alkalis or by potassiam. (Ettlinff.) It absorbs hydroddorieacid gas, but does not form with it a crystalline compound. (Ettlin^.)

It is much less soluble in alcohol than oil of turpentine. (Williams.)

4. Oil of Copaiba.

BoNASTRE. (1825.) J. Fharm. 11, 529; i\r. Fr. 12, 1, 180. Adeb. J. Pharm. 15, 95; Br. Arch. 30, 311; K Tr. 20, 1, 184. Gerbeb. Br. Arch. 30, 157. Blanchet. Ann. Pharm. 7, 156.

SouBEiRAN & Capitaine. J. Pluznn. 26, 70; abstr. Ann, Pharm. S4, 321.

Capm»a*6l* Eaenee de Capaku.

Source and BxtracUon. — In balsam of copaiba^ wbicb exudes from incisions in various species of Copaifera, — 1. The balsam is distilled with water (Soubeiran & Capitaine); per ae. (Blanchet). — 2. A solution of 100 pts. balsam of copaiba in 100 pts. alcohol of sp. gr. 0*837 is shaken up with 37*5 pts., soda-ley of sp. gr. 1*33, and 150 pts. water, and the oil which rises to the surface after standing is collected. (Ader.)

Properties. Transparent, colourless, mobile (yellowish-green according to Blanchet). Sp. gr. 0*9 {Schonberg, A. Gehl, 6, 494, Ader) ; 091 (Gerber ; Williams, Ann. Pharm. 107, 242) ; 0878 at 22*^ (Blanchet) ; 0-881— 0*885. (Soubeiran & Capitaine.) — Boiling point : 245° (Blanchet, Williams) ; 245—260°. (Soubeiran & Capitaine ) — Solidifies at —26°, partly in the crystalline state. ((Berber.) — llotatory power, 34*1 8° left. (Soubeiran & Capitaine.) — Expansion from 0° to 100^ = 0*83132; from 100° to 200° = 0104034. (Aubergier, J. P/iatm. 27, 278.) — Has an aromatic odour, like that of the balsam (according to Ader, it has a less agree- able odour when prepared by (2) than when obtained by distillation.) Tastes sharp,

and persistently bitter. (Ader, Gerber.) Keutral (Blanchet) ; slightly

acid. (Gerber.)

20 C 16 H

16 .... 11-76 ....

Blanchet. .... O0*74 .... OO'dd .... 11-66 .... 11-75

(?»H" 136 .... 10000 100-40 .... 100-30

Decompositions. 1. By continued boiling, the oil becomes brown and viscid. •— 2. Chlorine in sunshine makes it hot, colours it yellowish, bluo, and then green, and separates white crystalline masses. (Blanchet.) — 3. Iodine, slowly added to it, unites without detonation (Blanchet), with reddish>yellow to brown-black colour ; if the iodine be more quickly added, heating and frothing take place (Gerber) ; the product is a brown mass. (Stoltze, Berl. Jahrb. 27, 2, 200.) — 4. It explodes with fuming nitric acid in the cold (Blanchet), leaving a brown resin (Stoltze) inso- luble in the hot oil. (Gerber.) With nitric acid of sp. gr. 1'32, it resinises only when heated (Blanchet) ; according to Bonastre, it assumes

OIL OP COPAIBA. 287

a Tiolet tint at the beginning of the action. Weaker nitric acid forms with the oil a small quantity of yellow resin precipitable by water. ^Gerber.) — 5. OH of vitriol makes it hot and turns it red-brown. (Stoltze.) — With a few drops of oil of vitriol, it becomes hot and blackens; out when dropped into a larger quantity of oil of vitriol, it forms a red- brown solution of sulphoterebic acid. (Gerhard t, Compt. rend, 17, 314.) — - The brown viscid mixture gives off a sulphurous acid when heated. (Gerber.)

6. With hyd'i'ochloTio add gas, it becomes hot and coloured (Blanchet) ; it becomes brown and viscid, and on cooling, slowly deposits solid bihy- drochlorate of copaiba-oil. (Soubeiran & Capitaine.) — 7. It oxidises potassium, (Gerber.) — Potassium immersed in the oil becomes coated in three months with a thick soapy mass. (Gall, Sill. Am, p. 21, 63.) — 8. When shaken up with aqueous potash or soda, it becomes heated, acquires a brown colour, and yields to water a small quantity of resin, which does not pre-exist in the oil, but is produced from it by the action of the alkali. (Gerber.) — 9. Distilled with 24 pts. water and 8 pts. chloride of lime, it gives off carbonic acid and forms chloroform. — ] 0. Distilled with hypobromite of potash, it forms bromoform. (Chantard, Compt, rend. 34, 485.)

Combinations, With ffydrodiloric acid. — a, Bihydrochloraie of

copaiba-oil, C**H^',2HC1. Campkre de copahu; salztaures copahu, (Soubeiran & Capitaine.) Chhrhydrate de copahu. (Gerhardt.)

It is prepared by passing dry hydrochloric acid ^as through de- hydrated oil of copaiba, separating the crystalline mass which is deposited therefrom on cooling from the brown oil, pressing it between filtering paper, mixing its solution in ether with alcohol of sp. gr. 0*85, and washing the crystalline mass which separates with alcohol. (Blanchet.) — The crjrstals which separate from the oil when hydrochloric acid is passed through it are recrystallised from alcohol. (Soubeiran & Capitaine.)

Hydrochlorate of copaiba-oil forms short, transparent, right rect- angular prisms (resembling chlorate of potash, according to Blanchet), which melt at 77^. (Soubeiran & Capitaine.) — They are inodorous (Blanchet ; Soubeiran & Capitaine), have a faint camphorous odour, and an aromatic bitter taste. (Gerber.)

mean,

20 C 120 .... 57-4 67*95 .... 67-85

18 H 18 .... 8-6 8-73 .... 8*58

2 CI 71 .... 34-0 33-04 .... 38'4l

C»HW 2HC1 209 .... 100-0 99-72 .... 9984

The hydrochlorate heated to 140 — 150° gives off a large quantity of hydrochloric acid gas. (Soubeiran & Capitaine.) When set on fire, it burns with a bright flame. (Gerber.) Nitric acid, heated with it, gives off nitrogen gas [? Gm.]. (Blanchet.) Oil of vitriol with aid of heat dissolves it, and deposits it again in the crystalline form on cooling ; at a stronger heat, the solution gives off hydrochloric acid gas. (Blanchet.) Heated with stdphide of lead, it yields an oil having an alliaceous odour. Its alcoholic solution is precipitated by nitrate cf silver or Tnercurous nitrate, (Blanchet.)

288 NATURAL OILS, ISOMEMC WITH OIL OP TURPENTINE.

It is insolable in water and in cold alcohol^ sparingly soluble in hot alcohol, easily soluble in ether. (Blanchet.) The sJcoholic solution leaves when evaporated a thick oil, which smells like balsam of copaiba, and appears to hold in solution nndecomposed bihydrochlorate of copaiba- oil. (Soubeiran & Capitaine.)

h. Hydo'oMorate of Copahilene. (Soubeiran &, Capitaine.) The liquid portion of the product obtained by treating copaiba-oil with hydrochloric acid. It always contains in solution bihydrochlorate of copaiba-oil, which cannot be separated from it. (Soubeiran & Capitaine.)

It is a black, viscid oil, smelling like castorenm, and without action on polarised light. (Soubeiran & Capitaine.)

When distilled, it gives off hydrochloric acid gas, and yields a colour- less oil which is a solution of bihydrochlorate of copaiba-oiL (Soubeiran & Capitaine.) It burns with a faint odour of hydrochloric acid. It gives up a portion of its hydrochloric acid when shaken up with water. (Gerber.) Soluble in alcohol and ether. (Oerber.)

Oil of copaiba dissolves phosphorus when heated with it, and deposits part of it on cooling; the solution shines in the dark. It dissolves sulphur with aid of heat, and deposits part of it in reddish crystals on cooling. (Gerber.)

It dissolves glacial acetic acid, and hydrocyanic acid; mixes with alcoholic succinic add and benzoic acid, which remain combined with the oil after the evaporation of the solution. It mixes with solutions of oxalic acid, but not with citric acid. It absorbs ammotday becoming milk- white and viscid. (Gerber.)

It dissolves in all proportions of bisulphide of carbon* (Gerber.) It dissolves in 2*5 pts. of absolute alcohol (in all proportions, according to Stoltze), in 30 pts. of alcohol of sp. gr. 0*85 at 25^ ^Blanchet), and in 8 pts. of the most highly rectified spirit. (Schbuberg.) It dissolves in all propor- tions of absolute ether (Stoltze), in less than \ pt. of common ether. (Blanchet.)

5. Para-copaiba Oil.

SouDEinAN Capitaine (1840.) J, Pluimu 26, 70. PossBLT. Ann, Pharm, 69, 67.

Source and Extraction. lu a variety of copaiba balsam from Brazil. It is distilled with water, and the oil is dehydrated with chloride of calcium. (Posselt.)

Properties. Transparent, colourless viscid oil, of sp. gr. 0 91 (0-898 according to Soubeiran & Capitaine), boiling at 250°. It smells like the balsam and has a sharp burning taste. (Posselt.) Rotatory poivcr 28-553''. (Soubeiran & Capitaine.)

Posselt.

20 C 120 .... 88-24 83-13

16 H 16 .... 19-76 11-77

C»II>' 136 ....100 00 99-90

OIL OP ELEML 289

DecompasUwns. 1 . Becomes yellowish when bailed, afterwards brown, thick, tenacious, and charred. (Posselt.) (Marine converts the oil, with cvolation of hydrochloric acid, into a yellow sticky mass. The oil dis- solves iodine without detonation. — 3. With fuming nitric acid, it detonates even in the cold ; but nitric acid of sp. gr. 1*32 resinises it only with aid of heat. Dilute nitric acid, heated with the oil, dissolves it completely after a few days, giving off nitrous acid, carbonic acid, and other volatile acids. From the solution of the oil in nitric acid, water throws down, after evaporation, a reddish-yellow acid resin, sparingly soluble in hot water, easily soluble in alcohol and ether, whilst a peculiar acid remains dissolved, which, when the solution is concentrated by evaporation, crystallises in slender, colourless, transparent, laminsB, easily soluble in water, alcohol, ether, and rock-oil, inodorous, having a bitter taste, and a slight acid reaction. (Posselt.) — 4. The oil absorbs hydro- chloric acid gas with avidity, turning brown-red and fuming in the air, but not depositing any crystals on cooling.

The oil dissolves in all proportions in €the:i\ less easily in ahsoluU alcohol, still less in common alcohol.

6. Oil of Elemi.

Stenhousb. (1839.) PM. Mag. J. 18, 184; Ann, Fharm. 35, 304. Detillb. Ann. Chim, Phys. 25, 80; Gompt, rend. 12, 184; N, Ann,

Chim. Phya, 27, 88; abstr. Ann. Pharm, 71, 352; Pharm, CentrcUbl,

1849, 691.

Bitenee d*elemi.

Source and Extraction. In elemi-resin, the resin of Idea Icicariba, Dec., and Idea heptaphyUa, (Aublet.) Elemi-resin is distilled with water, and the oil, which passes over readily and floats on water, is separated from the watery distillate, and dehydrated by agitation with chloride of calcium. The process yields 3 — 5 pts. oil from 100 pts. resin (Sten- house) ; good elemi-resin yields 13 p. c. (Deville.)

Propetiieg. Limpid and mobile. Boils at 166^ (Stenhouse) ; at 174^ under 0*755 met. pressure. Sp. gr. 0*852 at 24** (Stenhouse) ; 0-849 at 11**. (Deville.) Refracting power 1*4719 at 14°. Rotatory power 90*3° to the left. Vapour- density 4*84. (Deville.) [Calculation = 4*7144 (p. 245).] Has a rather pleasant odour, like that of elemi-resin, and a sharp taste. (Deville, Stenhouse.)

Stenhouse. Deville.

20 C 120 .... 88-24 87*83 .... 88*05

16 H 16 .... 11-76 11-71 .... 11*90

C»Hw 136 .... 100-00 99*54 .... 99*96

Decompositions. Oil of elemi when set on fire bums, with a bright fuliginous flame. — 2. With iodine, it becomes heated, gives ofl* iodine- vapours, and solidifies to a thick red mass. — 3. Nitric acid colours it brownish yellow in the cold, and, when heated, converts it into a resin,

Toi,, xiy. V

290 NATURAL OILS, ISOMERIC WITH OIL OF TURPENTINE.

with explosion and evolation of nitric oxide. — 4. Oil of vitriol gives it a fine red colour in the cold, and chars it when heated. (Stenhouse.) — 5. It ahsorbs hydrochloric acid gas, and is converted into solid and liquid bydrochlorate of elemi-oil. (Deville.) It is not altered by potassium, bnt hydrate of potash, with aid of heat, converts it into a brown resin. (Stenhouse.)

Combinations. — TFiYA Hydrochloric Acid, A. Solid Bihydro- chlorate of Elenii-oU, C*H",2HC1. Dry hydrochloric acid gas is passed into oil of elemi, the stream of gas being kept up after complete satura- tion (100 pts. of the oil absorb 47'7 pts. of hydrochloric acid gas) ; the excess of hydrochloric acid is left to evaporate in the air, and the crystals which separate from the hitherto flaid mixture are collected. (Deville.)

Colourless crystals, optically inactive. (Deville.)

Deville.

20 C 120 .... 57-4 57-37

18 H 18 .... 8-6 8-70

2 CI 71 .... 34-0 83-93

C»H'«,2HC1 209 .... 100-0 lOOOO

B. Liquid Bihydrochlorate of Elemi-oU. (Gerhardt.) — The oil which remains liquid after the separation of the solid bydrochlorate above described. (Deville.)

Oil of elemi is insoluble in water, sparingly soluble in weak aleokoi, easily in alcoholic ether, (Stenhouse.)

7. Gauliherylene.

Cahours. (1844.) iV. Ann, Chim. Fhys. 10, 358.

Source. In oil of winter-green (Gaultheria procumhens), to the amount of -^^ mixed with -^ of methyl-salicylic acid (xii, 255).

Preparation. Winter-green oil is distilled with concentrated aqueous potash ; the distillate, consisting of wood-spirit, water, and gaultherilene, is washed, first with water containing potash, then with pure water ; and the undissolved oil is dehydrated with chloride of calcium and rectified over potassium.

Properties. Colourless, mobile, lighter than water; boils at 160^. Vapour-density 4*92 [by calculation, 4*7144 (p. 245)]. Has a rather I

agreeable peppery odour.

Cahoun.

20 C 120 .... 88-23 87-85

16 H 16 .... 11-77 12-25

C»H» 136 ... 100-00 100-10

OIL OF HOPS. 291

8. Oil of Oomart.

Dkyille. (1849.) J^. Ann. Chim. Fhys. 27, 90; abatr. Ann, Pharm. 71, 354; Pharm. CerUr, 1849, 692; J, pr. Vh^m. 48, 64.

Bunera-oel,

Source and Bxti^action, In fi^mart resin, the thickened resinons juice of Bursera gummifera. (Z.) It is obtained bj distilling the resin with water. The produce is 4*7 p. c. of coloured oil, which is set aside with solid hydrate of potash, and then rectified over potassium.

Properties. Colourless, transparent oil, smelling like turpentine. Vaponr-densitj = 4 •70.

			Deville.
			mean.
20 C ....	. . 120	•■.. oo «4 ...	.... 88-10
16 H ....	... 16	... 11-76 ...	11-86
C?»H»«....	.... 136	.... 100-00 ...	.... 99-96

Combinations. When strongly cooled and saturated with hydro- chloric acid gas, it yields silky needles^ like those of bihydrochlorate of lemon-oil, and exhibiting a dazzling whiteness, after pressure betweeu bibulous paper.

Deville.

20 C 120 .... 57-4 57-4

18 H 18 .... 8-6 8-8

2 CI 71 .... 34-0 33-8

C»H>«,2Ha 209 .... 100-0 1000

9. Oil of Hops.

Paten & Chetallier. (1822.) J. Pharm, 8, 214 and 533.

R. Wagner. J, pr. Chem, 58, 351; Dingl. poL J. 128, 217; abstr.

Chem. Centrhl 1853, 249. Pbrsonnb. Compt rend. 38, 309; N. J, Pharm. 26, 241 and 329;

27, 22; Ins(xt. 1854, Qb\ Chem. Centrbl 1854, 228.

Hopfendl, Enenee de houblon.

Source and Extraction. In hops, the female cones of Humulus Lupulus (Z.), and in lupulin, the dust contained therein. It is extracted by distilling lupulin (Payen & Chevallier), or fresh hop-cones (Wagner) with water. The product is 2 p. c. of oil (Payen &c Chevallier), 0*8 p. c (Wagner), together with valerianic acid, which remains dissolved in the water. (Personne.)

Properties. Transparent and colourless (Personne) ; greenish-yellow (yellow from old hops) (Payen k Chevallier) ; pale greenish-yellow (the dis- tillate between 125*' and 225° is colourleM, from 225"" to 2.35** yellowish) (Payen & Chevallier). Sp. gr. 0-91 (Payen & Chevallier); 0 908 at 16^

u2

292 NATURAL OILS, ISOMBRIC WITH OIL OF TURPENTINE.

(Wagner.) Boiling point between 125^ and 235" (Wagner) ; from 140" to above 300°. (Personne.) It volatilises partially below 100°; ^ of the oil boils at 175<>; | between 175° and 225°; | between 225° and 135^ ; and ^ remains behind. (Wagner.) It does not solidify at 17". (Personne.) Rotation to the right. — Smells of hops, pnngent and intoxicating (Payen & Chevallier) ; strong but not intoxicating (the portioii which disttlfl between 175^ and 225 **, hu a faint odour of rosemary). ^Wagner.) Tastes sharp (Payen & Chevallier) ; barning, slightly bitter, like thyme and origanum. (Wagner.) Neutral (Personne) ; when left for some time on litmus-paper in contact with the air, it reddens the litmus. (Wagner.)

Wagner. Wagner.

a. b.

20 C .... 120 .... 88-23 ... 16 H .... 16 .... 11-77 ...	88-9 11-9	20 C 18 H 2 0	120 .... 77-92 .... 18 .... 11-69 .... 16 ... 10-39 ....	.... 78-19 .... 12-00 .... 9-81
C»H".... 136 .... 100-00 ...	100-8	C»HWO«....	154 .... 100-00 ....	.... 10000

a. Distilled with alcoholic potash : resembles (he oil which boils between 125* and 175''. — b. Oil boiling at 210**. It corresponds to the formula C^HiH)^, and is a mix- ture of the hydrocarbon C'-^H^ and oil of i^erian (Personne); consists of a hydrocarbon C^H^' and an oxygenated oil C^H^^O^, isomeric with Bornean camphor, oil of cajeput, oil of bergamot, and campholic aldehyde. It contains sulphur (Payen & Cheralier; Will, Ann, Pharm. 52, 2), it is free from sulphur. (Wagner.)

Decompositions. 1. The oil gradually resinises when exposed to the air (Payen & Chevallier), turns acid (Personne.) Dries up to a sticky mass. (Wagner.) — 2. Bromine and tocftne turn it brown in the cold, and immediately resinise it, with violent action^ when heated. (Wagner.) — 3. With nitric acid it forms a yellow resin and valerianic acid. (Personne.)

4. With oil of vitriol it turns red, and forms a conjugated sulphuric acid. (Personne.) — 5. The oil a absorbs dry hydrochloric acid gas, and turns brown, but does not solidify on cooling. — 6. With meUing potassium, it thickens, turns brown, and gives off gas. (Wagner.) — 7. When dropt into meUvng potash, it forms a volatile hydrocarbon, C'^H^ having an odour of thyme, together with carbonate and valerate of potash (Personne). Heated with alcoholic potash, it turns brown, and gives off the volatile oil a, which smells like rosemary, leaving carbonate and apparently also caprylate and pelargonate of potash. — 8. Distilled with meUing mloride of zinc, it yields a colourless oil, apparently identical with a.

Combinations, It dissolves in 10,000 pts. of water, imparting its odour and taste, which however are easily removed by charcoal (Payen & Chevallier), in more than 600 pts. of water. (Wagner.)

10. Oil of Juniper-berries.

Tbommsdorpf. (1822.) Taschenb. IS22, 46.

Blanghbt. Ann. Pharm, 7, 165.

Dumas. InttU, 97; J- pr. Chem 4, 344; Ann. Pharm. 15, 158.

AscHOFF. N, Br, Arch. 40, 272.

OIL OF JUNIPBR-BBRRIES, 293

SouBBiRAN & Capitainb. J. Phorm. 26^ 78; abeir. Ann. Pharm. 34,

825. Zeller. Stud, uher ather. Oele Landauj 1850. Stber. Wien Akad. Ber. 1856; Chem. CerUr. 1856, 60.

WaehholderbeerClt Wachholderbeeregienx, Esunee de ffemivre. Oleum baccarum Juniptri,

Source and Extraction, In juniper-berries the fleshy scales of the female cones of JuniperuM communis {£,). — The ripe but still green berries are bruised and distilled with water (Aschoff), with water and common salt (Blanchet), after previous exhaustion with cold water. (Steer.) The oil thus obtained is rectified with water (Soubeiran & Capitaine), or with quicklime, after washing with salt water and dehy- drated by agitation with chloride of calcium. (Blanchet.) — By rectifi- cation it yields f colourless oil, } of oil which passes over coloured, and a small quantity of residual oil. (Soubeiran & Capitaine.)

Unripe juniper-berries yield by distillation a more volatile and a less volatile oil ; the ripe berries only the latter. (Blanchet.) — The yield of oil is only 0*77 p. c. (Tremlich, Bepert, 24, 484), 0*65 p. c. Martins, Bepert. 89, 24) ; from the ripe berries of first je&i^B plants, 0*39 p. c. ; from green ripe berries, by distillation with water and common salt, 1*56 p. c. (Blanchet) ; from ripe berries with water, 0*32 p. c. ; from fresh berries, 0*46 p. c. ; from unrljpe berries, 0*35 p. c. (v. Hees, Pharm, Centr. 1847, 380) ; from berries mixed with a small quantity of water, coarsely bruised and exhausted with cold water, 0*75 p. c. (Steer.)

Properties. Mobile oil. (Blanchet.^ Transparent, and colourless to slightly straw-coloured (Blanchet, Martms) ; greenish to brownish -yellow. (Zeller.) Boiling point of the most volatile oil from the unripe berries, 155° ; of the less volatile oil and of that from the ripe berries, 205° (Blanchet); of the first distillate, 155^—163^; of the last, 155**— 182°. (Soubeiran &, Capitaine.) — Sp. gr. 0-862 — 0*870 (van Hees, Pharm, Centr. 1847,380); 0*847— 0*881 (Soubeiran & Capitaine); 0-853—

0*870 (Zeller) ; 0853 (Trommsdorff) ; of the most volatile oU, 0-839 at 2^"" (ZeUer, Blanchet); 0*855 (Soubeiran & Capitaine); at 100^ » 0*804 (Anbergier, /. Pkarm. 27, 278); of the less voktile oil, 0*8784 at 25"" (BUnchet); 0*881 (Soubeiran &

Capitaine); of the fresh oil, 0*926; of older oil, 0*912. (Martins.) — Refracting power, 1*475 (Becquerel & Cahonrs, Compt. rend, 11, 867); 1474 (Deville, Com,pt, rend, 11, 867); 1474 (Deville, Compt. rend. 11, 865). — Rotatory power, 3*521° to the left. (Soubeiran & Capitaine,) — Vapour-density = 4*844 (Soubeiran & Capitaine), by calculation, 4*714 (comp. p. 245). — It has a strong odour of juniper, the volatile oil of the unripe berries smells abo like fir-needles (Martins, Blanchet) ; has an aromatic odour and an aromatic resinous taste. (Trommsdorff.) NeutraL (Aschoff, Zeller.)

Blanchet. Dumas.

a. h.

20 C 120 .... 88*23 88*41 .... 87.72 .... 87*7

16 H 16 .... 1177 ........ 11*52 .... 11-59 .... 11*7

C»HW 136 .... 100-00 99*93 .... 99*31 .... 99*4

a. The more volatile from the nnripe berries, b. Oil from the ripe berries. It is a mixture of the two non-separable oils, which are perhaps formed from the original oil daring the distillation. (Soubeiran Ac Capitaine.)

294 NATURAL OILS, ISOMERIC WITH OIL OF TURPENTINE.

Deeompositums, 1. The oil on cooling deposits juniper-camphor. (Bizio^ Brugn. Giom. 1 9, 360.) — 2. It oxidises in the air (Blanchet), and after a while, forms juniper-camphor (Zaubzer, Repert, 22, 415 ; Buchner, ReperL 22, 425) ; in contact with water, also a small quantity of formic acid, and then readens litmus. (Aschoff.) The oil is partly converted into formic acid daring the drying of the berries ; for the water which distils OTer with the oil colours litmusi and reduces mercury and siWer salts. (Aschoff.) — It absorbs

imolated oxygen ga9, thereby acquiring oxidising properties and turning sour. (Schbnbein, J, pr, chem. 52, 187.) — 3. Heated with VHxter to 40 , it deposits hydrated oil of juniper. (Blanchet) — 4. It explodes violently with iodine (Guyot, «/. Chim, mid. 1 2, 487 ; Tiichen), slightly with a small quantity of iodine (Schiitze, Br, Arch, 23, 200) ; it becomes very hot and detonates slightly, giving off violet vapours, and leaving a mobile, brownish green residue having a balsamic odour like that of the oil. (Winckler, Repei-t, 32, 271 ; Flaschoff, Br. Arch. 33, 225.) — The fresh oil of unripe juniper- berries explodes veiy violently with iodine (Blanchet), giving off grey vapours, and becoming greenish-brown and viscid (Zeller) ; older oil from the unripe berries explodes less violently with iodine (Winckler) ; becomes yellowish-brown and viscid, and deposits a less coloured liquid (Zeller) ; the oil of ripe juniper-berries does not explode with iodine. — 5. On gradually adding 6)'omtfM to the oil mixed with \ of its volume of water, the liquid becomes heated, and the colour of the bromine disappears, if 229 pts. of bromine are added to 100 pts. of the rectified oil, or 220 pts. bromine to 100 pis. of the crude oil, — that is to say, about 4 At. bromine. (Gr. Williams, Ck^m. Oaz. 263, 365 ; J. pr. Chem, 61, 20.) — 100 pts. of the oil take up 250 pts. of bromine. (Knop, Chem, Centralbl, 1854, 4S8.) — 6. ^xih fuming nitric acid, it forms, with strong crackling, a viscid, yellow resin (Uaaae) ; when heated with nitric acid, it assumes a yellowish colour, and gives off gas. (Zeller.) — 7. With oU of vitriol^ it thickens, becomes brownish-red, balsamic, and resinous (Zeller), and gives off sulphurous acid. (Hasse.) — 8. With acid chromate of potash and sulphuric add, it assumes a reddish, and then a yellowish-brown colour, which is not destroyed by heating. (Zeller.) — 9. With hydrochloric acid gas, it assumes a darker colour, and forms hydrochlorate of juniper-oil. (Soubeiran & Capitaine.) — 10. Mixed with aqueous hydrate of pota^, it gradually deposits hydtated oil of juniper. (Blanchet.) — 11. Distilled with 24 pts. water, and 8 pts. chloride of lime, it gives off carbonic acid with effervescence, and forms chloroform. — 12. Distilled with hypobromite of lime, it yields bromoform. (Chautard, Compt. rend, 34, 485.)

Combinations, 1. ffydrated Oil of Juniper, (Blanchet.) — Formed from oil of juniper by prolonged contact with water at 40°, and is gradually deposited in slender needles from a mixture of hydrate of potash and the juniper-water obtained by distilling the berries with common salt. It exhibits the properties of hydrated oil of turpentine (p. 256).

2. ffydrochlorate of Juniper-oil^ or Hydrochlorate of Juniperilene, (Soubeiran & Capitaine.) — Oil of juniper is saturated with dfry hydrochloric acid gas ; the mixture, which becomes coloured, but does not solidify, even at — 20^ is saturated with chalk, then mixed with chloride of calcium, and filtered through a mixture of animal charcoal and chalk.

Colourless oil, of sp. gr. 1 029 and laevo-rotatory power = 2'866.

LAUREL-OIL FROM GUIANA. 295

Soubcdran & Capitaine.

30 C 180 .... 64-99 6531

26 H 26 .... 9-38 9*03

2 CI 71 .... 25-63 25-66

C»H»«,HC1+CWH«,HC1 277 ....10000 100-00

Oil of juniper forms with \ pt. abtolute alcohol a clear solation, aud with 1 — 10 pte. a tarbid solution (Zeller); the more volatile oil of the unripe berries dissolves clearly in 1 pt., with turbidity in a larger quantity of absolute alcohol ; the oil of the ripe berries in 8 pts. (Blancbet.) It dissolves sparingly in alcohol of sp. gr. 0*85 (Blanchet) ; with turbidity in 10 to 12 pts. (Zeller.)

In absolttte ether it dissolves in all proportions. (Blanchet.)

Appendix to OU of Juniper-berrUs.

Juniper-camphor.

Zadbzer. (1825.) BepeH, 22, 415. BucKNER. Repert. 22, 425.

Obtained from oil of juniper-berries, which had been kept for 6 years in a half-filled loosely stoppered bottle ; purified by washing with alcohol.

Colourless, transparent, rhomboidal tables grouped in tufts, heavier than water, melting when heated, and volatilising without decomposition, solidifying in the crystalline form on cooling. Nearly destitute of taste and odour. Neutral. (Zanbzer, Buchner.)

Burns like a volatile oil. (Zaubzer.) When distilled with phos- phoric acid, it behaves like turpentine-camphor. (Buchner.)

With 200 pts. of cold water, it forms an incomplete solution, which becomes clear when heated, and remains clear on cooling. It is but slightly soluble in aqueous ammonia. Dissolves in acetic acid more readily than in water. (Buchner.) — From a hot solution in alcohol of sp. gr. 0*830, it separates on cooling in feathery crystals ; dissolves more readily in ether, (Zaubzer.)

11. Laurel-oil of Guiana.

Hancock. (1824.) QuaH. J. of Sc. 75, 47; N, Tr. II, 171; Br. Arch.

13, 291; J. Pharm. 10, 547, — N, Edvnh. J. of Sc. 8, 48; £r. Arch.

86, 333. Brandes. iV. Br. Arch. 21, 169. Stenhousb. Phil. Mag. J. 20, 273; J. pr. Ohem. 27, 251; Mem. Chem.

Soc. 1, 43; Phil. Mag. J. 25, 200; Ann. Fharm. 50, 155; Mem.

Chem. Soc. 2, 121.

Natural Oil of Laurel (Hancock) ; Ocotea-Gl (Lowig, Organ. Verb. 2, 1027.)

Source. In the stem of a tree growing in Spanish Guiana, and belonging to the lauraceous order (Hancock), and to the species Ocotea (Christison), or Pinus. (Stenhouse.)

296 NATURAL OILS, ISOMERIC WITH OIL OF TURPENTINE.

Extraction. By making inoisions in the stem of the tree near the root; whereby the receptacles of oil saturated under the bark are opened, and collecting the oil which runs out.

Purificatuyn. By distilling the crude oil with water, dehydrating with chloride of calcium, and rectifying in the oil-bath. (Stenhouse.)

Properties. Transparent, colourless oil, yellowish in the crude state,

of sp. gr. 0-864 at 133^ — Begins to boil at 149*5'', the boiling point

gradually rising to 162*8^. (Stenhouse.) Smells like oil of turpentine

and oil of lemon (Stenhouse) ; like oil of cajeput, and has a warm pungent

taste. (Hancock.) The crude oil contains in solution a small quantity of resin and some formic add, which reduces silver-solutions at the boiling heat (Stenhouse.)

Brandes. Stenhouse.

a. 6, e.

20 C 120 .... 88-24 77-15 .... 88-51 .... 8829

16 H 16 .... 11-76 9-97 .... 11-57 .... 11-57

C«>H" 136 .... 10000 8712 .... 10008 .... 9986

a. Crude oil; b, rectified oil which passed over at 149*5^; c. at 162*8^. It con. consists of two oils isomeric with oil of turpentine.

Decompositions, 1. Laurel-oil thickens and absorbs oxygen when exposed to the air« (Brandes.) — 2. It burns with thick smoke when set on fire. (Hancock.) — Iodine added in small quantities imparts to the oil a transient red colour, producing also a hissing noise, eyolution of heat, and a bituminous odour, but without appearance of fire ; larger quantities of iodine convert the oil into a black tarry mass. (Hancock .) — 4. OH of vitriol colours it brown for a while, but does not mix with it. (Hancock.)

Comhinatums, — With Water. — Laurel^urpentine-eamphor C*^H**0*. 8 pts. of laurel-oil are mixed with 2 pts. of nitric acid of sp. gr. 1*25 — 1-3, and 1 pt. of alcohol of 80 p. c, the mixture being frequently agitated at first, then left to stand quietly for some months ; and the deep yellow crystalline mass which separates is collected and purified by repeated crystallisation from alcohol, like turpentine-camphor (p. 259). (Stenhouse.)

Propertie9. White, rhombic, inodorous and tasteless prisms, which melt at 125°, and sublime at 130"".

20 C

20 H

40

			Stenhouse.
120	• •■■	70-19 ..	70-16
20	«••«	11-44 ..	11-65
32	• •••	18-37 ..	18-20

C»HW 4HO 172 .... 10000 10000

Isomeric or identical with turpentine-camphor. (Stenhouse.)

Decomponiiofu. 1. Laurel-turpentine-camphor yields by distillation with anhydrous phosphoric acid, a colourless oil which floats on water, and has the taste and odour of Guiana laurel-oil. — 2. Gently heated with oi/ of vitriol, it forms a red solution, which at a stronger heat gives off acid vapours and forms a tough resin precipitable by water. (Sten- house.)

OIL OF LEMON. 297

Gniana laurel-oil is insoluble in vHtier^ soluble in alcohol and eth^, A mixture of 1 pt. oil and 2 pts. alcohol floats on ether, although both the oil and the alcohol are heavier than ether. — When the oil is gradually mixed with rectified spirit of wine, the spirit floats for a long time on the oil in spherical drops.

Guiana laurel-oil dissolves camphor , eaoutchouc, pitch, resin and ails, both fat and volatile. (Hancock.)

12. Oil of Lemon.

Saussure. (1822.) Ann. Chim. Fhys. 13, 262; Pog^. 25, 370; Ann.

Fharm, 3, 157. BoissENOT. J. Pharm. 15, 325; Ann. Chim. Fhys, 41, 434; N. Tr. 20,

2,214. Dumas. Pogg. 26, 530; Ann. Pharm. 6, 255; Ann. Chim. Phys. 52,

405; Pogg. 29, 129; Ann. Pharm. 9, 61. Blanchbt <fe Sell. Ann. Pharm, 6, 280. Laurent. Ann. Chim, Phys. 66, 212. SouBBiRAN k Capitainb. J, Phamt. 26, 1; N. Br. Arch, 22, 171;

abstr. Ann. Pharm, 34, 317. Detille. Ann. Chim. Phys. 70, 81. — N. Ann, Chim. Phys. 25, 80. —

N, Ann, Chim. Phys. 27, 86; Ann. Pharm, 71, 349. Gerhardt. Compt, rend, 17, 314; N. Ann. Chim, Phys, 14, 113. Berthblot. N. Ann, Chim. Phys, 37, 223; 38, 44; 39, 5; 40, 36y

Ann. Pharm, 88, 346. Zbller. Sivd. uber dther. Ode. Landau, 1850.

Essence de Citron ; Citronen'Oel.

Source and Extraction. — In the rind of the lemon (Citrus limonum). The fresh rind is torn to pieces and pressed ; the oil which runs out is filtered (Saussure) ; or the expressed oil is distilled ; or the fresh rind is distilled with water. (Berthelot.)

Properties. Transparent and colourless, or yellowish (Saussure) ; pale yellow or greenish yellow to dark yellow (Zeller) ; after rectification with water, it is colourless at first, bat afterwards turns yellowish (Blanchet & Sell); mobile. (Saussure.) — Sp. gr. 0*8517 at 22"" (Saussure) ; 0*8514 at IS'' (Guibourt) ; 0*856 at 25° (Chardin) ; 0790 at lOO'' (Aubergier, /. Pharm. 27, 278) ; 0852 at 14*6 (Brix, Pogg. 55, 381) ; 0*838 at 0° (Frankenheim, Pogg. 72, 422) ; 0*84—0-86. (Zeller.) — Rectified : 0*847 at 22° (Saus- sure), 0*856 at 18'' (Chardin) ; 0848 (Soubeiran & Capitaine) ; distilled at 55"" in yacuo : 0*8514 at 14"* ; distilled at about 80^ in vacuo, 0*8506 at 65"^ (Berthelot) ; distilled with water : first distillate, 0*877 ; hat, 0*853. (Soubeiran & Capitaine.)

Boiling point 160°— 170° (Soubeiran & Capitaine) ; 146° (Aubergier) ; 176*1°. (Brix.) Distilled with water: first distillate, 167°; last, 173°. (Blanchet & Sell.) Expansion from 0° to 100° = 0*09821 ; from 0° to 135° = 0*138068. (Frankenheim, Pogg. 72, 422.) — Vapour^ensity = 4*73 (Soubeiran & Capitaine), by calculation 4-71 (comp. p. 245). — Specific heat (water « 1) = 0*45. Latent heat of vapour (raponr of water at 100* = 432) = 63*85. (Brix.) — Refracting power (water « 1-333) = 1*475 (Becquerel & A. Cahours, Compt. rend, 11, 867 ; Pogg. 51, 427);

298 NATURAL OILS, ISOMERIC WITH OIL OF TURPENTINE.

1-472, of old oil of lemon, 1*4808. (DevillOi CampL rend. U, 865 ; Po^g. 51, 483.) — Rotatory power, 80*484'' to the right (Biot, Ann. Chim. Phys, 69, 22) ; 79*494'' to the right (Sonbeiran & Capitaine) ; 72*5 to the right. (Berthelot.) — Of the oil rectified with water : first distillate 15*34 right (Soabeiran & Capitaine) ; distilled at 55^ in vacuo, 56*4° right. (Berthelot.) — Has an agreeable odour. Neutral. (Zeller.)

Saussnre. Dumas. _ Hermann,

a. b. c.

20 C 16 H	... 120 .... • • • X w ••■•	88-28 11-77	86-899 . 12-326 .	88-45 .... 11-46 ....	■••* 00-9 .... 11-5
C»H>« ....	20 C	10000 Blai &£ d, 86*72	99-225 99-91 .... ^^^ Berthelot. 88-1 85-3 11-4 11-4	.... 100 0
	16 H	11-57
	C»HW .	98*29		99-5	96-7

01 contained 0-775 p. c. nitrogen. (SaoBsnre.) «, distilled in Facao (at to) 56^; /, up to 80^ (Berthelot.)

From its behavioar towards hydrochloric acid, oil of lemon must be regarded as a mixture of citronyl and citryl, two compounds isomeric with each other and with oil of turpentine. (Blanchet & Sell.) It is resolved, under the influence of hydrochloric acid« into two isomeric compounds, citrene and dtrilene, which did not preriously exist in it. (Soubeiran & Capitaine.) It is for the most part isomeric with oil of turpentine, but always contains in addition a small quantity of an oxygenated oil. (Gerhardt^ Berthelot.)

DecomposUion^, 1. Lemon-oil absorbs oxygen gas^ gradually assuming a brownish yellow colour, whilst carbonic acid, nitrogen, and hydrogen go ofi*, together with the excess of oxygen. It absorbs in a week 0*8 vols., in the two following months, as a daily average, 1 '07 ; after four weeks, at 23^ daily 1*7 i within a year, 141*7 ; in uie following thirty months^ scarcely 2 vols, oxygen, and yields 16*6 vols, carbonic acid, 0*66 nitrogen^ and 0*29 hydrogen. (Saussure.) In contact with insolated oxygen

iSchonbein, J, pr, Chem, 52, 187), by very long contact with the air Williams, Ohem. Gai. 261, 831 ; J. pr. Chem. 60, 254), it acquires a pungent odour and oxidising properties. — Lemon-oil turns acid when exposed to the air either by itself or in contact with water ; the rectified oil, however, does not (Aschhoff, i\r. Br, Arch. 40, 273) ; it forms acetic acid and lemon-camphor, acquires a different odour, and yields by dis- tillation, acid water and an oiX while resin remains behind. (Boissenot.) — 2. The oil may be heated to 300° for several hours without alteration, but at 360% it begins to give off hydrogen and carbonic oxide. Its rotatory power begins to diminish when it is heated to 360^ ; after being heated for 34 hours to 200 — 240°, it exhibits a dextro-rotatory power of 72*70' ; after heating to 300° for an hour, it rotates 73° to the right ; to 360^ for an hour, 65*6° to the right. The permanence of the rotatory power of oil of lemon when it is heated to 300°, distinguishes it from oil of turpentine ; hence the presence of oil of turpentine in oil of lemon may be detected by the alteration of the rotatory power by a temperature of 300°. (Berthelot.) Lemon-oil, passed in the state of vapour through a heated porcelain tube, yields a non-inflammable gas, tar, and charcoal. (Saussure.) — 3. Cotton, saturated with oil of lemon, chars on the surface in dry chlorine gae, but does not take fire. (Bottger, «/• pr. Chem. 73,

OIL OP LEMON. 299

498.) In contact with 20 vols, water^ it decolorises bromine gradaally added to it, and forms hjdrobromic acid. The rectified oil absorbs 227-8, the crude oil, 242*8— 253*3 p. c. bromine. (Williams, Chem. Gaz. 263, 365 ; J. pr, Cliem, 61, 18.) — 5. With iodine^ it becomes heated, and gives off hjdriodic acid, together with violet and yellow vaponrs, (Guyot, J, Fkys. 5, 230 ; Walcker, Pogg. 6, 126) ; becomes reddish, yellow-green, and viscid. (Zeller.) — 6. Wiih fuming nitric acid, it froths strongly, and forms a orownish-yello w resin (Hasse, Grell. Ann. 1785, 1, 422) ; with ordinary nitric acid, it assumes a slight brownish colour, and gives off gas when heated (Zeller) ; with alcoholic nitric acid, it forms hydrated oil of lemon. (Deville.) With aU of vitriol, it turns yellowish brown (Zeller), and is converted, like oil of turpentine, into terebene and colophene (pp. 257, 279) (Deville) ; dropt into a large quantity of oil of vitriol, it forms a red -brown solution of sulphoterebic acid. (Gerhardt, Compt, rend. 17, 314.) — 8. When distilled with anhydrous phosphoric acid, it yields terebene and colophene. (Deville.) With hydrochUyiHC acid gas, it turns brown, (Thenard^ Mem, de la Soc. d'Arcueil, 2, 32), yellow if heated, expanding by 16*6, p. c. and increasing in weight by 41 p. c. (Sauuure;, and soliclifies to crystalline hydrochlorate of lemon-oil (Thenard), completely (Dumas), partially (Blanchet & Sell ; Soubeiran & Capitaine.) Lemon-oil, distilled in vacuo at 55°, solidifies partially when saturated with hydrochloric acid gas ; that which distils at 80°, solidifies completely. (Berthelot.) — 10. Lemon-oil remains unaltered when heated to 100® for three hours with anhydrous horacic acid. — 11. Heated to 100^ for 30 hours with crystallised tartaric or citric acid, it remains unaltered, but when treated in like manner with oxalic acid, it decreases in rotatory power, and loses the property of crystallising with hydrochloric acid. — 12. With potassium, it gives off a small quantity of hydrogen in the cold, more when heated. — The oil, which is thereby coloured brown, ceases to be decomposed after repeated distillation over potassium, and acquires a very agreeable odour. — 13. When left in contact with hydrate of potash, it deposits brown flocks, which settle npon the solid potash. The oil thns treated does not turn brown, but acquires a stronger and more agreeable odour. (Gerhardt.) -^14. Distilled with 8 pts. chloride of lime and 24 pts. water, it yields chloroform. (Chautard, Compt. rend, 34, 485 ; J, pr. Chem. 56, 238.) Distilled with hypo- bromite of lime and water, it yields bromoform. (Chautard, Compt, rend. 34, 485 ; J. pr. Chem. 5Q, 238.) — 16. The rotatory power of lemon-oil oil is diminished by twenty hours heating to 100° with cJUoride of zinc,

S Berthelot.) — 17. With a strong solution of bibasic acetate of lead, it brms a slight yellow precipitate. (Schindler, N. Br. Arch. 41, 140.) — 19. It is not altered by nitroprusside ofcoppe)\ (Heppe, N. Br. Arch^ 89, 57.)

Combinations. 1. With Water. HydrcUed Oil of Lemon ; Hydrate of Lemon-oil. — Isomeric and identical with turpentine-camphor. — It is produced by mixing 4 pts. of commercial oil of lemon, 3 pts. of alcohol of sp. gr. 0*85, and 1 pt. of commercial nitric acid, leaving the mixture to stand for 4 weeks, then collecting the resulting crystals and purifying them in the manner as those of turpentine-camphor. (Deville.)

2. With Hydrochloric Acid. a. Monohydrochlorate of Lemon-oil, (Deville.) C^'H^jHCl. Appears to be frequently present in small quantity in the portion of lemon-oil which remains liquid after saturation with hydrochloric acid gas (liquid lemon-carophor ; Soubeiran & Capitaine).

300 NATURAL OILS, ISOMERIC WITH OIL OF TURPExNTINE.

It is produced by saturating with hydroohlorio acid gas, a solution of lemon-oil in acetic acid or alcoholic oil of vitriol, and collecting the few crystals which separate, rarely however, and only under peculiar circum- stances. It forms crystals like those of artificial camphor, which melt at 100°, and volatilise without decomposition at higher temperatures. (Deville.)

6. BihydrocMorate of Lenbon-oil. C^fl^^HCl. Salzsaurer dtromen* campher (Dumas) ; Salzsaures Ciironyl (Blanchet & Sell) ; Muriate ciiri (Sausaure) ; Hydrochlorate de Citrene (Dumas, Laurent, Soubeiran & Capitaine) ; Biehlorhydrate iolide d*es9enee de citron. (Deville.) First prepared by Th^nard. {Mem. de la Soe. d'Arc. 2, 32.)

Formation. 1 . By the action of dry hydrochloric acid gas on rectified oil of citron (Thenard) ; with evolution of heat. (Saussure ; Blanchet & Sell.) — 2. By eight days contact and frequent agitation of aqueous hydrochloric acid with oil of lemon. — 3. By the action of dry hydro- chloric acid gas on turpentine-camphor (p. 268), with separation of water.

(Deville.) Lemon-oil, mixed with ^ turpentine-oil, does not yield any solid hydro- chlorate of lemon-oil when heated with hydrochloric add gas. (Berthelot, N. J, Pharm, 2^, 28.) — Rectified oil of lemon absorbs at 20% and under a pressure of 0*724 met., 286 vols, hydrochloric acid gas, and forms a semi-fluid mixture of crystalline laminn and liquid oil, which melts completely at 30^, and when pressed between filtering paper at 12% yields 44*5 p. c. bihydrochlorate of lemon-oil.

Preparation. Rectified and dehydrated oil of lemon well cooled^ is saturated with dry hydrochloric acid gas ; the crystals which separate after a while are removed from the brown mother-] iquor, pressed repeatedly between filtering paper, washed with cold alcohol, recrystal- lised from hot alcohol, dried in the air, then in vacuo or over oil of yitriol (Dumas), and once more crystallised from ether. ^Blanchet &

Sell.) — The mother-liquor which drains from the crystals (liquid lemon-camphor ; [Soubeiran & Capitaine], hydrochlorate of citryl [Blanchet & Sell]), cfystallises com- pletely in the end if left to evaporate freely in the air. (Dumas.) — Only a part of the lemon-oil forms crystals with the hydrochloric acid; crude lemon-oil, saturated with hydrochloric acid gas, acquires a very dark colour, solidifies when cooled below 10", does not yield half as great an amount of crystals as the rectified oil, and then likewise forms a black, very thick substance — a yellow substance (perhaps colouring matter of the lemon-peel)^ and a small quantity of a brown heavy liquid. (Saussure.) — Lemon- oil yields more than its own weight of the bihydrochlorate. (Dumas.)

Properties. Right four-sided prisms, often very much flattened (Saussure), white brittle laminaa. (Blanchet & Sell.) Heavier than water. (Saussure.) Melts at 41'' (Saussure), at 43° (Blanchet & Sell), at 44^ (Deville.) — No longer volatile; solidifies in the crystalline form on cooling. (Saussure.) — Sublimes for the most part between 50^ and 60*^ (Saussure) j at 50° without any decomposition. (Blanchet & Sell.) — Boils with decomposition at 162'' (Blanchet & Sell); 142^ (Cahours, Ann. Ckim. Fhys. 70, 101.) Optically inactive. (Soubeiran & Capitaine.) Smells like thyme (Saussure), like tuberoses. (Blanchet & Sell.)

Dumas. ^'^{jf Deville.

20 C 120 .... 67-5 67-20 .... 5776 .... 57-2

18 H 18 .... 8-6 8-75 .... 873 .... 8-7

2 CI 71 .... 33-9 34-05 .... 3348 .... 34-1

C»HWHC1 209 .... 100-0 100-00 .... 99-92 .... 100-0

Deeompotitiona. 1. When heated^ it gives ofi* hydrochloric acid gas (Saussure ; Blanchet & Sell ; Soubeiran & Capitaine ; Deville) ; a

OIL OF LEMON. 301

volatile oil (Saiissnre) ; an oil which solidifies again at 20° (Blanohet & Sell), and distils partially without decomposition. (Saussure.) When Quickly heated above 100°, it distils for the most part nndecomposed, the aistillate being merely covered with a trace of oil ; when it is moderately heated to 50 — 60°, part of it sublimes in large laminsB, whilst the rest distils over as a limpid oil, containing hydrochloric acid and still holding crystals in solution. (Saussure.) — 2. When set an Jire, it burns less easily than artificial camphor. (Saussure.) — 3. By distillation with tpater, it yields a watery liquid having an acid reaction. (Blanchet & Sell.) — 4. Chlorine gcu acts upon fused bihydrochlorate of lemon-oil, partially converting it after a while, with evolntion of hydrochloric acid, into chlorinated bihydrochlorate of lemon-oil. If this compound be gently heated to remove free chlorine and hydrochloric acid, an oil is obtained, consisting of 9 At. hydroMwate of chhrodtrenaK and 1 At. kydro^ chlorate of cUrene= 9(C>»H»*C]»2HC1) + C»H",2HC1. (Laurent.) — 5. With fuming nitric acid, the compound froths up slightly, and dis- solves in it after 1 4 days (Saussure) ; ordinary nitric acid does not attack it in the cold, but decomposes it completely when heated, giving off nitrous acid. (Blanchet & Sell.) — 6. Oil of vitriol poured upon the compound, eliminates hydrochloric acid gas. (Saussure.) — 7. Oently heated with potassium, it yields colourless oil of lemon, and by continued boiling with it at a higher temperature, it yields citrene. (beville.) — 8. When treated with potash, it gives off part of its hydrochloric acid, and is converted into an oil from which no further quantity of acid can be extracted by potash. (Blanchet & Sell.) — 9. Heated with lime or baryta, it yields citrene. (Saussure and others.) — 10. It is decomposed by nitrate of silver and mercuric nitrate, even in the cold ; but not by nitrate of lead, even with the aid of heat. (Blanchet & Sell.)

Combinations, Bihydrochlorate of lemon-oil is insoluble in VKiier^ soluble at 14° in 5'88 pts of alcohol of sp. gr. 0*806 (Saussure), soluble in ether (Blanchet & Sell), in oil of lemon. (Saussure.) The alcoholic solution deposits slender laminaa when mixed with water, and yields regular crystals by spontaneous evaporation ^Saussure) ; it likewise decomposes partially when evaporating. (Sonbeiran & Capitaine.)

e. Liquid Lemon-camphor, Hydroehlorate qf Cittylene. (Soubdran & Capitaine.) Hydroehlorate qf CitryL (Blanchet & Sell.) The compound which remains liquid after the saturation of lemon -oil with hydrochloric acid gas. The liquid is cooled to — 10°, to separate the solid bihydrochlorate which remains dissolved, and filtered through chalk and animal charcoal to remove colouring matter and free hydrochloric acid. (Sonbeiran & Capitaine.) Volatile oil ( Blanchet h Sell) ; without rotatory power. (Sonbeiran &, Capitaine.) It gives up hydrochloric acid when its alcoholic solution is precipitated bv water, or when it is filtered through chalk and charcoal. (Sonbeiran & Capitaine.) By saturation with dry hydro- chloric acid gas, it is completely converted into a white ciystalline mass, which, when dissolved in hot alcohol, does not yield any crystals on cooling, bnt a heavy oil and a specifically lighter acid, which remains dissolved in the alcohol, a few crystals of bihydrochlorate of lemon-oil likewise floating in the liquid. (Blanchet <& Sell.)

Oil of lemon dissolves phosphorus, and then resinises quickly on exposure to the air. With a amali quantity of phosphonia, it forma an oil imeHing

302 NATURAL OILS, ISOMERIC WITH OIL OP TURPENTINE.

like oQ of balm ; with a larger quantity of phosphonu, a solid man like spermaoeti. (Jonaa, Atm. Pharm, 34, 329.) — At 16° it absorbs 8*5 vols, of ammomortfot. (Saussure.) — It dissolves in all proportions of absolute alcohol (Saussnre, Zeller), in 7*14 pts. of alcohol of sp. gr. 0*837 at W (Saossore), and with turbidity in 10 pts. of alcohol of sp. gr. 0*85. (Zeller.)

Appendix to Oil of Lemon,

Lemon-camphor.

BoiSBBNOT. (1829.) J. Pharm. 15, 324; Ann. Chim, Phys. 41, 434;

N. Tr. 20, 2, 214. Blanchbt & Sell. Ann. Pharm, 6, 280. Mulder. J. pr, Chem. 17, 104; Ann. Pharm. 31, 69. Berthelot. iV. Ann, Chim. Phys. 40, 36.

Sitarqpiene qf Lemon-oil. Oitronen-campkor.

Source. In lemon-oil which has been long exposed to the air. ( Boissenot.)

Preparation. 1. By leaving oil of lemon to itself for some time in a bottle not quite full and frequently opened ; and : a. Collecting the crystals which form on the stopper ; — b. Distilling the thickened oil, cooling the water containing acetic acid, which passes over with the oil, to — 8^, and collecting the crystals which separate ; — c. Mixing the alco- holic solution of the distilled oil with water, leaving the water separated from the oil to evaporate at 37° — 40°, and collecting the crystaLs which separate on cooling. (Boissenot.) — 2. By distilling oil of lemon as long as the more volatile oil passes over, and collecting the crystals which separate from the residue on cooling. (Blanchet & Sell, Berthelot.)

Properties. Colourless, transparent, shining prisms. (Boissenot.) — Melting point 43''— 45* ^Boissenot) ; 46° (Mulder) ; above 100°. (Ber- thelot.) Boils above 100 , distilling over in drops which separate in the crystalline form on cooling (Boissenot) ; sublimes (Mulder). Odour faint (Boissenot) ; like that of lemon-oil. (Mulder.) Taste sharp and pungent. Neutral. (Boissenot.)

c H O	Mulder. 55*02 ... 8*98 .,., 36*00 ...	Berthelot. .... 58*00 .... 7*50 .... 34*50
	100*00 ...	100*00

Decompositions. 1. When thrown on red-hot ooals, it volatilises, without taking Jire, and is but partially decomposed in a red-hot crucible,

— 2. Heated with concentrated nitric acid, it gives off nitrous acid without forming oxalic acid ; in cold nitric acid it dissolves without decomposition.

— 3. With oil of vitriol, it forms a red solution having a peculiar aromatic odour, from which water separates a resin insoluble in water and hydro* chloric aoidy and not melting at 100°. (Boissenot.)

CITRENE. 303

•

Combinations. Lemon -camphor is iDSolnble in cold, but dissolves, abundantly in boiling water. — The solution solidifies in a crystalline mass on cooling (Boissenot) ; it is iridescent. (Berthelot.)

It does not absorb hydrochloric add gas, but dissolves in hydrochloric acid, — The solution becomes turbid when heated above 100 , but clear again on cooling. (Boissenot.^ — It dissolves in acetic add, alcohol, and ether, is insoluble in pure oil ol lemon, but soluble in the old oil containing acetic acid. (Boissenot.) The alcoholic solution partially solidifies on cooling in the crystalline form (Blanchet & Sell), gelatinous (Berthelot).

13. Citrene.

Saussube. (1820.) Ann. Chim. Phys. 13, 265.

Blanchet & Sell. Ann. Pharm. 6^ 286.

Dumas. Ann. Chim. Phys. 52, 405; Pogg. 29, 129; Ann. Pharm, 9,

61. SouBBiRAN & Capitaine. J, Phaiiu. 26, 1; N, Br. Arch, 22, 171;

abstr. Ann. Pharm. 34, 318. Deyille. N. Ann. Chim. Phys. 27, 86.

atrhie (Dumas, Soabdran & Capitaine); Citnmyl (Blanchet & Sell.) First prepared in 1820 by Saussure (p. 301.)

Preparation. 1. Bihydrochlorate of citron-oil is distilled three times over lime, and the oil which passes over each time is redistilled six times over baryta. (Dumas.) — Sanssnre distilled it over 5 pts. of lime between 50^

and 60"* 2. Bihydrochlorate of lemon-oil is first distilled by itself to

remove part of the hydrochloric acid, then passed in the state of vapour over lime heated to 180° (Soubeiran & Capitaine^, and the yellow oil which passes over is rectified over recently ignited lime, and finally over potassium. (Blanchet & Sell.) — Fused bihydrochlorate of lemon-oil is distilled over potassium, and the oil which passes over is collected. (Deville.)

Properties. Transparent and colourless. (Blanchet & Sell ; Dumas.) Sp. gr. 0*8569 (Blanchet & Sell); 0*847. (Soubeiran & Capitaine.) — Boiling point 165°. (Blanchet & Sell ; Soubeiran & Capitaine.) — Vapour-density 4*891 (Cahours, Ann. Chim. Phys. 70, 101) ; 473 (Soubeiran & Capitaine) ; by calculation « 4*71 (p. 245). — Optically in- active. (Soubeiran & Capitaine.) — Smells like oil of lemon (Dumas) ; less agreeably (Soubeiran & Capitaine) ; aromatic, like hydrochlorate of citron-oil. (Blanchet & Sell.

^'s^U^ Dumas. Deyille.

20 C 120 .... 88-24 8845 .... 88-32 .... 88-04

16 H 16 .... 1176 11-64 ... 11*77 .... 1182

C»HM 136 .... 100*00 100-09 .... 10000 .... 99*86

With hydroMorie add gas it becomes coloured, without producing crystals (Saussure), forming a liquid and a solid hydrochlorate. (Son* beiran &, Capitaine.)

304 NATURAL OILS^ ISOMERIC WITH OIL OF TURPENTINE.

14, Gitrilene.

SouBEiRAN k Capitatne. (1840.) J, Pharm, 26, 1; N. Br, Arcky 22, 171; abstr. Ann. Pharm, 34, 317.

Ok/ry/. (Blanchek & SeU.)

Prepared by distilling liquid lemon-oamphor over lime, and collecting the oil which passes over.

Properties. Sp. gr. 0*88. Boiling point 168°, gradually rising to 175°, and leaving a colonred residue. Vapour-density = 5*08. Optically inactive. (Soubeiran & Capitaine.)

15. Oil of Lime.

Dumas. (1833.) Instit. N. 97; J. pr. Chem. 4, 434. VoHL. N. Br. Arch. 74, 16; abstr. Chem. Centr. 1853, 318.

lAmeitol. Huile de limette.

Source and Extmction. In the rind of the lime (Citrus limetta). — The rinds are torn and pressed, or distilled with water.

Properties, Like oil of lemon.

		Dumas.
20 C ....	.... 120 .... 88-24 ..,	87-6
16 H ....	.... 16 .... 11-76 ..	11-4

C»H>« 136 .... 100-00 100-0

With a mixture of chromate of potash and oU of vitriol^ it becomes strongly heated, and forms limettic acid, G^H'0*^ (Vohl.)

16. Oil of Mandarin.

LuCA. (1857.) Compt. rend. 45, 904; J, pr. Chem. 75, 187; xV. J. Pharm. 33, 51; Instil. 1857, 393.

Mandarinol. Enenee de Mandarin.

Source and Extraction, In peculiar ceUs of the rind of Citrus U^a- radia sinensis and myi^ifolia. The rinds are pressed, after their surface has been lacerated, and the oil which runs out is filtered.

Properties. Pale yellowish ; after rectification, colourless, clear, and mobile. Sp. gr. 0852 at 10°; 08517 at 12°. Boiling point 178"*. Has an agreeable odour, different from the oils of lemon and orange, and a not unpleasant taste, like that of orange^oiL Rotatory power 85-5^ to the right.

OIL OF ORANGE PEEL. 305

Laca.

20 C 120 .... 88-23 87*58

16 H 16 .... 11-77 11-96

C»HW 136 .... 100-00 99-54

DecompoiUioTU. 1. With cold nittie acid, it assumes a faint yellow colour, and is decomposed by hot nitric acidy with evolution of nitrous acid, the mixture, on addition of water, depositing a nearly solid mass. — 2. With cold Oil of viiriol, it turns red, but is decolorised again when mixed with water ; hot oil of vitriol chars it, and gives off sulphurous acid. — 3. With hydrochlofic acid, it turns brown forming jsoHd bihydro- chlorate of mandarin-oil.

CombinaUoTu. I. With Water. Mandarin oil, left in contact with alcoholic nitric acid, fonns a crystalline mass, which is probably hydrated mandarin-oil.

2. With Hydrochloric Acid, — Bihydrochlorate of Mandarin^^ The oil is saturated with dry hydrochloric acid gas^ or shaken up with strong hydrochloric acid, and the crystalline mass which separates from the brown liquid after a few days, is collected, pressed between filteriner paper anJ dried. J". » F g

Small, solid, transparent laininsB, which melt when heated, volatilise without decomposition, have a peculiar odour, and are insoluble in water but solnble in alcohol and ether.

Mandarin-oil is insoluble in water, to which, however, it imparts its odour.

It dissolves in 10 pts. of alcohol, also in ether and in glacial acetic acid, and in every proportion of bistdphide of carbon.

It dissolves iodine, bromine, phosphorus, stdj hur, oils, both Jixed and ffolcUiU, wax, B,nd resins. (Luca.)

17i Oil of Orange-peel.

Gaubius. Adversaria. 30.

SouBEiRAN & Capitainb. J. Phai-m. 26, 65.

Zrllbr. Stttd, uber. other Oele, Landau, 1 850.

Essence d^ orange, Orangtnsehalenol, Pomeranzenschalenifl.

Source and Extraction. In orange-peel, the rind of Citrus Auran- tium (L,). — The lacerated rind is pressed or distilled with water, or the expressed oil is distilled with water.

Properties. Pale yellow to greenish yellow, mobile. (licwis, Zeller.) Sp.gr. 0.888 (Lewis), 0-835 — 0-837 (Soubeiran & Capitoine) ; 0-83 — 0-85; of older oil, 0*88 (Zeller). Boiling point 180^ Vapour- density 4'69. (Soubeiran <& Capitaiue.) Calculation = 4'714 (p. 245). SolifliHtf:< partially when coolt*d. (Bizio, Bntgn. Giom, 1 9, 360.) Rotatory power 125'59^

— 127*43'^ right. It has an agreeable odour. Neutral. (Zeller.)

vol.. XIV; X

306 NATURAL OILS, ISOMERIC WITH OIL OF TURPENTINE.

			Soabeiran &
			Capitaine.
20 C ....	.... 120	.... Oa £S .	88'44
16 H . ...	.... 16	.. 11-77 .	11-65

C»H" 136 .... 10000 100-09

Decompositions, 1. When itep^ in closed vesssels, it deposits crystalline, easily fusible, volatile clots, solable in water and alcohol, and ultimately turns viscid and brown. (Gkiubius.) With iodine, it gives off yellowish- red vapours with great violence, turning reddish yellow-brown, and assuming a resinous consistence. — 3. With nitric acid, it tnrns greenish- yellow, gives off gas when heated, and is converted into a brittle resin. — 4. Oil of vitriol colours it dark reddish yellow-brown. — 5. Mixed with an equal quantity of bihasic acetate of lead, it yields an orange- yellow precipitate, turning red in an hour, and becoming lighter after a week. (Schindler, N, Br. Arc!*,. 41, 140.)

Comhinaiions, With Hydrochloric Acid. — 1. Monohydrochloraie of Orange-peel-oil. The portion which remains liquid when the oil is saturated with hydrochloric acid gas. (Soubeiran & Capitaine.) — 2. Bihydrochlorate of orange-peel oil C®H"CO*. Solid HydrochJorate of Oranffe-peel'Camphor, Hydrochlorate of Hesperidene, The portion which solidifies when the oil is saturated with hydrochloric acid gas. Id crys- talline form and odour it resembles bihydrochlorate of lemon-oil. Melta at 50°. Has no rotatory power. (Soubeiran & Capitaine.)

20 C.

18 H.

2 CI.

		Soubdran &
		Capitaine.
120 .... 57-5 .	67-95
18 ..	8-6 .	8-61
71 ..	.. 33-9 ..	33-44

C20H»«,2HC1 209 .... 1000 100-00

It decomposes as easily as bihydrochlorate of lemon-oil. (Soubeiran & Capitaine.)

Oil of orange-peel dissolves in absolute alcohol, and with turbidity in 7 — 10 pts. of alcohol of sp. gr. 0-85. (Zeller.)

18. Oil of China Orange.

VoLKEL. (1840.) Ann. Pharm. 39, 120; Bepert. 80 164. Apfeisinendl.

Source and Extraction. In the rind of Citr^is aurantium sinensis. It is obtained by pressing the fresh lacerated rind or distilling it with water.

Veikel.

20 C 120 .... 88-24 88-38

16 H 16 .... 11-76 11-74

C=m»« 18G .... 100-00 100-12

OIL OF PBPPER. 307

19. Oil of Parsley.

Lowio & Weidmann. (1841.) Fogg, 46, 53; abstr. Repf^L 70, 163. Zeller. Stud, fiber, other. Ode; Landau, 1850.

Peiernlienolf Essence de pertilt Oleum petrogelini.

Source and Extraction. In parsley-seeds, the fruit of Apium petro- selinum. — The bruised seeds are distilled with water, and the more volatile oil which first passes over is collected. At the same time there passes over a less volatile oil, which solidifies to parsley- camphor. (Lowig & Wiedmann, inf.) The watery distillate must be kept for some time in the cold, in order to obtain the oil which then only separates from it. (Schutz, Bepet^. 1^, 275.)

Properties. Greenish yellow oil ; after rectification, colourless, trans- parent, and mobile. The crude oil boils above 210°, the rectified oil between 160° and 170°. (Lowig & Wiedmann.) It solidifies between 2° and 8°. Sp. gr. 1015 — 1-144. (Zeller.) Smells like parsley. (Lowig & Wiedmann.) Neutral. (Zeller.)

L5wig & Weidmann.

20 C 120 .... 88-24 88*04

16 H 16 .... 11-76 11-88

C»H" 136 .... 10000 99-92

Decompositions, 1. The crude oil thickens by boiling, finally becoming resinous, and when distilled per se or with water, is resolved into liquid oil which passes over and camphor which remains behind. (Lowig <& Weidmann.) — 2. Iodine dissolves slowly in the heated oil, and colours it brown-red. (Flaschofi*, Br. Arch. 33, 225.) It detonates with iodine, giving off yellow and violet vapours, and is converted into a dark red-brown resin. (Winkler, Repert. 32, 271.) — 3. Nitric acid colours it yellow or brown, and resinises it (Zeller) ; forms malic and oxalic acids. (Scheele, Optt^e. 2, 206.) Oil of vitriol colours it violet to dark red, without thickening it (Zeller) ; the solution mixed with water deposits resin. (Bley.) It absorbs hydrochloric acid gas, with rise of temperature, and turns brown. (Lowig & Weidmann.)

Oil of parsley dissolves in 2*5 pts. alcohol of sp. gr. 0*85. (Zeller.)

20. Oil of Pepper.

LuCAE. Taschenlmch, 1822, 81.

DoMAS. J. Chim. med. 11, 308; InstU. 97 j J. p7\ Ghent. 4, 435. SouBEiRAN & Capitaine. J. Pharm. 26, 75; abstr. Ann. Pharm. 34, 326.

Pfeffefol^ Buence de poivre. Oleum piperie.

Source and Extraction In black pepper, the unripe berries^ and in white pepper, the seed of Piper nigrum, (Z.) Bruised black pepper is distilled with water ; and the oil which passes over is rectified with

X 2

TiOS NATURAL OILS, ISOMERIC WITH OIL OF TURPENTINE.

salt-water, and dehydrated by agitation with chloride of calcium. (Son- beiran & Capitaine.) Black pepper yields TJT, white pepper, 1*04 p. c. of oil. (Lecann.)

Propertie$. Limpid and mobile. Sp. gr. 0*993 (Lncae); 0*864. Boiling point 167"5°, ultimately rising to 170°. Vapour-density = 4*74. Calculated 4'7 14 (p. 245). (Soubeiran d^ Capitaine.) Has a strong smell of pepper and a mild taste. (Lucae.)

Damas.

20 (• 120 .... 88-23 87*9

In H 16 .... 1177 11-7

C*H'« 135 .... 100-00 90-6

Decompositimis. 1 . By a few drops of oil of vitriol, it is heated and blackened ; but when dropt into a large quantity of oil of vitriol, it forms a red brown solution of sulphoterebio acid. (Gerhardt, CompL rend, 17, 314.) — 2. When saturated with dry hydroddoric acid gns^ it turns brown, and forms hydrochlorate of pepper-oil. (Soubeiran & Capitaine.) — 8 When set aside or heated with potoMium, it acquires an odour recalling that of pepper and of lemons. (Gerbardt, CompL rend. 17, 315; N. Ann. Chitn. Ph s. 14, 114.)

Combinations. WUh Hydrochloric Acid. Hydrochlorate of Pepper-oil. — The oil is completely saturated with dry hydrochloric acid ^s, and filtere<l through charcoal, which is completely covered with a layer of chalk. Colourless liquid, containing 6^2-69 p. c. C. 8*80 U, and 28-51 CI, and therefore approximating in composition to the formula C^H*'^,2HC1. (Soubeiran k Capitaine.)

21. Pepper-oil from Long Pepper.

Ddlono. J. Pharm. 11, 59; N. Tr. Jl, 1, 104.

In long pepper, the monospermic-berry-carrying flower-stalks of Chaviea Roxhxirghii and Ch. officinarttm. (Dulong ) They are bruised and distilled with water. — Limpid, lighter than water, with an nn- plea-sant odour and sharp taste.

22. Oil of Peiicedapiim OrsoseUaura.

SciiNRDBRMANN & WiNCKLER. Ann. Pharm, 51, 336.

Source and Extraction. By distilling the fresh herb of Peucedanum Oreoselinum with water.

Properties. Has a strong aromatic odour like that of juniper. Sp. gr. 0*840, and boiling point 163^

HYDROCARBON FROM OIL OF CHAMOMILE. 309

			SchQedermann & Winckler. a, 6.
20 C 16 H ....	.... 120 .. .... 16 ..	.. 88-23 .. .. 11-77 ..	88-36 .... 11-84 ....	.... 87-50 .... 11-79

C»HW 136 .... 100 00 100-20 99*29

a the first portion of the distillate ; b the last.

Combinations With Hydrochloiic Acid, The first portion of the dis- tillate above-mentioned absorbs hydrochloric acid gas abundantly^ and is thereby converted into a componnd analogous to monohydrochiorate of turpentine-oil (p. 265). The oil cooled to 0^ is saturated with hydro- chloric acid gas ; the resin which separates is removed, and the oil is shaken up with soda-solution, distilled with water, and dried over chloride of calcium.

Colourless liquid, gradually turning brown. Lighter than water; boils at about 190° ; smells like turpentine.

Scbnedermaon & Winckler.

20 0 120-0 .... 60-6 69*54

17 H 17-0 .... 9-9 9-71

CI 35-5 .... 20-5 20-86

C»H",HC1 172-5 .... 1000 100-11

23. Hydrocarbon from Oil of Chamomile.

Oerhardt. (1848.) C<mpt. rend. 20, 225; X, J, Pharm. 14, 52; A^. Ann. Chim. Pht/s, 24, 93: «/. pr, Cheni. 45, 321; Ann. Pliat-m. 67, 235.

Oil of chamomile obtained by distilling the flowers of Anthemis nobifis, is a mixture of a non-oxygenated oil with angelic aldehyde and a small quantity of angelic acid (x, 413). When it is heated in a retort with pulverised hydrate of potash, and the oil wliich passes over is rectified over potassium, angelate of potash remains behind (easily resoWed by excess of potash at a higher temperature into acetate and propionate of potash (Chiozza, N. Jnn. Chim. Phyt. 39, 435; J. pr. Chem. 61, 231 ; Awn. Pharm. 86, 261), and an oil is obtained, having an agreeable odour of lemons, boiling at 175'', and con- taining 87'8 p. c. C and 1 1*8 H, therefore isomeric with oil of turpentine. This oil does not form with oil of vitriol a compound analogous to sulpho> cymenic acid (p. 1 88), but it unites with chloride of calcium, forming crystals which are decomposed by water. The same oil is obtained by distilling oil of chamomile with alcoholic potash, mixing the alcoholic distillate with water, and syphoning off the oil which separates. (Gerhardt.)

Cmde oil of chamomile is bine (Dehne, Crell. ehem. J, 3, 25 ; Zeller), greenish, and distils to f between 180* and 190*, the remaining ^ pafining oyer between 190* and 210^; the latter portion contains 76*06 p. c. C. 10*67 H, and 13'27 O. (Gerhardt.) The fresh flowen yield 0*31 p.c. oil (Hagen), 0*047 (Lecanu); the dry flowers, 0*08 p. c. (Lecanu), 0*61 p. c. (Hagen) ; and the water which passes over contains in solution, acetic, butyric, valerianic, and perhaps propionic acid. (Wunder, J. jfr. Chem. 64, 499; Hants, /. pr. Chem. 62, 317.)

310 NATURAL OILS, ISOMERIC WITH OIL OF TURPENTINE.

24. OU of Savin.

Dumas. (1835.) J, Chim, mid. 11, 307; Ann, Pkarm. 15, 158;

J. pr. Cheni, 4, 435. Laurent. Hev. Sclent, 10, 127. Zbller. Stud, iiber cither. Oele; Landau, 1850.

Sadebaumiflf Seoenbaumdl, Sabinadl; Estence de Sabine; Oleum Sabina.

Source and Extracti^yn. In the leaves, young branches, and twigs of Juniperus salina (L.). They are cut to pieces while fresh, and distilled with water.

Properties. Pale to dark reddish yellow (Zeller) ; limpid after rectification. (Dumas.) Sp. gr. 089 — 0*94 (Zeller.) Boils at 155° — 161^. (Dumas.) Smells and tastes like the leaves and branches of the plant. Neutral. (Zeller.)

20 C 16 £1 ....	.... 120 ... 16	.... 88-23 ... .... 11-77 ...	Dumas. 88-6 11-7
C»H»« ....	... 136	.... 100-00 ...	100-3

DecompositionB. \ . When it is mixed with \ vol. water, and bromine is gradually added to it, the oil becomes heated, destroys the colour of the bromine, till 185 pts. of bromine have been added to 100 pts. of the crude oil, or 211*3 pts. bromine to 100 pts. of the rectified oil, and is converted into a colourless aromatic oil. (Williams, Chem. Gaz. 263, 365 ; J. pr, Chem. 61, 20.) — 2. With iodine, it becomes very strongly heated, detonates, gives on yellow and violet-red vapours, and forms a red-brown resinous mass, having the consistence of honey (Flaschoff, £r. Arch. 33, 225 ; Winckler, Repert. 32, 271 ; Zeller), and an empy- reumatic odour. (Winckler.) Iodine dissolves, with rise of tempera- ture, in an eqnal quantity of oil of savin, forming a red-brown solution which, when distilled to dryness, gives off a large quantity of hydriodic acid, and yields a distillate consisting of a brown oil, and finally of a balsam, which sinks to the bottom, while charcoal remains behind. (Guyot, J. Phys. 5, 230.) — 3. With nitric acid, it gives off gas with violence, becomes hot, and assumes a reddish-yellow to brownish-yellow colour. — 4. With oil of vitriol, it turns yellowish red (Hesse, Zeller) ; mixed with an equal quantity of oil of vitriol, and distilled with hydrate of potash, it yields 4 p. c. of an oil smelling like thyme. (Winckler, Repert. 92, 320) — 5. With bichromate of potash and oU of vitriol it assumes a pale brownish colour. (Zeller.) — 6. Distilled with 24 pts. of water and 8 pts. of chloride of lime, it gives off carbonic acid with effervescence, and yields chloroform. — 7. By distillation with kypa- hromite of lime, it yields bromoform. (Chautard, Compt. rend. 34, 485.)

Combinalions. Oil of savin dissolves in all proportions of absoluie alcoliol; clearly in 2 pts. alcohol of sp. gr. 0'85; with opalescence in 3 pts. or more. (Zeller.)

THYMENE. 311

25. Thymene.

DovERi. N, Ann, Chim, Phyt. 20, 174.

Lallemande. (1853.) C<ympt. rend. 37, 433; /. pr. Chem. 60, 433;

iV. Ann, Cliim, JPhys. 49, 155; abstr. Ann. Plhai^m. 101, 119;

102, 119. Stenhouse. Ann, Phaivn, 98, 308.

First obsenred by Doveri ; obtained pure by Lalleniand.

Source and Extraction, Id volatile oil of tbyme. It forms, together with cymene, the more volatile part of that oil. (Lallemand.)

Preparation, The portion of oil of thyme which passes over on fractional distillation between 166° and 185°, is repeatedly rectified over caustic potash, then per se, whereupon thymene passes over from 160° to 165^, and cymene at 175*^* The process does not, however, afford a complete separation of the cymene, which has hitherto not been attained. (Lallemand.)

Properties. Colourless oil, having an agreeable odour of thyme, boiling at 160° — 165°, and of sp. gr. 0-868 at 20°. It deflects polarised light to the left, but less strongly ^ter repeated rectification over caustic potash. (Lallemand.)

It dissolves in oU of vitriol, with rise of temperature, and yields by distillation the same products as oil of turpentine.

It absorbs hydroMoric acid gas, with slight rise of temperature, and forms a compound whicli remains liquid at — 20°, and, after purification with chalk and animal charcoal, contains 20 p. c. chlorine. (Lalle- mand.)

Doveri obtained by the fractional distillation of oil of thyme, a product boiling between 178° and 180^, which contained on the average 85 8 p. c. carbon, 10*9 hydrogen, and 3*3 oxygen, hot had a vapour-density — 8*31-1, whence he regarded it as a mixture of a hydrocarbon with thymol. This substance was scarcely attacked by anhydrous phosphoric acid, merely becoming slightly heated, and after two distillations therewith, still contained 86 p. c. C, 11*4 H, and 3 '6 O. It absorbed hydrochloric acid gas with avidity, becoming coloured and heated, and yielding, after the excess of hydrochloric acid had been driven out by a stream of dry carbonic acid, a thin red- brown liquid, which had an agreeable odour of camphor, solidified while immersed in a freexing mixture, and in which crystals made their appearance alter the lapse of a month.

From the volatile oil of the seeds of Ptychotit Ajowan, Stenhouse obtained by fractional distillation, dehydration with chloride of calcium of the portion which passed over below 176**, distillation over caustic potash, treatment with sodium, and rectifica. tion, a colourless strongly refracting oil, having a pungent, aromatic odour, different from that of oil of thyme, of sp. gr. 0*854 at 12", and boiling at 172". It formed with hydrochloric add gas, a brown, thin liquid. It contains 88*24 p. c. C, and 11*5 H, and is therefore C^H** (and perhaps identical with Lallemand*s thymene, Kr.) According to Haines, it is C^W\ therefore cymene {Ann, Pharm, 98, 315). See page 184.

312 NATURAL OILS, ISOMERIC WITH OIL OF TURPENTINE.

26. Tolene.

Dbtillb. (1841.) N. Ann. Chim. Phys. 3, 154 ; J. pr. Chem. 25, 323. £. Kopp. Compt. chim. 1849, 145; abstr. Campt rend, 24, 614; N. J. Pharm. 11, 425.

Souf'ce, In balsam of tola.

Preparation. 4 pts. of tolu-balsam are distilled with 3 pts. of water, and the distillate is repeatedly cohobated. The oil which passes over is a mixture of benzoic acid, einnamein (xiii, 283), and tolene, which passes over when the crade oil is heated for some time to 160^, and may be obtained pure bj frequent rectification over hydrate of potash (oontaininj^ a safficient quantity of water to keep it in the liquid state) and collecting the portion which first goes oyer (the latter portion which distils at 180^ contains 84*90 p c. carbon, 11*83 hydrogen, and 3*27 oxygen. (Deyille.)

Properties. Colourless mobile oil, boiling from 154° to 160^ (Kopp), at 170° (Deville), and of sp gr. 0*858. (Kopp.) It has a sharp, pungent, peppery taste, and smells like elemi-resin, different from tolu-balsam. ^Kopp.) Vapour-density somewhat below 5*71 (Deville) (bj calculation

4*714 ; see page 245.)

Deville. Kopp.

mean. nuen.

20 C 120 ... 88-23 88*60 .... 88*40

16 H 16 . 11*77 11*33 .... 11*45

C»H»« 136 ....100-00 99-93 .... 99-85

Aooordiog to DeviUe, it is C^W^ (calculation 88*9 p. c. C, IMl II), which agrees better with the analfiis, but not with the boiling point.

In yessels containing air, it becomes continually thicker, without colouring, and is finally conyerted into a soft oxidised resin, containing 75 2 p. c. carbon. (]^pp.)

27. Valerene or Bomeene.

Gerrardt a Caiiours. (1841.) -ZV. Ann. Chim. Phys. 1, 62. Prlouzb Compt rend. 11, 365 ; abstr. J. Pharm. 26, 645; /. pr.

Chem. 22, 379 ; Ann. Pharm. 40, 326. Gebiiardt. iV. Ann. Chim. Phy». 7, 275 ; Ann. Pharm. 45, 29 ; abstr.

Compt. rend. 14, 832 ; J.pr. Chem. 27, 124, Jeanjean. C(ympt. rend. 42, 857; Indit. 1856, 176; J. pt\ Chem.

69. 204; Ann. Pharm. 101, 94; Chem. Centralbl. 1856, 575. PiEKLOT. N. Ann. Chim. Phyn. 56, 291.

The non-oxygenated constituent of yolatile oil of yalerian, G^rhardt's Bomeene, and Pierlot's Valerene, is, according to Gerhardt, identical wliL the hydrocarbon of the camphor-oil examined by Pelouze, and with

VALERENE OR BORNEBNE. 813

the hjrocarbon whioh that chemist obtained from borneol by the action of anhyilrons phoephorio acid ; according to Jeanjean, it is identical with the hydrocarbon of madder fosel-oiL The identity of these bodies being doabtfo^ we shall in the following distingnisb ss Yalerene the hydrocarbon from oil of Talerian, as bomeene that firom oil of camphor, and as madder-bomeene that from madder fasel-ot). (Kr.)

A. Vdlerenefrcm Oil of Valerian, — Oil of valerian obtained by dis- tillation with water, the root of Valeriana off. is a mixture of valerianic acid, yalerol (xi, 396), yalerene (bomeene, according to Gerhardt), and borneol, mdnally formed therefrom by the action of the air. If the portion which passes over first in the uuctional distillation be rectified over fused hydrate of potash, whereby the valerol is converted into yalerate of potash, a mixture of borneol and valerene is obtained, from which the borneol may be entirely removed by repeated fractional distillation, the product which passes oyer first being each time collected apart. (Gerhardt.) — Oil of yalerian is a mixture of 5 pts. valerianic acid, 25 pts. valerene and 70 pts. yalerol, which last (difl*erent from Gerhardt's valerol) contains -f^ water, f^ resin, and \^ valerian- camphor, or is resolved into these constituents by distillation. Valerian-oil when distilled gives off between 120^ and 200^ an acid yellow oil which, when rectified over fused hydrate of potash, yields valerene below 200°, while yalerate of potash and Pierlot's valerol remain in the residue. (Pierlot.)

Properties of Valerene. Colourless oil, boiling at 1 60° under a pressure of 0-76 met. Vapour-density 4*60 (by calculation » 4 7144, p. 245). Lighter than water. Smells like oil of turpentine, but more agreeably. (Ger- hardt, Pierlot.)

Gerhardt.

20 C 120 .... 88-23 88-08

16 H 16 .... 11-77 11-86

C»H»« 136 .... 100-00 99-94

Deeompodtions. 1. It is not conyerted into camphor by dry oxygen. — 2. In contact with excess of hromiaey it gives off hydrobromic acid, and becomes yellow and viscid. — 3. It absorbs hydroMo^ic acid gas and becomes crytstalline. — 4. Nitric acid docs not act upon it in the cold, but attacks it violently when heated, if the valerene is free from bor- neol, no common camphor ia produced, thongb Gerhi*rdt formerly obtained this sub- stance by the action of nitric acid from valerene containing borneol, and supposed that it was produced from the bomeoL — 5. It is not altered by melting hydrate of potash, but when set aside for some time with potash-ley and then dis- tilled, it is converted, wholly or partially, into borneol, especially in presence of alcohol. (Gerhardt.)

B. Bomeene from the Camphor-oil of Dryabalancps Camphor a. — The younger stems of the camphor-tree (Dryabalanops Camphora)^ which grows in Borneo and Sumatra, contain oil of camphor, which exudes from incisions made in them, whereas the older stems are destitute of oil, but contain borneol in their cayities (Pelouze; comp. also Martins, Ann. Fharm. 27, 63 ; Blanchet & Sel]^ Ann, Pharm, 6, 802). In the natural state, it contains a resin in solution, from which it may be freed by dis- tillation. (Pelouze.)

Oil, of lower specific gravity than water, boiling at 165^, having an

314 NATURAL OILS, ISOMERIC WITH OIL OF TURPENTINE.

odour of tarpentine-oil, and isomeric therewith. Rotatory power 39 8^ to the left. (Gompt rend. 1 1, 371.) It absorbs oxygen gas with avidity, and is thereby converted into G^H^'O^ without forming carbonic acid.

(Pelouze.) Pebaze does not state that he obtained comraon camphor in this manner, tiioug^h Gerhardt (N. Ann. Chim, Phyt. 7» 282), attributes this statement to him. Kr.) — It absorbs as ranch hydrochloric acid as oil of turpentine. (Pelouze, Compt, rend, 11, 367 ; abstr. Ann» Pkarm. 40, 326.)

CamphoT'Oil from Laurus camphora. Martins ( Ann. Pharm. 27, 63) examined camphor-oil imported from China, which, according to his later statements (AT. Report » 1, 541), was obtained from Laurut camphora. As this tree yields common camphor, but not borneol, the camphor-oil obtained from it was probably different from that of the Dryabalanops camphora examined by Pelouze, which is associated with borneol ; and it is doubtful whether the camphor dissolved in the camphor-oil which Martius examined was common camphor, or borneol (as supposed by Gerhardt, N, Ann, Chim* Phy». 7, 284), since, in 1838, the distinctive characters of the two kinds of camphor were not known with certainty. Commercial, dark wine- yellow camphor-oil, of sp. gr. 0*945, is a mixture which deposits a large quantity of camphor by cooling or spontaneous evaporation. When subjected to fractional distillation, it leaves, after ^ has passed over, a residue which contains a larger quantity of camphor and solidifies on cooling, while the distillate, on being redistilled till j^ has passed over, yields rectified camphor-oil free from camphor. This oil is transparent, colourless, strongly refracting, mobile, smells like camphor and cajeput-oil, and has a density of about 0*91. It contains 8203 p. c. C, 11*35 H, and 6*62 O, and according to Martius is C^H^H).

Rectified camphor-oil evaporated in a watch-glass leaves resin but no camphor. It does not appear to take up oxygen, but absorbs dry hydrochloric acid gas, with rise of temperature, forming a wax-yellow liquid, which fumes from excess of hydrochloric acid, and when cooled to — 8 , solidifies to a soft butter, without depositing crystals. When dry chlorine gas is passed through the rectified oil, it assumes a transient ruby- red colour, gives off hydrochloric acid, and forms, after washing with water, an oU similar to that produced by hydrochloric acid.

Rectified camphor-oil (probably that of Martius, Kr.) is C^H^^O, and is converted into camphor by nitric acid. (Macfarlane, Ann. Pharm, 31, 72.)

In light yellow camphor-oil of unknown origin, which yielded no camphor when distilled alone, and only traces when distilled with water, Mulder {J, pr, Chem. 17* 106; Ann. Pharm, 31, 71) found, after drying over chloride of calcium, 80*41 p. c. C, 10*84 H, and 8*75 O, and accordingly regarded it as a mixture of common camphor and a non-oxygenated oil, C^H^^.

C. Madder Bomeenefrom Madder Fiisel-^dl, — The fusel-oil contained in the alcohol produced by the fermentation of madder-sugar yields liqnid products when distilled at temperatures rising to 230^, while at higher temperatures Isevo-rotatory borneol sublimes. From the former, by digestion with caustic potash, then with chloride of calcium, and repeated fractional distillation, a liquid may be separated which boils at 160", contains 88*23 p. c. C, and 11*81 H, has a vapour-density of 485, and is probably therefore borueene C^W\ (Jeaojean.) — Laevo- rotatory borneol from madder fusel-oil yields by distillation with anhy- drous phosphoric acid, a hydrocarbon smellinc; like oil of bergamot and oil of lemon (Jeanjean), which, according to Gerhard t's statements (p. 313), should be identical with madder bomeene.

Appendix to Valerene,

1. Crude Oil of Valerian, Constituents (pp. 312, 313.) According to the (older) statements of Kraus, it is an oxide of oil of turpentine C**H'*0 ; according to Ettling {Ann, Phann. f>, 40) it is a mixture of oxygenated

XANTHOXYLENE. 815

and non-oxygenated oil. — According to Haranlt {N.J. Pharm. 12, .96), the oil does not exist in the root ready-formed, inasmuch as ether does not extract any of it, hut is produced from the root by the action of water. The same view is maintained by Bonchardat, but Pierlot con- siders it erroneous.

Properties of tJie crude oil. — Mobile oil, of pale yellow, or greenish to yellowish brown colour. (Trommsdorff, N. Tr. 18, 1, 3.) The root of the plant growing in woods yields a green oil, that which grows in marshes a yellow oil. (Pierlot.) Roots a year old yield 1 82 p. c. of oil (Bley, Bepert. 48, 84). Sp. gr. 0*90 to 0*96 (Zeller) ; 0-936 at 10^. (Pierlot.) It does not solidify at —40°, but at — 15° it deposits white flocks of valerianic acid. (Pierlot.) its odour is fresh and agreeable, strong and pungent, like camphor, It is neutral, either in the fresh or in the rectified state (Gerhardt) ; acid (Zeller, Pierlot, and others). It is resolved into its constituents by distillation, as described at page 313.

Oil of valerian resinises when exposed to the air^ acquiring an un- pleasant odour, and forming valerianic acid, in consequence of its contain- ing valerol. (Gerhardt.) After the ready-formed valerianic acid in the valerian-oil has been removed, it is not possible by any means to obtain an additional quantity of that acid from the oil. — When oil of valerian is exposed to the air, the greater part of the non-oxygenated oil, of the valerianic acid, and of the water escapes, and the oxygenated oil becomes resinised. (Pierlot.) — It dissolves iodine with evolution of heat, giving off a small quantity of greyish yellow vapours, and acquiring a dark red- brown colour. (Zeller.) — With \ pt. of nitrio acid at 24°, it turns violet (Bonastre, J. Pharm, 12, QQ), blue, afterwards yellow, acquires a viscid consistence ^Rochleder), and forms oxalic acid. (Bonastre.) According to Rochleder, it does not form oxalic acid, but on distilling the mixture, it gives off nitrous acid, and forms common camphor preoipitable by water, a volatile substance which attacks the eyes strongly, a less volatile body which reddens potash-ley, and a fixed yellow resin. — When oil of valerian is heated with nitric acid, a blue resin is formed, heavier than water, insoluble in alcohol and in potash«ley, and similar to that which exists in the root ready-formid. (Pierlot.)

With oil o/vitnol, it turns dark brown-red to violet ; with bichromate of potash and oil of mtriol, greenish. (Zeller, Studien uher dtlier. Oele, Landau, 1 850.) Oil of valerian treated with potash-ley, yields a resin and a neutral oil which forms common camphor with nitric acid. (Roch- leder, Ann. Phatm. 44, 1.) It does not form any compound with caustic potash or soda. (Pierlot.)

Oil of valerian dissolves in an equal quantity of alcohol of sp. gr. 0*85, and in every proportion of absolute alcohol. (Zeller.)

28. Xanthoxylene.

Stenhouse. (1858.) Pharm. J, Trans, 17, 19; Ann. Fliarm, 104, 236; J. pr. Chem. 73, 179; Chem. Centralbl 1858, 237.

Source and Extraction, In the seed of Spanish pepper (Xanthoainfium piperitum, Dec). — The bruised seeds are distilled with water ; the oil,

816 NATURAL OILS, ISOMERIC WITH OIL OF TURPIiXTlNE.

mixed with solid xanthoxjlin, is collected and cooled, the separated xanthozylin is removed by filtration, and tlie oil is dehydrated with chloride of calcium and rectified over potash, then over potassium.

Properties, Colourless, strongly refracting. Boils at 162^ Has an agreeably aromatic and persistent odour.

20 C 16 H

120 .... 16

88-23 11-77

Stenhouse. 88-08 11-60

C»OH" 136 .... 10000 99-68

Xanthoxylene forms a liquid compound with hydrochloric acid. (Stenhouse.)

Appendix to Oils Isomeric with Oil of Turpentine, {Oil of Wormseed and its Products of Decomposition,)

Oil of Wormseed.

Trommsdorff. (1819.) N. Tr. 3, 1, 312.

VoLCKEL. Ann, Pkarm, 38, 110; abstr. JSepert. 80, 176. — Ann, Pharm^

87, 312; abstr. J, pr. Chem, 61, 515. — Ann, Pkarm, 89, 358. Zeller. Stud, iiber other. Ode, Landau, 1850. HiRzJiL. Zeiischr. f, Phatm, 1854, 3; 17; 65; 80. — Ibid. 1855, 2; 33;

49; 65; 81; 98; 114; 130; 144; 161; 179.

Wurmsamenoel, Oil or Essence qf Setnen contra, Oleum cifue.

Source and Extraction, In Levant and Barbary wormseed, the un- expanded flower-buds of Artemisia Vahliana Kosteletzky, Artemisia contra Vahl, aud Artemisia Siberi, — It is obtained by distilling the bruised wormseed with water. — The water which passes over with the oil con- tains acetic acid. (Wunder, J, pr. Chem, 64, 499.)

Properties. Transpnrent and colonrless to pale yellow (Trommsdorfl* and others) ; pale yellow to brownish yellow. (Zeller.) The crude oil is brownish yellow ; that which is obtained by distilling the seeds with milk of lime, and boils between 160° and 170^, is transparent and colour- less (Hirzel) ; after distillation over hydrate of pota&h, it boils at ISO**, and is transparent and colourless. (Volkel.) — Mobile (the crade oil m fili(?htly Yiacid). (Hirzel.)— Sp pr. 0*9258 at 11° (Wackenroder. Kasin, Arch. 11, 78 ; iT. Tr. 14, 2, 3) ; 0*936 (Volkel) ; 0 92— 093 (Zeller) ; 0*946 at 1 1°. (Hirzel.) — The oil rectified over hydrate of potash, and boiling between 175° and 180", has a sp. gr. of 0*9 19 at 20** (Volkel) ; that which is obtained from the seeds liy distillation with milk of lime has a sp. gr. of 0*945 at 8°. (Hirzel.) — Boiling point of the crude oil, 170°— 220° (VSlkcl); 175^—180° (Hirzel); of the rectified oil, 175°. (Hirzel.) The oil treated with alcoholic potash and then distilled with water, boils at 175° (Volkel); that which is obtained from the seed by

OIL OF W0RMSE12D. 317

distillation with milk of lime, begins to lyoil at 1 60^^ boils chiefly between 175° and 177°; after rectification, between 174° and 175. (Hirzel.) — It smells like the seeds (Hirzel) ; more like camphor than the seeds (Trummsdorff) ; wormseed oil from Baltimore smells more like cheno- podium. (Buchner, Hepert, 12, 438.) Its taste is sharp and somewhat bitter (Trommsdorff) ; burning and aromatic. (Wackenroder.) It reddens litmus (Zeller) ; is neutral. (Hirzel.)

				ViJIcktl.		Hirzel.
			a.	b.	c.	d, e.
24 C ..	144 ....	8000	/0*44 ....	77 89 ....	79-83 ....	78-92 ... 78-49
20 H ....	20 ....	11-11	... 10-65 ....	10-58 ....	11-31 ....	11-43 .... 11-40
2 O ...	16 ....	8-89	... 10-91 ....	11-53 ....	8-86 ....	9-65 .... 10-11

c«H»or.. mo ... 10000 loo-oo ... loooo .... loo-oo .... loo-oo .... loo-oo

a the first; b the la»t dUtillate corresponding to the formula C^^H^^O* (Volkel); the first distillafe rorresponds to the formula C'^H^O, according to which 3 At. oil a CH^^O^, by giving np 3 At. H and taking np 3 At. O, forms santonin QWHisoe (Heldt, Ann. Pharm. 63, 55); c, the oil rectifit»d over hydrate of potash, corresponds to the formula (J^lf O'; d, oil obtained from the seeds by diatillation with water ; e. with milk of lime ; the former corresponds to the formula C^H^'O', the latter to the formula i:»HWO*. (Hirael.)

Wormseed oil is nazed with another oil which changes even by distillatio.i (Volkel) ; it is a miitnre of cinscbene, ci^iaebene- camphor, a small quantity of propionic acid, and oxide of propyl, the differences in its properties being doe to the varying proportions of their constituents. (Hirzel.)

D€comj}os{ticn&, I. When set on Jtre, it burns with a clear luminous flame. (Volkel, Hirzel.) — 2. It disi^olves iodine quickly, without evo- lution of vnponr or rise of temperature, forming a yellowish red brown, viscid mass (Zeller) ; it dissolves ^ t0;|- of iodine^ with rise of temperature, and is converted into a dark brown-red, viscid, opaque, stinking liquid, which, on cooling, deposits black crystalline laminae, apparently consist- in^: of iodine and cin»bene. (Hirzel.) Water shaken up with the solu- tion of iodine in wonuseed-oil extracts from it acetic, propionic, and hydriodic acids, together with a substance smelling like opium, probably iodide of propyl. The solution of iodine in wormseed-oil gives off when distilled, aqueous propionic acid, hydriodic acid, iodoform, and especially a mobile, dark brown, peculiar-smelling oil, consisting chiefly of cinssbene- camphor, cineebene and cymene, together with hydriodic acid both dis- solved and chemically combined, also hydriodate of ciniebene, and small quantities of angelic acid and cinacrol, whilst there remains a solid, blue- black, easily inflammable body which bums, though very slowly, with a dear, luminous flame, and consists of cinsephene, cinaephone, and cina»- phane. — 3. With nitric acid, it acquires a reddish yellow colour (Zeller), and when heated therewith gives off gas with violence, and is converted into a yellow resinousi mass insoluble in water (Zeller, V5lkel) ; with dilute nitric acid, it forms oxalic acid (V5lkel) ; heated in small quan- tities with nitric acid, it forms toluylio acid, a small quantity of oxalic acid being formed only when strong nitric acid is used. (Hirzel.) -^ 4. With oil of vitriol, it acquires a red-brown colour (Zeller), becomes hot and viscid, and after some time gives off sulphurous acid. ^Volkel.) — o. It absorbs hydrochloric acid gas, and when saturated tnerewith forms a dark red oil, which on cooling deposits crystals of wormseed-oil camphor. (Volkel, Hirzel.) — 6. Heated with anhydrotis phosphoric acid, it forms a black mass, which en boiling yields as, liquid products, aqueous propionic acid, cinaebene, ciuaDphene and cinacrol (Hirzel) ; it becomes

318 NATURAL OILS^ ISOMERIC WITH OIL OF TURPENTINE.

partially resinised, viscid^ and b converted into cynene. (Volkel.) — 7. Distilled with hydrate of potash, it yields a mobile, limpid oil having an agreeable odonr (like oil of peppermint, according to Volkel), and a warm burning taste ; easily inflammable, bnrning with a clear flame, having a sp. gr. of 0*93, consisting of an equal number of atoms of cina&- bene, cinaebene-camphor and a compound containing C^^H'O, with \ At. propione, and boiling at 175° — 176^*5. Hydrochloric acid gas colours this oil red, and forms with it, shining very deliquescent needles. Oil of vitriol renders it viscid and dark brown, and when heated with it, gives off sulphurous acid ; nitric acid converts it into liquid volatile products and fixed resinous products ; distilled with anhydrous phosphoric acid, it gives off propionic acid, an oil consisting of 4 At. cymene, 2 At. cinsBbene, and 1 At. cinsebene-camphor, together with smaller quantities of cinso- phene and cinacrol. (Hirzel.)

CombinatioTU. With Hydrochloric Acid, Wormssed-oil camphor. — Obtained by passing dry hydrochloric acid gas into wormseed-oil, cooling the saturated red oil, and pressing the separating crystalline mass between filtering paper. — Colourless slender needles. Odour aromatic, like that of camphor; taste mild and warming. When exposed to the air, it deliquesces and takes up water (Volkel) ; without taking up water (Hirzel). When heated, it melts into a nearly colourless oil, which gives off hydrochloric acid by distillation. Deliquesces quickly when covered with water. (Volkel, Hirzel.)

Wormseed-oil dissolve's in 1000 pts. of water, readily in alcohol and ether (Troranisdorff), in every proportion of absolute cueohol, and in an equal quantity of alcohol of sp. gr. 0*85. (Zeller.)

Cinaephane. C»H«.

Hirzel. (1855.) ZeUschr. J. Pharm. 1855, 163, 182.

Formation. By distilling wormseed-oil with iodine (p. 317).

Preparation. The thick brown liquid produced by dissolving iodine in worm<<eed-oil is distilled, and the resulting brown oil is heated to above 360% whereby a distillate is obtained, consisting chiefly of cinsebene-camphor, cinsBbene, cinacrol, and cymol, while a mixture of cinsBphane, cinsBphene, and cinsephone remains behind. The residue well boiled with alcohol, gives up cinaaphene to that solvent, and after the adhering alcohol has been evaporated, is itself soluble in chloroform. On mixing this solution with 20 pts. of alcohol of sp. gr. 0*84, it deposits a 'resin, which, after washing with hot alcohol and water, is a mixture of cinsephane and cinsephone. The latter is dissolved out by ether, and the residual cin»phane is purified by solution in chloroform, preparation with alcohol, and washing with ether. The cinephone is preci- pitated from the ethereal solution by alochol.

Properties. Very soft, loose, nearly velvet- black powder, without taste or smell.

Hirzel.

20 C 120 .... 93-75 9329

8 H 8 .... 6-25 6*40

C'H8 128 .... 190-00 99-69

ClNiiSBENE. 319

Dec&inpmhions and Comhinalions. Cinsphene, when firated, burns away with a glimmering light, without melting or leaving any residue. It dissolves in chloro/omif but not in etiter. (Hirzel.)

Cinsephone. C«»H»

Hirzel. (1855.) ZeiUchr, J. Pharm, 1855, 163, 182.

Formation, By distilling wormseed-oil with iodine (p. 317).

Properties, Soft, loose, light, kermes-brown powder, which adheres strongly to glass, to paper, and to the fingers ; tasteless and inodorous. It has not been obtained quite free from iodine.

Decompositions and Combinations, When heated, it melts to a black mass, gives off empyreumatic vapours, and leaves a light charcoal which bums away easily and completely. When set on fire^ it burns with a yellow non-fuliginous flame, leaving a large quantity of pure charcoal. It dissolves readily in chloroform, ether, and wormseed-oU, but is insoluble In water, alcohol, and aqueous alkalis, (Hirzel.)

Cinabene. C«*H».

Hirzel. (1854.) Zeitschr.f. Pharm, 1854, 7, 67. — 1855, 52; 68^ 82; 147; 182.

Source, In wormseed-oil, together with cinsebene- camphor, and small quantities of propionic acid and oxide of propyl.

Formation. By distilling wormseed-oil with anhydrous phosphoric acid, whereby the cinsDbene-camphor is dehydrated.

Preparation. By distilling wormseed-oil with anhydroos phosphoric acid in a retort, so long as, together with aqueous products, a light oil passes over with brisk but ultimately quiet ebullition, and till only a small quantity of oil remains mixed with the phosphoric acid ; shakin^ir up the oily distillate with water and carbonate of baryta ; and rectifying it over anhydrous phosphoric acid after dehydration with chloride of calcium.

Properties. Transparent, colourless, slightly iridescent, refracting, mobile. Sp. gr. 0*878 at 16^. Boiling point 172°. Odour slightly aromatic, more like that of oil of amber when heated. Cinsobene from wormseed-oil, prepared by distilling wormseed with milk of lime, smells like oil of lemon. Taste slightly warming, afterwards burning.

Hirzel.

20 C 120 .... 88-23 88-27

16 H 16 ... 11-77 11-71

0»H'^. 136 .... 10000 99-98

Isomeric with terebene. Probably identical with Volkel's cynene. (Schwanert.)

320 NATURAL OILS, ISOMERIC WITH OIL OF TURPENTINE.

Decompositions I. Cinaebene, when set on Jir«, burns with a clear flame , — 2. Heated with an equal volume of nitric acid of sp. gr. ri6, it gives off, with violent intumescence and evolution of nitrous acid, — first, water containing propionic or acetic acid, and floating t hereon, a thin colourless oil which has a fruity odour, leaves when evaporated, flocks smelling like camphor, is very volatile, is easily set on fire, and bums with a clear flame, — and, ultimately, hydrocyanic acid with a small quantity of bitter almond-oil, while a viscia resin remains. This resin has a peculiar odour like anise and fennel, and yields, by renewed boiling with nitric acid of sp gr. 1*16, a solution which, on cooling, deposits tcluylic and nilrotoluylic acids, also an undissolved viscid oil which appears to be anisylous acid. No oxalic acid is formed. A small quantity of cinsebene added to stroiig nitric acid colours it dark red ; the mixture froths up strongly when heated, and contains a small quantity of oxalic acid. GinsBbene, heated with oU of vitriol, acquires a red-brown colour. — 3. Dry hydrochloric cudd gas colours it wine-red without separating crystals ; on dissolving the cinsebene thus coloured in alcoholic potash, and adding water, a colourless oil separates, having a strong and agreeable odour of camphor, and decomposing when heated.

CoTnUmyatums. 1. With Water. Cinasbene-camphor, Ilydrated Cinm- bene, C"'H*®0*. Occurs in worm-seed-oil, together with propionic acid and oxide of propyl, but cannot be separated in the pure state. (Hirzel.)

2. With Hydriodic Acid. HydiiodaU of CincBhene, 2C*H",HI.— Obtained by rectifying the oil which passes over when wormseed-oil is distilled with iodine ; collecting apart the last portion of the distillate, extracting the cinacrol from it by repeated agitation with aqueous potash; washing the residual oil with water, then distilling it with water, and collecting separately the last portion of the oily distillate, which must then be washed with water and dehydrated with chloride of calcium.

Limpid to pale yellow, tolerably viscid ; has an agreeable camphorons peristent odour. Neutral.

40 C 33 H I	.... 240 .... 60*00 .... 33 .... 8*22 ..... ... 127 .... 31-78	Hirzel. ... 69-60 ... 8-64 ... 31*59
2C»HW HI ....	.... 400 .... 100-00	... 99-83

It becomes reddish by exposure to the air, and is decomposed by dis- tillation, even with water. (Hirzel.)

CinsBbene is insoluble in water, bnt dissolves readily in alcohol and ether. (Hirzel.)

Cynene. C>*H«.

VoLKBL. Ann. Pharm. 89, 858.

Formation and Preparation. Wormseed-oil is repeatedly distilled with anhydrous phosphoric acid ; the oil, which resinises and becomes

CIN^PHENE. 321

viscid, is mixed with oil of vitriol ; and the layer of liquid which floats ou the acid is removed, distilled with water after washing, and again per se, after dehydration with chloride of calcium.

Fj'operf.ies. Limpid and mobile. Sp. gr. 0*825 at 16^. Boils at 173° — 1753. Odour peculiar, like that of wormseed ; taste &int, after- wards burning.

Vmkel.

24 C 144 .... 88-89 8874

18 H 18 .... 11-11 1114

C^^H" 162 ..,. 10000 99-98

Formed from wormseed-oil, C?*H*02, by separation of 2 At. water. (Volkel.) Probably identical with Hirzel's ciciebene. (Schwanert.)

Decompositions and Combinations, 1. Burns with a bright fuliginous flame when set on fire, — 2. With cold strong nitric acid, it becomes yellowish-brown; boiled with strong nitric acid, it forms, with violent action, a solution which deposits a heavy yellow oil when mixed with water; b^ warm JUute nitric add it is not altered. It dissolves in fuming oil of vitriol, forming a conjugated acid. It is insoluble in water, easily soluble in alcohol and ether. (Vblkel.)

CinflBphene. C»H"orC*^H«-

HiRZB/i. Zeiiscii, f, Fharm. 1854, 1 7, 1 82. ~ 1855, 162, 182.

Formation, By distilling wormseed-oil with anhydrous phosphoric acid or with iodine.

Freparation. 1. The oil which passes over on heating wormseed-oil with anhydrous phosphoric acid, is freed from admixed aqueous products, and the portion which goes over between 35° and 825°, when it is rectifiod perse, is collected and dried over chloride of calcium. — 2. The brown oil obtained by distilling wormseed-oil with iodine is rectified ; the li^ht brown viscid residue is extracted with strong aqueous potash, washed with water, and heated to 360° as long as oil continues to distil over ; and this oil is freed from admixed cinacrol by agitation with warm dilulo aqueous potash, then with water, afterwards dried with chloride of calcium, and rectified.

Fropei'ties, Transparent and colourless by transmitted light, but exhibits an indi^-blne iridescence by reflected light; viscid; lighter than water. BoSs at 315° — 325°. Nearly destitute of taste and smell.

		Hirsel.
20 c ....	.... 120 *... oo*24 •»..	.... 88-03
16 H ....	.... 16 .... ll*/6 ....	.... 11-63

C«>HW 136 .... 10000 99-66

Probably isomeric with colophene. (Hirzel.)

Decompositions and Comhinaiums, 1. When heated, it becomes mobile and gives off vapours smelling like amber ; burns with a very smoky flame when set on fire. — 2. When heated with strong sulphuric

VOL. XIV. Y

322 NATUBAL OILS, ISOMEBIC WITH OIL OF TURPENTINE.

aeid^ it is converted into a yellow resin^ which lias a peculiar mosk-like odour, and when distilled with aqueous potash, yields, with £rothing, a distillate smelling of ammonia.

Cinnphene is insoluble in wUer, sparingly solnble in oold dhoholf easily in hot alcoMf dker, and volatiU cSlt.

Cinacrol. C«H"0*.

HiRZBL. Zeitichr./. Pharm. 1855, 84; 98, 130.

FarmaUon, From wormseed-oil : a. by heating with iodine ; h. by distillation with anhydrous phosphoric acid j c. by heating with hydrate of potash.

PrepatxUion, Wormseed-oil is distilled with j — )- iodine ; the mobile, dark brown iodated oil which pSBses over is separated from the aqueous distillate, and rectified per Be; the nearly black beavy oil which passes orer towards the end of the distillation is collected and shaken up with strong aqueous potash ; the potash^ley, which thereby acquires a dark brown-yellow colour, is heated till it becomes inodorous, then distilled with a slight excess of dilute sulphuric acid ; and the oil which passes over is rectified over chalk, and dehydrated by agitation with chloride of calcium.

Properties, Colourless to pale yellow; viscid. Sp. gr. 1-05 — 1*15. Boiling point about 250^ — Has a faint, not unpleasant, smoky odour, a sharp, caustic taste, and produces white, pamfully burning spots on the tongue. Mixed with hydrochloric acid, it does not colour fir- shavings, rennanent in the air.

26 0	... 156	•••• 7v*7o ••* .♦.. o / % «•*< .... ID'utj •••	Hinel. 75-45
18 H	... 18	912
4 0	... 32	15-43
C»H»0<	... 206	.... 100*00 ...	100-00

It becomes mobile when heated, and bums quickly with a smoky flame when set on fire.

It dissolves sparingly in watery readily and in auy quantity in aqueous alkalis and their carbonates, in aqueous alkaline earths, and in ammoitui. — The aqueous solution forms with neutral acetate of lead, after addition of ammonia, a flocculent white precipitate (cinacrol with oxide of lead) ; with basic acetate of lead, an immediate precipitate, soluble in excess of the basic acetate. It colours sesquichloride of iron bluish green, affording a delicate reaction, but not in presence of alcohol. From nitrate of silver it throws down pale yello.w flocks, reducing the silver when heated. — Cinacrol dissolves in alcohol, ether, and acetic acid. (Hirzel.)

OIL Of iUiBBB. 32S

O. VolatUe JBmpyreumaHe OiU.

1. Oil of j&mber,

Anthok. (1835.) S^pert. 54, 76.

Elsneb. J. pr. Chem. 26, 101; Phcu^ CerUr. 1842, 454.

Pellbwer 8c Walter. JT. Ann. Cf^im. Pkys. », 99; J.pr. Ckm. 31,

114; Fharm. Centr. 1843, 910. DoppiNa. Ann. Pharm. 54, 239; N. Br. AnA. 43, 147. Marsson. i\r. Br. Arch. 62, 1; abatr. Pharm. CentraJhl. 1850, 413. Zbller. Stvd. uber. other. OeU. Landau, 1850.

Hwl€ de wccin pyrogen6e,''^emiieinoi, Bem9tem€upiofh

Formation. The emp3rreamatic oil which passes over in the diy^ distillation of amber, either consists entirely of hydrocarbons having the composition of oil of turpentine, or contains such hydrocarbons mixed with other substances. — it ia conYcrted Into rectified ofl of amber by separation of the simultaneoatly formed raocinic acid, and repeated recttfication ^«r m (Martiuf, Repert, 12,426\ or with water (Pharm. Bortut. Bd. vi), whereupon, however, only a siuall quantity of the oil passes over (Marsson), or over pounded glass mixed with a small quantity of paste of chloride of lime. (Schttti. Rtptrt, 16, 274). — Amber yields 25 to 31 p. c. of the crude oil (Bley & Diesel, N. Br. Arch. 56, 171.)

Preparation of the Hydrocarbon from Oil of Amber. — 1. In the dry distillation of amber, two different oils are obtained, the first of which passes over below a red heat, the second at a dull red heat. In rectifica- tion^ the first distils between 110"* and 260°, the second between HO"* and 300 ,^ and at the end of the process, a solid substance like ozocerite remains ; but even repeated rectification does not yield products of con- stant boiling point. The two oils are scarcely or not at all affected by hydrate of potash ; but oil of vitriol attacks them violently, imparting a dark colour. If the two oils are repeatedly shaken up with strong sulphuric acid, decanted, distilled per se, a^in shaken up with sulphuric acid, and so on, they both yield the same colourless mobile oil, which is no longer coloured by strong solphnric acid, and boils between 130'' and 400^ This oil, after rectification over potassium and anhydrous phos- phoric acid, or over anhydrous phosphoric acid alone, has the composition given below, and that which distils between 130* and 175^ has a vapour- density = 4*3; hence Pelletier and Walter assign to it the formula C"H** (calc. vapoor-density 4-23). (Pelletier and Walter.)

2. When oil of amber is shaken np with potash-ley, it yields to this liquid a brownred substance, and nothing afterwards to oil of vitriol. The oil treated with potash-ley, dilute sulphuric aoid, and lumps of potash, begins to boil at 140% after standing over chloride of calcium, then distils over till the temperature rises to J70*or even higher, while a thic dark-coloured residue remains. The portion which distils between 160° and 170° is Ddpping's oil a. Potassium separates a small quantity of gas from it> probably because it contains water; if this oil be left in contact with quicklime for a week, and then rectified, it boils between 170' and 190% and then forms the oil b. When oil of amber purified by hydrate of potash is mixed carefully and without heating, with several volumes of oil of vitriol, and the mixture is left at rest, it separates into two layers, the upper of which, if removed and washed with oiostio

T 2

324 NATUBAL OILS, ISOMERIC WITH OIL OF TURPENTINE.

potafih (if repeatedly treated with oil of yitriol, it would nltimately dii»olve altogether), then brought in contact with quicklime and rectified, boils partly between 190^ and 200^ (oil c), and differs from the oils a and &, in odour, specific gravity^ boiling point, and refracting power. — Between 210° and 220°, an oil d passes over, yellow and smelling like poppy-oil, whilst a yellow residue is left, which after cooling is solid and inodorous. (Dopping.)

3. Marsson obtained the oil which he examined, by rectifying crutle oil of amber, dehydrating and de-acidising the distillate with pulverioei

<|uicklime, and rectifying till \ had passed over.

4* For the preparation of bis amber-eapione (which appears to be identical with the hydrocarbon obtained by method 1 or 2,) Eisner mixes rectified oil of amber, gradually, with agitation, and avoiding rise of temperature, with 18 vol. oil of vitriol, decants the layer which separates after standing for some time, washes it with water, dries out over chloride of calcium, and rectifies.

Properties. Transparent, colourless, or pale yellow, mobile or viscid oil, of no constant boiling point, and varying in specific gravity according to the temperature at which it has distilled ; it alters partially in boiling point at each repetition of the distillation, and leaves a residue (on which account also its vapour-density cannot be determined.) (Dopping, vid. sup.)

Crude oil of amber varies in colour from yellow to brown-black. (Anthon.) Sp. gr. 0-87— 093 (Anthon) ; O'Ol— 0*936 at 20"* (von Hees, iV. Br. Arch, 61, 18); 0-85— 0-89. (Zeller.) Sp. gr. of the crude oil 0-9003 and 0*9219 at 15^ (Marsson) ; of the rectified oil, 0-8795 at le"" ; of the oil rectified with water, 0*8841 at 15^; of the most volatile distillate, 0*8403; of amber-eupione, 0*645 at lO"" (Eisner); of that which passes over between 180° and 190^ 0*9928 (Doppinor) ; of the most volatile distillate, 0*8798 ; of the later distillate, 0*9176. (Marsson.) Boiling point, 130° to 260° and higher; of amber-eupione, 280° (Eisner); 130°— 270° and higher (Pelleticr k Walter); 160°— 166° and higher (Marsson); 140° — 170° and higher. (Dopping.) — Taste and odour pecu- liarly unpleasant and pungent. — Amber-eupione smells like ripe fruit. (Eisner.) Neutral, (Dopping, Zeller.)

	20 C 16 H	. 120 . 16	.... 88*24 .... 11*76	Pelletier & Walter. 87-39 to 89-19 11-30 .... 1010
	C»H"	.. 136	.... 100-00 IXSpping. mean.	98*69 ....	99*29 Marraon. mean.
c . H .	a* 87-03 11-54	•••• •«••	b, c. 87*97 .... 87-48 11*53 .... 12-06	d. .... 87-32 .... 11-98	e, 86*67 11-70
	98*57	•«••	99*50 .... 99*54	.... 99-30	....•.•. <mO'v7

Eisner found in rectified oil of amber 84*0 p. c. C, 8*6 H and 7*4 O ; in amber- eupione 84*55 p.c. C, 11*98 H and 3*47 O, whence be assigns to the latter, the formula CH^O or C^H^O. Dopping and Marrsson regard Eisner's analyses as in- correct. Pelletier and Walter's formula, C^W*, requires 88*53 p. c. C and 11*47 H, (comp. page 323.)

Deeompoaitums, 1. Oil of amber, even after rectification, leaves when eKsliUed a dark brown riAold residue (amber-colophony). (Eisner,

OIL OF AMBER* 325

Dipping.) — 2. It bums with a very smoky flame when set on fire. (Dopping.^ — It does not absorb oxygen when exposed to the air. ^DoppiDg,) — 3. Rectified oil of amber is coloured brown by iodine, but does not become heated (Eisner) ; it is partially resinised thereby. (Zeller.) — Amber-eupione dissolves iodine with red-brown colour. (Eisner.) — The rolatile portions of rectified oil of amber, not yet treated with oil of vitriol, acquire a transient blue colour when treated with cJiloriney and finally give off hydrochloric acid, become viscid, and heavier than water ; the less volatile portions are scarcely altered thereby.

iPelletier <fc Walter.) — 4. Oil of amber absorbs a small quantity of ydrochloric acid gas, acquiring a dark colour, but becoming colourless again, on addition of water. (Dopping.) Oil of amber treated with hydrochloric acid gas is altered in colour and smell, .but does not form an artificial camphor. (Pelletier and Walter.) — 5. Oil of amber prepared by method 1, imparts a reddish colour to strong nUphwie acid, but remains itself colourless. (Pelletier and Walter.) Oil of amber prepared by 2, dissolves when repeatedly treated with oil of vitriol, partially each time, and completely in the end. (I^opping.) (Por the behaviour of the crude oil, and of the rectified oil not purified with oil of vitriol, see page 323.) — 6. In contact with nitric acid, oil of amber acquires an odour of musk, and becomes resinised. (Marggraf, Ann. Chim. 73, 182.) The resin thus produced is the so-called artificial musk. — Nitric acid of sp. gr. 1*36 colours oil of amber cherry-red, and afterwards brown (Anthon); acid of sp. gr. ] *28 colours it violet (Zeller) ; more dilute acid colours it yellowish brown. (Dopping.) Cold fuming nitric acid or hot dilute nitric acid yields artificial musk. (Foltz, Bepert, 4, 226, and others.) Fuming nitric acid colours amber-eupione dark red-brown, whereupon water, after a few hours, throws down artificial musk. (Eisner.) Respecting artificial musk, see especially Elsnsr, /. pr, CAem. 26, 97; Foltz, Reperi, 4, 226; Mai-sson, N. Br. Arch. 62, 8.) — When rectified oil of amber is boiled for 14 days with nitric acid of sp. gr. 1*3, an acid distillate is obtained containing acetic, propionic, and butyric acids, whilst a whitish vellow resin separates from the residue, and a larger quantity of it on addition of water. (Marsson.) It is to the presence of the volatile acids just mentioned, that artificial musk partially owes its odour. (Marsson.) — 7« Rectified oil of

amber, and amber-eupione, do not act u^n poUunum. (Eisner; Pelle- tier and Walter.) Neither is purified oil of amber altered by aqueous potash or ammonia.

Oomhinations. Oil of amber dissolves at the heat of the hand in 50^ pts. of alcohol of sp. gr. 0*855, likewise in 2 pts. of alcohol of sp. gr. 0*8 (Anthon), in 15 pts. alcohol of sp. gr. 0-85. (Zeller.) — The saturated solution, on cooling, deposits an oil which redissolves on the application of heat. (Anthon.) — Crude oil of amber yields to alcohol of 0*83, a dark yellow oil haying a balsamic and penetrating odour (75*33 G, 14*04 H, 10'63 0) ; and &om the residue, ether extracts a transparent kneadahle resin (78*60 C, 1282 H, 8*58 0), leaying a yellow crystalline residue (79*87 C, 14*92 H, 5*21 0), which burns without flame. (Drapie«, Sckw. 30, 119.)

Oil of amber dissolves readily in ellier (Eisner, Dbpping), in 2 pts. of ether r Anthon), in oils hoih Jlxed and volatile. (Eisner.)

Oil of amber, when heated, dissolves a large quantity of gulphur, which crystallises out on cooling ; it dissolves a large quantity of caatU* ehouc, and a very small quantity of ambers (D&pping.)

326 NATURAL OILS, ISOMERIC WITH OIL OF TURPENTINE,

2. Empyremnatic Oil of Birch.

SoBBBRB. (18420 -^^* •^- I^^rm. 2, 207; Ann. Pharm. 44, 121,-- N. J. PUrm. 8, 288.

Briwslichei Birken9l. Saenee de Bouleau,

Occurs in the tar obtained in Bossia by tbe drj distillation of birch- bark. — When the tar is distilled by itself^ and the acid oil which floats on the watery distillate is repeatedly treated with potash-ley and rectified in a stream of carbonic acid, a colourless oil passes over at 156^ having a sp. gr. of 0-847, containing 88-05 p. c. C, and 11-05 H, therefore C*H'* (calculation 88*23 p. a C, 11*77 H); as the distillation proceeds and the boiling point rises, it becomes mixed with oxygenated oils containing less carbon and hydrogen.

The oil which passes over at 156^ solidifies partially at IG"* — \T ; has a vaponr-density of 4*975 (calculation =? 4*7144, [p. 245]), smells like oil of turpentine, but fainter and disagreeably. — It takes up oxygen and lesinises when exposed to the air ; yields by distillation with nilrio acid a green oil (which loses its colour and deposits resinous flocks at 100°), and 1 — 2 p. c. hydrocyanic acid ; and when distilled with a mixture of 2 vol. nitric acid and 8 vol. water, becomes yellowish brown, thickens and sinks to the bottom of the distillate. It absorbs 3% p. c. hydro- chloric acid gas, becoming black, but without forming artificial camphor, and dissolves sparingly in ufoterf easily in alcohol and in ether.

3. Gaoutchin.

HiMLT. (1835.) Diss. 05tting. 1835, 47; Ann. Pharm. 27> 41; abstr.

Repert. 60, 105, C. Qbbvillb Williams. Proceedings of the Boydt Society ^ 10, 517.

KmUsekin* Discovered and invotigatad by Hlmlyi Aurtfaer by Williams.

Source and Extraction. Caoutchin occurs, together with many other substances in oil of caoutchouc. (Himly, vid. inf.) Obtained also from gutta percha. (Williams.) Oil of caoutchouc boiling at 140^—- 280"", obtained by fractional distillation, is repeatedly shaken up with dilute snlphnric acid, washed with water, then alternately with potash-ley and with water, and distilled with water several times. The liquid which passes over is dehydrated with chloride of calcium, and rectified per sf, the portion which goes over between 160" and 175^ being collected apart, and from this, by repeated rectification and removal of the portions which distil over below 166^ and above 174^ caoutchin is obtained, boiling between 168^ and 171^ By repeated fractional distillation, this product may be broilght to boil at 171 ; or the purification may be efiected by passing dry hydroehlorio acid gas into the cooled oil previously dried over chloride of cafcinm (whereupon it turns blackish green), whereby hydro- chlorate of caootehin is formed, decanting this liquid from the resin after it has stood for several days, dissolving it in absolute aloohol, and preoi-

CAOUTCHIM. 327

pitaiiDg with water. The hydrochlorate of oaoutchin again dehydrated and repeatedly distilled over oaustic lime or baryta, then oyer potassium as long as the metal beoomes colonred, yields pure caoutchin. (Himly.) Frapertiei. Transparent^ colourless, mobile ; makes grease-spots on paper which soon disappear, leaving a faint odour. Sp. gr. 0*8423 at 16^ boiling point 171*5^ at 075 met. pressure. Does not solidify at — 39^ Vapour-density 4*461 (Himly) ; 4*65 (Williams). Has but little electric conducting power. Smells like oil of China oranges (Apfelrinenol p. 304), but less agreeably. Has a peculiar aromatic taste, burning but not bitter. (Neutral, Himly.)

Himly. ViUiamt. 20 C 120 .... 88-23 87*00 .... 88*1

16 H 16 .... 11'77 11*56 .... 11'9

-*— -

C»HW 136 .... 100*00 98*66 .... 100*0

Vol. Densitj.

C-Tapour 20 8*3200

H-gM 16 1-1088

Caoutchin-Tapour 2 9*4288

1 4*7144

Winiama'a nnmben are the mean of three analyse!, two of which were made with eaotttchin obtained from gattA percha.

DecamposUians^ I. Caoutchin volatilises partially when exposed to the aiTf leaving a residue produced by ahiorption of oxygen; by prolonged contact with the air, it acquires a persistent bitter taste, and is finally converted into a yellow, tough, bitter resin (which appears to oontain nitrogen)* Caoutchin kept for a year in bottles containing air and not quite closed, does notdeposit crystals, but becomes yellow^ bitter, and less soluble in alcohol and ether than before t it gives off gas-bubbles with potassium, often with a rapidity amounting to ebullition ; and is for the most part decolorised by agitation with aqueous potash, yielding to it a bitter substence. (Himly.) Peroxide a f hydrogen cony eriA caoutchin into a resin. (Himly.) — 2. With ddorine it turns brown, becomes heated to inflammation, gives off hydrochloric acid, and forms chlorocaoutchin. — 8. With bromine^ it gives off hydrobromio acid, with effervesence, but remains colourless and transparent ; it readily abstracts bromine from its solutions in water, alcohol, and ether, forming heavy drops of oil. Caoutchin mixed with \ vol, water decolorises bromine till 248 pts. bromine have been added to 100 pts. caoutchin (Williams, Chem, Oat. 263, 365 ; •/. /)r. Chem, 61, 20) ; according to more recent determinations by Williams (Ft'oe. Roy. Soe. 10, 517), 0*1091 grm. caoutchin decolorises 0*2527 grm. bromine (in 20 cub. cent of water), which is in the ratio of 231*7 pts. bromine to 100 pts. caoutchin, or nearly 4 At. bromine to

1 At. caoutchin (calculation 235*3 bromine to 100 pts. caoutchin). [Oil of turpen- tine likewise decolorises bromine in the ratio of 1 At. to 4 At. bromine. (Williams.)]

4. By the alternate action of bromine and todium on caoutchin [or oil of turpentine], 2 At. hydrogen are removed, and cymene, C^H*^^ is produced, having exactly the same odour as that obtained from oil*of cumin (p. 184). (It gave as the mean of three analyses 89*4 p. e. C and 10*4 H.) At the same time there is produced an oil (paracymene) having the composition of cymcne but boiling at 300^ (Williams, Froo, Boy. Soc, 10,517.) —

5. With iodine, caoutchin acquires a black brown coloor, especially when heated ; and, if dropt upon iodine, giTes off hydriodio acid with effer- vescence, but without taking fire. From aqueous alcoholic or ethereal solutions of iodine^ it abstracts the iodine, forming iodocaontchini which

328 NATURAL OILS, ISOMERIC WITH OIL OF TURPENTINE.

is a black-brown oil, giving off bjdriodic acid when distilled, easily <1econipo8ed by heating witb oil of vitriol, bromine, cblorine, fuming nitric acid, or potash, nearly insolable in water, but soluble in alcohol and etber. Cnoutcbin, distilled with excess of iodine, forms a colourless, fragrant oil, similar to that which is produced by the action of oi of vitriol on caontchin, giving off at the same time a large quantity of hydriodic acid. (Hiinly.) — 6. With nitric oxide, oaoutchin gradually turns yellowish ; with nili^tis acid, yellow and green, and is gradually converted into a very sharp and bitter- tasting yellow resin, soluble in alcohol and etber. — 7. It is not altered by dilute nitric acid; but con-- centrated nitric acid colours it rose-red, yellow, blue, then again yellow, with rise of temperature, evolution of nitric acid, and formation of a yellow resin ; fuming nitric acid acts still more strongly. The yellow resia thus formed is brittle at 0**, tough and ductile when moderately heated, melts at a stronger heat, swelling up and giving off white, very offensive vapours, and ultimately takes fire, burning with tlame, and leaving a large quantity of spongy charcoal; distilled with potash, lime, or baryta, it gives off ammonia having an empyreuiratic odour; it dissolves very readily in aqueous potash, carbonate of potash, and ammonia, easily in alcohol both hot and cold, and is separated by water from the bitter solution in the form of a yellow powder; when repeatedly distilled with faming nitric acid, it forma oxalic acid. — 8. Caoutchin gradually heated with concentrated aqueoue chloric acid, becomes hot, and forms chlorocaoutchin and perchloric acid. — 9. It is decomposed by iodic acid. — 10. Boiled with crystale ofdiromic acid, it forms a yellow resin. — 11. When dropt into oi^ of vitriol, it becomes heated, eliminates sulphurous acid, and forms a brown unctuous acid, yielding with carbonate of baryta, a soluble barjrta-salt, which, when decomposed by sulphates, forms non-crystalline salts, soluble in water. (Himly.) The formula of this acid is C^'H^'S'O* ; ita lime-salt gave by analysis 8*3 p. c. calcium, the formula C^H"CaS*0*, requiring

8*5 p. c. (Williams.) Caoutchin is coloured red-brown to black by oil of vitriol, becoming viscid, giving off sulphurous acid, and separating after 24 hours, r colourless oil floating on the surface which appears to be impure eupione. This oil, washed with water and dehydrated with chloride of calcium, has a specific gravity of 0*86, boils at 203", smells like rock-oil, has an aromatic taste, volatilises without alteration, and is neutral ; it is not decomposed by fuming nitric acid, absorbs only a small quantity of hydrochloric acid gas, is but slightly altered by boiling with oil of vitriol, and dissolves in alcohol in all proportions. When the thick add liquid below this oil is mixed with water, and left at rest, an oil separates from it and collects on the surface of the ■cid water. This latter oil has an odour different from that of caoutchin, aromatic like that of rosemary ; it is soluble in alcohol, still more in ether, and yields by distillatioa a strong- smelling oil, easily soluble in alcohol and ether, decomposed by fiuning nitric acid and hot oil of vitriol, — also a resin, which separates from its ethereal solution on addition of alcohol, as a yellow, Inodorous and tasteless powder, which melts below 100**. Dilute sulphuric acid does not act upon caoutchin. •^12. Caoutchin, boiled with telenic acid of sp. gr. 2*23 turns brown, and gradually decomposes. — 33. It is not decomposed hy phosphoric or phosphorous acid, — 14. With dry hydrochloric acid gas, it becomes hot, acquires a brown colour, and is converted into hydrochlorate of caoutchin. — 15. Hydi'iodic and hydros hromic acids act m like manner. — 16. With arsenic acid it turns yellow, blackens on boiling, and leaves an insoluble residue. — 17* Distilled with potassium, it gives off a few gas-bubbles, covers the metal after a while with a grey film, then remains unaltered ; it is likewise unaffected by sodium, potash, soda, baryta, or lime, -^ IS, It converts cupric oxide on boiling into cuprous oxide ; permanganate of potash, on boiling, into per- oxide of manganese ; but exerts no de-oxidising action, even at the boiling heat, on protoxide of lead, minium^ peroxide of lead, mercuric oxide, or ehromate of potash, 19, Heated with tercMoride of gold or bichloride of

CAOUTCHIN.; 329

pkUinum, it gives off Ljdrooblorio acid and forms clilorocaoutcliiii. — - 20. With terMoride of arUimcny, it torns yellow, and on boiling, dark green, and forms impure hjdrochlorate of caoutchin. Similarly wben boiled with mercuric chloride, it forms bydrocblorate of caoutcbin ; with mercurous chloride, no action takes place. — 21. With tesquichloride of iron, it forms a black-brown mixture.

Combinations, Caontchin absorbs in 14 days, 45 yoIs. oxygen, with- out becoming saturated ; in 3 weeks, at 20°, it absorbs 2 vols, oxygen.

It dissolves in 2000 pts. of water. It takes up a small quantity of water in the cold, and at higher temperatures, a larger quantity, which separates on cooling. It may be dehydrated by agitation, but not by distillation witli chloride of calcium.

It does not absorb carbonic oxide, marsh gas, or oUfiant gas, but takes up 11 vols, carbonic acid, Caoutchin, saturated with carbonic acid^ absorbs oxygen and evolves in 3 weeks 6 vols, carbonic acid.

Of phosphorus^ it dissolves a small quantity in the cold, more when heated. The hot solution, which shines in the dark, deposits the greater part of the phosphorus on coolings at first in fused globules, afterwards in small rhombohedrons.

Of sulphur, it dissolves a little in the cold, \ pt. when heated. The hot solution deposits on coolinc:, slender shining needles, and at last octohedrons, still however retaining in solution a quantity of sulphur larger than that which caoutchin can take up in the the cold. Caoutchin does not absorb sulphuretted hydrogen, but dissolves bisulphide of carbon in all proportions. Selenium and selenious acid do not dissolve in caoutchin.

With Hydrochloric A cid, Hydrochlorate of CaotUch in . Monochlorhydrate de caouiehine Uquide. (Gerbardt.) Caoutchin cooled with ice is completely saturated with dry hydrochloric acid gas, and the dark brown liquid, which is transparent only in thin layers and fumes strongly in the air, is shaken up with water, to remove free hydrochloric acid.

Brown. Sp. gr. 0*95 at 15^ Does not solidify at 39^ Odour strongly but repulsively aromatic, like that of thyme ; persistent ; taste, mild but disagreeable.

Himly.

20 C 1200 .... 69-6 70*08

17 H 17-0 .... 9-9 9-67

CL 35-5 .... 205 2030

C»HW,HC1 172-5 .... 100-0 100-05

When set on fire, it bums with a red, strongly fuliginous flame, green at the edges. Gives off hydrochloric acid gas when distilled. Treated with chlorine or bromine, it gives off hydrochloric acid gas, and is con- verted into chloro- or bromo-caontchin. It is not decomposed by aqueous potash or soda, but when distilled over lumps of potash, soda, lime, or baryta, it gives up its hydrochloric acid to the alkali.

It dissolves in absolute alcohol, in ether, and in acetate of ethyl, but on adding water or weak alcohol to either of these solutions, the whole of the caontchin is precipitated.

With Ifydrobromic Acid, caoutchin forms a componnd analogous to the hydrochlorate ; also> but less easily, with hydriodic acid^

330 NATURAL OILS, ISOMERIC WITH OIL OP TURPENTINE.

Caoutchin dissolves in the cold a small qnantity of iodide of sulphur ; the solution, when boiled, ^ives off sulphuretted hydrogen, and leaves a black thick residue. It dissolves a small quantity of iodide of phosphorus, forming a brown solution which is decolorised by water. From an aqueous solution of bromide of iodine, it withdraws the whole of that compound, forming a bluish-green balsam^ in which neither bromine nor iodine can be detected by metallic silver. It does not dissolve mercuric iodide in the cold ; but with the aid of heat, it forms a yellow solution which, on cooling, deposits almost all the mercuric iodide m yellow scales, which after a while become red again.

It absorbs in five weeks 5 vols, nitrogen, a small quantity of nitrous oxide, and assumes a yellowish tint after some time by contact with nitric oxide. It absorbs 3 vols, amrnonia gas. It does not anite with aqueous ammonia. It does not absorb cyanogen gas, but hydrocyanic acid gas is absorbed by it^ and chloride of cyanogen, in almost any quantity.

It dissolves a small quantity of iodide of carbon when heated there- with, and deposits it in shining laroiniB on cooling. When boiled with iodide of carbon, it turns brown. It dissolves with fiicility the chlorides of carbon, sulphur, and photphorvs. Mixes in all proportions with xanlhic acid.

Caoutchin is slightly soluble in concentrated formic and acetic acids. The solutions prepared with aid of heat, deposit on cooling nearly the whole of the caoutchin in combination with formic and acetic acids. Caoutchin dissolves malic acid in very small quantity; oxalic, citric, and tartaric acids, not at all. All these acids, boiled for some time with caoutchin, produce a brown glutinous substance. Caoutchin, with aid of heat, dissolves a large quantity of benzoic acid, which partially separates in the crystalline state on cooling. It does not dissolve tannic, mudc, or succinic acids.

Caoutchin dissolves in all proportions in absolute alcohol, ether, and acetate of ethyl, but is not soluble in chloride of ethyl. The alcoholic solution deposits part of the caoutchin on addition of weak alcohol, and the whole when mixed with water. From the ethereal solution, water does not separate the caoutchin, unless alcohol is likewise added. The alcoholic solution burns, when set on fire, with a bright flame, which, if the right proportions have been chosen, does not deposit any soot.

Caoutchin dissolves in oUs hoih^ed and volatile.

Appendix to Caoutchin.

1. Chlorocaontchin.

HiMLY. (1835.) Dissertation, G5ttingen, 1835, 79.

Chhrkautsehin, Formed by the action of chlorine on caoutchin ; also by boiling caoutchin with terchloride of gold or bichloride of platinum.

Preparation. Dry chlorine gas is passed into a flask having a layer of caoutchin at the bottom, the delivery-tube not however reaching to the surface of the liquid, but terminating a few lines abovo it, and the mixture being at first cooled with ice ; and the resulting oil, — which is brown at first, but, when completely saturated with chlorine, becomes colourless and viscid, and gives off a larger quantity of hydrochloric acid gas, — is washed with a very weak soda solution, then with water, and finally dehydrated over oil of vitriol.

ISOPRBNB. 331

FrojyfHies. Transparent^ colonrless, viscid. Sp. gr. 1'433. Does not become crystalline on cooling. Has a peculiarly strong ethereal odour, and an intolerably and persistently sharp, burning tasto. Neutral.

VecomposUioiu. 1. When distilled, it gives off extremely irritating hydrochloric acid vaponrs. — 2. Boiled for some time with oU of vitriolj it gives off hydrochloric acid and becomes carbonised. — 3. By distillation with potash, lime, or baryta, it yields a variety of oily products.

Combinations. It dissolves in hot nitric acid and in hot oil of vitriol, separating out unchanged on cooling.

It dissolves sparingly in water, easily in alcohol and ether, and is precipitated from its alcoholic solution by water.

T 2. Isoprene. C'm\

C. O. Williams. (1860.) Froeeedings of the Sayal Society, 10, 616.

Produced, together with caontchin, by the dry distillation of cauotohouc and gutta pereha; purified by repeated oohobation over sodium.

It is an exceedingly volatile liquid, of sp. gr. 0*6823 at 20^ Boils between 37° and 38^. Vapour-density 2*44.

WiUiami, Vol. Density.

IOC ....60 .... 88*23 880 C-vaponr 10 .... 41600

8 H .... 8 .... 11-77 121 H-gas 8 .... 0-5544

C">H».... 68 ....100-00 100*1 V«p. of Isoprene 2 .... 4-7144

1 .... 2-3572

Thit experimental oompotitlon Is the mean of five analytea, three of apedmens from caoutchouc and two from gutta pereha* Isoprene is polymeric with caoutcbin being related to it in the same manner as amjlene to paramylene. From the similarity of compositioD between isoprene, caoutchin, and pnre caoutchouc, Williams is of opinion, that the decomposition of caoutchoac by heat is simply the disruption of a polymeric body into substances having simple relation to it.

Oxide of lioprene, C*^H"0. Isoprene exposed to the air for some months, thickens, and acquires bleaching properties, owing to the absorp- tion of oione. On distilling the ozonised liquid, a violent reaction takes place, the unaltered hydrocarbon distils off, and the residue solidifies to a pure white, amorphous mass, containing :

WillUms.

IOC 60 .... 78-95 78-8

8 11 8 .... 10-52 10-7

O 8 .... 10-53 10-5

C»«H»0 76 .... 10000 1000

332 PRIMARY-NUCLEUS C»H»«.

Bomeol or Bomeol-alcohol.

C»H»«0* = C»H",2H0.

Pelouzb. (1841.) Compt, rend. 11, 365; Ann'Phami. 40, 326; alwtr.

J. pr. Chem. 22, 379; J. Pharm. 26, 645; Bepert, 72,'364. Gerhardt. N. Ann, Chim. Pliys, 7, 286; Ann. Phai^. 45, 38; abstr.

Compt. rend. 14, 832; J. pr. Chem. 27, 124; further, 28, 46. Berthelot. N. Ann. Chim. Phys. 56, 78; abstr. Compt. rend. 47, 265;

Ann. Pharm. 110, 267; PepertoiredeChimie pure,l,6i; Ann.Pkai-m,

112,363.

BekUing especially to the Modifications of Bomeol : Jramjean. Compt. rend. 42, 857; farther, 43, 103; J. pr. Chem. 69,

204; Ann. Pharm. 101, 94; CAm. Ceniralbl. (1856.) 575 aud 672.

Oxyde de BomHe. (Laurent) Camphol, Alcohol eampholique. (Berthdot) Fester Borneo -camphor t Camphre ttoltde de Borneo; Baroe-campher, Sumatra'Cam" pher, Dryohalanopt'Campher, Camphora Sumairana, C. Bomieniis, C. MalagoMU Capuhr Barruhq of the natives.

Source and FormcUion. 1. In the cavities of old stems of Z)ryo- balanopa Campho7U (fiolebroohe), a tree growing in Samatra^ especialiy in the province of Baros, more rarely in Borneo. (De Yne&t, Nederlana»eh, Kruidkundig. Aixhiff^ 3, 1 ; Hooker^ s Journal of Botany ^ 1852, 33 and 68; abstr. Pha)*m. J. Tram. 12, 22; y. Kessel, Wien. Akad. Ber. 8, 418.) It is scooped out of fissures in the stems of hewn trees with small pieces of wood or nails. (De Vriese.) It occurs in the cavities of the stems generally mixed with camphor-oil (p. 314), and as a crystalline sublimate in the upper part of the cavities, when they are not quite filled with the oil. (Motley, Pharm. J. Trans. 12, 300.)

2. Oil of valerian contains borneol (and the other constituents mentioned at page 313), which, on rectifying the most volatile portions, sometimes, but not always, sublimes in the neck of the retort ; hence it appears to be produced occasionally from valerene by the action of hydrate of potash, just as it is obtained (p. 313), sometimes abundantly, sometimes but sparingly, on setting aside a mixture of valerene and potash-ley, and subsequently distilling it. (Gerhardt.) The crystals thus obtained are not borneol, but valerian-camphor, C'*H**0*, either existing ready formed in the oil of yalerian, or produced from the valerol by distillation. (Pierlot, N. Ann. Chim. Phys. 59, 291.) This Tievr does not agree with Gerhardt's analyses; moreover, both Gerhardt and Rochleder obtained from oil of valerian, common camphor, which probably can be produced only from bomeol. (Kr.)

3. From common Camphor. When camphor is heated with alcoholic potash, borneol is produced, either with evolution of oxygen :

C»HWO» + 2HO « C»HWO* + 2 0;

or with simultaneous formation of camphic acid :

2C»HM0> -f 2HO » C»HWO» + C»HWO,

slowly at loo**, more quickly at higher temperatures. (Berthelot.) When 2 pts. of common camphor are sealed up in a tube with 1 pt. hydrate of potash or soda and 5^-6 pts. alcohol, and heated in the oil- bath to 180°— 200° for 8 or 10 hours, or to 100° for several weeks, a

BORNEOL» 333

prodact is obtained from which water separates an oil, and a solid mixture of borneol and common camphor. The oil decanted and filtered, and submitted to fractional distillation, yields, below 240^ an additional quantity of this mixture, a viscid oil afterwards passing over, and a rosidne being left in the retort. This mixture may be purified from oil by pressure and sublimation, and then contains about 10 per cent, of common camphor with 90 per cent, of borneoL To remove the former, the mixture is heated with 2 pts. of stearic acid to 200° for several hours (or to 160° — 180^ for sevenU days), whereby the common camphor is volatilised : the residual stearate of borneol is decomposed by heating it to 120° with i pt. finely pulverised soda-lime, and the borneol which sublimes in the neck of the retort, leaving a residue of stearate of lime, is collected : it amounts to about -^ of the camphor employed.

Properties, Small, white, transparent, easily friable crystals (Pelouze, Oerhardt, Berthelot) ; six-sided rhombohedral prisms. (Pelouze.) Native borneol forms small lumps of round and oval shapes, fiat, white, thin, and | inch in diameter, mixed with yery small dirty white granules, (v. Kessol.) Lighter than water. (Pelouze.) According to Christison, it is heavier than water. [N, Br, Amh. 48, 32.) Melts at 1 98° (Pelouze), less easily than common camphor. (Gerhardt.) Boils without decomposition at 212° (Pelouze), a little below 220° (Berthelot.) It is less volatile than common camphor. (Gerhardt, Mosley.) Sublimes even at common temperatures, and boils at a temperature not far from its melting point. (Berthelot.) Rotatory powerof native borneol 33 '4° to the right (Biot, Uampt rend, 11, 370), of the artificial, 44'9° to the right. (Berthelot.) Borneol, prepared with camphor obtained from oil of amber, exhibits 10 times less dextro-rotatory power than artificial borneol. (Berthelot) Borneol smells 4ike common camphor and at the same time like pepper (Pelouze, Gerhardt, Berthelot) j its odour is more agreeable (Motley) ; it has a burning taste like a volatile oil. (Pelouze.)

Gerhardt. Berthelot. mean,

20 C 120 .... 77-92 77-69 .... 77*6

18 H 18 .... 11-69 11-85 .... 11-6

2 0 16 .... 10-89 10-46 .... 10-8

C»Hi»02 154 .... 100-00 100-00 .... 100-0

Gerhardt examined borneol from oil of valerian; Berthelot, that from common camphor. — - Borneol is related to common camphor in the same manner as alcohol to •Ideliyde.

DecampotUioM. 1. Borneol heated with moderately <?anei0n^ni^ nitric aeid, ' gives off red vapours, and is converted into an oil which floats on the acid, and from which water separates common camphor. A similar decomposition takes place, slowly in the cold, more quickly and violently with strong nitric acid* (Pelonze, Berthelot):

C»HWO» = 2H + C^WH>\

2. By dbtillation with anhydrous phosphoric acid, it is resolved into water and a hydrocarbon C^H^* (Pelouze), which, according to Gerhardt, is identical with his bomeene and that of Pelouze (p. 313). — 3. Heated with moderately strong hydrochloric acid, it forms hydrochlorate of

834 PRIMARY-NUCLEUS C»W».

boraeol. Slightly heated borneolt or its cold alooholie lolntion, abi«be but a small quantity of hydrochloric acid gas. (Berthelot.) — 4* Heated for some time to 200'' in a sealed tabe with benzoic acid, h fomifl benxoate of bonijeol ; with stearic add^ stearate of borneoL (Berthelot.)

Bomeol dissolres sparitifflj in toaier (Peloose) ; not at all. (Ber- thelot.)-—It dissolves readily in o/coAoZ and in ether, (Pelouse, Ber- thelot.)— From a solution of 2 pts. bomeol in 10 pis. absolute aloohol, 100 pts. of water separate, after three days standing, 1*2 pts. of bomeol, and on agitating the liqnid with ether^ the ether takes up an additional 00 pi. of bomeol. (Berthelot.)

Compounds Isomeric frith Bomeol.

1. Laevo-rotatory Borneol,

Ooonrs in the alcohol produced bj fermentation of madder-sngar, and is obtained by collecting the Umin» which crystallise out from the liqnid on standing, or in the fractional distillation conducted as described at page 813. It 18 pressed between filtering paper, and then purified by wasning with a large quantity of water and repeated crystallisation from ether.

(Jeanjean.) — > It appears to be produced from the bomeene of madder Ihael-oil. (Jeanjean.^

Properties. Crystalline laminin resembling boraeol, or white powder smelling like pepper and <H>mmon camphor. It deflects polarised light to the left as much as ordinary boraeol deflects it to the right.

20 C	... 77-92 .. .. 11-69 .. ... 10-89 ..	Jeanjean. mean, 77-76
18 H	12-05
2 0	10*19
C»HM02	... 10000 ..	100-00

Deeomposiiions, 1. LsBTo-lioraeol is conyerted by boiling nitric acid into Imyo-rotatory camphor isomeric with common camphor. — 2. Dis- tilled with anhi/drous phosphoric acid or chloride ofsine^ it yields a hydro- carbon resembling oil of lemon or oil of bergamot. (Jeanjean.) Comp. Vaterene (p. 313).

Comhina4ions. Sparingly soluble in tpaier, — Rotates like common camphor when thrown on water. — Dissolyes readily in aeetio aeidt in alcohol, and in ether. (Jeanjean.)

2. Oil of Cigeput.

Pfupp. System de Mat, med. Leverkohn. Hepert, 34, 129 ScHONPBLDBR. JUpcrt. 30, 132.

OIL OP CAJBPUT. 335

OuiBOURT. J. Chm. mid. 7, 586; Beperi^ 39, 261.

DoBBRBiNE* Schw, 63, 484.

Blanohst. Ann. Pharm. 19, 214.

Zellbr. Stud, uher Hiker, Oele, Landau, 1850.

Baence de Cqfeput, dtfeputdl, Oiewn a^eputi.

Source. In the leayea (also in the flower-buds, aocording to Lesson), of Melaleuca trinervis, M. l&uoodendron (Dec.), M. CktjepuU {Boah.)

Extraction. Bj distilling the leaves with water (after they hare become heated by being left over nifht closely pressed in a sack : Bump.) The water which passes over with the oil reddens litmus. (Schonfelder.;

— From the leaves of Melaleuca hyperic^folia, Stickel obtained by distillation with water, 0'4 p. o. cajeput-oil.

Properties. Pale green (Gartner, Blanchet, Stickel); grass-green (Dobereincr) ; greenish yellow to pale green (Zeller, w'rf. i^f.) ; after rectification with water, the first i are transparent and colourless, the last \ green (Schonfelder), the first | transparent and colourless (Dobe* reiner, Blanchet), the last | pale to dark olive-green (Ouibourt), trans* parent and colourless (Dobereiner, Blanchet) ; after agitation with animal char- coal, it is transparent and colonrless (Vasmer, Br. Arch. 37f 248); transparent

(Dobereiner, Blanchet, Stickel) ; mobile. (Pfaff.) Sp. gr. 0*978 at 9"* (Gartner), 0 915 (Schonfelder), 0-9492 at 18^ (Dobereiner), 0-9274 at 25*> (Blanchet), 0-916—0-919 at 18^ 0-913 at 24*» (Guibourt), 0'91— 094 (Zeller) ; rectified with water : first distillate 0*907 (Schonfelder), 0 897 (Leverkohn^, 0*9196 at 25'' (Blanchet), last 0917 (Schdn folder), 0*92 (Leverkdhn). — Boiling point 175^. (Blanchet.) The first distillate boils at 173% the ]ast at 175** ^Blanchet), the most volatile nearly at 100'. (Dttbereiner.)

— Odour pungent, like that of camphor (Pfaff) ; aromatic, fainter after

rectification. (Blanchet.) — Cajeput-oil from Amboina smells like turpentine, caaaphor, peppermint, and roses } that from Paris, like rae and rosemary ; after rectifi. cation with water, it has a pungent odour rather like turpentine than acid ; the latter distillate is less pungent, more like that of rose-wood or aloe-wood. (Guibourt.)

— Taste burnin£^ (Pfaff), warming. (Blanchet.) — Neutral to litmus. (Schonfelder^ Zeller.)

20 C 18 H	.... 120 ... 18	.... i/wm .•• ..„ 11*69 ... .... 10-39 ...	Blanchet. 78-00 11 •48
2 0	.... 16	10-52
C»H»0«	... 154	.... 10000 ...	10000

Consists of two volatile oils (Leverkohn); of dadyl (p. 245) and water, in equal numbers of atoms «C*0H*,HO (Blanchet.) Commercial cajeput-oil generally contoins copper in solution, whereby its original green colour is deepened (Stickel) ; it exhibits a greenish colour, however, even when no copper is present- (Guibourt.) The copper which gets into the oil, when it is sent out in copper Tessels, cannot accordiog to Dobereiner, be always recognised by its usual character of imparting a blue colour to aqueous ammonia on agitation ; it is also not easily precipitated from the oil by potassiun, iron or sine, but better by the electric current. 'When the polar wires of a Toltaic battery are dipped into cajeput-oil mixed with water, the positive pole, if the oil con- tains copper, becomes covered with cuprous oxide, and the wire at the negatlTe pole gives off hydrogen ; if aqueous ammonia be added, gas is evolved at both poles, flakes of copper are likewise formed at the negative pole, and the oil turns yellow. — Copper dissolved in the oil may also be detected by shaking it up with aqueous ferroeyanide of potassium, which produoea a red precipitate of ferroeyanide of copper. (Guibourt.)

336 PRIMART-NUCLBUS C»HP«.

Copper may be removed from the oil by dintiUationj inasmncb ae it passes over only with the last portion of the distillate (Schonfelder and others) ; by agitation with animal charcoid (Vasmer, Br. Arch. 37» 348). — A sample of dgepat-oU from Paris contained according to Gaibourt, 0*22 p.c of copper*

Decompositions. 1. Grade cajeput-oil^ when heated^ yields a colourless distillate, and leaves a resin whicn colours ammonia blue, and bums away completely when set on fire (Blanchet) ; when distilled with water, it leaves a dark green syrupy mass which smells like aloe-wood or elemi^ and is nearly as heavy as water. (Gaibourt.) — 2. It dissolves iodine withoat explosion (Blanchet), giving off a small quantity of yellowish red vapours, and exhibiting a slight rise of temperature ; the rectified oil forms with iodine, a greenish brown coagvdum, which changoB to a dry crumbling mass. (ZeUer.)-<-3. Mixed with an equal quantity of nitric acid, it acquires a brown or black-brown colour withoat losing its odour (Bonastre, «7. Fharm.

11, 129); becomes blnish-red if heated, and gives off gas with violence (Zeller); forms, with crackling noise, a soft yellow resin. (Hesse, CreU. Ann. 1785, 1, 422.) — Nitric acid has no action upon cajeput-oil. (Blanchet.) — 4. With cold oil of

Vitriol, it turns yellow (Blanchet), orange, then carmine-red, with evolu- tion of sal])hurous acid (Dobereiner), brown-red, forming a balsam which gradually becomes black-brown. (PfafT.) — 5. It absorbs hydrochloric acid gas, acquiring a blue, violet, and finally an amethyst-red colour. -^ Cajeput-oil coloured amethyst-red by hydrochloric acid gas, turns violet in moist air, and when mixed with alcohol, deposits a heavy oil, and tarns dingy yellow. (Dobereiner.) — 6. Potassium abstracts oxygen from cajeput-oil without turning it brown. (Blanchet.) — It does not act on cajeput-oil more strongly than on oil of turpentine ; the evolution of gas, which is weak even at first, soon ceases. (Dobereiner.) -^ 7. Green oil of cajeput becomes yellow by contact with aqueous amtnonia (Ddbereiuer), sometimes quite colourless (Guibourt), the ammonia likewise remainiog colourless (Dobereiner), assuming various shades from greenish blue to blue (if the oil contains copper ?) (Guibourt) — 8. When shaken up with fiqueoixB ferrocyanide of potassium^ it is decolorised, or acquires a greenisU yellow colour, and deposits a red powder (in case it contains copper?) (Guibourt.) — 9. Boiled with nitroprusside of copper, it yields a black precipitate, and turns brown. (Heppe, N. Br. Arch. 89, 57.) — 10. When it is continuously agitated with ^ of corrosive sublimcUe, calomel is separated, and the oil acquires a blae-brown colour, which afterwards continuously increases in depth. (Simon, Po^. 37, 557.) — 11. When kept in copper vessels, it dissolves copper and turns green. (Guibourt.)

Cajeput-oil dissolves readily in alcohol. (Gnibonrt, Zeller.)

3. Oil of Coriander.

Trommsdorff. N. Br. Arch. 2, 14.

Kawalibr. Wien. Akad. Ber. 9, did; J. pr. (Sum. 5%^ 226; abstr.

Ann. Fharm. 84, 831; Chem. Centralbl. 1852, 746; N. J. Fharm.

23, 479.

Source and Extraction, In coriander, the fruit of (Joriandrum sativum, L. --« The braised fruits are distilled with water.

J

OIL OP 0SMIT0PSI8. 337

Properties, Colourless oil (Trommsdorff), pale yellowish. (Kawalier.) Sp. gr. 0-859 (Trommsdorff), 0-871 at 14°. (Kawalier.) Boiling point 150'^ (bat not constant). (Kawalier.) — Smells like coriander, but more agreeably ; tastes aromatic, but not burning (Trommsdorff), like coriander. (Kawalier.) Neutral. (Trommsdorff.)

	.... 120	.... // 9m ... .... 11-69 ... .... 10-39 ...			Kawalier.
20 C	a. 77-82 11-67 10-51	• ••• • ••• • •••	b. 77-73 11-63 10-64	c. .... 85-67 .... 11-58 .... 2-75	.... 85-47
18 C		.... 11-59
2 O	.... 16	.... 2-94
C»H»02 ....	.... 154	.... 100*00 ...	10000	••••	100-00	.... 100-00	.... 100-00

a. Oil dried over chloride of calcium and rectified; b. Its most volatile part; both according to Kawalier, are isomeric with liquid turpentine-camphor, c. The most volatile product of an oil merely dehydrated with chloride of calcium, but not heated to the boiling point ; d. The oil distilled therefrom at 200°; both c and d, according to Kawalier, are composed according to the formula C^H^'O' — 4 C?^W^ •»- 2 HO or 2C»H'« + 2(0»H»«,HO).

Decompoiiiiona. 1. The oil explodes strongly with iodine, — 2. With 2 pts. of fuming nitric acid, it forms a yellow resin (Hesse, OreU. Ann. 1 , 422), a greenish resin having a peculiar odour, and becomes very hot. (Trommsdorff.) — 3. Mixed with ot^ of vitriol, it yields a saffron-yellow liquid, which gradually becomes dark red and ultimately brown red, and chars rapidly when heated. (Trommsdorff.) — 4. When repeatedly distilled over anhydrous phosphoric acid, it is converted into a jellowish offensive -smelling oil isomeric with oil of turpentine (containing 88-28 p. c. C, and 11-78 H). (Kawalier.)

Combinatiotu. With Hydrochloric Acid. CH^^CPO. (Kawalier.) Dry hydro- chloric acid gas is passed into coriander-oil cooled with ice ; and the oil which remains liquid after saturation, is washed with aqueous soda, then with water, and dehydrated by agitation with chloride of calcium. (Kawalier.)

Calculation according to Kawalier. Kawalier.

40 C 240 .... 67-81 67*51

35 H 35 .... 9-89 1000

' 2 a 71 .... 20-04 20-40

0 8 .... 2-26 2-09

(0»H",HO + HCl) + (C»H",HC1) 354 .... 100-00 10000

Ooriander-oil dissolves readily and abundantly in glacial acetic acid, alcohol, ether, andjlxed oils, (Trommsdorff.)

4. Oil of Osmitopsis.

V. Ooaup-BssANEZ. (1854.) Ann. Fharm, 89, 214; abstr. J, pr. Chent. 61, 513; Ohem, CentralbL 1854, 299.

Osmiteiiol, Essence d'osmitopeis. Source. In Osmitopsis astcriscoides, a South African plant.

VOL. XIV. z

338 FRllfAUT NUCLEUS Cm^\

ProperHa. Yellow or bintly greenish ; that which diBtils between 178^ and 188^ iB colonrless, mobile, and feels rough between the fingers. 8p. gr. 0-931 at 16-2" ; 0*921, rectified at 178''— 188^ Boiling point not constant, bat ranging chiefly between 176" and 188". It begins to boil slightly at 130", boils regularly at 176% two-thirds distilling over rapidly at 178". It does not solidify on cooling. Odour penetrating, un- pleasantly like camphor and cajepui-oil ; more delicate, after rectification net ween 178" and 188^. Has a burning taste, and produces a scratching sensation in the throat Neutral.

20 C 18 H	... 120 ... 18	.... 77-92 , .... 11-69 , .... 10-39 .	Gorap-Betanes. 77-36 11-53
2 0	... 16	■•«•••■• A JL AX
C»HttO»	... 154	.... 100-00 .	10000

Decompoaitiona. 1. The crude oil when dktiUed finally gives off a yellowish liquid between 188" and 206", afterwards camphor sublimes between 207^ and 208", and a dark-coloured resin remains. — 2. With cold nitric acid, it remuns unaltered, but with the hot acid a violent evolution of nitrous gas takes place. — 3. It turns brown with oil of vitriol, — 4. With potcunum, it gives off a small quantity of gas, the metal at the same time becoming oxidised. — It does not form a hydro- carbon by distillation with alcoholic potash. — 6. From ammoniauxU 9ilver-8oluiion8j it reduces the metal only after long-continued boiling. — 7. It dissolves iodine without explosion.

Combinations, — It dissolves in all proportions of alcohol and ether. — It is nearly insoluble in VHXter^ but forms with it a turbid liquid having the odour of the oil.

Camphor. C"H»«0» = C»H",0«.

Hanbl. (1703.) Din, de camph, Lugd. B, 1703.

Dbhachy. Dessen. Lahorant in Grossen, 1, 242.

Ferber. Beitrdge zur Mvneralgeschichte, 1, 370.

KosEOARTBN. Diss. dc camphora, ^c, Gott 1785.

Bouillon Laoranob. Crell, Ann, 1799, 2, 301.

Saussubb. Ann, Ckim. Phye. 13, 275; 8chw, 28, 389; further, 29, 173;

N. Tr. 5, 2, 112. Dumas. Ann, Chim, Phys, 48, 430; further, 50, 225; Pogg, 28. 531;

Ann. Fharm. 6, 259; Sehw, 66, 89. Liebiq. Pogg, 20, 45; Ann, Chim. Phys, 47, 95. Blanchbt & Sell. Ann, PhaiTn, 6, 304. Laurent. Ann, Chim, Phys. 63, 207; Ann. Pharm, 22, 135; J, pr.

Chem, 11,287. — Comp^. rend, 10, 532; J, pr, Chem. 20, 498. — -ff«r.

soient, 11, 263; J, pr, Chem. 28, 333.— A^. Ann, Chim. Phye, 7, 291.

— Compt.chim. 1845, 150. — Cbmp^. rend, 20, 511,-^ Rev, scienl.

19, 1.59.

CAMPHOR. 339

Mabtius. Ann. Pharm. 25, 305; further^ 27. 44. — N. Bepert, I, 641. Dumas & Stab. iV. Ann. Chim. Phys. \, 48; Ann, Pharm. 38, 184. Delalandb. iT. Ann. Chim. Phys. 1, 120; J.pr. Chem, 23, 887; i<«n.

Pliarm. 38, 337. DuTBocHBT. Compt. rend, 12, 2, and 29, and 126, and 598. Clau& Peterab. Acad. BvU. 9, 229; Bev. sclent. 9, 181; J.pr. Chem. 25,

257; iVr. i5r. Arch. 30, 170. Gebhabdt. i\r. Ann. Chim. Phys. 7, 282; J. pr. Chem. 28, 46; Ann.

Pharm. 45, 34. RocBLEDEB. Ann. Pharm. 44, 1 and 3 and 9. DoppiNO. Ann. Pharm. 49, 353. BiNEAU. N. Ann. Chim. Phys. 24, 337; J. pr. Chem. 46, 296; Ann.

Pharm. 78, 276; abatr. Eepert, 110, 176; Pharm. CentraM. 1849,

5%', Compt. rend. 27, 184. Bebthelot. N. Ann. Chim. Phys. 56, 78; abstr. Compt. rend. 47, 266;

Ann. Pharm. 110, 367.

Memoirs relating especially to the Modifications of Camphofi\

Dessaignes & Chautabd. N. J. Pharm. 13, 241; J. pr. Chem. 45, 45;

abstr. Ann. Pharm. 68, 342. Chautabd. Compt. rend. 37, 166; N. J. Pharm. 24, 168; J. pr. Chem.

60, ]39; Pogg. 90, 622; abstr. Chem. Centralbl. 1853, 636; N. Pr.

Arch. 76, 168. Jeanjban. Compt. rend. 42, 857; farther, 43, 103; Jnst. 1856, 176 and

260; /. pr. Chem. 69, 204; Ann. Pharm. IQl, 94; Chem Centralbl.

1856, 675 aTk^ 672.

CmnpAora, Can^hre, Campher ; Laurua eampher; Dextro-eamphor, Camphre droit ; Kisteneampher oder ekinennher oder FbrmoBae-eampher : Tubbeneampher, or Bataman, Dutch, Japanese Camphor. Oxyde de eamphene (Berthelot) Aldehyde eampholigue (Berthelot.) Not known to the Greeks and Bomans; first introduced into Europe by the Arabians; first noticed by Actius towards the end of the fifth oentnry ; regarded by Agricola (de naturafoenlis) as fossil resin ; by others, as a resin or a tree-gam.

Source and Extraction. In all parts of tbe camphor-tree (Laurus Camphora, L.\ indigenoos in China and Japan. It is obtained in those oonntries by boiling the oomminnted parts of the plants with water in kettles, which are covered with rushes or rice-straw, and with an iron helm : crude camphor then sublimes into the straw, and is converted into refined camphor (generally in Europe) by sublimation, either per se or with chalk or lime. Camphor- trees raised in hot-houses, likewise yield camphor. (Goppert, N. Br. Arch. 20, 93.)

Formation. 1. By heating bomeol with moderately strong nitric acid. (Pelouze, Compt. rend. 11, 365 ; Ann. Pharm. 40, 326 ; J. Pka:rm. 26, 645.) An oil forms on the surface of the acid, and from this oil camphor separates on addition of water. (Pelonze.) — 2. By the action of platinnm- black on eamphene (p. 271). (Berthelot, Compt. rend. 4!7, 266.) — 3. By distilling oil of valerian with fuming nitric acid (Rochleder) ; out, according to Pierlot {N. Ann. Chim. Phys. 56, 291), camphor is not formed in this manner (see page 322). — 4. When oil of sage is dropped into fuming nitric acid, a solution is formed, from which common camphor

z 2

340 PRIMARY NUCLEUS C»H»«.

sablimes on distillation. (Rochleder.) — 5. By distilling oil of tansy with bichromate of potash and sulphario acid. (Persoz, Compt. rend. 13, 483 ; Vohl, N. Br, Arch. 74, 16 ; Phaitti, CerUr, 1853, 319.) —6. By the action of chlorine gas on oil of sassafras. (Faltin, Ann, Pharm. 87, 376.) — 7. Common camphor is formed by distilling amber with nitric acid, and may be separated by neatralising the distillate with potash and extracting with ether. (Dbpping.) - 8. Macfarlane obtained common camphor by heating camphor-oil (p. 314) with nitric acid.

Propeii>ies, White, translucent, tongh mass, generally with a crystal lo- granular structure, made up of octohedrons or segments of octohedrons. When crystallised by slow spontaneous sublimation during a space of three years, it forms perfectly transparent, six-sided tables, some of which have a diameter of 7 or 8 millimetres, and a thickness of 2 milli- metres, the greater number, however, being only ^ to ^ a millimetre thick. Crystalline system, the rhombohedral. Combination of the terminal face p (Fig. 133) with the pyramid r and the six-sided prism 8 (Fig. 135). p : r = 1 1 8'' 9' ; whence follows r : r at the base = 123'' 42'. Negatively double-refracting. (Descloizeaux.) May be impressed with the nail, cut with a knife, and pulverised, not per se, but when moistened with alcohol, and easily crumbled to small angular lumps, it forms dendritic crystals, the form of which is not influenced by light or by the solvent. (Reinige, N. Br, Arch, 48, 307.) A solution of a small quantity of camphor in a drop of alcohol leaves, when evaporated on a glass plate, crystals, which, when examined by the microscope with polarised light, exhibit beaatiful colours (a property which distinguishes natural from artificial camphor). (Bailey, Sill. Ann. J. Mau 1851; Chem, Ceniralbl. 1851 592.)

Sp. gr. 0-9887 (Brisson), 0-9968 (Newton); 100 from 0° to 0♦6^ 0-998 at 6-25, 0*992 from 10° to 12*5°. (Brisson, N', Br. Arch. 48, 327.) Camphor in small lumps floats on water at 15°, has a specific gravity equal to that of water at 6'25°, and floats on it again at 11"^. (Brisson.) Camphor, at the temperature at which water possesses its maxim am density, does not follow the same law of expansion as water, but contracts continuously as the temperature falls. (^Muncke, Repert. 48, 246.)

Camphor melts at 150° (Venturi), 175° (Gay-Lussac), 142-2°. (Thomson, Ann. PhU. 1820, 392.) It boils at 204° (Gay-Lussac), 204-4° (Thomson), and may be sublimed without decomposition ; it volatilises in the air even at ordinary temperatures. Vapour-density = 5-468. (Dumas.) Tension of the vapour at 15-5°= 0-004 met. of a column of mercury.

Rotatory power 37*4° to the right, diminishing however as the solution

becomes more dilute. In solutions of camphor in acetic acid, the rotatory power Taried with increased dilution from 36*2** to 30*6** to the right \ in absolute alcohol, from 37-28<* to 34-23*' to the right. (Biot, N, Ann. Chim. Phys. 36, 257 ; Compt. rend. 85, 233; Ann. Pharm. 84, 160. The rotatory power of camphor increases with the refrangibility of the rays more than that of most other bodies. (Arntsen, N. Ann. Chim. Phye. 54, 417.) It is only camphor melted by heat, not solid crystallised camphor, that acts upon polarised light. (Descloizeanx, JV. Ann. Chim. Phye. 66, 220.)

Camphor has a peculiar, aromatic, penetrating odour. The odour is disguised by addition of musk (Fleisohmann, Bepert. 104, 252 ; Pham^ Centrabl. 1850, 432); and completely destroyed by mixture with J«a- foetidaf galbanum, sagapene, animS, or tolu-haUam ; partially by mixture of dragorCe blood, olibanum, mastic, benzoin, opoponax, tacamahac, guaiac, or gum ammoniaeum; the odour is not destroyed by admixture of jalap,

CAMPHOR. 341

resin, gamboge, euphorbium, bdellium, amber, myrrh, scammany, iandarach, pine-resin, colophony, or Chinor-resin. (Planche, N. Br. Arch. 22, 107.)

Camphor is not altered by expos are to light or air. Its taste is warming, bitter, and burning.

Small lumps of camphor thrown upon water, exhibit a rotatory motion. The cause of this movement has been supposed to be : 1. An electric current between the camphor and the sides of the vessel containing the water. ^Romieu, MSm, de VAcad, 1756.) — 2. An odoriferous elastic fluid, which, by surrounding the camphor, impedes the action of air and water upon it. (Prevost, Ann. Chim. 21, 255.) — 3. The attraction of camphor for air and water, and its simultaneous solution in the one and the other. — 4. The expansion of an oil, which, being given off from the camphor in the form of vapour, is attracted by the surface of the water and forms a thin layer thereon, this expansion being visible in the force with which all foreign particles floating on the water are repelled. (Ventury, Ann, Chim, 21, 262; Corradory, Ann. Chim, 37, 38.) — 5. The efflux of the camphor itself into the water and into the air. (Serullas, J. Phys. 91, 172.) — 6. The volatilisation of the camphor and its simultaneous solution in the nearest particles of water. (Matteucci, Ann. Chim. Phys. 53, 216.) — 7. The attraction of the water for the camphor, and the repulsive action exerted by the latter upon the water, two opposite directions of one and the same force, which acts in a curve, one extremity of whose major axis corresponds with the neighbouring bodies from which this force proceeds. (Dutroohet.)

1. Sanssure. 2. Gobel. S.Thomson. 4. Ure. 5. Damas.

20 C 120 .... 78-94 74-38 .... 74-67 .... 738 .... 77-38 .... 78-03

16 H 16.... 10-53 10-67.... 11-24.... 14-4.... 11-14.... 10-39

2 0 16 .... 10-53 14-61 .... 14-09 .... 11-8 .... 11-48 .... 11-58

C20H16O3 152 .... 100-00 99-66 .... 100-00 .... 100*0 .... 10000 .... 100-00

6. Ldebig. 7. Blanchet 8. Laurent 9. Dumas & Stubs. 10. Claus. & Sell. a. b.

C 81-76 .... 78-33 .... 77*93 .... 78-91 .... 79-04 .... 79*59

H 9-74 .... 10-61 .... 10-53 .... 10-65 .... 10-55 ... 10-52

O 8-50 .... 11-06 .... 11-54 .... 10-44 .... 10-41 .... 9-89

10000 .... 100-00 .... 100-00 .... 100-00 .... 100-00 .... lOO'OO

11. Gerhardt. 12. Rochleder. 13. Vohl.

C

H

O

		a.		d.
78-3	••••	78-84	• •■•	79-15	»•••	81-05
10-8	•••fl	10-40	■ »«•	10-37	• •••	10-96
10-9	• •••	10-76	• •••	10-48	»•••	7-99

100-0 .... 100-00 .... 100-00 .... 100-00

VoL Density.

C-vapour 20 8*2300

H-gas 16 1'1088

O-gas ...*. 1 1-1093

Camphor-Vapour 2 10-4481

1 5-2240

1 contains also 0*84 N; 2. Schw. 40, 356; 3. Ann. Phil. 1820, 392; 4. Phil. Trans. 1822, 11; Schw. 39, 335; 11. from borneol obtained from oil of valerian; 12. a from oil of valerian : b from oil of sni^e ; 13. from oil of tansy.

342 PRIMARY NUCLEUS Om^.

According to Sanssnre, camphor Is prodnoed by the onion of 1 at. cariKmic oxide and 5 At. oil-gaa ; according to Liebig's firat analytia, it corresponds to the fonnnla C^H"0; according to Dnmas, it agrees with the formnla C^HH), and consists of 1 toI. camphogen and i ▼ol. oxygen, wUle Blanchet & Sell supposed it to contain a multiple of the radical C^H', in combination with oxygen. Common camphor is related to bomeol in the same manner as aldehyde to alcohol. (BertheloL)

Deeomponliofu. 1. Camphor -yapoar, passed through a red-hot glass or porcelain tabe, yields a combostible gas, which explodes with 2 vols, oxygen, producing 1 *45 vol. carbonic acid (Cmikshank) ; a volatile oil containing camphor, easily soluble in alcohol ; a combustible gas of sp. gr. 0'8397> 1 vol. of which absorbs by explosion 1'4554 oxygen^ producing 0*955 vols, carbonic acid : no charcoal separates from the camphor vapours. (Saussure.)

2. Camphor loses its odour completely when an electric current is passed through it for some time; the camphor thus deprived of smell remains inodorous for a while, even when removed from the action of the current and in contact with the ground, and recovers its odour after a longer time. (Libri, Ann. Chim. Phys. 87, 100 ; Schw. 53, 175.)

3. Camphor, when set on fire, bums with a smoky flame, producing carbonic acid and water. A small quantity of camphoric acid (f Gm.) is formed at the same time, and charcoal remains behind. (Bouillon- Lagrange.) Spongy platinum laid on camphor begins to glow when the camphor is set on fire, continues glowing after the flame is blown out, and penetrates through the camphor^ while the camphor-vaponn in the neighbourhood form an arborescent crystalline sublimate. (Stratingh, BepeH, 21, 410 j Van Dyk, RepeH. 21, 235.)

4. Moist MorvM converts camphor, with evolution of hydrochloric acid, into a liquid compound (hydrochlorate of camphor). (Claus.) Chlorine, passed into an alcoholic solution of camphor, decomposes the alcohol, and at last slowly decomposes the camphor. (Claus.) Camphor melts in chlorine gas to a liquid, which is scarcely heavier than water, rotates to the ri^ht, gives off chlorine in the air, leaves dextro-rotatory camphor, explodes readily in sunshine, and deposits camphor. (Deville, Anil, Chim, Phys. 75, 58.) Burning camphor goes out in chlorine gas, but bums away in it with a dark red flame and deposits charcoal, if it be wrapped up in tinfoil, and the tinfoil sprinkled with powdered sulphide of antimony. (Meerten & Stratingh, Schw. 3, 442 ; N. Tr, 16, 300.)

6. Heated with iodine^ it gives off hydriodic acid gas (Colin & Gaul-

thier), only after long-continued action (Guyot, J. Fhys. 5, 233) ; compare lodocamphor,

7. By prolonged boiling with nUric acid, it is converted into cam- phoric acid. (Bouillon- Lagrange.)

8. Camphor, heated with oil of vitriol to 100° for 12 — 13 hours, is resolved into camphrene (p. xiii. 156), sulphurous acid gas, and charcoal. (Chautard, Compt. rend. 44, 66 ; J. pr, Chem. 71, 310.) Heated for an hour with excess of oil of vitriol, it is converted into a volatile oil, which has the chemical properties and. composition of camphor, but less rotatory power, and, when heated with potash to nearly 200"^, is converted into a solid camphor, whose rotatory power is less than that of the original camphor, but greater than that of the oily camphor. (Delalande. Jn$tit. 307, 399.) According to Gerhardt (Traits, 3, 694), the oil obtained by Delalande is probably cymene ; according to Chautard, it is camphrene containing camphor. Camphor, heated with oil of vitriol forms, with evolution of sulphurous acid gas, a brown mass, from which water

CAMPHOR. 348

aeparates a brown Bubstanoe; on continning the heai^ Bnlphurons aoid gaa goes off^ togeilier with water, a yellow oil smelling like pepper- mint, and camphor, and lastly, sulphuretted hydrogen, which decomposes with the snlphuroos acid; and there remains a black-brown mass, of which 49 pts. dissolve in water or in alcohol, while 51 pts. remain nndissolved. (Hatchett ; Cheyreul, Ann, Chim, 78, 68 ; Gilb, 44, 164.) When camphor is heated with water and a small quantity of sulphuric acid, the escaping vapours redden litmus. (Buohner, Bepert, 9, 184.)

9. Camphor, distiJled with anhjfdrous photphoric add, is resolved into water and cymene. (Delalande, N, Ann. Chim, Phyt. 1, 868.) Heated with concentrated hydrated phosphoric acid, it volatilises for the most part nndecomposed, the acid ultimately acquiring a black-brown colour. (Buchner, Mepert 22, 420.)

10. TercMoride of phoiphortu, or eUorvne gas, converts camphor into qaadro- or sexH^hlorinated camphor, according to the quantity of the cnlorine passed in. (Glaus.) Distilled with pgnta-cMorid^ of phoapho^iLa^ it is converted into a crystailine substance, which has the appearance and odour of mono-hydrochlorate of turpentine oil, is sparingly soluble in alcohol, yields by repeated distillation a chlorinated oil smelling like turpentine and probably containing C^IVKj], and is itself composed of G^H^'Cl' : it remains dissolved in the chlorophosphoric acid which passes over at the same time, is precipitated from this solution by water, and is not decomposed by alconolic potash. (Oerhardt, Ti*aite, 8, 694.)

0»H»«03 + PCT - PCI»0» ■•- C»H>»CP.

Camphor dissolved in bromine, is decomposed by terbromide of phos- phorus, with rise of temperature and evolution of hydrobromic acid, yielding only bromocamphor. (Claus.)

11. Camphor is set on fire by ckloroehromic add, (Thomson, Pogg. 81, 607 ; PkU. Trans. 1827.)

1 2. By pentachloride of antimony, at 100°, camphor is converted, with violent intumescence and sudden evolution of hydrochloric acid, into a red-brown viscid mass. ' This mass, when shaken up with water, deposits powder of algaroth having a brown tint, while hydrochloric acid and a small quantity of chloride of antimony remain in solution. The alcoholic extract of the precipitated algaroth-powder leaves on evaporation a soft resin, having an agreeable odour, but not like that of camphor, and a sharp taste, producing a scratching sensation in the throat ; this resin, when distilled, gives off hydrochloric acid gas and an oil, colourless at first, but afterwards becoming coloured, and having a pleasant taste, like that of peppermint, and leaves a bulky, shining charcoal. The algaroth- powder, after exhaustion with alcohol, still yields a black brown resin to ether. (Claus.)

18. When camphor-vapour is repeatedly passed, under pressure, over heated potash-lime, camphilate of potash is produced. (Delalande, N. Ann, Chim, Phys. 1, 1 20 ; Ann. Pharm. 88, 827.) Camphor^ enclosed in a sealed tube with alcoholic potash or soda, and heated in the oil-bath to 180"" — 200° for 8 or iO hours, is converted into bomeol (p. 382), with which a little camphor generally remains mixed. (Berthelot.)

14. Camphor continuously boiled with aqueous permaiiganate of potash reduces it, with formation of camphorate of potash. (Cloez & Guignet, Compt, rend. 46, 1110 ; J. pr. Chem. 75, 177.)

15. When camphor- vapour is passed through a red-hot tube filled vfiih fragments of lime, a strongly coloured oil passes over, which has a

344 PRIMARY NUCLBUS C»H".

strong and peouliar odour, is lighter than water, boils at 75"^ after recti- fication, and dissolves in alcohol and in ether, but not in water. This is Fremy 8 camphrone = C«>H**0', and contains 85-03 p. c. C, 16-25 H, and 4-72 0 (calculation 85*71 p. c. C, 10*47 H, and 3*82 O). If the lime is raised to a very bright red heat, the camphrone is further resolved into carbonic oxide, carbnretted hydrogen, and naphthalin. (Fremy, Ann, Chhn. Phys, 59, 16 ; J. pr, OhenL 5, 355 ; Awn. Pharm. 15, 286.)

16. When camphor- vapour is slowly passed over red-hot inm^ water and benzene (xi, 134) are produced, or an oil isomeric therewith, which boils at 140"*, has a pale yellow colour, is lighter than water, and has a peculiar aromatic odour. (Compondon, see xi., 137.) At a very high temperature, naphthalin is likewise produced. (D'Aroet, Ann, Chim. Phys. 66, 110 ; /. pr, Chem 13, 248 ; Ann, Pharm. 28, 83.)

1 7. Camphor, mixed with 2 pts. of alumina or clay, and distilled, is

resolved into carbonic acid, carburetted hydrogen, empyrenmatic oil, and

a residue of charcoal. There is formed at the same time a small quantttj of cam- phoric acid (? Om.). (Bonillon-Lagrange.)

18. With melting Moride of nnc, it is resolved into water and cymene (Gerhardt p^ 183) :

C»H"0> « 2HO + C»H".

19. Heated with corrosive sublimate, it emits an odour like turpentine and gives off hydrochloric acid gas, leaving a black-brown mass, which, when exhausted with alcohol, leaves charcoal and calomel. (Glaus.)

Combinations. With Water. — Camphor dissolves in 1000 pts. of water (Giese); the solution acquires the odour and taste of camphor, becomes turbid with aqueous potash, not with aqueous ammonia or soda. — Heated with water in a Papin's digester, it dissolves more abundantly, apparently with decomposition, without separating on cooling. (Pfaff, Syst. d. Mat. med.) — Its solubility in water is increased by the presence of the stronger acids, but not of carbonic acid. (Giese, Brandos.) — la boiling water, camphor volatilises for the most part with the aqueous vapour. (Bnchuer, Bepert, 9, 284.)

Camphor melts with phosphorus when the two are heated together, the compound subliming without taking fire or shining.— The sablimate shines when rabbed, but not by the mere heat of the hand. — Phosphorus heated in camphor- vapour melts without shining. J. Davy, N. Ed. Phil. J. 15, 48 ; Schw. 68, 384.)

Camphor may be melted with sulphur. — At medium temperature and pressure, it absorbs sulphurous acid gas abundantly, and when saturated therewith, forms a colourless liquid, which is heavier than water, gives off sulphurous acid gas on exposure to the air and leaves camphor, and, on addition of water, deposits camphor, and dissolves iodine. — The quantity of sulphurous acid gas absorbed by camphor depends upon the pressure and temperature. (Blneau.)

100 pts. camphor absorb of sulphurous acid gas under a pressure of 0-70m.

at i'O** 70-6 parts.

„ 8*0 58-6 „

„ 10-0 54-0 „

„ 12-5 48-9 „

„ 14-0 46-8 „

„ 15-5 44-3 „

ff 20*11 .M>.<i 37*«9 i»

24-0 33-1

>» *» " "^^ * »»

CAMPHOR.

345

Camphor dissolves in 0*36 pts. of cold, or in a amall Quantity of warm ail of vitriol, forming a compound which is liquid like pitch while warm, solidifies on cooling, and is soluble in alcohol (Wenzel) ; it dis- solves in 4 pts. oil of vitriol at 100^, forming a dark yellow liquid (Chautard, Compt, rend, 44, 66, J, pr, Chem, 71 y 310); from the solution when fresh, the camphor may be separated by water. (Chautard.) — Camphor, if well cooled, slowly unites with anhydrous sulphuric add-, almost without evolution of gas, to a soft brown mass, from which water separates the greater part of the camphor in its original state. (Bineau.)

— Camphor does not absorb sulphuretted hydrogen, (Bineau.) — It dissolves in bisulphide of carbon, forming a liquid which mixes with alcohol, but not with water, and is not precipitated by water. (LAm- paditts.)

Equal parts of camphor and iodine triturated together form iodo- camphor. (Glaus.) — According to Guyot (J. Fhys. 5, 233), eoual parts of iodine and camphor do not unite at ordinary temperatures, but after some time, the mixture liquefies and gives off iodine without losing the odour of camphor. — Camphor dissolves a small quantity of io<line in the cold, and when heated with it, melts to a dark red-brown mass which solidifies on cooling and has the odour of its constituents (Winckler, Bepertf 32, 273); triturated with -f^ of its weight of iodine, it forms a black-brown mass producing yellow stains. (Voget, iV. Br. Arch, 16, 155.)

Camphor dissolves abundantly and without decomposition in bromine (Clans), forming a nearly inodorous mass which on cooling solidifies in a crystalline mass (Balard, Ann. Chim. Fhys, 32, 377), consisting of beau- tifully crystalline bromocamphor. (Laurent.) — The solution of camphor in bromine is converted by phosphorus into liquid bromide of camphor, with formation of terbromide of phosphorus, evolution of hydrobromic acid, and great rise of temperature. (Clau&)

Camphor absorbs a small quantity of dry chlorine in sunshine, thereby acquiring a yellow colour in a few weeks.. (Clans.) — Camphor melted at } 70° does not absorb chlorine, but volatilises undecomposed. (Claus.)

— Camphor unites with hydrochloric acid gas in proportions varying according to temperature and pressure. (Bineau.)

100 pts. of camphor absorb of hydrochloric acid gas, according to Bineau :

It 3-0" »	ndund	er 0*738
„ 30		0-232
» 7-0		0-740
,. 70		0-230
„ 90		0-288
„ 130		0-322
,. 15-6		0-744
„ 18-6		0-735
„ 200		0-740
» 240		0-747

170 24-0 16-3 15*8 15-3 20-5 20-4 200 19-0

ft

If t»

»t

tf

Camphor no longer absorbs hydrochloric acid gas :

at 12*0'' and under 0*22 met. pressure. „ 150 „ 0-34

,. 200 „ 0-39

„ 240 „ 0-42

n tl

348 PRIMARY NUCLEUS C»H><.

•7. Phys. 6, 223, an empyreamatio odoar), and consisting of camphin, a small quantity of colophene (p. 279), camphocreosote (vide inf.), concen- trated aqueous hydriodic acid, a little undecomposed camphor, and free iodine, whilst in the retort there remains a hiack campho-resin contami- nated with charcoal, a little camphin, colophene, campho-creosote, and iodine (2C«'H"0»+I=1 at. camphin (C^*H"), 3 at. water, 1 at. hydriodic acid, 1 at. camphoresin (C**H"), 2 at. carbon, and 1 at. oxygen, which is expended in the formation of camphocreosote)? — Aqneous alkalis decom- pose iodocamphor, separating the camphor in its original state.

lodocamphor is insoluble in watei', but dissolves easily, with hyacinth- red colour, in alcohol and ether* (Claus.)

2. Bromide of Camphor.

Laurent. (1840.) J. pr, Chem. 20, 498. — Rev, icient. 11, 263; J.pr.

Chem. 28, 333; Conipt. rend. 10, 532. Claus. J. pr. Chem. 25, 260.

Bromcamphorf Bromure de camphre, Camphre bromnr^, oxyde de eamphene bromurS. (Laurent.)

Formation. By dissolving camphor in bromine. (Laurent) — When phosphorus is gradually added to a solution of camphor in bromine, oily bromide of camphor is formed, and may be separated from the solution by water. (Claus.)

Preparation, Camphor is dissolved in cold bromine, and the crystals which separate from the mother-liquor immediately or after a few nours (though not always) are quickly pressed between paper, and protected from the action of light. (Laurent.) — The warm solution of camphor in bromine deposits unaltered camphor on cooling. (Laurent.)

Properties. Red, right rhombic^ or rectangular prisms.

Laurent.

C»Hi«0» 152 .... 51-2

2 Br 160 .... 48-8 51'2

C»H»«0»,Br» 312 .... 1000

Glaus considen Laurent's analysis incorrect, owing to the proneness of the bromide of camphor to decomposition.

Decompositions. — Bromide of camphor, when exposed to the air, deliquesces, gives off bromine, and leaves camphor. — When distilled, it yields bromine, camphor, a small quantity of hydrobromic acid, and a brominated oil. — In aqueous potash it deliquesces, and deposits camphor, after continued agitation.

It dissolves in water, the red solution gradually depositing camphor. (Laurent.)

SEXCHLORO-CAMPHOR. 349

3. Quadrichloro-camphor. C*>H»Cl*0^

Claus. (1842.) J. pr, Chem. 25, 259; Bev. sdent. 9, 181. Camphre quadrichiorS, Vierfach'CJdorcampher,

A solution of camplior in 3 pts. terchloride of phosphor ns is com- pletely saturated with chlorine ; the solution which forms at first, with evolution of hydrochloric acid, is ultimately heated to 1 00^; the clear, pale yellow, balsam- thick product is washed with water and aqueous soda ; and the hydrated chlorocamphor which then separates as a cream-like mass, is collected and freed completely from water by heating it in the water-bath, and passing a current of dry air through it. — In this manner, according to the quantity of the chlorine passed through, other chlorocamphors may be formed, containing 1 — 6 at. chlorine. (Glaus.)

Properties. Greenish, nearly colourless, transparent, unctuous oil having at 1 00" the consistence of olive-oil. It has an agreeable aromatic odour, and a bitter camphorous taste, afterwards sharp and scratching.

20 C 12 H	120 12	.... 41 «)o ... .... 4 xo ... .... 40-9/ ... .... 0'5Z	a. 44-52 4-54 45-12 5-82	Claas. 6.
4 CI 2 0	142 16	.... 51-0
0»HMC1^0» ...	.... 290	.... 100-00 ...	100-00	• •• •

a. not completely saturated with chlorine, or a mixture of C^H^'Cl'O^ and C'H'^Cl^O'. b. obtained by completely saturating with chlorine, a solution of camphor in terchloride of phosphoms, ultimately heated to 100**. (Claus.)

Decompositions, Heated above 100% it gives off hydrochloric acid gas, yields a chlorinated oil, colourless at first, afterwards pale rose-red, green, and ultimately black-brown, and leaves charcoal. A wick soaked in chlorocamphor bums as long as it is held in a flame, but is extinguished when taken out. Chlorine converts it, when heated, into sexchloro- camphor. A drop of pentacklorid^ of antimony turns it purple-red^ then indigo-blue, and frequently, on addition of water, green. (Claus.)

Combinations, Quadrichloro-camphor is insoluble in water, but forms therewith a cream-like mass ; it dissolves readily in alcohol and ether.

4. Sexchloro-camphor, C«H"Cl«0».

Claus. (1842.) J, pr, Chem. 25, 259; Bev. Sdent. 9, 181. Osyde de chlocamphdhse. (Laurent)

Produced by passing chlorine gas for some time through quadrichloro- camphor heated to 100**. Colourless mass, of waxy consistence, otherwise resembling the quadrichlorinated compound.

350 PRIMARY-NUCIiEUS C»W\

CUiu.

20 C 120 .... 83-42 3480

10 H 10 .... 2-79 3-10

6 CI 218 .... 59-47 67-74

2 O 16 .... 4-32 4-36

C»H»«C1«0» 359 .... 100-00 100-00

It is not altered by the continued action of a stream of MoHne, (Glaus.)

Compounds Isomeric with Campkor.

1. Laevo-camphor.

Source. In the oil of Matricaria Farthenium. (Dessaignea & Gbautard,)

Formaiion, By boiling IsBYo-bomeol from madder-spirit with nitric acid. (Jeanjean.)

Preparation. The oil of Matricaria Parthenium is subjected to fractional distillation ; the portion which goes over between 200° and 220 is cooled to — 5° ; and the mass, which often solidifies completely, is pressed between paper. (Dessaienes <& Chautard.)

Properties. Like those of ordinary camphor. It melts at 170°, boils at 204 (Dessaignes k Chautard), but possesses Levo-rotatory power. (Chautard.)

20 C 16 H	120 16	.... 78-94 . .... 10-53 . .... 10-53 .	Dessaignes & Chautard. 78-74 10-69
2 O	16	10'67
C»H»«0» ...	152	... 100-00 .	100-00

Decompositions. By prolonged boiling with nitric acid, it yields IsBYO-camphoric acid. (Chautara.)

2. Non-rotatory Camphor.

Separates from the volatile oils obtained from several plants belonging to the order Lahiatce. (Proust.) The camphor which separates from oil of lavender (78-14 C, 10-47 H, and 11-39 0, according to Dumas) is destitute of rotatory power; (Biot, Compt rend. 15, 710.)

3. Oil of Wormwood.

Leblanc. iT. Ann. Chim. Phys. 16, 333; abstr. Compt. rend. 21, 379. Zeller. Stud, uber other. Dele, Landau, 1850. Sasche. Zeitsch. Pharm. 5, 14.

Wermuth6lf Essence d'aMnthe. Source and Extraction. In wormwood, Artemisia absinthum, L.

OIL OF WOKMWOOD. 351

The flowering plant, either fresh or dried, is distilled with water. It yields 0*312 p. c. of oil. (Ruchner, Martins.)

Properties. Dark green (Leblano), dirty green (Martins), dark yellow, brown (Zeller). it does not become colourless by repeated rectification. (Leblanc.) The green colour of the oil is dne to a peculiar colouring matter ; when worm- wood-oil is distilled with oil of lemou and oil of cloves and water^ colourless wormwood- oil passes over first, and at last green oil of cloves. (Sachse.) Sp.gr. 0*973 at 24^

(Leblanc) ; 0-90— 0*96 ; from the leaves, 0-92 ; firom the flowers, 094. (Zeller.) Distils between 180° and 205°, and, after repeated rectification over lime, almost wholly at 205°. Rotatory power 20-67° to the right. Vapour- density = 5*3. (Leblanc.) Has a strong penetrating odour of worm- wood and a burning taste (Leblanc) ; its taste is peculiarly ethereal, sharp, and bitterish. (Martins.) Neutral (Zeller.)

Leblanc

20 C 120 .... 78-9 78-9

16 H 16 .... 10-5 10-6

2 0 16 .... 10-6 10-5

C^HWQ* 152 .... 1000 100-0

Vol. Density.

C-vapour 20 8'3200

H-gaa 16 11088

O-gaa 1 1.1093

Vapour of Wormwood-oil 2 10*5381

1 5-7691

DeeampoaUioiu* 1. The oil becomes darker and more viscid by exposure to the air. — 2. With iodine it thickens, without fulmination

or rise of temperature. Old wonnwood-oil» or that which has been exposed to the air, becomes heated in contact with iodine, and gives off vapours up to the point of sublimation. Fresh oil from the leaves yields a grass-green syrupy residue ; older oU leaves a brown thicker residue ; and oil from the flowers leaves a tough mass which solidifies. (Zeller.>*— 3. The oil takes up 2*156 pts. of bromine, and acquires a darker colour. (Knop, CTiem. Centr, 1854, 498.) — 4. Nitric acid decomposes it with yiolence, forming a non-crystalline resin.

(Leblanc) ^th \ pt. nitric acid of sp. gr. 1*25, it assumes in a few minutes a green colour, changing to dark green and black brown. (Voffet, Br, Arch, 19, 169 ; Zeller.) — 5. With oil of vitriol it becomes blackish (Leblanc), blue to deep yiolet (Zeller). — 6. When repeatedly distilled over anhydrous phosphoric add, it gives off water, and yields volatile campho^en, C*°H^^ (LebUnc.) — 7. With penlaehloride of phosphorus it gives up its oxygen, and exchanges 1 At. H for 1 At. CL (Cahours, Gompt, rend. 25, 725.)

c»Hwo« + pa» = c»H«ci + Hci + po»a».

8. It is not decomposed by aqueous potash, but partially by heated potash or sodorlime, inasmuch as it blackens and partially distils over without alteration. (Leblanc) — 9. Bichromate of potash and sulphuric acid immediately convert it into a dark flocculent resin. (Zeller.) — 10. When boiled with nitroprusside of potassium, it yields a brown black deposit. (Heppe, N. Br. Arch, 89, 57

y

Conibinations. It dissolves in all proportions of absolute alcohol, and in alcohol of sp. gr. 0*85. (Zeller.)

352 TRI MARY-NUCLEUS C»H>«.

4. Volatile Oil of Fulegium micranthom.

BoTTLEROW. (1854.) Petenb. Acad. Bull. 12, 24]; abstr. Pharm. CerUrdlhl. 1854, 359.

Source, In Pvleaium micranihum, a plant growing on the southern steppes of Russia, especially round Sarepta and Astrachan.

Properties. Yellowish; after rectification, colourless or slightly Yellowish, mobile. Sp. gr. 0*932 at 17*". Begins to boil at 202"", and Doils with tolerable regularity at 227°. It does not solidify at — 17°. Smells and tastes like the oils of peppermint and sage.

20 C 16 H	.... 120 .... 10	.... /O ^4 ... .... JU oo ...	Buttlerow. 78-45 .... 79-16 .... 10-63 .... 10-69
2 0	.... 16	10-92 .... 10-) 5
C*H»60« ....	.... 152	.... 100-00 ...	10000 .... 100*00

Decompositions, 1. It absorbs oxygen from the air, becoming yiscid, specifically heavier, and brownish yellow, without giving off carbonic acid. — 2. With fuming nitric acid, it forms chiefly acetic acid, together with small quantities of propionic acid and other fatty acids. — 3. With hydrochloric acid gas, it turns brown without solidifying. — 4. By boiling with strong aqueotis potash, it is converted into a brown, amorphous, acid, brittle resin, insoluble in water, soluble in alkalis and in alcohol (77-96 C, 3-59 H, 13*15 O), and a volatile, altered oil, mixed with an acid liquid containing a fatty acid. When dropt into melting potash, it turns brown and decomposes partially, yielding acetic, valeric, and other fatty acids. Heated with hichromaie of poiash and sulphuric acid, it forms chiefly acetic acid and other fatty acids. Distilled with hypockffirite of lime and water, it yields chloroform.

Combinations. It dissolves readily in alcohol^ ether, and oUs,

5. Oil of Pennyroyal.

5. In pennyroyal, Mentha puUgium, L, The herb is distilled with water. Sp. gr. 0-9721 ; of the rectified oil, 09255. Boils between 183'' and 188^

Kane. mean.

20 C 120 .... 78-94 77*79

16 H 16 .... 10-53 10-85

2 0 16 .... 10-53 11-36

C»H«0« 152 .... 100-00 100-00

Occurs generally mixed with oil of turpentine. (Kane, Land, B, Mag. J. 13, 440; J.pr. Chem. 15, 160.

UTDROCHLORATB OP fiORNEOL. 353

Gamphic Acid.

C»H"0* = C»H",OM

Bbbthblot. (1858.) if. Ann. Chim. Phys, 56, 94; abstr. Ann. Pharm. 112, 367.

See p. 332. Formed, together with bomeol, by heating common camphor for 8 or 10 hoars with alcoholic potash to loO — 200 in sealed tobes. The oontcDts of the tabes are exhansted with water; the andecomposed camphor and the bomeol are removed by filtration ; the solation, containing potash and camphate of potash, is concentrated bv evaporation after nentralisation with snlphuric acid ; the mother-liqaor is decanted from the snlphate of potash, which separates on cooling, and evaporated to dryness; the residue is exhansted with alcohol; the alconolic solation is evaporated over the water-bath ; the residae is again exhansted with alcohol ; and the camphate of potash, which remains as a syrap after the evaporation of the alcoholic solntion, is decomposed by dilate salpharic acid.

The add forms a nearly solid resin more or less coloared. It ii difficult to obtnn pore.

When heated, it yields an oil, a crystalline, not acid sablimate, and tar, leaving spongy charcoal. Heated with nUrie acid, it forms a nitro- eomponnd.

It is more or less solnble in toater, and combines with basee to form salts.

Camphate ofpaUuh is an nncrystallisable deliqnesoent syrap ; so like- wise is camphke ofeoda; both these salts dissolve sparingly in concen- trated aqneoos alkalis, and separate from the solutions on evaporation, iu the form of resinous soaps, easily soluble in pure water. The eamphatee of nne-^mde, lead-oxide, ferric oxide, euprie cxide, eUver-oxide, and /errous oxide are thrown down from the a<|ueous solution of metallic salts by aqueous camphate of soda, as precipitates which are soluble in a large quantity of water and likewise in acetic acid.

Camphic acid is readily soluble in alcohol. (Berthelot.)

Hydrochlorate of Bomeol.

C»C1H" = C»H",HCa. Bbbthblot. JT. Ann, C%%m, Phye. M, 78.

Campkol ehiorkydriq^t Cklorbomafer.

Bomeol is sealed up in tubes with 8 to 10 pts. of aqueous concen- trated hydrochloric acid, and heated to 100^ for 8 or 10 hours ; and the product is washed with dilate aqueous potash, then with water, aad crystallised from alcohol. In most of its properties it resembles mono- hydrochlorate of turpentine-oil. Rotatory power to the right, but weaker than that of bomeol, different from that of mono-hydrochlorate of turpentine-oil. (Berthelot.)

VOL. XIV. 2 ▲

354 PRIMARY-NUCLEUS C»Hh.

Berthelot

20 C 120-0 .... 69-56

17 H 170 .... 9-85

CI 35-5 .... 20-59 . 20*0

C»H",HCl 172-5 .... 100-00

Iflomerie with mouohydrochlonte of tarpentine-oil (p. 265).

Melts and sublimes when healed^ g^y^^g off a small qnantitj of hydro- chloric acid. Ignited with quicJdime, it gires off bomeol^ and leaves chloride of calcium.

It unites at ordinary temperatures with bihydrochlorate of turpen- tine-oil, forming a compound which melts at the heat of the hand.

Benzoate of BomeoL

BbrthxIiOT, y. Ann* Chim. Phys, 56, 78.

Campkol benMoigue, Berutbomeiter,

Borneol and bensoic acid are heated together to lOO"* in sealed tubes for 8 or 10 hours; the product is washed with aqueous carbonate of potash and caustic potash to remoTe excess of benioic acid, and the residual mixture of borneol and benzoate of borneol is heated to 150% till it no longer has a camphorous odour.

Colourless, inodorous, neutral oil, soluble in alcohol and ether. Heated to 120° with ioda-lime, it yields borneol and benioate of soda. (Berthelot)

H Appendix to Bomeene. (p. 813.)

Oil of Dryabalanops Camphora.

Lallbmand. Riude sur la c<ympo9ition de quelqu/e$ eueneet. W. Ann. Chim, Phy9. 57, 404; abstr. Bep. chim. pure, 2, 89; If. J, Phcarm, 37, 287; Ann, Fharm, 114, 193; Jahretber. d. Chan. 1859,502. — Short notice of results, Compi. rend. 49, 857.

This oil, which was originally brought from Sumatra, by Jnnghnhn, is there obtained by boiling the different parts of the tree, cut up into small pieces, with water, and collecting the oily layer which floats oa the surface. -* The oil thus produced appears to ^ essentially the same as that whidL rans oat from iDcisions in the tree, although the properties of the latter, as described bj Pelonxe (p. 314), differ oonsiderabljr from those assigned by LaUemand to tbe oil obtained by boiling the plant with water. Hence liaUemand concludes that the oil ezamined by Pelouse could not hare been obtained from Dryabalanops campbora. — It is a viscia,

reddish oil, havinff a strong balsamic odour, and turning the plane of polarieation of light to the right It begins to boil at about 180% but the boiling point quickly rises to about 255'' and then to SOO**! at which

OIL OF DRYABALANOPS CAMPHORA. 355

iemperatare the whole of the volatile portion has passed orer, and there remains a resin^ amounting to about half the weight of the original oil. The distilled oil is further resolved by repeated fractional distillation (mostly conducted under diminished pressnreWnto a more volatile and a less volatile oil, both having the composition (^H^*.

cu More volatile oil. This oil, which constitutes the smaller portion of the distillate, begins to boil at 180% the boiling point however quickly rising to 190^. The portion which first passes over (at 180°) has a lower specific gravity (0'86 at 15°), and greater dextro-rotatory power, than tnat which passes over at the higher temperature H^owards 1 90°). — The oil becomes heated by contact with oil of vitriol, — With hydrochloric otdd, It forms a compound which remains liquid at all temperatures, but which, when treated with strong nitric acid, yields a solid nydrochlorate C*^H^*^HC1, resembling artificiiJ camphor (p. 265) in all its properties, excepting that it possesses dextro-rotatory instead of Isevo-rotatory power.

6. Leu volatile oU, — Somewhat viscid, sparingly soluble in alcohol of ordinary strength, somewhat more in absolute alcohol. Begins to boil at 255°, the boiling point afterwards rising to 270°, and the greater portion distilling at 260°. The specific gravity of the distillate rises with the boiling point from 0*90 to 0*921 at 20°. The distillate is at first lievo- rotatonr, then dextro-rotatory ; the dextro-rotatory power increases till the boiling point rises to 260°, then diminishes, ana the portion which distils at 270° is optically inactive.

The oil b gives by analysis 88-74 p. a C and 11*76 H, agreeing nearly with the formula C^n^. — It becomes heated by contact with oU of vitriol.

HydrochloraU of (HI h. (FH^2HG1. — The oil unites with hydro- chloric acid, becoming heated at the same time, and forms a compound which is liquid at first, but solidifies partially after some days, and when recrystaJlised from ether-alcohol, forms colourless four-sided prisms. It turns the plane of polarisation to the left, whether prepared from hevo- or dextro-rotatoiy or optically inactive oil. Melts at 125°.

Lallemand.

30 C 180 .... 64-98 64-80 .... 64'66

26 H 26 .... 9-38 9*45 .... 9*59

2 CI 71 .... 25-64 25-55 .... 25-92

C»H««.2HCL 277 .... 10000 9980 .... 100-17

It decomposes at 175°, giving oflF hydrochloric acid. It is decomposed by oxide of lead or mercuric oxide at 100°, more readily by alcoholic potash-ley, with separation of the hydrocarbon (which then exhibits a tp. gr. of 0*90 at 25% poeaesies iBvo-rotatory power, boils at 260*, and unites with hydro- chloric acid, reproducing the original compound).

The hydrochlorate is sparingly soluble in ether, moderately soluble in

tdcohoL

e. Resin. C*^^0^ f — The resin left in he first distillation of the oil of Dryabalaniyps Camphora is a neutral, dark red, brittle substance, which softens at 100°, and melts at a somewhat higher temperature. It turns the plane of polarisation strongly to the right. It is somewhat soluble in alcohol, more readily in ether. By solution in absolute alcohol, it may be rendered colourless, but cannot be obtained in the ciyatalline state. It is neutral, and does not unite with bases. It gare by analysis 81*32 p. c. C and 11*08 H, the formula requiring 82*19 C, 10*50 H and 7*31 O. Lallemand supposes

2 ▲ 2

356 APPENDIX TO PRIMARY-NUCLEUS C«>H>«.

it to be formed from the hydrocarbon C?^B^, by anamption of 6 At. oxygen and elimination of 2 At. water (C»H«CH « 2 C»H3* + 0« — 2 HO).

The oil of Dryabalanopa Camphora examined by Lallemand did not contain bomeoL

Volatile of Lauru9 Camphora. — Mobile, nearly colourless, having a stronp; odoar of common camphor and considerable dextro-rotatory power. By fractional distillation it is resolved into an oil boiling at 180^ and a portion boiling at 205° ; the latter appears to be essentially the same as common camphor. — The oil boiling at 180° is very macn like oil of lemons, possesses strong dextro-rotatory power, and forms with [hydro- chloric acid, a crystalline compound which melts at 42°, and gives by analysis, 57*84 p, c. G, 8*Q U and 83*83 01, agreeing with the formula CJ*Il",2HCl (calcolation 57-42 C, 8*61 H, 33*97 CI). If

Appendix to the Primary Nacleus C*^u>«.

VolaHUe OiUt not yet included in the System, togethet* with the Camphon

or Stearoptenes which separate from them,

(Arranged alphabetically.)

1. Oil of Acacia.

The ethereal extrlMst of the flowers of Aeaeia alba, L., leaves by spontaneous evaporation, a yellow, warty mass, which sticks to the fingers, and has a strong and persistent smell of acacia : it appears to be a product of the decomiKMition of the oil. — This mass yields by distillation an empyreumatic oil having an unpleasant o<£)ur; it is soluble in boiling alcohol, the solution on cooling depositing flocks which exhibit the characters of wax. (Favrot, 1838, J. Chim. m^d. 14, 212.)

2. Volatile Oil. (AeeUe de amady.)

In the branches of an unknown tree growing in the neighbourhood of Bogota. It exudes spontaneously when the branches are cut, and so plentifully that a litre of oil may be obtained in a few minutes. — Yellowish, mobile, not solidifying at a few degrees below 0^. — Smells like oil of neroli, or rather like oil of rose and essenoe de cicari ; its taste is sweet at first, afterwards sharp and bitter. It is used in Bogota for adulterating balsam of copaiba. (Leroy, 1846, If. J. Pharm. 9, 107.)

OIL OF ANGUSTURA. 357

3. Volatile Oil of Acorns.

Obtained by diatilliDg braised acorns^ the fruit of Querent rolyur and Q. pedunctUata {Willd.}, after maceration with water. — Buttery, lighter thim water ; has a strong peculiar odour. Appears to consist of an oil soluble in ether, and another oil soluble in alcohol of sp. gr. 0*85. (Bley, N. Br. Arch. 2, 124.)

4. Alyzia-camphor.

Separates from the inner surface of the bark of Alyxia Beiiiwardu, (Blume), a tree growing in Java and Ambojna. — White, neutral, capillary crystals, having an agreeable odour of Tonka beans and a slightly aromatic taste. — Sublimes without melting when heated to 75 — 87^ ; melts and turns brown at a stronger heat. Distils partially with vaponr of water. — Nitric acid of sp. gr. 1*2, colours it yellow without dissolving ii — Dissolves very sparingly in cold, more easily in toarm wetter, and does not separate from the solution on cooling. — Dissolves readiljjr in aqiteatu potcuh, carbonate of potash, ammonia, ko., without neutralising them ; also readily in acetic acid, alcohol of sp. gr. 0*85, ether, and oil of turpentine. (Nees v. Esenbeck, Br. Arch. 28, 1.)

5. Oil of Angelica.

By exhausting with alcohol the comminuted roots of Anffeliea Mtxva, M,, concentrating the solution, precipitating with water, and distilling the separated balsam with hydrate of potash, a colourless oil is obtained lighter than water, of penetratiug odour and camphorous taste. — The same oil is obtained by distilling the comminuted roots with water, and rectifying the resulting oil over hydrate of potash, angelate of potash then remaining behind — The oil obtained by either of these processes becomes coloured, and rcsinises on exposure to the air. (A. Bnchner, Repert, 76, 161.) — Bucholz & Brandos {N. Tr. 1, 2, 128) obtained by distillation, 0*7 p. o. of oil; John (Chem. Tab. 4, 17), obtained 0*6 per cent.

6. Oil of Angustura.

Angnstura-bark, the bark of Galipea officinalis, Hane, yields by distillation with water, 0*75 p. c. of oil. — Light wine-yellow. Sp. gr. 0-934. — Boiling point 266°. — It cannot be rectified with water or solution of common salt. — Has a peculiar aromatic odour, and a mild taste with scratching after-taste. Contains 79*60 p. c. C, 12*31 H, and and 8-09 0, and is therefore perhaps C»H»0 = C*H* + C^HH), that is to say, a mixture of oxygenated and non- oxygenated oil. (Herzog, N. Br. Arch. 93, 146.) It is not apparently atta^ed by melting ^ycfrote <if potash. — Does not combine with alkaline bisulphites, (Kraut.)

358 APPENDIX TO PRIMARY-NUCLEUS CPH".

7. Oil of Anim^

Tn animi, the resin of the locast-tree, Hymmuxa CourbarU, JL — The resin is distilled per »e. Colonrless oil, with a strong not unpleasant odour and a burning taste. Volatilises without residue; is coloured deep orange-yellow by oU of vitriol; dissolves without turbidity in alcohol. (Paoli, Bruffti. Oiom. 16, 326.)

8. Oil of Ants.

In the red ant, Formica rufa, L. rcompare vii. 271) — The ants are distilled with water or alcohol, the aistiilate repeatedly cofaobated (Marggraf, N&lle), and the oil which floats on the surface, collected. — The process yields 0*12 p. c. of oil (Nblle), 1 p. o. rHermbstadt) — Transparent and colourless, with an agreeable odour (Nolle) ; its taste is not burning (Marggraf, Chym. Sehriften^ 1, 342) ; sparingly soluble in altolute aloohoL (Marggraf; Nolle, iiT. Br. Arek. 31, 183.)

9. Oil of Andca.

Woherleidl — a. In the flowers of Arnica montana, L.— -Obtained by distillation with water. — Blue (Heyer, (}reU, chem, «7. 3, 100), yellow to brownish green, with a peculiar odour (Zeller), like that of chamomile (Heyer); reacts slightly acid. (Zeller.) -— In contact with iodiney it becomes slightly heated, reddish yellow-brown and riscid. With nitric acidf it assumes a brownish yellow colour, and If heated gives off a laige quantity of gas, and forms a solid resin. ^- With oil of vitfiol, it assumes a yellow to reddish brown colour. — It dissolyes in 100 pts. ofcUcohol o sp. gr. 0*85, becoming turbid and flocculent ; with 10 — 60 pts. of abnluie (ucohol, it forms a turbid liquid, becoming clear only when heated. (Zeller.)

b. In the roots of Arnica montanaj L,, whence it is obtained by distillation with water. — Wine-yellow to brownish yellow. Sp. gr. 0'98 — 0'99. Reacts slightly acid. (Zeller.) — It dissolves tWtn«, with- out rise of temperature or evolution of gas, becoming red-brown and viscid. With nitric acid, it becomes hot, gives off gas, assumes a grass- green to yellow-brown colour, and after a while becomes viscid. — With oil of vUriolf it turns purple-red. — It dissolves in 2 pts. of alcohol of sp. gr. 0*85, and in all proportions of absolute alcohol. (Zeller, Stud, iiber, other. Ode, Landau, 1850.)

BASIL-CAMPHOR. 359

10. Oil of Asanun.

ObIgeb. (1880.) Diss, inaug. de asara eitrop. OdttiuKen, 1830. Zbllbr. JBr. Arck. 86, 266. — Stud, iiber other. Ode, Landan, 1850. Sell & Blaiiobet. Awn. Fharm. 6, 296.

In asarabaccai the root of Asarum eurapantm, L, — It is exhausted with alcohol, the lower stratam of the extract, consisting of the oil and asarum camphor, is separated from the upper, and distilled ; the residual, oil J, thick mass is rectified over hjdrate of lime ; and the oil is decanted from the asarum-camphor which separates at the same time, and dehy- drated orer chloride of calcium. (Sell k Blanchet)

Froperties. Yellowish (Grager), greenish yellow (Zeller), viscid, lighter than water. (Grager.) Sp. gr. 1*018. (Zeller.) Smells like yalerian, and has a sharp bnming taste. (Grager.) It is neutral. (Zeller.) Contains 75-41 p. c. C, 9*76 H, and 14*83 0, but still retains asarum-camphor in solution. (Sell & Blanchet.)

Asarnm-oil, treated with iodine, gives off yellowish red vapours, and forms a yellow*brown resin. Heated with nitric acid, it gives off gas, and forms a yellow-brown solid resin. — "ByaU of vitriol, it is coloured brown to bloocUred and resinised. (Zeller.) — • It dissolves sparingly in water, more readily in alcohol, in ether, and in oUs both ^fixed and volatile. (Grager.)

11. Oil of Balm.

Zellbb. &ud. iiber other, Oele, Landau, 1850.

In the herb of Melissa officinalis, L. at the flowering time. — Obtained by distilling the herb with water. — Colourless, pale yellow. Sp. gr. 0'85 — 0*82. Has a peculiar odour. Reddens litmus slightly. — According to Bizio (Brv^. Oiom. 19, 860), it contains a comphor in ' solution. — It dissolves iodine, with great rise of temperature and evolu- tion of yellowish-red and grey vapours, and becomes viscid. With nUric acid, it turns brown, gives off a large quantity of gas when heated, and becomes resinised. — It dissolves in 5 to 6 pte. alcohol of sp. gr. 0*856.

12. Basil-camphor.

C«^H«0« = C«>H",6H0?

BoNABTBB. (1831.) J. Pharm. 17, 647.

Dumas & Pbligot. Ann. Chim. Phys. 57, 834; J. pr. Okem. 4, 386; Ann, Pharm, 14, 75.

JBasHieum-'eamphor, Eaenee de boiilic,

Basil, Ocymum hasUicum, X., distilled with water, yields about 1*56 per cent, of a yellowish green oil, lighter than water (Ray baud, J. Pharm.

860 APPENDIX TO PRIMARY-NUCLEUS C^H".

20, 447), which when kept, solidifies almost whoUj as orystalline basil- camphor. (Bonastie.)

Solid oil. Crystallised from alcohol : foar-sided prisms having a faint smell and taste; crystallised from water, it forms white, transparent nearly tasteless tetrahedrons. (Bonastre.) Neutral.

20 C.

22 H

60

120	• (M	6315	68-8
22	....	11*58	11*5
48	....	25-27	24*7

C»HW6H0 190 .... 100*00 100*0

laomeric or identical with crystalliMd turpe&tiiie-camphor (p. 262, Dumai ft Pdigot)

It bums with odonr and flame when $et on fire; reddens in contact yni^i. oil of vitrioL (Bonastre.)

Dissolves sparingly in cold, easily in hot watery in nitric acid, acetic €teid^ and aqueotu ammonia, imperfectly in cold, perfectly in hot alooholf scarcely at all in 6 pts. of ether, (Bonastre.)

13. on of Bay.

BoNASTRB. (1824.) J. Fharm. 10, 36; — 11, d. Bb ANDES. If, Br. Arch. 22, 160.

Oa qf Laurel, Lorhcerdi.

Source and Extraction. In bay-berries, the fruit of Laurus nobilit, whence it is obtained by distilhition with water, or by arranging the berries in alternate layers with straw, and distilling with steam. (Forcke, iiT. Br. Arch. 17, 177.) Or it is distilled with water and a little sulphuric acid, the latter serving to decompose starch and mucus. (Bonastre.) The yield of oil is 0*26 p. c. (Blev, JRq>ert. 48, 96.)

Properties. ' Pale yellow (Bonastre, Brandes) ; the most volatile portion, or the oil rectified with water, is transparent and colourless, while the less volatile is yellowish. Lighter than water. (Bonastre.) Sp. gr. 0*91 4 at 150*^ ; of the most volatile oil 0*857 ; of the less vohitile, 0885 (Brandes). Liquid at 31% semi-solid at 12*5^ ; at low temperatures perfectly solid and dirty white. Smells like bay-berries; the most volatile portion, like oil of cajeput ; the less volatile has a similar odonr but less pure, and, after rectification with water, also like that of camphor (Brandes) ; the oil obtained by distilling bay-berries with sul- phuric acid and water, has a less agreeable and emnyreumatic odour. (Bonastre.) Tastes strong and bitter. (Bonastre.) It is neutral (the crude oil is slightly acid). (Bonastre.)

			Brandei.
c H 0	a. ..-M. oU'oO .... 11*76 .... 7*64 ....	b. 80*55 11-26 8*19	e. .... 80*56 .... .... 10*14 ....	d. 78*85 11*14 10*01	.... .... ...a	€. 8214 11*54 6-32

100*00 .... 100*00 .... 100*00 .... 100*00 ..M 100*00

OIL OF BIRCn -LEAVES. 361

a was obtained by rectifying the crude oil per m in the firat instance ; h that which passed over on rectifying the erode oil with water ; c a portion boiling at a higher temperatore; d that which has the highest boiling pomt; e obtained by rectifying the cmde oil with concentrated aqneons potash. The latter has the composition of crude oil of camphor. (Brandes.)

Decampomiumi. 1. Bay-oil absorbs oxygen from the air (Brandes). — 2. With 2 pts. of fuming nUrie acid it froths up, and forms a soft jrellow resin^ which separates on addition of water. (HassOi Crell, Ann. 17S5, 1, 422.) — 8. When agitated with potcuh, it forms after some time an oil, which floats on the sorfiuse, and a brown liquid, which, after saturation with hydrochloric acid, yields a white precipitate soluble in ammonia. Distilled with ctqueoua potash, it yields a neutral oil (e), havinff an odour of camphor and cajeput-oil, but not very pungent. (Brandes.)

Combinations. Mixed with ammonia, it yields a turbid liquid, and with eausUe harffia a white viscid liquid. (Brandes.) It is easily soluble in alcohol. The least volatile portion of the oil dissolves but partially in alcohol, aqueous potash, and ammania, leaving a brown oil, while the alcoholic solution contains a crystalline substance ; the potash- solution, a substance which separates on supersaturating with hydro- chloric acid, and is soluble in potash and in ammonia; and the ammoniacal solution contains a substance which forms a white precipitate with chloride of calcium.

Bay-oil dissolves readily in ether and in oils, both jixed and volatile; with the aid of heat, it dissolves tallow and wax, (Brandes.)

14. Volatile Oil of Beans.

Formed spontaneously in pulverised dry beans, Phaseolus communis: I. On moistening the powder with water. — 2. On evaporating the alcoholic extract and mixing the residue with almond milk. Bean-flour, exhausted with alcohol, does not form any oil when moistened with water. (Ed. Simon, 1842, N. Br. Arch. 29, 186.)

15. Oil of Birch-leaves.

In the leaves of the birch, Behtla alba, L. By distilling them with water, 0*86 p. o. of oil is obtained, floating on a milky distillate. Colourless, mobile ; the last distillate is yellowish and viscid, lighter than water ; becomes somewhat turbid and viscid at 0^, retains scarcely any fluidity at — 5^ ; solidifies at — 10% but not in the crystalline form ; melts at the heat of the hand. Its odour is very agreeably balsamic, persistent and exciting, like that of vonng birch leaves and oil of roses. Its taste is at first mildly sweetish, afterwards peculiarly balsamic, sharp, and heating. The oil becomes pale yellow after some time, and when dropped upon paper makes a waxy spot, which may be extracted by boilinff water, forming a solution which deposits white flocks on cooling. The oil appears to contain a waxy substance in solution (Befn/tii, Gm.).

362 APPENDIX TO PRIMARY-NUCLEUS C«H'«.

It dissolves in 8 pts. alcohol of sp. gr. 0'85 at 12'5°, fonning a clear liquid^ which becomes turbid at 0° ; it dissolves slowly in ether^ separating out slowlj at 0^. (Qrassmann, RepeH. 33, 337.)

16. Volatile Oil of Botany Bay Besin.

Obtained by distilling the resin of Xanthcrrcea arharea (12. Brown) with 6 pts. water. Colourless ; has an agreeable odour and very sharp aromatic taste. (Trommsdorff, Taschenb, 1826, 9.)

17. Camphor of BupJUkalmum maritwiunL

In the flowers of Buphthalmum maritimuniy a plant growing on the shores of Greece. The flowers, which have an agreeable odonr of roses, are distilled with water ; the distillate is oohobated, and the crystals which separate from it at about 0^ are collected, bellow, pointed crystals, having a silky lustre, and melting at the heat of the hand to a yellowish oil, having an agreeable but not powerful odonr. Reddens litmus slightly. Soluble in o^AoZ ; the solution is rendered tnrbid by water. (Lauderer, Kepert, 79, 233.)

18. Oil of Cardamom,

In cardamoms, the seed of Elettarxa Oardcmomum. {WhiL 4s Mat.)

They are distilled with water. The water likewise contains acetic acid. (Wnnder, J.pr, Chem. 64, 499.) Pale yellow. (Neumann, Zeller.) Sp. gr. 1'92 — 094. Tastes and smells like the seeds. Neutral. (Zeller.) Probably a mixture of a liquid and a solid oi), inasmuch as Dumas & Peligot (Ann. Chim. Fhys. 57, 334; J.pr, Cliem. 4, 386; Ann, Pharm, 14, 75) found in it colourless prisms, which according to them contain 64*0 p. c. C, 11 '4 H, and 24*6 0, a composition agreeing with the formula C^H^*,6H0. so that they are isomeric or identical with turpentine* camphor. Oil of cardamom, treated with iodine^ gives off yellowish-red and grey vapours, and becomes reddish yellow-brown and yiscid. With nitric acid, it yields a pale brownish-yellow resin. (Zeller, Hasse.) With oU of vitriol, it acquires a red-brown colour, with ckivmate of potash and sulphuric add, greenish-brown. (Zeller.) It dissolves in aieohol of sp. gr. 0*85. (Zeller, Stvd. uber. either, Ode, Landau, 1850.)

19. Oil of Carrot.

From the roots of Dauetu Carota, L. They are cut up while fresh and distilled with water, whereby 0*0114 p. c. of oil is obtained. Colonr- less. Sp. gr. 0*8863 at 11 '2. Has a peculiar strongly penetrating odour, and a taste of similar character, but at the same time warming and some- what unpleasant. It dissolves sparingly in tccUer, readily in ahohol and ether. (Wackenroder, Mag, Pharm. 33, 145.)

OIL OF CONVOLVULUS SCOPARIUS. 363

20. Oil of Cascarilla.

Tbommsdorff. (1833.) N. Tr, 2, 136. YoLKBL. Ann. Pharm. 35, 306; R^^, 80, 169.

In cascarilla bark, the bark of Croton Elateria {Schw) It is com- minnted and distilled with water. The quantity of oil obtained amounts to 0-35 p. c (Bley, Report. 48, 97), to 0*87 p. c (Trommsdorff.)

PropeHies, Dark yellow (Trommsdorff, Vdlkel) (sometimes of TarioQS shades from blue to yellow, or greenish : Trommsdorff) : the first distillate is oolonrless, mobile, and refractive; the later portions yellowish and more viscid ; the last very thick. (Volkel.) Sp. gr. 0*938 (Trommsdorff) ; 0*909 ; of the first distillate, 0*862. (Volkel.) Boiling point 180° and higher; of the first distillate 173^ Smells aromatic, like camphor, thyme, and lemons (Trommsdorff); its odour is agreeable; that of the last distillate less agreeable. (Volkel) Taste aromatic, rather bitter. (Trommsdorff.)

VttlkeL a. h,

\^ ...«•••• MM ...••..• 04 Oaf .M..M. Ow Sfv

H 10-49 10-27

O 4'82 8-83

100-00 .. 100-00

a The fint distillate obtained on rectifying with water; & the last distillate. The cnide oil is a mixture of at least two oils, the most Tolatile of which is probably free from oxygen. (V5ikeL)

DeeompotitioM and Conibinatums, The oil is decomposed by the stronffer adds, bnt not by alkcUts. (Volkel.) Vi^ith fwnvag niirie acid, it yields a yellow fragrant resin, without taking fire. (Trommsdorff.)

Dissolves readily in alcohol; the solution r^dens litmus. (Tromms- dorff.)

21. Oil of Convolvulus scoparius.

RoitnhokSl. In the wood of the root and stem of the plant. Pale yellow, mobile, lighter than water, with an odour of roses, cubebs, and balsam of copaiba, somewhat viscid, and a bitter aromatic taste. It becomes reddish after some time. It absorbs iodine vapours in a few hours, and becomes brown and black. With \ pt. nttric acid, it acquires a pale brown colour, without losing its odour. (Bonastre.) In nitrous acid vapours it acquires a dark yellow colour. Mixed with an equal number of drops of oil of vitriol, it forms a brown mixture, having an odour of cubebs. (Guibourt, iT. J. Pharm. 15, 347.)

864 APPENDIX TO PRIMARY-NUCLEUS C»Hm.

22, Oil of Culilawan.

Exists in the bark of dnfiafnomum CtUilawan {I^ees), and is obtained therefrom by distillation with water. Colourless, heavier than water, smells like the oils of cajepnt and cloves. With fuming nitric acid it becomes heated, without however taking fire, and forms a crimson liquid, which, on being mixed with water, deposits a brick-red resin (Schloss) ; heated with 5 pts. of fuming nitric acid, it swells np strongly, gives off nitrous gas, and, when repeatedly distilled, yields oxalic acid amounting to ^ pt. of the oil. (Daryk.)

23. Oil of Gastoreom,

Obtained by distilling castoreum repeatedly with water, and constantly pouring back the distillate ^Bohn), or by exhausting with cold ether, evaporatiug the extract, and distilling the residue repeatedly with water, as long as oil passes over. ^Brandes, N. Br, Arch, 1, 183). — Pale yellow (Bohu, Brandes) ; viscia (Bobn) ; heavier than water (Brandos) ; lighter than water (Bohn) ; has a strong odour of castoreum (Bohn, Brandes) ; and a sharp, bitter taste. (Bonn.) — If left for six weeks in contact with the water which has passed over with it, it is partially con- verted into an oil, which floats on the water, leaves resin when distilled, is completely resin ised by contact with the air, especially if likewise exposed to light, but remains unaltered if protected from air and light. (Brandes.) — It dissolves sparingly in toaUr, readily in alcohol, (Bohn.)

24. Camphor of Gat-thyme.

AmherJcratU^ampkor. — In all parts of cat-thyme, Teticrium Marum^L, — The dry herb is distilled with water, and the distillate repeatedly cohobated over fresh quantities of the green herb. — White, crystalline, transparent, brittle mass, consisting of thin laminfe, and sinking in water. Has an unpleasant odour and aromatic taste. (Bley, 1827, i^. Tr, 14, 2, 87.)

25. Oil of Celery.

Sellerei-ol. — In the seeds (Tietzmann), the herb (Vogel) of celery, Apium graveoUm, L. — It is obtained by distillation with water. — Transparent and colourless (Vogel), pale yellow (Tietzmann), lighter than water (Vogel), of sp. gr. 0*881 j has a pungent, sweetish heating odour. Dissolves sparingly in water^ readily in alcohol and ether, (Voge^ Schw, 37, 865 ; Tietnnann, Ta9chenbuchy 1821, 45.)

OIL OF WILD CHAMOMILE. 365

26. Oil of Wild Chamomile.

Zeller. (1827.) Bepert, 26, 467. — Stud, uber ather. Oele, Landau ,

1850. Steer. JRepert, 61^ 85. BoRNTRAOER. Ann. Pharm. 49, 244; abstr. Bepert, 90^ 215.

KamilieHol, B98€hc€ de eamomitte hleue.

Source and Extraction, In the flowers of wild chamomile, Matricaria

ChamomUla, X. — The herb recently dried is distilled with water or

with steam. — Tin receivers are used for collecting the distillate, because

all the oil then collects on the surface of the water which passes over

with ity whereas in glass receivers, a portion of the oil adheres obstinately

to the sides of the vessel. — Distillation with steam is preferable to

distillation with water, because it obviates the risk of burning the

chamomile-flowerSy which swell up considerably ; the steam must however

be passed through without interruption, to prevent the chamomiles from

adhering in lumps, which would interfere with the passage of the

vapour. (Steer.) — The water which passes over contains a colourless oil, having a different odonr from the oil which floats on the surface ; this oil may be extracted from the water by agitation with ether, and it remains behind after the evaporation of the ether. (BomtrKger.) The water which passes over with the oil contains acetic acid. (Hauts, J,pr, Ckem, 62, 317.)

The yield of chamomile-oU is less as the flowers are older ; dry chamomiles yield 0'113 p. c., (Oumprecht, Br, Arch, 7| 108); chamomiles four years old yield in foar distillations 0'04 p. c.; recently dried chamomilea yield by two distillations with steam the distillate being collected in tin vessels, 0*416 p. c. of oil. (Steer.)

Properties. Dark blue, amre-blue, nearly opaque ; perfectly fluid at 12^, viscid at 5^ (Zeller) ; of the consistence of honey at — 4 , solid at —a® (Bizio, Brugn, Oio-n. 19, 360) ; solid from -10° to -12*' ; melting again at — 5°. (Zeller.) According to Bomtrager, it merely becomes thick below 0°, but does not solidify. — Sp. gr. 0'92 — 0*94. — Has a strong odour of chamomile, and an aromatic warming taste. (Zeller.)

Bomtriger.

/ C ^

a. 0, c.

C 79-83 79-56 78-26

H 10-64 10*83

0 9-53 9*61

10000 100-00

a, erode oil ; b rectified ; e the last distillate. Its composition is nearly the same as that of common camphor. (Geriiardt, TVaiti, 4, 363.)

Decompontiont. 1. When exposed to air and light, it assumes various shades of colour from green to brown, and finally becomes greasy. The fresher the chamomiles used in the preparation, the longer does the oil retain its colour on exposure to air and light. (Zeller.) — 2. When distilled, it leaves a small quantity of brown resin ; distilled with water, it passes over blue from first to last, while the water which goes over at the same time is colourless. (Borntrager.) — 3. With iodine, it becomes

386 APPENDIX TO PRIMART-NUCLBUS C»H»«.

heated wittiont detonatiog; ftWeB off a few jeUowiah red vapoara becomes greenish to yellowish brown, yiscid, and at last solid and mable. (Zeller.)^4. With fuming nitric acid it assames a dark brown coloar, and then yields with water a yellow-brown resin smelling like mnsk (Hasse, OreU. Ann. 1785, 1, 422) ; with nitric acid of sp. gr. 1*28 it tarns green, then dark red-brown, gi^es off gas with riolenoe when heated, and leaves a brittle, friable resin. (Zeller.^ — 5. With oil of fdtriol, it assames a dark red-brown oolonr, and forms a soft resin (Zeller) ; on adding water to the mixture, it takes fire with explosion. (Hasse, CrdL Ann, 1786, 2, 36.) — 6. With bichromate of potaA and tulphurie acid, it becomes yellow-brown and thickens. (Zeller.) It dissolves in 8 to 10 pts. of alcohol of sp. gr. 08*5 easily and with blue ooloar in ether. (ZeUer.)

27. Oil of Chenopodinm Ambrosioides.

M. Martini. (1737.) Diss, de Chenop, ambrosioid. Bley. j^. Tr. 2, 32. — Eepert. 48, 96. Becker & Hirzel. Fharm, Zevtschr, 1854^ 8.

Me»ieam$che9 Traubenkrauioi.

Source and Extraction, In Ohenopodium ambrosiotdes, L,, a plant growing in Mexico. The plant, distilled with water, yields 0*31 p. e. oil (Martini), 0 319 p. o. (Bley), 0-78— 1-17 (Becker^

Properties, Pale yellow or pale greenish yellow (Bley) ; transparent and coloorless after rectification (Hirsel) ; very mobile (Bley) ; strongly refractive after rectification (Hirzel). Sp. gr. of the rectified oil, 0'902 ; boiling point 179° — 181^. (Hirzel.) When floating on water at low temperatures, it solidifies with the consistence of tallow or wax. (Martini.) Has a strong odonr like that of the plant (Becker), and at the same time like that of onions. (Bley.) Tastes stongly aromatic, somewhat bitter and burning (Bley); cooling like oil of peppermint.

(Beckel.)

Decompositions, 1. The oil easily takes fire (Hirzel), and barns with a very smoky flame. (Bley, Hirzel.) It is violently attacked \yj fuming nitric acid, — 3. With oU of vitriol it tarns red and resiuises. (Bley.)

Combinations, With aqaeoaa ammonia it forms a permanent liniment. (Bley.)

It dissolves sparingly in watery easily in ailcoholf ether, and oUs both fxed and volatile (Bley) ; in 3 pts. of alcohol and in 30 pts. of water. (Becker.)

28. Oil of Coffee.

Ocean in roasted coffee. To obtain it, coffee roasted at a gentle heat is covered with 10 pts. of water, and left to stand for two honn^ and the whole is then distilled from a retort, which is connected with four receivers joined together by tubes ; the contents of the third receiver, which consists of solid inodorous oil and a watery distillate smelling

OIL OF DAHLIA. 867

strongly of coffee, are collected, and the latter is agitated four times in sacoession with \ of its volume of ether, the ether heing each time decanted after standing for a quarter of an hour, and then left to eyaporate. It is advantageous to fill the third and fourth receivers with lumps of chloride of calcium, connect them with the fourth by means of a chloride of calcium tube ; cool the fourth receiver to 20° — 30° daring the distillation ; extract its contents as before with ether ; and leave the ether to evaporate. A volatile empyrenmatic hydrocarbon distils over at the same time, and collects in the last receiver in neater quantity in proportion as the coffee has been roasted at a stronger heat.

Oil of coffee is orange-yellow, and has a strong odour of coffee, it consists of two oils, one of which is less volatile and liquid than the other, and appears to be produced by alteration of the other which possesses the fragrant odour. (Payen, Compt rend. 23, 244; J, pr. Ohem. 38, 478; If. Ann. Ghim. Phys. 26, 116; abstr. N. /. Pharm. 10, 270.)

29, Oil of Cnrcuma.

In the root of Cwcu/ma langa, L. The comminuted root is distilled with water, and the distillate is cohobated several times. Lemon-yellow, mobile, with a penetrating odour and burning taste. (Vogel & Pelletier, 1815; J.Pharm. 1,291.)

30. Oil of Gurcnina Zerabet.

ZiiterwwnmL — In the tubers of Curcuma Zervbet CRoxhourgh), from which it is extracted by distillation with water. Pale yellow, turbid, viscid, heavier than water ; has a peculiar, strongly camphorous odour, and a rather bitter, fiery, camphorous taste. (Buokholy, 1817; Alman, 1817, 45.)

31. Oil of Dahlia.

In the roots of several species of Dahlia. They are bruised to a pulp and distilled with water. The oil is lighter than water, has a strong odour like the roots, and a sweetish taste, with slightly acrid after- taste in the throat. It changes after a while into a reddish resin in- soluble in alcohol. In VKtter, it gradually sinks to the bottom, becomes buttery and indistinctly crystallme ; melts when heated, and forms on cooling long prisms of benzoic acid, whilst the oil separated therefrom does not crystallise. It forms with water a permanently turbid emulsion, which runs through the filter. It dissolves in aleo^u>l, and is left with amber-yellow colour when the alcohol evaporates. (Payen, 1824, J. Pharm. 9, 884 ; 10, 239 ; abstr. BeperU 20, 337.)

368 APPENDIX TO PRIMARY-NUCLEUS Cr»U».

32. East Indian Grass Oil.

This oil appears to be identical with OU from Namur^ though the latter, according to Royle, is obtained from Calamus aramaticut. lb occurs in Andropogon ivaranctuaj a grass growing in the East Indies. It is yellow, but becomes transparent and colourless after distillation with water; floats on water; boils between 147° and 160°, or partly at higher temperatures. Has a pungent aromatic odour, similar to, but Winter than that of rose-oil, less agreeable after distillation with water. Tastes sharp like lemon-oil. Contains 8d'51 p. c. G, 11 '46 H, and 5*03 0. In contact with sodium, it quickly gires off hydrogen, deposits a reddish resin, and if then distilled, yields an oil which quickly resinises, contains 88 '37 p. c Cj and 11 '56 H, and is therefore isomeric with oil of turpentine. (S teahouse, 1844, Phil. Mag, J. 25, 201 ; Ann, Fharm. 50, 157 ; Mem. Chem. Soe. 2, 122 ; Chem, Qaa. 1844, 294.)

33. Oil of Elder-flowers.

FiiederbUUhendlf HoUvnberbmhmSl. — In the flowers of the elder, Samr hucus nigra* The dried flowers are distilled with water, and the dis- tillate is seyeral times redistilled oyer fresh quantities of the flowers ; or yery concentrated elder-water is agitated with ether and the ether left to evaporate. The flowers yield scarcely 0*32 p. c. of oil. (Pagen- stecher.) buttery (Lewis) ; crysmline and of waxy consistence, greenish- white (Eliason), light yellow, mobile, floats on water, smells strongly of the flowers (Pagenstecher) ; has a rather bitter burning taste, with cooling after taste. (Eliason, Pagenstecher.) The oil becomes dark brown and yiscid when exposed to the air, — Chlorine gas, passed into elder- water, at first produces thick fumes, and afterwards imparts a dark yellow colour to the drops of oil which float on the water, and finally sink to the bottom, whilst the water acquires a strong odour of radish, contains but little hydrochloric acid after saturation, and, when eyaporated at a gentle heat, leaves a chlorinated oil having a sharp biting taste, mixed with crystals. Bromine acts like chlorine, yielding a brown brominated oil, wnich sinks in water. — Elder- water mixed with hydrochloric add, yields a small quantity of sal-ammoniac when evaporated ; the ammonia which it contains results from the decom- position of a constituent of the flowers ; the oil is free from ammonia. (Pagenstecher, Repert, 73, 35.) — The oil dissolves in absolute alcohol and ether, sparingly in alcohol of sp. gr. 0*85, in oil of rosemary and in water; the aqueous solution is neutral. (Eliason, JT. Tr. 9, 1, 246.) Fr. Miiller (iv. £r. Arch, 45, 153), by distilling recently dried elder- flowers with water, obtained a yellow water, which, when treated with alkalis, became darker in colour, gradually deposited yellowish non- crystalline flocks, which when dissolved in ether, coloured it yellow, and remained when the ether was evaporated in the form of yellowish transparent scales, soluble with yellow colour in carbonate w potash, and precipitated by acetic acid.

OIL OF GALE. 369

34. Oil of Feverfew,

Obtained by distilling common feverfew, Tyrethrum Partheniwm while in tbe floweriDg state, with water. Greenish ; passes over between le^"" and 220''; the largest portion between 205"" and 220°, leaving a coloured residue. Deposits camphor on standing, this deposit being formed most abundantly in the oil which passes over between 212° and 220 I on cooling. Oil prepared in 1845, did not yield anj camphor on standing.

Desiaignes & Chantard.

0. b, c. d» €, f,

C 77-60 .... 77-96 .... 76-92 .... 77-02 .... 85-77 .... 86-46

H 10-37 .... 10-60 .... 10-37 .... 10-24 .... 11-22 .... 11-58

87-97 .... 88-56 .... 87*29 .... 87-26 .... 9699 .... 98-04

a, Oil separated from the deposited camphor; h^ oil containing only a small quantity of camphor; c, oil boQingat 216'' — 220''; d, at 212*" — 21 6""; e« at 170" — 180**; ft at 160" — 167"» repeatedly rectified over potash. The oil contains camphor, a hydrocarbon, and an oil richer in oxygen than camphor. (Dessaignes & Chantard, J\r. /. Pkarmf 13, 251; /. pr. Chem. 45, 45.) — The camphor contained in oil of fever- few is IfEYO-camphor. (Chantard, Compt. rend, 37, 166.)

35. Oil of Oalanga.

Oalffonidl. — In the root-stocks of Alpinia Oalanga {Schwartz), They are pulverised and distilled with water. The water which passes over with the oil hajB the odour and taste of the roots, and contains carbonate of ammonia. Yellowish white, transparent and colourless after rectification ( Vogel) ; brownish yellow (Rayband, J, Fharm. 20, 455) ; lighter than water (Vogel, Raybaud) ; not very volatile ; smells like oil of cajeput Contains 73*91 p. c. C, 11*67 H, and 14*42 0, and has therefore tbe composition of cajeput-oil (p. 335). Loses its odour and becomes viscid on exposure to the air. Dissolves partially in aqueous potash, completely and readily in alcohol and ether, (A. Vogel, jun., Repert, 83, 22.)

36. Oil of Gale.

Obtiuned from sweet gale, M}frica Gale, Z., by distilling the fresh leaves with water and cohobating the distillate several times. The yield of oil amounts to 0*65 per cent. — Brownish yellow. Sp. ^. 0*876. Solidifies partially at 17*5 , and changes at 12*5'' into a thicKish, slightly crystalline mass, mixed with tough, transparent, yellowish lamiuce. Odour peculiar, balsamic, and agreeable ; taste, mild at first, then tran- siently burning and permanently astringent. Neutral. — Contains about 70 p. c. camphor, and consists of 81*75 p. c. C, 3*00 H and 15*05 0. — It dissolves iodine without explosion, becoming viscid and olive-green. By fuming nitric acid at mean temperature, and by ordinary nitric acid at 100^ it is converted, with evolution of nitrous acid, into a gold-coloured

VOL. XIV. 2 B

870 APPENDIX TO PRIMART NUCLEUS C^H".

thickish liquid, which becomes tarbid on cooling, and does not form a clear solation in water. — With oil of pitrud^ it forms a dark brown mixture. — It dissolves In 40 pts. of alcohol of sp. gr. 0*875 at 15°^ more abundantly in ether. (RabeDhorst, BerL Jahrb, 35, 2, 220; Bt^ert, 60, 214.)

37. Oil of Oenm arbaniim.

Nelkenwurzol. — In the root of wood avens, Oeum urhanuniy Z., whence it is obtained bj distillation with water, the yield being 0*04 p. c. — Greenish yellow, buttery. (Trommsdorff.) Smells like doves. Consists of an acid oil, which unites with alkalis and separates from the solution on addition of acids. (Baohner, Seperi, 85, 19.\ — Dissolves readily in alcohol and ether. (TrommsdorS; 1818, N, Tr. 2, 1, 55.)

38. Oil of Ginger.

BuoHHOLZ. (1817.) Alnumach, 1817, 111. MoRiN. J. Pharm. 9, 253; BepeH. 20, 376.

Papousbk. Wien. akad. Ber, 9, 315; J. pr. Chem. 581, 228; abetr. Ann. Pharm, 84, 252,

Inffwerdl, Baenee de gingtmbre.

Source and Extractum. In ginger, the Mots of Zinmb&r afieinale (Boee,)^ whence it is obtained by distillation with water.

Proper6ieB, -i-^ Yellowish (red, according to NeumasB, greeni^ Ua«, according to Moria), very mobile. (BuchlwLE.) Sp. gr. 0*893. — Bailing point 246°. Has a strong odour of ginger, and a bnmioff aromatio taste (PbpoBsek) ; ittther milo, with somewhat biting and bitter aftertaste. (Bachhoix.)

J^hydfrnied. FHM>iiMk.

80 C 480 .... 81-49 81-03

69 H 69 .... 11-72 11-68

5 O 40 .... 6-79 7-39

C»H" + 5HQ 689 .... 100-00 100*00

Such according to Papoosek, ia its oompositiQn when slowly distilled at a heat below 150''.

Deoompoeitume. 1. When strongly heated* It becomes darker and gives up water. — 2. By repeated distillation over anhydrous phosphoric acid, it is converted into a yellowish oil isomeric with oil of turpentine (87-99 C and 11-88 H).

Combinations. With Hydrochloric acid. C«»H«C1» =3(C»H",HC1) + C*H** f ^ — Obtained by passing hydrochloric aci<l gas to saturation into oil of ginger, washing and distilling the brown product with water, and dehydrating over chloride of calcium.

OIL OF HYSSOP. 371

PapoQwk.

80 C 480'0 .... 73-45 73*39

67 H 67-0 .... 10-25 10*36

3 CI 106-5 .... 16-30 16-25

3(C»HW,HC1) + C»H>« ., 658-5 .... 100-00 10000

This if tlie fonniilft urigned to it by Papoufek.

39. Oil of Hedwigia.

In the balsam of Htdwigia hahemifera ot Bvrmra halsamifera, -^ Obtained by distillation witk water. Yellcrtr, transparent oil, whieh floats on water, has an agreeable odour of turpentine, and a burning taste. — With \ pt. nUrie aeid, it becomes first flesh-colonred, then crimson, then dark amaranth-coloured, and after 24 hours, brown, bet colourless again on being mixed with water ; when boiled with 2 pts. of nitric acid, it assumes a jeliow colour and becomes resinised. — With M of tntriol, it turns first yellow, then yellowish red, soon acquiring an empyreumatic taste and odour. — With hydroMoric add, it assumes first a rose-, then an amaranth-red colour. '>— It dissolves completely at first in more than 4 pts. of €deohol, and in all proportions of ether. (Bonastre^ 1S26, J. Fharm. 13, 486.)

40. Volatile Oil of Hemp.

In hemp {Oannahie sativcu) — The fresh herb, just after flowering, is distilled, and the oil-drops which float on the milky dietilUtte containing carbonie aeid, are oollected. -^ The yield of oil is 0*8 per cent. — Pale yellow, lighter than water, smells like the fresh herb, tastes aromatic, not burning but strong ; its vapour, when inhaled, produces head-ache and slight delkinm ; a row drops taken internally produce warmth in the throat and ntowwoh, heaviness in the head, and giddiness, but no abdominal derangement. (Bohlig, Jc^rb. pr. Fkourm* 3, 4.*-£^pertf. 80, 808.)

41. Oil of Hyssop.

Stknhousb. (1842.) PhiL Mag. 20, 274; J. pr. Chem. 27, 255; Mem.

Ckem, Soc. 1, 43. Zelleb. Stud, uber Hther. Otle, Landau, 1850.

HytiopOU Ytopoly Buenee d'hysope.

Source and Extraction. In hyssop, JETy^sopue officinalis, L. It is obtained by distilling the fresh herb or the fresh leaves with water. — The yield of oil is very large. (St en house.)

Froperties. Transparent and colourless (Stenhouse), greenish yellow. (Zeller.) — Sp. gr. 088— 0*98. (Zeller.) — Passes over between 142° and 162*8^, the last portions being coloured. — Has a peculiar odour and a sharp camphorons taete. (Stenhouse.) Neutral. (Stenhouse, Zeller.)

2 B 2

372 APPENDIX TO PRIMARY NUCLEUS C»H«.

Stenhooae.

a» b, c.

C 84-18 .... 81-29 .... 80-31

H 11-00.... 10-95.... 10-45

0 4-82 .... 7-76 .... 9-24

100-00 .... 10000 .... 10000

a distilled at 142** ; b at 148-3^ ; e at 168-3**. It U a mixture of aereral, or at least of two oils. (Stenhonse.)

Decompositions. 1 . The oil when exposed to the air gradaallj becomes yellowish and resinous. (Stenhonse.) *— 2. With iodine it becomes hot, /^yes off yellowish red vapours, turns reddish yellow-brown and thickens. (Zeller.) — 3. Heated with nitric add-, it yields a yellow resin (Zeller) ; with 2 pts. of fuming nitric acid, it crackles and forms an unctuous resin. (Hasse, CrelL Ann, 1785, 1, 422.) — 4. With oil of vitriol, it turns dark yellow-brown, and becomes thick like a balsam. (Zeller.) — 5. Dropped upon melting hydrate of potash, it is for the most part converted into a brownish resin, and a volatile oil, which does not smell like hyssop, and is not completely deoxygenated by repeated distillation over hydrate of potash (86-65 p. c. C, 11-41 H, and 1*94 O). (Stenhouse.)

Combinations, Dissolves easily in absolute alcohol, forms a dear solution in 1 — 4 pts. of alcohol of sp. gr. 0*85, and a slightly opalescent solution with a larger quantity of alcohol of sp. gr. 0*85. (Zeller.)

42. Camphor of Iris florentiusu

A. VooBL. J. Pharm. 1, 483.

Dumas. J. Pharm. 21, 191; J. pr, Chem, 4, 484; Ann. Pharm. 15, 158.

When iris root is distilled with water, camphor in white scales floats on the distillate (Vogel), and may be separated by filtration. (Damas.) Nacreous crystalline laminsd. (Dumas.)

CalcnUtioii aooording to Dumas. Dumaa.

16 C 96 .... 66-67 672

16 H 16.... 11*11 11*5

4 0 82 .... 22-22 21*3

C^HMO* 144 .... 10000 lOO'O

It is insoluble in water. (Dumas.) Dissolves readily in alcohol; the solution has an agreeable odour of violets, and is rendered milky by water.

43. Jasmin-camplior.

Separates in the cnrstalline form from oil of jasmin when exposed to cold, and may be purified by pressure between paper, solution in alcohol

VOLATILE OIL OF LANCON BALSAM. 873

>

and reoiystallisatioD. Transparent, colourless, shining laminae, or white

translucent granules, of tallowy whiteness, lighter than water; melts

at 12° — 15 ; has a faint agreeable odour, and a heating camphorous

taste. When set onfire^ it bums with a bright flame, like rose-camphor.

Heated with iodifie, it forms a liquid, yarjing in colour from brown to

dark red, and becoming miss green when more strongly heated. With

strong nifyie <icid^ it volatilises without evolution of gas, colouring, or

formation of oxalic acid. With strong hydrochloric add, it becomes

slightly yellow^ forming bubbles and partly dissolving. It does not

oxidise potassium. It dissolves sparingly in water, imputing its odour ;

is quite insoluble in acetic acid, but dissolves with moderate facility in

alcohol, in ether, and in oils, hoihjixed and volatile, (Herberger, Repert,

48, 1081.) As jasmin-oil generallj contaios a fixed oil, jasmin camphor -is perhaps a fixed hltXj add. (Gm.)

44. Oil of Jonquil.

From Nardesus JonquiXla, Z. Fresh, recently opened jonquil flowers are introduced into a displacement apparatus, and exhausted by ether made to pass slowly through them ; the yellow ethereal solution which runs through and Boats on the top of a greenish watery liquid, containing a little salt, is separated from the latter, and distilled in tne water>bath ; the residual solution is separated by pressure from the jonquil-camphor, which crystallises in warty masses during the distillation and cooling of the liquid ; and the ether is left to evaporate spontaneously. Full-blown joDqail-fiowers yield jonquil-camphor in yellowish, odourless, snblimable nodules. The oil is yellowish, buttery, melts at the heat of the hand, and has a strong odour of the flowers. Boiling point above 1 00^ By keeping , it gradually becomes opaque, does not melt even at 100°, and becomes mixed with yellow, granular jonquil-camphor, which separates when the oil is dissolved in ether. Blackens metallic iron when in immediate contact with it.

Brown JonquU'Oil, Contained in peculiar cells of jonquil-flowers, which are not penetrated by the ether. To obtain it the flowers, after having been exhausted with ether, are treated with alcohol, and the alcohol is distilled off from the extract. It is a brown viscid oil, which has an unpleasant odour like that of train-oil, and deposits a few yellow crystals : it is soluble in ether. It unites with alkalis, acquiring at the same time a darker colour. (Robiqnet, 1835, Jl Pharm, 21, 834.)

45. Volatile Oil of Iian9on Balsam.

Obtained by distilling the balsam with water. Pale amber-yellow, colourless after rectification, transparent, lighter than water ; solidifies at — 12° ; has a peculiar odour like that of tar ; tastes sharp, but less 80 than oil of turpentine and somewhat bitter. Mixed at 20° with ^ pt. nU$Hc acid, it becomes rose-red in 5 minutes, wine-red in 10 — 12

374 APPBUDIX TO ratMART NUCLEUS C?nV».

minutes, dark violet in 20 — 25 minates, and finallj blue* Diasolvea in 10 — 12 pts. alcohol of sp. gr. 0*85, forming a somewhat tarbid liqaid, and in all proportions of eti^, forming a clear solution. (Bonastre, J. Fharm. 15, 668.)

46. Oil of LaT^oder,

Th^ard. (1811.) Ifem de la Soc. d'Arc 2, 32.

Saussurb. Asm. CUm. Phy$. 4, 313; 19, 273; SAw. 29, 172; Pogg. 25,

370; BibU vaiiv. 4&, 15d; Atm. Pharm^ 3» 1^3; Ann. Chim. Phy$.

49, 159. Vauquelin. Ann. Chim. Phyt. 19, 279; Schw. 35, 435; N. Tr. 7, 1,

286. Kanb. Land. Ed. Mag. J. 13, 444; /. pr. Chem. 15, 163; Ann. Pharm.

32, 287. Bell. Pharm. J. Trans. 8, 276; J. Chim. mid. 25, 487; Pharm. CentrbL

1849, 191. Zeller. Stud, uber other . Ode, Landan, 1850. Lallbmanp. N". Ann. dwn. J?hy$. 57, 404; abslr. Ann. Pkarm. 114,

197.

Bstenee d§ Uivande. Lavaudetolf LawmdeUnenx.

Source. In the flowers and leaves of the lavender, LeKvandnla anguMtifolia {Ehrhardt). There are two kinds, vis. : a. Lavenders-oil, in the leaves and flowers of Lavandula augwstifolia (Bhrhardt), and b. SpHc' oil, Buile d^aspic, in the leaves and flowers of Lavandula Uxtifidia. (JEhrhardt)

Extraction. Fresh or dried lavender flowers stripped from the stalkB are distilled with water or with steam, the lavender-water which passes over with the oil being used for the subsequent distillations. The jield of oil varies with the state of the flowers, and the amount of water distilled from them, as well as with the quantities used ; with small quantities of the flowers, the loss of oil is comparatively greater than with larger quantities. The quality of the oil is considerably better, when the flowers are distilled without the stalks : for the disagreeable odour sometimes perceptible in the commercial oil, proceed« from tha stalks, which when distilled alone, yield an oil possessing this bad odour in a high degree. (Bell.) Dry lavender* flowers yield 1 p^ e. oil (Tan Hee^ Pharm. Centr. 1847, 880X 1*4 p. c. (Bell.)

Properties, a. Of Oil of Lavender: Pale yellow, very mobile. Sp. gr. 0-87 — 0-94 (Zeller) ; 0-893 (Pfaff, Syst. d. MaJt, med.) ; 0*936 (Lewis, 2honi8on'8 Syst) ; 0*898 at 20°; when rectified, the first part of the distillate has a sp. gr. of 0*877 (Saussure); 0*9174; that which distils between 1 85'' and US'' has a ep. gr. ^ 0*8865 to 0*8745 (Kane) ; the commercial oil, 0*917; oil prepared by van Hees, 0*892 (van Hees). Boiling point 185°— 188°. (Kane.) Tension of vapour: 7-3«™ of mercury at 13*75° (Saussure). Has an agreeable odour like that of the flowers ; less agreeable if the flowers and stalks have been distilled together. (Bell.) Its taste is buming, somewhat bitter, sharp, and aromatic Neutral to vegetable colours. (Zeller.) Deposits camphor on cooling. (Bisio, Brugn. &icrn. 1% 369.)

OIL OF LAVENDER. 375

5. Of Oil of Spike : Yellow, mobile j ep. er. 0-87 — 0-89. (Zeller.) Its odoar is less agreeable than that of ou of layender j more like turpentine.

SaisBiire. Kane.

a. h» 9m

C 75-50 .... 75-77 79-45

H 11-07 .... 11-73 11-30

0 13-07 .... 12-50 9-25

99-64 .... lOOOO 100-00

a if nia to ootitain 0*30 p. c. N ; b dirtilled it 185* ; e, at IBS'".

Oil of lavender is a mixtare of volatile oil and camphor, corresponding to the formnla C^H^O*, of which the speoifioftllj heavier oil contains a comparatively larger quantity. Oil of lavender, from Mnrcia, contains i pt., English oil of lavender \ pt.^ Spanish also \ pt camphor. (Proost.) The camphor of lavender-oil is identical with common camphor. (Donias, Ann. Chvm. Fhy9. 50, 225.)

IT Both oil of lavender and oil of spike are resolved by distillation into a hydrocarbon, isomeric with oil of turpentine, and a camphor similar to or identical with common camphor. The hydrocarbon from oil of lavender, appears to be the same in molecular condition as the hydro- carbons which are produced from all the oils, G^H**, by the action of oil of vitriol on fluoride of boron. It boils at 200^ — 210^ and turns the plane of polarisation to the right. The hydrocarbon from oil of spike, boils at 175^, and turns the plane of polarisation to the left. Both these hydrocarbons form liquid compounds with hydrochloric acid. The portion of oil of spike which distils between 200^ and 210° contains a large quantity of camphor, which may be isolated by nitric acid, and acts on polarised light in the same manner and in the same degree as common camphor. (Lallemand.)ir

DecompatUiofu. 1. Oil of lavender, hsaUd lor some tim« above its boiling point, forms a small quantity of acetic add. (Oay-Lussac, Compt, rend. 1841, 21; Irutit. 369, 21.) — 2« it absorbs Large quantities of oxpgen gos at ordinary temperatures, and gives off carbonic acid. At 24'' it absorbs the following quantities of oxygen r In the first 1 2 hours, none; in the two following days, 1*89 vols, daily; in the following week, 6' 17 vols, daily; altogether in 4| months, 111 vols.; in the following 30 months, 8 vols.; therefore, in 34^ months, 119 vols.; in the same interval it forms 22-1 vols, carbonic acid, and becomes some- what yellowish. Kept over mercury in the shade daring four winter- months, below 12^, it absorbs 52 vols, oxygen, and forms 2 vol& carbonic acid. (Saussure.) It absorbs yMolaied owygen, thereby acquiring oxidising properties and the power of reddening Iitmos. (Schonbein, J,pi\ Chein, 52, 187.) — 3. When tronune is slowly added to the oil mixed with \ of its volume of water, beat is produced^ and the colour of the bromine disappears till 2l7 pt8« = 4 At. bromine have been added to everj 100 pts. of the rectified oil. (O. Williams, «7ir pr, Chem, 61, 20.) With iodine, it rapidly gives ofl* yellowish-red vapours, becomes reddish yellow-brown and viscid, and acquires a balsamic, somewhat acid odour. (Zeller.) It decomposes but slowly with iodine in the cold (Guyot, J. Chim. med. 12, 487)i and after an hour or two, forms a thick mixture which dissolves easily in the rest of the oiL (Guyot, J. Phye. 5, 230.) It becomes heated with iodine and explodes, the iodine volatilising.

376 APPENDIX TO PRIMARY NUCLEUS CJ»HW

(Walcker, Pogg, 6^ 126.) Oil of spike reacts with iodine like oil of lavender, but with less violent detonation. (Zeller.) — 5. With nitric acid it assumes a brownish to reddish-brown colour, and on heating the mixture, strong evolution of gas takes place and a soft yellow resin is formed (Zeller), together with oxalic acid. (v. Grotthuss, N. Geld, 8, 709.) Spike-oil, mixed with nitric acid, turns pale yellow to yellow, and, when heated, gives off gas and acquires the consistence of balsam. (Zeller.) With strong sulphuric acid, oil of lavender thickens and assumes a dark red-brown colour. (Zeller.^— 8. With hydroehlot'ic acid gasy it becomes blackish (Thenard), reddish-black to black, and specifically heavier but not solid. (Saussure.) It absorbs 68*7 vols, hydrochloric acid gas (Th6nard) ; 210 vols, without being saturated. (Saussure.) — 9. With arnvMnia-gas it becomes turbid, and at 20° absorbs 47 vols, of the gas. (Saussure.) — 10. Distilled with 24 pts. water and 8 pts. chloride of lime, it gives off carbonic acid gas with effervescence and yields chloroform. (Chautard, Gompt. rend. 34, 485.) Distilled with nypohromite of lime, it yields bromoform. (Chautard, Compt rend. 34, 487.) — 12. With bichromate of potash and sulphuric <icid, it assumes a greenish to brown-yellow colour, and partly resinises. (Zeller.) — 13. When boiled with dry nitroprusside of copper, it yields a slate-grey deposit, the depth of colour varying with the quantity of oil. (Heppe, N, Br. Arch. 89, 57.) — 14. It decolorises very thin films of sulphide of lead, converting that compound into sulphate of lead. (Williams, J. pr. Chem. 59, 5043 — 15. When shaken up with \ of coirosive sublimate, it quickly turns brown, without dissolving much of the salt. (Simon, Pogg. 37, 857.)

Combinations. % The hydrocarbon (C^H^') contained in oil of layender (p. S78), combines with hydrochloric add, forming an instable compound which nas the composition of hydrochlorate of lemon-oil, G'^H'*,2HG1, remains liquid at all temperatures, and does not yield any solid com- pound when treated with fuming nitric acid. (Lallemand.) The hydro- carbon, C^H^', contained in oil of spike, forms with hydrochloric cuid a liauid compound from which nitric acid separates a small quantity of a solid hydrochlorate, which turns the plane of polarisation to the risht, but in other respects exhibits the properties of hydrochlorate of oil of turpentine.ir

Oil of lavender dissolves in acetic acid ; according to Lallemand, it always, even when recently prepared, contains acetic acid, both free and combined, probably abo, valerianic acid. — 80 vols, of the oil shaken up with 80 yols. acetic acid of sp. gr. 1*075, take up 45 vols, of the acid, and leave a weaker acid containmg oil, which, if shaken up with 80 vols, of fresh oil, produces 110 vols, of oil containing acetic acid, while 5 vols, of still weaker acetic acid remain, containing a large quantity of oil separable by water. The oil charged with acetic acid gives up the greater part of that acid when agitated with an equal volume of water, and the whole when agitated with four times the quantity of water, a certain Quantity of the oil dissolving in the water at the same time. (Vauquelin.)

Oil of lavender dissolves in all proportions of absolute alcohol aud of alcohol of sp. gr. 0'8d (Zeller), of sp. gr. 0*83 (Saussure). It dissolves in 2-5 pts. of alcohol of sp. gr. 0*887 at 20"". (Saussure.) Oil of spike dissolves in alcohol like oil of layender. (Zeller.)

OIL OF LILAC. 877

47. Ledum-camphor,

Rauchfuss. (1796.) A. Tr. 3, 1, 189.

Meissner. Beil. Jahrb, 13, 170.

Grassmann. Repert, 38, 53.

BucHNER. EepeH. 38, 57; iiT. Beperi. 5, 1; Chem, Centrdlbl. 1856, 400;

N. J. Fharm. 29, 318; InsUt. 1857, 82. WiLLiOK. Wien. akad. Ber. 9, 302.

Camphor iff Manh Wild Ronmary, Porsch'eampher, First obtenred by Grass- mann, 1833.

Source and Extraction, In the Tolatile oil of marsh wild rosemary Ledum palvstre, L, This oil consists for the most part of a hydro- carbon isomeric with oil of turpentine, and of an oxygenated oil, and when recently prepared corresponds to the formula C^U''0^ (Willigk.) It consists of 2 pts. camphor to 1 pt. Tolatile oil, the camphor existing in it ready formed, and not being produced from tbe oil by the action of the air. (Grassmann.) The flowering plant or the leaves are comminuted and very quickly distilled with water ; the oil which floats on the dis- tillate is remoyed and pressed between paper after solidification (Grass- mann) ; and the solidified oil is washed with cold alcohol, and purified by pressure between paper, solution in ether, and recrystallisation. (Buchner.) By slower distillation, the volatile oil passes over first, and afterwards the camphor. (Grassmann.)

Properties, Colourless, slender, transparent prisms (A inch long, according to Grassmann) ; when crystallised from alcohol : very delicate silky prisms and efflorescent crysUUs. (Buchner.) Melts at a gentle heat« sublimes at a stronger heat ^Buchner), difiusing a pungent odour which produces headache and giddmess. (Grassmann.) Smells slightly of the herb (somewhat like oil of roses and oil of turpentine), and has a warming aromatic taste. (Buchner.) Neutral. (Grassman.)

Calculation according to Buchner, Buchner.

50 C 300 .... 81-74 81-25

43 H 43.... 11-71 12-28

3 0 24.... 6-55 6-47

C»H«0* 367 .... 100-00 10000

It contains a hydrocarbon isomeric with oil of turpentine, and a hydrate of that hydrocarbon ; 5(C"H«) + 3H0. (Buchner.)

Heated on platinum foil, it takes fire, and burns with a highly luminous, sooty fiame. (Buchner.) It is nearly insoluble in water. (Grassmann, Buchner.) Dissolves sparingly in hydrochloric add, still Jess in acHic acid, not at all in aqueous ammonia, readily in alcohol and ether, (Buchner.)

48. OU of Lilac.

In the fiowers of the lilac, Syringa vulgaris. The fresh flowers are exhausted with ether in a displacement apparatus ; the^ yellow ethereal

378 APPENDIX TO PRIMARY NUCLEUS C«HW.

solution which runs through and floats on the surface of the watery liquid, is removed ; the greater part of the ether distilled off*; the residue left to eyaporate ; and the oil which remains mixed with a solid mass is separated by filtration. Amber-yellow, with an odour like that of the flowers. Deposits solid masses (Syringarcampher, Sehto.), when left to itself. Scarcely blackens iron (an effect produced in a greater degree by oil of jonquil, p. 373). (Favrot, 1838, J. Ghim. med, 14, 212.)

49. Camphor of Lily of the Valley.

Campher der Maiblumen. — The fresh flowers of lily of the valley, Ccnvallana majalis, X., are suspended in the (Sapltal of a still and distilled with six times their weight of water, and the camphor which

floats on the watery distillate is collected. This watery liquid is slightly tarbid and has no acid reaction ; its odoar is fragrant after a few days, bttt is disagreeable and prododBg headache if smelt too closely. The camphor iS ft tadio^Ciystalline

mass. (Herberger, Eepert. 52, 397.)

50. Oil of Iiime4owef .

Brossat. (1820.) /. Pharm. 6, 396; abstr. Jlepert, 53, 105.

Landerer. JRepert. 58, 103.

BuGBNER. JV. JBr. Arch. 8, 70.

WiKCKLBR. Pharm. CerUrcUbl. 1837, 781 ; abstr. Bepert. 70, 16.

Source and Extraction. In the flowers of the lime, TUia SuropcBOy L. The fresh, just opened flowers are distilled with water, and the milky distillate is cohobated over fresh quantities of fresh flowers (Brossat, Landerer), or the distillate is mixed with common salt and shaken up with ether ; the ethereal layer is remoYcd and left to evaporate, and the residual oil is rectified over chloride of calcium. (Winckler.) When fresh lime- flowers are exhausted with ether in the displacement apparatus, the ethereal solution dehydrated with chloride of calcium, and the ether distilled off*, there remains a greenish-yellow aromatic residue, which solidifies on cooling, and is deprived by ether of its odour of lime-flowers; the ethereal solution leaves when evaporated a small quantity of wax and chlorophyll, but scarcely any oil. (Buchner.) The amount of oil obtained is 0*1 p. o. (Herberger, Repert. QQ, 1) ; 0'042 p. c. (Winckler.)

Properties. Colourless, mobile (Landerer, Winckler), yellowish (Brossat) ; lighter than water, yery volatile (Landerer) ; has a strong odour of fresh lime-flowers (WincKler) ; extremely pleasant odour and sweetish taste. (Landerer.)

Decompositions. 1. Reddens on exposure to light. (Landerer.) — 2. Alters slightly on exposure to the liffht. (Winckler.) — 3. It dis- solves iodine without rise of temperature, forming a brown liquid, soluble in all proportions of alcohol and etber. (Winckler.)

Soluble in alcohol, (Landerer.)

MARJORAM^CAMPHOR. 379

51. Oil of UaijoraiiL

Kanb. (1838.) L(md. Ed. Mag. J. 13, 489; J. pr. Chen. 15, 157;

Ann. Pharm, 32, 285. Zbllbb. Stud, fiber, dtker. Ode, Landan, 1850.

M^faranol, Btnnee de nufjolahu.

^ Source and Extradtion . In marjoram, Origanum mcoorana, L ., whence it 18 obtained by distillation with water. It must be freed from dissolyed camphor by ret>eated distillation. (Kane.) The water which passes over with the oil contains acetic acid. (Hautz, J, pr. Chem. 62, 317.)

Froperfieg, Yellow-green to pale-green (Zeller) ; sp. gr. 0*8901 ; rectified, 0-8673 (Kane), 0*89 (Zeller). Boiling point nearly constant at 163^. (Kane.) Has an extremely pungent odour like that of the herb, and a warming acrid, somewhat bitter taste. Slightly acid. (Zeller.)

Kane.

a. b.

C 86-32 ........ 84-48

H 11-41 10-80

0 2-27 4-72

100-00 ........ 10000

a rectified; b distilled at 173-8^

Deeompositians. 1. Deposits camphor when cooled to — 15^ (Trommsaorff, N. Tr, 20, 2, 24.) With iodine, it becomes heated and gives off yellow-red vapours without fulmination, acquires a reddish yellow-brown colour, the consistence of a balsam, and a rather acid balsam-like-odour. With nitric acid, it becomes reddish-brown colour, quickly gives off gas, and acquires the consistence of balsam when heated. — 4. With oil of vitriol, it acquires a slight bluish-red tint. — - 5. With bichromate of potash and sulphuric acid, it becomes greenish brown-yellow, and deposits resinous flocks. (Zeller.)

CombinaiioM. It dissolves without turbidity in 1 pt. alcohol of sp. gr. 0*85, and with opalescence in 2 or more pts. (Zeller.)

62. Maijoram-campfaor.

QdvTBvn. (178^;) -4?m. 1783, 134.

Mulder. Ji pr. Chem. 17, 103; Ann. Pharm. 31, 69.

Obeerred in old oH of maijoram as early as 1606, by Krilger (Higeeil. N&t. €kr. Otrm. Dfc. 2, Amm, h, (Mt. 38), Neumann {Chymia Medico, Z, I, 182) and Dehne {CrtU.ekem. J. I, 41).

Formation. Whan oil of marjoram is kept id loosely dosed vossela. (Oiinther, Mulder.)

380 APPENDIX TO PRIMARY NUCLEUS C»H".

Properties. White hard crystals (Mulder), brittle (Gunther), heavier than water (Mulder), melts and yolatilises completely (Mulder), subliming in laminsD like benzoic acid. (Giinther.) Smells and tastes like the oil. (Giinther.)

Mulder.

C - 6007

H 10-70

0 29-23

100-00

According to Mulder, ita compodtion may be eipreued by the fommla C^^H^O*.

Decompositions, I. Heated to 112°, it gives off 1*42 p. c. water with- out becoming turbid (Mulder) ; does not volatilise so readily as common camphor. (Griinther.) — 2. When set on fire it burns with flame, which however does not deposit soot. (Giinther.) — 3. It is coloured red by oil of vitriol. (Mulder.)

Combinations, It dissolves in boiling watei\ (Giinther, Mulder.) Absorbs 12*95 p. c. hydrochloric acid gas, producing a very acid com- pound, from whose alcoholic solution nitrate of silver throws down chloride of silver. (Mulder.) It dissolves in 10 pts. of concentrated nUric acid. (Giinther.) It dissolves in aqtuous potask. Does not absorb ammonia-gas. (Mulder.) Dissolves in atcoJid and in ether (Mulder), in 10 pts. of alcohol, forming a solution which is not rendered turbid by water. (Giinther.) It dissolves in 10 pts. of oU of turpentine^ in 10 pts. of boiling oil of almonds, crystallising from the latter solution after a while. (Giinther.)

OU qf Wild Marjoram— wt (HI qf Origanum (p. 391).

53. Oil of Hassoy.

In massoy-bark, the bark of Cfinnamomum Kiamis, Nees, The comminuted oark is distilled with water, and the milky distillate is separated from an oil which floats on the surface, and another oil which sinks to the bottom, together with a camphor.

a. Light oil. Nearly colourless, mobile, transparent, wifh an aromatic odour like that of sassafras-oil, and a sharp pungent taste. — * With strong nitric acid, it becomes flesh-red and ultimately cherry-red. — It dissolves readily in alcohol^ ether, and strong acetic acid^ and is sepa- rated from the latter solution by the addition of 3 pts. of water.

6. Heavy oil. More viscid and less volatile thi^n the former. Smells and tastes like sassafras-oil, the odour being fainter than that of the light oil, but the taste equally strong ; becomes turbid and thickens at — 10°, but does not crystallise. — With cold nitric acid^ it becomes flesh- coloured^ and when heated therewith, forms a mixture which deposits a small quantity of oxalic acid, and has no bitter taste. — The heavy oil dissolves in all proportions of alcohol, ether, and strong acetic add, from which last solution it is precipitated by water. Mixes imperfectly with aqueous potash, soda, ammonia, baryta, and strontia, and when shaken up with the two latter^ becomes white, thick and turbid, but separates again when left at rest

OIL OP MASTERWORT. 38 1

c MasBoy-camphor, — White powder, heavier than water, less soft to the toQch than fatty snbstances. — It does not become electrical by friction, is inodorous and nearly tasteless. — It is related to laarin and caryophyllin. — Nitric acid colours it pale yellow, perhaps only in con- sequence of the presence of a small portion of oil. — Dissolves in hot dUohcl and in ether, (Bonastre, 1829, J. Fharm. 15, 204.)

54. Oil of Masterwort

Waokbnrodbr. (1831.) Br. Arch. 37, 341.

HiRZBL. J. pr. Chem. 46, 292; Ghem, OewtrdUbU 1849, 37; Mitth, d. Zwrkh, naturfarsch, Oesellsch, 1848, 27.

Meisterwurtolf Etnnee eTimperatoire.

Source and Extraction. In the root of Imperatoria OstrtUhium, L. — The comminuted root is distilled with water ; the oil which floats on the distillate is removed ; the water is shaken up with ether ; the ethereal solution evaporated; the residual oil, together with the portion pre- viously removed, is rectified with a small quantity of water ; and the distilled oil is dehydrated by agitation with chloride of calcium. (Hirzel.) «— The yield of oil is 0-78 p. c. (Bartels), 0*18 p. c. (Lecana.)

Properties. Transparent and colourless (Hirzel), pale yellow (Wack- enroder), mobile (the portion which distils between 20^ and 22^ is more viscid). Boils between 170^ and 220*^ ; has an aromatic odour (somewhat empyreumatic between 200° and 220^ (Hirzel); penetrating (Wacken- roder) ; its taste is strongly heating (Hirzel) ; oamphorous Gke that of poppy-oil. (Wackenroder.)

Hind.

H 0

a. •••••.••. od-D7 .... 11-45 .... 2-98 ....

b. e» d. 84-40 .... 81-43 .... 81-74 11-38 .... 11-32 .... 11-27 3-22 .... 7-25 .... 6-99

100-00 .... 100-00 .... 100-00 .... 100*00

a and b distilled from 170"^ to 180^ ; e from 200* to 220^ The oil is a mixture of leTcral hydrates of a hydrocarbon isomeric with oil of turpentine, corresponding to the iormalc 4(C»>H") + HO and 3(C»»H>) + 2HO. (Hinel.)

Decompoeitions. 1. Bums when set on jire with a bright fuliginouB flame. — 2. It absorbs Motvm^ with rise of temperature and evolution of hydrochloric acid gas, being thereby converted into a yellow, viscid oil, which sinks in water, has a peculiar odour, and a biting taste. — 3. It is decomposed in like manner by bromine^ with evolution of hydrobromic acid. — 4. By distillation with ankydrotu phosphoric acidj it yields a transparent, colourless oil, which has an odour of rosemary and an aromatic taste, agrees in composition (87*76 p. c. C, 11*76 H) with the formula C^W\ and is therefore isomeric with oil of turpentine. — This oil absorbs hydrochloric acid gas, assuming a reddish yellow colour, and

382 APPENDIX TO PRIMARY NUCLEUS C»H».

forming, after complete satumtion, rectificatioii with water, and dehy- dration with chloride of oaleiam, an oil which has an agreeable odoor, an aromatic taste and a compoeition (74*98 C, 10-86 H, 13*28 CI) sgmmg with the formuhi 3(C»H«) + flCl. (Hirael.)

65. Oil of Matico.

In the leaves of Piper <uperifol%umy a plant growing in Ouiancu {Euiz. and Pav.) — The leaves are distilled with water, and the oil which slowly sinks to the bottom of the milky distillate is collected. — Pale green, thickish ; has a strong and persistent odonr, and a persistent camphorous taste. — By keeping, it becomes thicker, and ultimately crystalline ; by nitric aeid, it is coloured amber-yellow and remnised.^ — It dissolves in ail of wtriol, forming a carmineHSolonred Uqaid which becomes milky on addition of water. It dissolves readily in alcohU and ether, not in aqtie<nu potash or ammonia, (Hodges, 1844, Phil. Mag. J. 25, 204 ; Mem. Chem. Soc 1, 123.)

56. Mentral Oil of Meadow-sweet.

Lowia & WBiDUAJfK. (1839.) JPcgsf. 46, 57; PAarm. Omtn 1339,

129. Ettlxno. ^4iiik Fkarwk, 35, 241; Fkarm. Centr. 1340^ 837.

Neutral oil fff Bpbrma.

Source. In the flowers of meadow-sweet, Spirma ttlmaria, together with salicylotis acid and crystalline camphor. (Ettling, comp. xii, 235.)

Preparation. 1. The watery liquid which passes over on distilling the flowers with water, is shaken ap with ether ; the ethereal solotion is separated from the water and shaken up with potash-Iey to remove salicyloas acid ; and the residual ethereal liquid is evaporated at a gentle heat. (Lowiff & Weidmann.) — 2. The oil obtained by distilling the flowers is shiJcen up with potash-ley of sp. gr. 1*28, redistilled either alone or with water, and rectified after dehydration with chloride of calciunL The yield of oil is ^q. (Ettling.)

Properties. Transparent, colourless oil, which floats on water, boils more readily than crude oil of meadow-sweet ; is neutral ; has a strong odour somewhat like that of salicylous acid, and a slightly burning taste. (Ettling.) — It solidifies partially in the cold. (Lb wig & Weidmann.) Lavrig & Weidmann found in the oil 71*21 p. c. C, 10'35 H, and 1844 O : benoe it is perhapi C»H»80<. (Gm.)

Decompositions. 1 . When exposed to the air, it turns first yellow, then darker-coleused, without taking up oxygen. — The oil which last passes over in rectifieation gradually turne brown and deposits small colourless spicular crystals. (Ettliug.) — 2. It is violently attacked by chlorine, with evolution of hydrochtorle acid, becoming viscid but not solid. (Lowig & Weidmann ; Ettling.) — 3. OU of vitriol colours it brown-red, the solution on addition of water becoming milky white and depositing a small quantity ef apparently unaltered oil. — 4w It leaves potassium unaltesed and does not redden solutkma of ferric saUs. (Ettling.)

It dissolves readily ia ether and ia alookoL (Ettling.)

OIL OF MIGNONETTE. 388

57, (HI of Mecca Balsam.

Obtained from Balsamodendron gtleadense (Kunth.) by distillation with water, the quantity amoautiug to 10 per cent. (Bonastre), 30 p. o.

iTrommsdorn, N, Tr. 16, l» 72.) — Transparent, colourless, mobile. Bonastre, Trommsdorff.) Sp. ^. 0*^76. Does not solidify at — 12^ Has a strong odour of turpentine (Bonastre) ; agreeable like that of the balsam (Trommsdorff) ; has a strong taste, somewhat pungent, not bitter but cooling. (Bonastre.) Neutral. Contains 80*03 p. c. C, 11*50 H, 8 '42 0. (Trommsdorff.) ^^ Bums with a bright flame when set on Jlre, Dissolyes iodine with a brown colour and without explosion. (Tromms- dorff.) It is scarcely coloured by strong nitric add (Bonastre), but mixes with it quietly, the mixture becoming warm after a while, giving off nitrons acid, and depositing, on addition of water, a brittle pale yellow resin which has an agreeable odour like that of musk. (Trommsdorff.) — With oil of vitriol, it becomes saffron*red (Bonastre), dark red without rise of temperature; the mixture, on addition of water, deposits a fragrant pale yellow resin. (Trommsdorff) — It dissolves with turbidity in 12 pt8. of alcohol (Bonastre) ; clearly and in all proportiona in ether, easily in roek-oil,fimd oils, strong ttoetie acid (Trommsdorff), not at all in aqueous pQiash (Trommadorff), soda aod ammonku (Bonastre, J. Pharm. 18. 97.)

Sa Volatile Oil of Mentha Tiridis.

Obtained by distilling spear mint, Mentha viridis, L. with watez;. Sjp. gr. 0*939 (prandes) ; 0*91 42, after separation of the dissolved cam- phor by rectiGcation, 0*876. (Kane.) Boils wiUi tolerable regularity at 160^ Contains 84*21 p. c. C« 11*23 H, and 4*56 0, and is therefore 7C»H* + 0. (Kane, Zoni Sd. Mag. 13, 440; J, pr. Chem. 15, 163.)

59. Oil of Mercurialis amma.

Obtained by distilling the dry herb with water (the fresh herb does not yield any oil). -* It eontains numerous white crystals ; becomes coloured and thftckene by ke^ng. (lU^od, 1834» J. Pharm., 20, 461.)

60. Oil of Mignonette.

In the flowers of mignonette, Reseda odorata, L, They lose their odour when dry, but yield by dbtillation with water, an aqueous liquid, having an odour of mignonette, but at the same time a disagreeable graasy odour, and with alcohol, a distillate of not very agreeable odour. ^- To prepare the oil, the flowers are exhausted with ether ; the green ethereal layer of the extract is separated from the lower watery layer,

384 APPENDIX TO PRIMARY NUCLEUS C»HW.

and left to evaporate spontaneously. — Soft dark green mass, smelling strongly of mignonette, and consisting of chlorophyll, wax and oil ; the oil cannot he separated from it. (Bachner, N, Br, Arch. 8, 70.)

61. Oil of MiUefoil.

Bley. (1828.) N. Tr. 16, 1, 247; further, 16, 2, 9e. — EepeH. 48, 95.

FoRCKB. N. Br. Arch. 17, 177.

Zbllbr. Stud, uber dther, Ode^ Landau, 1 850.

Schqfparbenol.

Source and Extraction. In millefoil, Achillea miUrfoliam, L. Ohtained hy distilling with water the flowers, herh, roots, or seeds. — Water distilled over the flowers oontains propionic acid together with the oil (Kra- mer, JV. Br, Arch. 54, 9) ; water distilled oyer the roots contains acetic acid together with the oil (Bley). — The roots yield 0*032 p. c. ; the dry herb, 0*065 ; the fresh dried flowers, 0*114 ; the air-dried seeds, 0*052 p. c. oil (Bley).

Properties. 1. From the flowers : Dark blue (Zeller) ; from Achillea millefolium var. dHatata, yellow to green ; from var. contracta ; blue (Forcke). Sp. gr. 0*92 to 0* 928. Has a slight aci4 reaction. — (Zeller.) — 2. From the herb : Blue, darker than oil of wild chamomile ; viscid, nearly buttery in the cold, lighter than water; from the plant while flowering, 0*852 — 0*917. Has a strong smell and tastes like the herb, producing a slight scratching sensation in the throat. (Bley, Zeller.) — 8. Ft*om the roots: Colourless, slightly yellowish, lighter than water, with a peculiarly unpleasant odour, somewhat like that of valerian, and a disagreeable taste, but neither strong nor burning. (Bley.) — 4. From the seeds : Greenish. (Bley.)

Decompositions. 1. By exposure to the air, it becomes brown, strongly acid and resinous. »- 2. Stirred up with iodine, it becomes heated, without detonating, and gives off yellowish-red vapours, at the same time acquiring the consistence of a balsam. (Zeller.) — 8. With nitric acid, it acquires a reddish-brown colour ; with filming nitric acid, greenish- brown ; when heated therewith, it quickly gives off gas (Zeller), and leaves a soft resin. (Bley, Zeller.) — 4. Oil of vitriol colours it brown imd thickens it to the consistence of a balsam, giving off a peach-like odour. (Bley. Zeller.) With bichromate of potash and sulphuric acid, it becomes turbid and thickens. (Zeller.)

Combinations. — With aqtieous potash or ammonia, it forms a soapy compound. (Bley.) — It dissolves readily in alcohol and ether (Bley) ; without turbidity in 1 pt. of alcohol of sp. fi;r. 0*85 ; with a larger quantity, even with 40 pts., it forms a turbid solution, holding flocks in suspension ; absolute alcohol dissolves it in all proportions. (Zeller.)

62. OU of Noble MiUefoU.

From Achillea nobUis, L. — Obtained by distilling the flowering plant, or the flowers, herb, or seeds with water. — The dry flowers yield 0*24 p. c. ; the di*y herb, 0*26 ; the seeds, 0*09 p. c. oil — Pale yellow, viscid ;

OIL OF NASTURTIUM. 385

of sp. gr. 0*988 ; if obtained from the herb, 0*970 ; has a very powerful odoar, finer than that of the oil obtained from common millefoil, bat resembling it, and also like that of camphor. Tastes aromatic, like cam- phor, somewhat bitter. — With iodine, it forms, without explosion or rise of temperature, a solution, which, on addition of water, deposits a brown resin having a burning taste. — With fuming nitric acid, it becomes hot and yellow, thickens, and on addition of water, yields a soft, floating resin. — With oil of vitriol, it becomes red-brown and viscid; on addition of water, the mixture deposits a dirty-yellow soft resin. — The oil dis- solves in ether, alcohol, and oiU, both faed and voUUiU, (Bley, N. Br. Arch. 2, 124.

63. Oil of Mngwort

BeifimOl, In the root of mugwort^ Artemisia vulgaris, L. — The root is comminuted and distilled with water. — Pale greenish-yellow, buttery, ciTstalline, lighter than water ; boils above 100"^ has a peculiar pungent odour, and an unpleasant, somewhat bitter taste, burning at first, after- wards cooling. Neutral. — It is not easily inflammable, but when once set on/rcy bums with a light yellow, sooty flame, which diffuses an offen- sive odour. — It is quicldy thickened by dilate nilric acid, giving off nitrous acid, and yielding a tough brown resin, soluble in alcohol. — The oil dissolves readily in luoohol, ether, oil of rosemary, oil of turpentine and poppy-oil. (Brets & Eliason, 1826, TaschenXmch, 1826, 61.)

64. OUofMyrUe.

In the leaves, flowers, and fresh fruit of Myrtus communis. — Ob- tained by distillation with water. — Yellow to greenish yellow, lighter than water. (Raybaud, 1834, J. Pharm. 20, 463.)

65. OU of

MiiLLBR. (1838.) Ann. Pharm. 25, 209; N. Br. Arch. 14, 265;

Reperl. 70, 286. Bbranos. Repert, 88, 382. Gloez. BecueU de trav. de la Soc. d'emul. p. I. scienoes pharm. 1847, 41;

abstr. iV^. J. Pharm. 12, 69.

KapuxinerkmsenSol, HuUe etsentieile de eagmcine.

In the garden nasturtium, Tropcsolum majus. L. — The plant (espe- cially the seeds, according to Bemays) yields hy distillation with water 2*17 p. c. of oil. (Miiller.) — The water which passes over with the oil, gives off a large quantity of sulphuretted hydrogen when heated with zinc and oil of vitriol, (bemays.)

VOL. xiv. 2 o

386 APPENDIX TO PRIMARY NUCLEUS C»Hu.

Yellow (Mtiller, Bernays) ; heayier than water. (Beniay^, Cfloes.) Boiling point between 120 and ISO*'. (Cloez.) Has a peculiar, strongly aromatic odour, which irritates the eyes and nose (^iiller), Ifke oil of garlic (Bernays). Taste acrid and burning (Muller), pungent (Ber- navs). It irritates the bkin much tnore strongly than oil of mustard. (Miiller.) — It contains siilphur (Bernays, Cioec), but not phosphorus, as Bracounot supposed. (Bemays-) -^ Itihoiild have been trotted as described ^ page 50, ToLz.

66. OU of NerolL

BoNABTBB. (1825.) J. Pharm. 11, 529; ilT. Tr. 12, 1, 180.

BouLLAT. t/. Pharm, 14, 496.

Zrllbb. Stud, iiber dlher. Ode, Lahdati, 1850.

Itdatvng etpecudly io Orangt^fiomr iaater,

Ader. (i6St)^ J. Pharm, 16, 412.

Le Roy. J. Ohim, med, 6, 3 fa.

Wahart DimssKAL. J, Pharm. 16, 410; iT. 3!V. 23, 1, 30T.

SouBBTRAN. J. Pharm, 17, 619; N. JV.'28, 1, ^07.

BouLLAT. Bull Pharm, 1, 337.

OtJisMET. J, Cfhm, med, 22, '352.

OU qf OhtHffe'Jbw^, PomeramsendliUhenSlt OranffeMUikeiait Essence de

mroli.

Source opfid Extraction, In the flowers of the orange, CUrus Auran-^ tium^ L, — They are distilled in the fresh state with water. The oil which passes over is a tnixture of 'two t^ils, one easily soluble in water and rery fragrant ; the other, sparingly soluble, of less agreeable odour ; the latter floats upon the watery distillate, and is easily separated. (Sonbeiran.^

Properties. Transparent, colourless (Bonastre), yellow to brownish yellow. (Zeller.) Sp. gr. 0*85 to 0*90. (Zeller.) — das a very fragrant odour. (Bonastre.) Neutral. (Zeller.) Contains neroli-camphor in solution.

Decompositions 1. Becomes reddish yellow by keeping. (Bonastre.) — 2. With iodine, it frbths o^, gives ^ff violet and yellowisn red vaponrs, and is converted into a soft yellowish brown mass. (Zeller.) — 3. With nitric acidf it assomei^ a yellow colour gradually changing to that of iron- rust, and becoming red-brown after six hours, and ultimately loses its odour (Bonastre) ; on applying heat, the mixture rapidly gives off gas and acquires a resinous consistence. (Zeller.) — 4. With oil of vitriol^ it acquires a dark orange-yellow colour (Paoli), dark red-brown, and beeomes viscid. (Zeller.) — 5. Bichromate of potash colours it red-brown and separates resin from it. (Zeller.) — 6. In oontibct with platinum^Uick, it produces a peculiar aeid. (Dbbereiner.)

Combinations. It dissolves clearly in 1^ t)arts of aloohol of sp. gr. 0*85, and with turbidity in a larger quantity, ({teller.)

Appendix; Orange-flower water. ^^t*a nffjpAtf . — This is the aqueous distillate which pajsses over on distilling fresh orange-flowers with

J^{l$AQLIrCAMPHO|IU 387

waier, — frwd from tbe oil of peroli which floats on the Buriace. — It contains especially the moxe fragrant and more volatile oil of the flowers, which dissolves mpst readily in w:ater (Soubeiran), and cannot therefore be prepared by agitating the neroli-oil with water (Le Roy), or by agitating with wrater neroli-oil triturated with magnesia (Cot- terean), or by distilling a mixture of neroli-oil and water. (Sou- beiran.)

Fresh orange-flowers, which have expanded in warm weather, are distilled with water, till the distillate amounts to three times their weight. — Neutral water ^en .passes over first, , aftec^ards water containing acetic apid ; if flowers freed fi^om the flo:wer-leavos are distilled, the dis- tillate is nenti^al to the end, but has a less agreeable odour. — Water, free f)rom acetic acid, is obtained Ity distilling orangoiflowers with water mixed with about 0*75 p. c. of calcined roagpesfa. — Transparent,, colour- less, with a pleasant odour of orange-flowers, more or less powerful,— iragaut in the highest degree when prepared with orange-flowers which have expanded in warm weather. (Boullay.) — By keeping, it readily turns sour« from formation of acetic acid, but does not lose its odour.

iJoumeil, J. Chim. wM, 18, 752). — With nitric add^ it acquires in a ew minutes a rose-red colour (Ader and others), — or crimson with a larger quantity of acid, or if the mixture is heated. (Ader.) The colour of a mixture of nitric acid and orange-flower water in equal volumes remains unaltered for a long time, and is especially lasting in a mix- ture of nitric acid with orange*flower water containing aqueous potash, ammonia, or baryta ; it disappears in this mixture on addition of potash, but re-appears on supersaturating the liquid with nitric acid. (Ader, Wahart, Dunesmal.) — With oU of vitriol it becomes rose-coloured (Le Roy); not, however, with pure oil of vitriol, but only with the com- mercial acid containing nitric acid. (Ader.) — It is not coloured by phosphoric or hydrochloric, acid. (Ader.)

Ether, almond-oily and cattor-^il abstract from orange-flower water the whole of the volatile oil ; the ether solution, mixed with nitric acid, immediately assui^es, a roserpolour, and leaves on evaporation a fi-agrant volatile oil. (Ader, Soubeiran.) — Artificial orange-fower water, pre- pared by agitating with water,, either oil of neroli, or the same triturated with magnesia, or by distilling a mixture of neroli-oil and water, difiers from real orange-flower water by its stronger, but less agreeable, odour, which soon disappears when the oil is exposed to the air, — as well as by being not at all, or but slightly, reddened by nitric acid. (Ader, Sou- beiran, Gbbisney.)

'67. Neroli-camphor.

BoxTLLAY. (1828.) J, Pharm. 14, 496.

Pmsson. J. Pharm. 15, 152; N. Tr. 20, 1, 189; abstr. Ann. Pharm.

40, 83; J. Phaj-m. 20, 63. Lai4DERBR. Bepert^ 56, 84.

tAurade^Aurmdine. (Pliflson.)

Source and Mxtractian. Contained in solution in fresh oil of neroli. — Separates from the oil when kept for some time (Landerer) from the

2c2

388 APPENDIX TO PRIMARY NUCLEUS C»HW.

alcoholic oil by slow evaporation. (Plisson.) — To prepare it, oil of neroli is mixed with alcohol of sp. gr. 0*85, as long as a white precipitate is thereby produced ; the liquid is filtered after a while, and the precipitate washed with cold alcohol (Boallaj), then dissolved in ether, and the sola- tion either precipitated by alcohol or left to evaporate in the air. Fresh oil of neroli yields 4 p. c. of the camphor ; oil a year old, yields less and older oil, none. (Plisson.)

Property. White crystals, having a pearly lustre ^Plisson) ; slender needles (Bonllay) ; rhombic prisms (Landerer) ; resemoling spermaceti. (Plisson.) Sp. gr. 0*913 at 17'5^. Becomes soft at 50°, melts at 55° ; solidifies on cooling to a waxy, translucent mass; volatilises and sublimes at a stronger heat. (Plisson.) — Melts at 100°. (Bonllay.) — Without taste or odour. (Plisson.) Smells like neroli-oil, and has a sharp taste. (Landerer.) Neutral. (Plisson.)

C 83-76

H 1508

0 1-16

100-00

DeeompoHtions. 1. Unaltered by exposure to the air, volatilises partially when heated in vessels containing air, and leaves a brown residue. (Plisson.) — 2. Boiled with nitric ocuZ, it volatilises partially and partly remains undecomposed. Impure crystals thus treated give off vapours smelling like musk and ambergris. (Plisson.) The nitric acid solution deposits wax when mixed with water. (Landerer.) — 3. Heated wit^ oil of vitriol, it chars and evolves sulphurous acid. (Plisson.) It is not decomposed by hydrochloric acid, — 5. Folath does not saponify it. (Plisson, BouUay.)

C<mbinations. Neroli-camphor is insoluble in wate7' (Blisson, Boullay) ; sparingly in cold, readily in hot alcohol (Bonllay, Landerer) ; in 60 pts. alcohol of sp. gr. 0*9, separating in indistinct scales on cooling. It dissolves abundantly in ether, and is precipitated from the solution by addition of water or alcohol. (Boullay, Plisson.) It dissolves in hot acetic acid (Landerer), very easily in not oil of turpentine, separating completely in transparent lamins^ on cooling. (Plisson.)

68. OU of Nigella.

SchwarzkHmmelifl, In the seed of Nigdla ioUva, Z. Prepared by dis- tilling the bruised seeds with water. Transparent, colourless, exhibiting a bluish iridiscence by reflected light ; lighter than water ; smells like a mixture of oil of fennel and bitter almond-oil. Distilled with aqueous potash, it gives off a non-iridescent oil having a faint odonr, while there remains a strong-smelling residue, which, after supersaturation with sul- phuric acid, smells like camphor and deposits an abundance of white flocks. On washing these white flocks with ether, and evaporating the adhering ether, they change into a buttery oil smelling like camphor, which exists ready-formed in the original oil (is probably produced there* from by the action of hydrate of potash : Gm.). It dissolves in alcohol and ether, the solution exhibiting a bluish iridescenoe by reflected light. (Reinsoh, Jahrb. pr. Pharm* 4, 387.) .

NUTMEGkCAMPHOR. 389

69. Oil of Nutmeg.

Blbt. y. Tr. 14, 1, ZA. — BepeH. 48, 94.

MuLDBB. J. pr. Ohem, 17> 108; abstr. Ann. Fhamu 81, 71.

Mttteainuuol,

In nutmeff, the seed of Myristica aromatica. Lam. The seeds distilled with water yield 6 p. a of oil. (Bley.)

Frcperties. Transparent, colourless, mobile (Hasse, Crdl. Ann. 1785, 1, 422), nearly colourless (Bley). Sp. gr. 0*948 (Lewis), 0*920 (Bley). Smells of nutmeg and camphor, and has an aromatic burning taste. (Bley.^ It contains 81*13 p. c. C, 10*83 H, 8*04 0, and is a mixture of oil ana camphor. (Mulder.^ Consists of two oils, one lighter than water, the other heayier. (Hasse.)

DecompodtionB and Combinations. 1. The oil gradually turns yellowish when exposed to the air. (Hasse.) — 2; With fuming nitric aeidj it becomes yery hot, and forms a yellow fatty mass (Bley), a brown solid resin (Hasse). — 8. With oU of vit)ioly it forms a red-brown resinous mixture. — 4. Heated with mercuric cJUoride, it first turns brown, then black, giying ofl* a large quantity of acid yapours. (J. Davy, Phil. Trans. 1 822, 360.) It unites with aqueous alkalis^ forming a soapy mass. (Bley.) It dissolyes readily in alcoJCol^ forming a solution which becomes milky on addition of water. (Hasse.)

70. Nutmeg-camphor.

John. (1821.) Dessen chem. Schrifien, 6, 61; Schw. 83, 249.

Bley. Jl. Tr. 1, 56.

MuLDBB. J. pr. Chem. 17, 102; Ann. Pharm. 31, 62.

MyrUlicin, Muteaieamphor.

Deposited from nutmeg-oil ; purified by recrystallisation from water.

Transparent, colourless, long, yery thin prismatic tables, with dihedral summits ; by rapid crystallisation : stellate groups of needles (John), friable, white hemispheres, heavier than water (Mulder), lighter than water (Bley). Melts aboye 100°, and evaporates, leayin^ charcoal (Bley); sublimes completely at a higher temperature in white very slender needles. (Mulder.) Has an aromatic taste and odonr (John), like oil of nutmeg (Mulder).

Mulder.

C 62-1

H 10-6

\/ ..........M.........«.......M«.M«»». Z/*0

100-0 Agrees with tbe formula Om^Kfi (Mulder) ; C»H»0< (Gm.)

It yields by distillation, first a transparent and colourless, then a yellow volatile oil, and an alkaline water, having an aromatic burning

390 APPENDIX TO PRIMARY NUCLEUS C»H'«.

taste and smell. (John.) HecUed in a glass tube, it gives off vapoars, having at first an agreeable, aller#ar<b a fllttj odour. Heated on platinum-foil| it hums away completely without deposition of soot (Mulder), leaves charcoal (Bley). With fuming nutria aeid, it tani» brown and acquires an odour of musk. (Bley.)

It is sparingly soluble in cold water, but dissolves in 19 pts. of boiling water; the hot solution, which is sometimes acid, sometimes alkaline, solidifies in the crystalline form on cooling. (John.)

It absorbs ll"8d p. c. hydrocklorie add- gas, melting to a transparent mass, the aqueous solution of which hha a* strong acid reaction, and ia precipitated by nitrate of silver.

Nutmeg-camphor dis^olvcis iti (»ld tiUric add and aqueotU potash (Mulder), easily in alcohol and ftket' (John, Mulder), iti warm oi^, both* Jixed and volatile (Bley).

71. Oil of Nutmeg-flower.

In the arillus of the nutmeg, which, when comminuted and distilled with water^ yields a turbid aromatic water, with films of oil floating on its surface. (Henry, Hepert. 18, 105.) By cohobating four times, 4*7 p. c. oil is obtained (Hoffmann, Bepert. 43, 2d6) ; from old nutmeg- flowers, 4-1 p. c. (Bley, iv. Tr. 14, 1, 61; Bepert. 48, 94). — Transparent, colourless. Sp. gr. 0*931. Smells strongly of nutmeg-flower, and has a burnine aromatic taste. With aqueous soda it yields a soapy oompoond () Om.) ; with amnuyMa, a liquid, permanent liniment.

72. (HI of Olibaxmui.

In frankincense, the gum-resin of BonoeHd Jtortbundci, (Boyle,) and B, eerrata {Stockh.), Pulverised frankincense is distilled with water, and the oil which floats on the distillate is dehydrated by agitation with chloride of calcium. The product is 0*4 p. c. of limpid oil of sp. gr. 0-806 at 24"", and boiling point 162^ It smells l^e turpentine but more agreeably.

C 83-83

H 11-27

O 4-90

10000

It is isomeric with the oil of MftUha ffiridie, and agrees with the formula CH'O (Stenhouse); it contains an oxygenated and a non- oxygenated oil. (Lowig, Org. Verb. 2, 1027.) Bums when set on fire with strongly lummous, sooty flame. Mixed with nitric acid, it assumes a dark brown colour, and, when heated therewith, detonates and acquires a resinous consistence Oil of vitriol colours it red in the cibld and chars it when heated. Heated with caustic potash, it is converted into a brown resin. It dissolves in all proportions in absolute alcohol and etherj less in weaker alcohol. (Stenhouse^ 1840, Phil, Mag, J, 18, 185 ; Ann, Pharm. 85, 306.)

OIIi OF: PARMELIA PARIETINA. 391

7a. Oil of Origanum.

Kane. lond. Ed. Mag. J. 13, 43^; J. pr. Qhen^, 15, 157;. 4.n^.

Pharm. 32, 285. Zellbr. Stud, fiber ather. Ode, Landau, 1852.

X>o«toi% ^99€Hee 4' Origan, W qf WildJ^arjmnuju.

Somrce c^n^ Extimuiian. In wild narjpraxD, Origfpifum wdgcare^ L. Qbiained \xj distilling the plant in the flawennff state with water.

Properties. Pale to bxowniah-yellow. (Zellei:^) Sp. gr, 0-909 (Brand); 0-8901 — 0909, rectified, 0 8673 (Kanq). ; 0-87 — 0 97 (Zeller). Boila almost constantlj at 161°. (Kane,) pmells strongly of the plant, and has a sharp %romi^tiQ t^us^ I^eutiia).

Blane.

^ ^ s

C 86-71 .... 8608 .... 86-33 .... 8d-18

til 11-11 .... 11-44 .... 11-44 .... 11-64

O 2-18 .... 2-48 .... 2-23 .... 2-18

100-00 .... 100-00 .... 10000 .... 100-00 It is a mixture of oil an^csmpluu^ Qgns^ponding to.tlie fonnuk C*^H^O.

Deoompositiom. 1 . Deposits camphor after long standing. — 3. With iodine^ it becomes stronffly heated- and detonates, giving off violet and jellow-red vapours and becoming viscid. (Zelier.) — 3. With niirie add^ it becomes brownish-red to yellow-brown, ^ving off gas with violence when heated, and leaving a solid yellow resin. (Hasse, Zeller.) — 4. With oU irfvUrioly it becomes dark blood-red. ^- 5. With bichromate of potash and sulphuric acidy it becomes dark brown. (Zeller.) — & heated with a concentrated aqueous solution of bisulphite of ammonia or soda, it is resolved into a permanently liquid hydrocarbon belonging to the campheues, and a white solid mass which, when washed with lucohol, ether, and water, present^ the appearance of a white amorphous powder not containing either sulphur, or ammonia, or soda. (Rochleder, Wien, Ahad. Ber. 13, 169; J. pr. Chem. 64, 29; Chem! Centr. 1854, 723.)

Comhinaiions. Dissolves in 12 — 16 pt& alcohol of sp. gr. 0*85, forming a turbid liquid. (Zeller.)

74. Oil of Pai'mdia parietina (Achard.)

The lichen is distilled with wntei^ 20 lbs. of it yielding 5 gnuns of the oil. Light green (colourless, ac^rding to Hinterberger {SSpert. 47, 199), of buttery consistence, lighter thi^n water. It has a musty smell and taste, prodpcing an after-sensation of scratching in the throat. (Gumprecht, 1824, N. Tr. 1, 1, 62 ; Repert. 18, 241.)

392 APPENDIX TO PRIMARY NUCLEUS C»HW.

75. Oil of Pelargonium.

Recluz. (1829.) J. Pharm, 13, 529.

C. and P. SiMONNBT. i^. J. Pharm. 13, 43.

GuiBOURT. iV. «7. Pharm.. 15, 846.

Source and Extraction, In Pdargonium odaratis^mum, P, roBetan^ WUld,, and P. eapitaiumj Art. The fresh flowers and leaves are distilled with water, and the distillate is repeatedly cohobated over new portions.

Properties. Transparent, colourless, viscid like palm-oil (Simonnet), pale-jellow, mobile (Ouibonrt) ; solidifies in a white dystalline mass below 1 8° (Recluz), becomes turbid, without solidifying, when cooled to 0° (Guibourt) ; smeUs like roses (Simonnet) and lemons (Guibourt), and has a warming taste (Guibourt). It contains pelargonio acid (xiii, 369) and a neutral oil. (Pless, Ann. Pharm. 59, 54.)

In iodine-vapour it becomes brown after a few seconds, then black. In nitrous acid vapours it turns apple-green. Mixed with oU of vitriol^ it yields a brown oil, having a strong and unpleasant odour. (Guibourt.) It dissolves readily in alcohol of sp. gr. 0*85. (Simonnet.)

76. Oil of Pimpinella.

a. From the root of the common Bumet-saxifn^, Pmpindla Saxifraga, L. The root is distilled with water ; the yellow oil-drona which pass over with the water are collected ; and the water is partly redistilled to obtain the oil. Gold-yellow, mobile oil, which floats on water, has a strong penetrating odour like parsley seeds, and a disagree- ably bitter taste with scratching after-sensation. — Fuming nitric acid colours the oil red, and converts it into a brown, balsamic, resinous mass.

— It dissolves slightly in water, easily in alcohol and ethevj imparting to those liquids its strong taste and odour. (Bley, N. Tr. 12, 2, 62.)

h. From tho root of Pimpinella nigra^ tVilld. — The root contains 0*38 p c. of the oil, which is obtained from it by distillation with water.

— Light blue oil which floats on water. Its odour, like that of the rooty is less penetrating than that of the preceding oil ; its taste, also like that of the root, is burning, and afterwards scratching. — In sunshine, it turns green after a few weeks, even in closed vessels. — Fuming nitric acid converts it into an odourless crystalline resin. — Oil of vitriol forms with it a brown odorous resin. — It dissolves slightly in wcUer^ easily in alcohol^ ether, and oils, hoth Jlxed and volatile.

77. Oil of Poplar-bads.

In the buds of the black poplar, PopuLus nigra, whence it Is obtained by distillation with water. — Colourless, fragrant oil, which floats on water. It makes stains on paper which are completely dissipated by heat ', bums with black smoke when set on fire; is sparingly soluble in alcohol, very soluble in ether. (Pellerin, 1822, J. Pharm. 8, 428; abstr. 15, 237.)

Oil qf Pyrethrum-^Bee OilqfFevetfew (p. 369).

OIL OF ROSES. 393

78, Baspberry-camphor.

Expressed raspberries are distilled with water; the flocks which separate after a while from the distillate are collected and dissolved in etner; and the solation is left to evaporate.^ Small laminsB, some of which float on water, while others sink. — Volatilises readily when heated. With cold aU of vitriol^ it assumes a yellowish coloar, without losing its odour ; with hot oil of yitriol, it turns yiolet-brown^ giving off a large quantity of sulphurous acid. — It dissolves in tocUsr, in aqueous ammonia, and in aqueoui potash^ with the odour of violets when heated. — It dissolves In alcohoC and in ether. (Blej, 1887, iV. Br. Arch, 132, 48.)

79, Oil of Boses.

Saussurb. (1828.) Ann. Chim. Phys. 13, 337.

Blamohbt. Ann. Pharm. 7, 154; Eepert. 50, 134.

GoBEL. Schw. 58, 473.

OuiBOURT. jr. J. Pharm. 15, 845.

Zbller. Stud, fiber other. Ode, Landau, 1850.

Boaendl, Etnnce de roie.

Source and Extraction. In the flowers of Hosa cent^folia, L., JR. mo8c?uUaf Oem. R. Bempervirens, Z., and R. damcucinaj Mill. — The fresh rose-leaves are distilled with water, the solidifying oil which floats on the watery distillate is removed ; and the water is cobobated several times over fresh quantities of roses. — In India, the oil which floats on the water is collected by dipping into it sticks covered with cotton, and then pressing the cotton. (Ch6reau, J, Pharm. 1826, 486.) — A larger quantity of rose-oil is obtained, by leaving the roses freed from their calices, in contact with water for some days before distillation, till they begin to ferment and acquire a vinous odour. (Cenedella, Gasa. eclet. di Chim. med. Agosto, 34.) — In Arabia, roses are distilled with solution of common salt without cooling ; the distillate is poured into earthen vessels buried in the ground, and the solidified oil which rises to the surface is removed. (Landerer, Repert, 77,378.) — In Macedonia, the expressed juice is exposed to the sun for 5 or 6 days (Landerer, Repert, 96, 401), in Bengal, roses steeped in water are thus exposed, and the oil which then floats on the surface is soaked up with cotton. (Monro, Rttll. Pharm. 8, 177.)

Properties. Transparent, colourless (Saussure), slightly coloured (65bel, Blanchet), greenish yellow (Guibourt), brownish yellow. (Zeller.) Sp. gr. at 33* = 0*832 (Saussure) ; at 25% 0 867 — 0872 (Chardin, Ann. Pharm. 7, 154); German rose-oil, 0'814; Persian, 0-882. (Zeller.) — Solidifles above 0° to a buttery mass (Saussure), to a white, transparent, laminated mass (G5bel), at 26^ (Blanchet), at various temperatures (Guibourt), at 25^ (Zeller.) — When slowly cooled, it remains trans- parent, and appears traversed by slender, shining, iridescent laminie (when adulterated with spermaceti, it becomes opaque) ; by rapid cooling

394 APPENDIX TO PRIMARY NUCLEUS C»H".

it becomes turbid and cloudy.) (Guibourt.) Melts at 29°— 30^ (Saus- snre\ at 22-5° (Gobel), at 37'5\ (Zellcr.) — Tension of the vapour at 1 4*5° = 8™" of mercury. (Saussure.) — Has a penetrating odour of roses (Saussnre) ; strong, pleaeant only when diluted with alcohol ; yerj persistent. (Gobel.) — Taste, mild, rather sweetii^h. (8au8sure.)'-7- Has a strong add reaotipn. (Zeller.)

Saospun. BUncliet; OObsl. a. k, Ci

V .•••••^•■t... O2*v0 •«.«■•«• rvQoi ..« U9wO

H laiia . , 1214 1606

O 3-95 „ 13-78 U;28:

99tl3 100-00 100*00

a contains 0*87 p. c. nitrogen. It is a mixture of volatile oil and camphor (Saussnre); contains } pt. camplior in solntioa (Blanchet).

Decompogitions: 1 . Iodine ipipafts io qil of> roses a faint crimson colour (Zeller) ; in vapour of iodine the oil remains colourless. (Guibourt.) — 2. With 2 pts. of fuming nitric acid, it froths up^ and, after addition of water, deposits white, tallowy, kneadable lamiii» (Has<je^ Orell. Ann. 1785, 1, 422); assumes a pale brownish yellow colour and becomes somewhat more tenacious. (Zeller.) — 8. In nitrous acid gas^ it acquires a deep yellow colour. (Guibourt) — 4. With an equal volume of oil of vitriol f it turns brown, and acquires a more agreeable but fainter odour. (Guibourt.) — 5. With bichromate ofpota^ and sulphuric aeidj it becomes brownish and, after a time, violet. (Zeller.)

Combinations, The oil dissolves sparingly in water. — At 18*7°, it dissolves in 160 pts. of alcohol of 8]>. gr. 0*815 (Gobel) ; at U"* in 143 pts., at 22° in 83 pts. alcohol of sp. gr. 0'806. (Saussure.) — The oil is not separated from its alcoholic solution by water (Blanchet) ; but from its aqueous solution it is taken up by platinum-black and puitinic oxide, which thereby acquire the property of glowing when dried and heated to loo"". (Dobeireiner, Schw. 66, 298,)

80. Bose-camphor.

Saussure. (1820.) Ann. Chim, Fh^s. 13, 337. Blanchet. Ann. Fkarm. 7, 154. Herbebger. liepei't. 48, 102.

Solid Awf -o«/. StsaropUne qf ItoM-oil.

Source and Extraction* In rose-oil. — Separaies from rose-water in the cold. — 1. The oil is cooled and pressed between bibulous paper when solid. (Saussure.) — 2. Rose-oil is mixed with 3 pts. aloohol of sp. gr. 0*875 ; and the crystalline mass which then separates is dissolved in ether, precipitated therefrom by addition of aloohol, and freed from adheritt}? oil by repeated washing with alcohol. (Blancbel.)

Properties. Transparent, colourless, shining lainina (Sausaura) ; six- to eight-sided crystals (Herberger), whidi exhibit the colours of Uie rainbow. (Guibourt^ N, J. Pharm. 15, 345.) — It has the oonsiAtenoa of

OIL OF ROSEMART. 395

wax (SaQMtie) ; when sepaxsted from rose-water, it iff a white, buttery, crystalline mass (Blanobet) ; from coDeentrated rose-water it crystallises in siK-sided laminaa. (Steinaeher.) — Lighter than water, lighter also thaa rbse^oil eontaining the camphor (Saussure, Heiberger) ; heavier than alcohol (fierberger.)>— It is- battery and crystalline at 25% melts at 35% boils without decomposition at ^0*'-— dOO'^(Blancfaet) ; melts at dd^ — 34*^ (Sanssure) ; melts to a colourless oil at 15% and at a higher temperature solidifies in the crystalline fonn, leaving a small quantity of chareoal (Herberger) ; after being kept for a year, its meltuig point rises from IS'' to 20% (Bixio.) Solidifies again at 85% (Blanobet.) Tension of vapour = 0*0005 met. at 14*5°. (Saussure.) — Has a faint odour of roses. (Blanchet, Herberger.) Smells of roses, even after being three times sublimed over ignited charcoal, or after its alcoholic solution has been treated with animal charcoal. (Herberger.) Has a somewhat warming aromatic taste. (Herberger.)

C 86-74 81-09

H 14-89 14-39

101-63 95-48

Agreef with the fonnnla C><H^. (Blanchet.)

Decompo&iUoni. — 1. When ul on fire^ it bums with a bright non- f uliginous flame. (Blanchet.) — 2. Chlorine passed into an alcoholic solution of rose-camphor, produces a white odourless precipitate. — 3. With niiric add, it turns yellow, dissolves with slight evolution of gas, loses its odour, and forms oxalic aeid* — 4. It is dissolved and turned brown by oil of vitriol. — 5. It is not altered by potamum, (Herberger.)

CornbincUioiu. Very sparingly soluole in water. (Herberger.) After being moistened with aloohol, it unites with iodine^ without rise of tem- perature or detonation ; the compound partly volatilises undecomposed when heated* It dissolves very sparingly in hydrochloric acid, with difficulty in uqneoui poUuhy more easily in aqaeoua ammonia. — The solution of rose-camphor in alkalis and alkaline carbonates does not possess any odour of roses, &s even acquire it after supersaturation with acids. (Herberger.)

£o6e-camphor is soluble in acetic add, (Herberger.)

It dissolves sparingly in akoholy, readily in ether, (Blanchet.) — It dissolves in 500 pts. alcohol of sp. gr. 0*85 at 14"^ (Saussure), in 490 pts. of alcohol of sp. gr. 0*85 at 15^; more easily in absolute alcohol; the alcoholic solution is clouded by water, and yields ciystalline laminae when evaporated. (Herberger.)

It dissolves in vtdatile oiis. (Herberger.)

81. Oil of Bosemary.

Sau88¥Sb. (1820.) Ann. Chim. Phps. 13, 278. •

Kans. Lond. Ed, Mag. J. 13, 437; J. pr. Chcm. 15, 156; Ann.Pharm,

32, 284; abstr. Bepert. 70, 161. Zbllkr. StMd. fiber, other. Oele, Luidau, 1850. VoLH. N. Br. Arch. 74, 16.

RoMMorit^tU, Butuce de roemarin or romarin, Ohum Anthoe.

396 APPENDIX TO PRIMARY NUCLEUS C»H«.

Source and Extra/stion, In Boanarinus offieinoUis, L, — It is obtained by distilling the fresh leaves and flowers with water.

Properties. Transparent^ colourless (Sanssnre), yellowish to yellow. (Zeller.) Sp. gr. 0*983 at 15^ ; rectified 0*886 (Saussare) ; 0*897 ; after repeated rectification, 0*8854 — 0*8875 (Kane), 0-88—0*91. (Zeller. — Boiling point 166*5 to 168'' (fi[ane) ; of the firesh oil, below lOO"" ; of old oil, ld2<' (Kane); of the rectified oil, 165°. (Sanssure.) — Tension of vaponr at 16''=0*0095 met. of mercury. (Sanssure.) It has a oam- phorons taste and smells like the plant. It is neutral. (Zeller.) Turns the plane of polarisation of light to the right. (Lallemand.)

Saotsore. Kane.

a. b.

C 82*21 83*40

H 9*42 11*66

O 7*73 4-94

99*36 100*00

a contains 0*64 p. c nitrogen ; h may be represented by the formnla C^H'H)' » 9(C*U^) + 2HO. It is probaby a mixture of a hydrocarbon isomeric with oil of turpen- tine and an oxygenated oil. (Kam*.) See next page.

Decompositions. 1. Spanish oil of rosemary leaves on evaporation -|^ of camphor. (Proust.) — 2. When cooled to between — 27** and — 30", it deposits camphor. (Trommdsorfi^, N. Trs. 20, 2, 24.) — 3. With iodine it becomes hot, but does not explode, gives off a small quantity of yellow- red vapours, and thickens witnout sJteration of odour. (Zeller.) — It becomes heated by contact with iodine, sufficiently to volatilise the iodine with explosive violence. (Walcker, Fogg. 6, 126.) — 4. With niirie acidf it assumes a pale yellow to yellow colour, becomes heated, and gives off gas with violence, without thickening. (Zeller.) — With fuming nitric acid, it emits a crackling noise and forms a brown-red balsam. (Hasse, Crell. Ann. 1785, 1, 422.) — 5. With oU of vitriol, it becomes black (Kane), reddish-brown (Zel!er): the mixture saturated with lime contains the lime- salt, soluble in water, of a peculiar acid ^Unverdorben, Fogg. 8, 484), — of a sulphuretted acid, and yields by distillation Kane's rosmarine, an oil isomeric with oil of turpentine, having an alliaceous odour, of sp. 0 8678, and boiling point 173*8*^. — Oil of rosemary yields with oil of vitriol, a brown mass of the consistence of a balsam (Hasse, Crell. Ann. 1786, 2, 36), an easily fusible resin, soluble only in hot oil of vitriol, and an oily acid. (Unverdorben, Fogg. 8, 484.) — 6. With hydrochloric acid gaSf it blackens and forms a heavy oil, but no solid compound. (Cluzel, Ann. Chim. 52. 270.) —At 22'' it absorbs 218 vol. hydrochloric acid gas, becoming black and turbid. Sanssure.) — 7. With bichromate of potaA and sulphuric acid^ it becomes strongly neated, assumes a yellowish brown colour (Zeller), and forms limettic acid. (Vohl.) — 8. Distilled over hydrate of potash or lim^, it yields rosemary-camphor, which sublimes. (Meyer, Chem, Vers, iiber ungelbschtem KcUk. 1764, 81.) — 9. Heated with hypochlorite of lime, it yields carbonic acid and chloroform. — 10. Distilled with hypobromite of lime, it yields, in like manner, carbonie acid and bromoform. {Chn,ut&Td, Compt retid. 34,485.) — 11. Finely divided sulphide of lead is converted oy oil of rosemary — through the action of the ozone contained therein — into sulphate of lead. (Over- beck, N. Br. Arch. 79, 138.)

OIL OP SAFFRON. 397

Combinations. Oil of rosemary at 29^ absorbs 9*75 vol. ammonia^ gets, (Saussare.) — It dissolves in every proportion of alcohol of sp. gr. 0*85 (Zeller), at 18'' in 40 pts. alcohol of sp. gr. 0*887. (Saussure.) — It dissolves abundantly copal and caovichorAC,

IT According to Lallemand {N, Ann, Chim. Pht/s, 57, 404), oil of rosemary may be separated by fractional distillation into two oils, one boiling at 165'', the other between 200° and 210^. — a. The former is a mobile hydrocarbon which turns the plane of polarisation to the left : it unites with hydrochloric acid, the combination being attended with rise of t€(piperature, and forms a compound which remains liquid if left to itself^ but, when treated with nitric acid, yields a considerable quantity of a crystalline hydrochlorate apparently identical with artificial camphor (p. 265). The same oil quickly absorbs moist oxyeen in sun- shine, forming crystals which are similar to those produced in like manner from oil of turpentine, but disappear if subjected to the further action of oxygen, yielding a brown acid soluble in water.

h. The portion boiling between 200° and 210^, deposits at low tem- peratures a large quantity of camphor, resembling common camphor in all respects, excepting that it has rather less dextro-rotatory power. An additional quantity of it may be obtained by treating the mother-liquor with dilute nitric acid. %

Camphor qfMarth Wild RoMemary — lee Ledum<ampkor (p. 37 7).

82. Oil of Saflfron.

AsoHOFF (181 8.) Berl. Jahrb. 1 81 8, 5 1 .

Dbhnr. Crell. CAem, •/. 8, 11.

Henry. J. Pharm. 7, 400.

Bouillon-Laoranob & YoGEL. Ann» Chim. 80, 195.

Quadrat. Wim. Akad. Ber. 6, 546; further, J. pr. Chem. 56, 68.

Sk^ranOl, Buemee de iq/ron.

Source and Extraction. In saffron, the stigmata of Crocus satimis, Z.

— 1. Obtained by distillation with water. (Bouillon <fe Vogel, Quadrat.)

— 2. Saffron distilled over a quick fire, with 8 pts. of saturated solution of common salt and 4 pts. of aqueous potash of sp. gr. 1*24, yields 9*4 p. c. of oiL (Henry.)

Properties. Yellow, mobile, heavier than water (Henry, Bouillon <fe Yogel), lighter than water (Quadrat). Smells like saffron, and has a burniug, sharp, rather bitter and caustic taste. (Henry, Bouillon & Vogel.)

It gradually changes into a solid mass, which makes its appearance, even during the distillation of saffron with water (Bouillon, Dehne), and sinks in water. (Henry, Quadrat.) — Easily soluble in water. (Bouillon.)

398 APPENDIX TO PRIMARY NUCLEUS C»H»,

63. Oil of Bage.

Ilisch. (1811.) A, Tr. 20, 2, 7.

Hbrbbrger. Beperi. 34, 131.

RoCHLEDBfi. Anru Fharm. 44, 4; abstr. Beperi. 79, 810.

Zeller. Shtd. fiber ather. Ode, Landaa, 1850.

Saivtiol, SMeiol, Stftnce de mtuffe.

Formniiou. By boiling oil of rmvtacd ^tli 'aqneonS'Sodft. (Hiasi- weiz, Wien. Akad, Bei\ 5, 189):

lOC«H»CyS» + 12NaO » AC^W^O + 2C«H«NaO* + lONtCyS*.

Source imd Extraction, In Salvia ofickiaiiB, X. — Obtained by. dis- tilling tbe fresh herb with water.

Properties. Greenish to brownish yellow (Zeller); from yoang plants : green, soon turning brown ; from old plants in antumn : yellow (Cartheuser) ; distilled from oil 8 years old at 128° — 130^, or from oil 2 years old at ISO'': .colourless ; ^om the least volatile part of a iwo years old oil, by distillation with water : pale yellow. (Bochleder^ — Sp. gr. 0-864 (Ilisch); 0 86—0-92. (Zeller.) — Boils between 130** and 160'^. but not at a constant temperature. (Rochleder.) Smells and tastes like the plant, when distilled from oil 8 years old oil at 128*' to 130°; burning and camphorous, from oil 2 years old at 150°; disagree- ably like rum. — Neutral. (Zeller.)

Rochleder. Hlasiwets.

tt. b, e. a. §.

C 80-25 .... 77*97 m.. 78-33 .... 80-64 ., '80-63

H 10-91 .... 10-69 .... 10-64 .... 10-95 ........ H*70

O 8-84 .... 11-34 .... 1103 .... 8-41 767

100-00 .... loo-oo 100*00 .... leoroo lootoo

a. The first tenth, distilled at 135^ of a sample of sage-oil 8 year^ old, redistilled per 9e in the oil -bath between 128* and 130^ till ] had passed, ofter. — » 6..' The distiUate from 8 years old oil, between 1.30° and 140**, redistilled over chloride of calcinm between 96** and 103\ — c. The distillate from. 2 years old 4>il bdow 160*, distilled at ] 50* per $e over ehloride of i^ilokim. — d. The product obtained b^ distiUipg. wjth .water at 130* — 145*, the least Tolatile of a 2 y«an old oil, rectified, imt.m over chlonde of calcium. — e.'Prepai^d from oil of mustiBrd. —^Sage-oil is a mixture of several oils, of whicha and <f eerrespond tolho fofurala Oja}^0, ^ a«d c to the formvla (Pm^HP, (Rochleder.)

DecomposUions. 1. Sage^dil wben exposed to the air: for some time, deposits campbor (Herberger), and .beoomesj slightly OLCid. (Zeller.) —

2. The Spanish oil when evaporated, leaves i pt. camphor (Puoust) ; German-oil becomes resinous without Leaving camphor. (Ili«oh.)

3. With iodme, it gives off yeUowish red and grey vapours without fulmination, and forms a soft, extractive mass. (Zeller.) — It forms with iodine, without losing its odour, a thick magma easily soluble in the rest of the oil. (Guyot, J. Pht/B. 5, 230.) — 4. With cold concentrated nitric acid, or with weaker nitric acid, if warmed, it acquires a brown-red colour (Rochleder), reddish brown (Zeller), and deposits a red resin, with rise of temperature and brisk evolution of gas. — This resin oonsists of

SAGB-CAMPHOR. 399

unaltered oil j a yellow resin solable with red colonr in aqneoas potash ; and nitrate of camphor, whi6h, when distilled ivHf^ water, yields a vola- tile oil having a peculiar odoar^ and a residual, yellowish red, brittle resin. — The mixture dropped into fuming nitt'ic acid, becomes heated, gives off carbonic acid and nitric oxide, and forms common camphor. — On distilling the nitric acid solution of this mixture with 4 pts. of water, common camphor sublimes. TRochleder.) — 5. Oil of inti'iol colours It brownish red to crimson. (Zeller.) — 6. Distilled with hydrate ofpotash^ it yields volatile oils, with evolution of hydrogen at last, then turns brown, «ud leaves earbonate of potash. -— 8age-oil two yearn old distilled with a «mall qfumtity of hydrate of potash, yields — at firet without evolution of gas -^ a eolourless oil smelling of oil of torpefttiile (84-40 C, 1 1 *87 H, 3-78 0), then anotiber oil (83-17 C, 11-26 H, 5-67 0 = C»H»0'), and at last, with evolution of hydrogea, an x)il having a strctag burning odour of sage and peppermint ^7687 p. a C, 11-50 H, 983 0 = C»H«»0*); sage oil 8 yeam old, dfiBtilled after di^e^ion-at a gentle heat with a large quantity of hydmte of polash, yiekb a oolontlfess oil having an empyren- matic odonr (82-65 C, 1252 H, 4-83 0 = C*'H*»0) and leaves car- bonate and hydrate of potash tiiiged with brown. (Roohleder.) — 7. With bichromate of potash and sulphuric a&idy it aequlres a dark brown eolonr, afterwards -beooming. greenish. (Zeller.) — 8. BoHed with n«6-o- prvmde jof oapper, it yields - a riate-grti^y deposit and aequires a darker colour. (Heppe, N. JSr. Arch^'Sd, 57.)

It dissolves in every proportion of alcohol of sp. gr. 0*85. (Zeller.)

84. Sage-camphor.

This substance was found in sage-oil which had been kept for a long time in a badly-closed vessel, and was purified by pressure between slightly wanned filteriag paper. *^ Yellowish white mass, lighter than water, melting at 31— 37 , having an odour like that of turpentine- camphor and slightly like that of sage-oil, and a persistently sharp and bitterish cooling taste. Neutral. ^ When strongly heated, it swells up, diffusing a smoke which produces a scratching Bensation in the throat, and a strong od^our of turpentine-camphor, and yielding a slight sab- limate. — When set' on fire; it burns with a bright flame, leaving shining charcoal. — WHh wUrie-aeid oi sp< gr. 1*27, it becomes slightly heated, and yields a yellow resin but no oxalic acid. — With oil of ifitiiol it becomes brown-red and acquires a resinous consistence. — With hoi hydrochloric acid, it forms a reatnous mass. — With eattstic alkalis, it forms a yellow-brown resin. — Sage-camphor dissolves in 450 pts. of cold and SOO pts. of hot u^er; the solution yields crystalline films when evaporated, but does not deposit crystals on cooling. — It dissolves with- out alteration in dilute sulphuric acid, — It dissolves in 5 pts. alcohol of sp. gr. 0*82, in all proportions of Mer, easily in oil of turpentine, less easily in rock-oU, easily infixed oils. (Herberger, Hepert, 34. 131.)

400 APPENDIX TO PRIMARY NUCLEUS C»HW.

85. Oil of Sweet Sedge.

Trommsdorff. (1809.) Ann, Chim, 81, 332; A. Tr. 18, 2, 122. ScHNBDBRMANN. Ann. Phoi'm, 41, 374. Zbllbr. Stttd, uher dther, OeU, Landaa, 1850.

Kalmutdif Baenee d*acore.

Source and Extraction. In the root-etooks of the sweet sedge, Acortu ecUamuB, L. — The roots fresh or at least not too old, yield when eom- minated and distilled with water, 1 p. o. of oil (Martins, Repert. 39, 240), 1*09 p. c. (Bley Repert, 48*96) ; dry roots a year old yield 1*36 p. c. ; fresh, slightly dried roots, 0*73 p. c. (van Hees, Pharmm CentralU. 1847, 380.)

Properties. Pale yellow to dark yellow (Trommsdorff, Martins) ; light brownish yellow (Bley); pale to reddish yellow and brown. (Zeller.) According to Schnedermann, the most volatile portion of the oil is oolonrlea. — Sp. gr. 0-899 at 25** (Trommsdorff), 0-89— 094 (Zeller), 0*950— 0984. (van Hees.) — Boiling point 195'' (after the most Tolatile nortion has been distilled off). (Schnedermann. — Has a strong pungent oaonr, like that of the roots, and an aromatically bitter, bnming, slightly camphocons taste. (Trommsdorff.) — Neutral. (Zeller.)

Schnedermann. a. b,

C 80-82 79-53

H 10-89 10-28

O , 8-29 ........ 10-19

100-00 100-00

a, distilled at 195^; 5, at 260^ It is a miztnre of several non-separable oils; the most Tolatile. containing 1} p. e. oxygen, is in the pure state, most probably G"*U'*; the less volatile, boiling at 260 , is a mixture of resin and oQ, the Utter passing off when the mixture is heated, and the resin remaining. (Schnedermann.^

Decompotitums. 1. It becomes darker in colour by exposure to light (Trommsdorff.) — 2. When exposed to the air, it thickens and turns slightly acid, but does not yield any camphor. (Hasse, Crell. Ann, 1785, 1, 422.) — 3. Gently heated with iodine, it gi^es off a small quantity of greyish yellow rapours without explosion, and is converted into a tough, reddish yellow-brown mass. (Zeller.) — It takes up l*5*i pts. of bromine J and acquires a blackish green colour. (Knop, Chem, Centralbl, 1854, 498.) — 5. With nUric acid, it acquires a yellowish red- brown colour, and is converted into a solid resin (Hasse), crumbling. (Zeller.) — With oU of vitriol, it resinises. — 7. Alcoholic potash turns it reddish yellow-brown. — 8. With bichromate of potash and sidphuric addp it forms a dark brown, thickish, turbid mass, (zeller.)

It dissolves without turbidity in absolute alcohol and in 1 pt. of alcohol of sp. gr. 0-85.

VOLATILE OIL OP TAGETES GLANDULOSA, 401

86. Oil of Serpentarla.

In yir/i^inian snake-root, AriOclochia SerpentariOj L. — It is obtained by distilling the comminuted root with water. — The root contains 0*5 p. 0. of oil. (Buchholz.) — Light brown; in single drops, brownish yellow. Lighter than water. Smells and tastes like valerian and cam- phor. (Grassmanu, Repert. 35, 463.)

Neutral Oil qf Spirasa, see Neutral Oil tf Meadowsweet (p. 382.)

87. OU of Squill.

Meernifieheldl. — From ScUltu maritimtii, L, — Obtained by crashing the fresh plant and distilling it with water. — Greenish yellow, viscid ; has a disagreeable and persistent odour, sharp, but not so penetrating as that of niudtard-oil ; produces bums on the skin. — Soluble in alcohol; the solution irritates the skin. — The oil is different from that which is obtained by distilling fermented squills with water. (Landerer, N. Br. Arch. 95, 260.)

88. Oil of Syringa«

Unachtea Jaaniinol — In the flowers of the syringa, Fhiladelphus COronariiUy L, — The flowers lose their odour when dry, and, on being distilled with water, yield an aqueous distillate having rather a repulsive than a pleasant odour, but acquiring after some time an odour of roses. — To obtain the oil, the fresh flowers are exhunsted with ether in a displacement-apparatus ; the upper ethereal layer is separated from the lower gummy watery liquid ; the ether is carefully distilled off, and the residue is collected in a basin and filtered when cold. There then remains on the filter a yellow buttery mass, which loses its odour by washing with cold alcohol ; and a watery liquid smelling strongly of the flowers runs off. The latter is shaken up with ether, and the ether is removed, shaken up with chloride of calcium, and left to evaporate. — Golden-yellow oil, having an intoxicating odour in the mass, fragrant in the dilute state. (Bnchner, N. Br, Arch. 8170.)

Oil qfSyringa vulgarie, see OH qf Lilac , p. 377.

9. Volatile Oil of Tagetes glandulo8a.

Light yellow, strongly anthelmintio. (Fr. Eiseubeck, Br, Arch, 8, 421.)

TOL. XIT. 2 D

402 APPENDIX TO PBIMAKY NUCLEUS C^W*.

90. Oil of Tansy.

Fromhcrz. If<iff. Pharm. S, 85.

Persoz. Oompt, rend. IB, 483; J. pr. Chem. 85, 60; Ann. Pkarm.

44, 81. Zbllbr. Stud, uher other. Ode. Landau, 1850. WoHL. N. Br. Arch. 74, 16; abttr. Fharm. CentraJbl. 1853, 818.

Rai^farren^, Si$enee de tatudiie^ oleum ienaeeH.

Source and Extraction. In tlie herb and flowers of tlie tansy, Tana- cetum viUgare, L. — Obtained by distilling either the fresh or the dried plant with water.

Properties. Pale yellow from the leaves, gold-jellow from the flowers (Fromherz) ; the plant grown on a damp soil yields yellow oil ; that grown on a dry soil yields green oil. (Geoffrey.) Sp. gr. 0'946 (Lewis); 0*952 at 20"* (Fromherz); from the flowers, 0*921 ; from the herb, 091 8. (Zeller.) Smells like the herb ; tastes burning and bitter. (Fromherz.) Neutral (Zeller.)

Decompoettions. 1. It dissolves iodine, becoming viscid and brown- red (Flaschoff, £r. Arch. 33, 225), slightly warm and acid at the same time (Winckler, Pepert. 33, 185) ; without rise of temperature or forma- tion of vapour. (Zeller.) — Heated with nitric acid, it gives off eas with violence, acquires a reddish brown to reddish yellow colour and becomes resinous. — 3. With oil of vitriol, it becomes reddish yellow. (Zeller.^ — 4. Heated with 5 pts. hichromcUe of potash, 11 pts. oU of vitriol, ana 40 pts. water, it yields common camphor. (Persoz, Vohl.) — 5. With nitroprusside of copper, it yields a brown-black precipitate. (Heppe, j^. Br. Arch. 89, 57.)

Dissolves readily in alcohol.

OH qf Tropmolum, see Oil qf Nasturtium, p. 385.

91. Oil of Tea.

M OLDER. (1838.) Pogg. 43, 163.

Source and Preparation. In tea, the dried leaves of various species of Tlua. — 1. A hundred grammes of tea are digested for 48 hours with 1 litre of ether ; the ether is then poured off, and distilled till only 3 oz. are left ; the residue is mij^^d with 1 oz. water; the mixture is distilled to dryness, in the sand-bath ; the upper ethereal layer of the distillate is separated from the lower and shaken up with chloride of calcium ; and the ether decanted therefrom is left to evaporate. — Chinese Hyson yields 0*79 p. c, Conffo 0*60 p. c, Java Hyson 0*98 p. c. of oil. — 2. One part of tea is uistilled with 1 pt. of common salt and 6 pts. of water ; the milky distillate, which has an intoxicating smell of tea, is shaken up with ether ; the ethereal solution which floats on the liquid when left at rest is dehydrated with chloride of calcium and distilled to & small residue, and the ether is left to evaporate spontaneously therefrom.—- No oil is obtained by repeatedly distilling the watery distillate over common salt — ^Tea distilled with dilute sulphuric add, yields a distillate having a faint odour, but no otL

OIL OF VITIVERU. 403

Propetiiei, Lemon^jellow ; ligbter than water ; solidifles easily when cold (becaase it contains camphor in solution) ; smells strongly of tea, and so intoxicating that it acts like a narcotic ; tastes of tea, but not astrin- gent. — The oil prepared by the second method resiuises quickly when exposed to the air.

92. Oil of Wild Thyme.

Herberqer. (1830.) Repert, 34, 41. Zeller. Stud, iiher. other. Oele, Landan, 1850.

QuendeKfi,

Source and ExtracUon, In wild thyme, 7%ymu$ SerphyUum, L, — Obtained by distilling the herb with water. --^The aqueous distillate A-om old herb contains toetio acid as well as oil. (Trommsdorff, N% TV. 25> 2^ 149.) — The

yield of oil amounts 0*08 to 0'09 p. c.

FropeHiei. Oold-yellow (Herberger) ; wine-yellow to brown. (Zeller.) Sp. gr. 0*89 to 0'91. (Zeller.) Has an agreeable odonr of lemons and thyme, and an aromatic bitter taste. (Herberger.)

Decompositions. 1. It is not decomposed by iod'vnB in the cold, bnt when heated with it to 75^, forms, without violent explosion, a mixture which gives off iodine-vapours, takes fire, and after the combustion leaves a resin. (Herberger.) It quickly evolves yellowish red vapours with iodine, — especially the oil obtained from the dried herb, — thickening at the same time and acquiring a reddish yellow-brown colour. (Zeller.) — 2. With niiric acid, it acquires a dark yellow-brown colour, gives off gas when heated, and leaves a soft resin. (Zeller.) Nitric acid of sp. gr. 1'28 does not act upon the oil at 22*5°, but when the mixture is heated to the boiling point, it explodes, gives off nitrous acid, and leaves a resin. (Herberger.) — 3. With oil offfitriol, it acquires a dark brown-red colour and the thickness of a balsam. (Zdler.) — 4. Strang hydrochloric acid does not act upon the oil below 75°; but at that temperature, it produces ebullition, the mixture becoming viscid on cooling, and appearing to be mixed with blackish green oil-drops. (Herberger.) — 5. With bichromate of potash and sulphuric acid^ it assumes a greenish brown-yellow colour. (Zeller.)

Combinations. The oil dissolves in all proportions in alcohol of sp. gr. 0'85. (Herberger, Zeller.)

03. Oil of Vitiveria.

In the root of a grass which grows in India. ' — The grass is cut np and distilled with water ; the oil which passes over is collected ; the milky water which goes over towards the end of the distillation is exhausted with ether, and the ether is left to evaporate spontaneously from the solntion. — The more volatile portion of the oil is yellowish, transparent, lighter than water ; the less volatile is turbid, viscid, heavier

2 d2

404 APPENDIX TO PRIMARY NUCLEUS C«H>«.

than water, and sticks to the reoeiyer. This latter is probably a mixta re of oil and resin ; on treating the oil with aqneons soda, the resin unites with the soda, and may be separated from the solution by supersaturation with nitric acid. (Cap, 1833, J. Pharm. 10, 48 ; Ann. Fharm. 7, 83.)

94. Oil of Fine-leaved Waterdrop.

In the seeds of Pkellandrium aqtuUicum, L, — They are bruised and distilled with water, yielding, according to Remler, 0*8 p. c. of oil. The plant distilled with \ pt. carbonate of potash, ^ pt. lime, and 6 pts. water, yields a milky, ammoniacal, aqueous distillate having a strong taste and smell : on this distillate there floats about 0*67 p. c. of oil. (Frick- hinger.) — Pale yellow, lighter than water (Pfieiff) ; viscid, heavier than water (Rayhaud, J, Phai^m. 20, 458); when obtained by distilling the seed with potash, it is brownish yellow, viscid, of sp. gr. 0'8526 at 19^ (Frickhinger.) Has a penetrating odour and a persistent aromatic taste, like that of tne seed. (Pfaff, Frickhinger.) Neutral. It does not exert any narcotic action on animals, unless administered in rather large quan- tities (Frickhinger, jBeiptfr^. 68, 1.) — It fulminates with toe^tn^ giving off violet vapours and leaving a brittle resin. With fuming nitric acid, it becomes dark brown, then colourless and tenacious.

95. Gil of Water Horehound.

In the fresh herb of water horehound, LycopiOi Europanti, L,, whence it is obtained by distillation with water. — Green, buttery oil, which smells like the plant and has a sharp taste. (Geiger, 1823, Reperi, 15, 2.)

Second Appendix. Ferment Oils.

{Arrange aJphabHieaUy,)

FermenioUa.

These are volatile oils, produced by the fermentation of various plants, not originally contained therein, and essentially different from the oils which are extracted from unfermented plants by distillation with water. According to Becker {N. Br, Arch, 55, 161), they were known to the alchemists, and by them designated quintessences. The number of them known to exist has increased, since Biichner {ReperL 53, 299) in 1835, first separated an oil of this nature from the fermented herb of ErytJircea CerUaurium Pers. by distillation. — Ferment-oils are for the most part much more soluble in water than ordinary volatile oils.

FfiRMENT OILS. 405

— According to Berzelius (Jahresber. 27, 541), they are perhaps peculiar alcohoJs, related to fusel-oil, and forming compound ethers with salt- radicals and acids.

1. Feitnent-oil of ChoBrophyllum sylvestre. — The flowering plant is left to ferment in water; the liquid distilled when the fermentation is ended ; the distillate mixed with common salt, and shaken up with ether ; and the ether removed from the aqueous solution and left to evaporate : the ferment-oil dissolved in it is then left hehind.

— Brown, lighter than water, with a strong and peculiar pungent odour, and an aromatic taste, not hitter, hut slightly scratching. — Evaporates quickly even at 18®; burns when set on ^t-e, with a clear, luminous flame, difl*using a vapour which excites coughing. — Chlorine' footer converts it into yellow flocks retaining the odonr ot the oil. It dissolves iodine. It is decomposed with violence by niiric acid. By oil of vitriol it is coloured brown, without losing its odour ; the solution is rendered milky by water. It forms an emulsion -wMh. aqueous ammonia, dissolves sparingly in water ^ easily in alcohol^ ether, and oils^ both fixed and volatile. It dissolves resin. (Bley, N. Br. Arch, 45, 50.)

2. Ferm^ni-oil of CheUdonium majus, L. — Obtained from the roots, in the same manner as the ferment-oil of Chasrophyllum sylveUre, — Lighter than water ; has an agreeable odour like the bouquet of wine, and a per- sistent biting taste. It is not very volatile. — With iodine it forms a violet solution. With nitrie acid it evolves nitrous gas, and with oil of vitnol it forms a slightly coloured solution, which is scarcely clouded by water. — It dissolves sparingly in vfotery readily in alcohol, ether, and oils, hoih fixed and volatile. (Bley, N. Br. Arch. 48, 156.)

3. Femient^oU of Conium maculatum, — Obtained from fresh hemlock in the same manner as the ferment-oil of Chanrophyllum sylvestre. — Colourless ; has a peculiar odour, not like that of hemlock, and a sharp burning taste ; it is not poisonous. — Dissolves with facility in alcohol, ether, and oils "bo^ fixed and volatile. (Landerer, Bepert. 94, 237.)

4. Ferment^oU ofErythrcea Centaurium, Pers. — The plant, after mace- ration in water for 12 hours, gives ofi* a perceptible odonr, which increases Qp to 60 hours maceration and then ceases. (BUchner.) — The aqueous distillate is pale yellow, with white turbidity ; has a persistent enliven- ing, aromatic odonr, which is not pleasant when close, and irritates the eyes and nose ; its taste is excessively burning, like that of creosote, but not persistent. It reddens litmus, but not permanently (Blichner, Bepert, 53, 303), and when heated with ammonia and nitrate of silver, reduces the solution to the metallic state. (Biichner.) — To prepare the oil, firesh herb is macerated in water for 48 hours, the whole distilled, the odoriferons distillate redistilled, and this process continued as long as drops of oil pass over with the watery vapour. — Thin greenish oil, having a peculiar, but not disagreeable, odour : it is not poisonous. (Biichner, Bepert. 53, 299.)

5. FermeniroU of Echivm vul^are, L, — The plant in the flowering state is distilled with water after maceration ; the distillate is shaken up with ether, and mixed with common salt ; and the ether decanted therefrom is distilled off. — Pale yellow oil lighter than water, and smelling like other ferment-oils. — Easily soluble in alcohol and in tther. (Bley, N. Br. Arch. 30, 167.)

406 APPENDIX TO PRIMART NUCLEUS C»HW.

6. Ferment-oil of Erica vulgar%$. — The fresh berb is distilled after maceration witb water ; the distillate is cohobated and repeatedly dis- tilled after addition of common salt, then shaken op with ether as lon^ as the ether acquires anj odour ; and the ether is carefully distilled off from the dissolved oil. The oil obtained amounts to 0.023 per ceut.

— Greenish yellow, mobile, lighter than water, with a peculiar odour^ and a sweetish, aromatic, burning taste; reddens litmus. — When ut on firtf it bums with a clear, blue-edged flame, without leaving any residue. — It is not deodorised by Morine-water. '•—It dissolves iodine without detonation. — "VfiiYi fuming nitric acid, it froths up, and the solution mixed with water deposits resinous flakes. — With oil of vitriol, it becomes darker, without losing its odour. (Bleyi iT. £r. Arch^ 21, 302.)

7. Ferment'OiL of Tumlago farfara, L. — The fresh bruised herb ia macerated in water for 10 or 12 days, during which it turns light

freen and acquires the odour of pickled girkins ; the whole is then istilled ; the distillate, which has a vinous odour, is saturated with common salt and redistilled ; this second distillate is shaken up with a large Quantity of ether ; and the ether ia taken off and evaporated, the dissolved oil then remaining behind. — Yellowish, lighter than water, very volatile, with a peculiar, strongly aromatic, penetrating odour, and an aromatic taste, neither burning nor cooling. — It easily takes fire, and bums at first with a whitish, afterwards with a reddish, sooty flame. — It dissolves iodine abundantly, dissolves in oil of vitriol with yellowish colour, without losing its odour, and turns brown when heated with it. — With potash, it forms a whitish, soapy compound (Qy. Gm.). — It dissolves sparingly in vKtter^ readily in alcohol and e^€r. (Bley, Repert. 62, 406, N. Br. Arch. 13, 38.)

8. Feiyncnt-oU of Marrubium vulgare, L. — The comminuted herb is soaked in water and exposed to the sun, whereby it acquires an ofiensive odour ; the liquid is then distilled ; the distillate ^saturated with common salt ; the flocks thereby separated, are collected on a filter and dissolved in etiicrj and the ether is left to evaporate slowly. — The distillate saturated with common salt yields when htjatea, a second aqueous distillate, from which oil may be extracted by agitation with ether. — Lighter than water ; has a peculiar, sweet, ethereal odour, and an aromatic, slightly biting taste. — When set on Jire, it burns with flame, without leaving charcoal. It dissolves in dilute nitric add, and yields a bitter substance with strong nitric acid. With oil of vitriol, it becomes heated and acquires a peculiar odour. — With chlorine-water, it emits an odour of roses and forms a film of reein.

— It dissolves in aq^ieoiu alkali and in water. (Bley, i\r. Br. Arch. 10,67.)

9. FeimeniroU of Achillea Millefolium, Z.— The fresh flowering plant is macerated in water and left to ferment ; the whole is distilled, with cohobation ; the blue oil which floats on the disiillate is removed ; the residual water, after addition of conunon salt, is agitated with ether; and the ether which separates is left to evaporate. —Yellow-brown oil, having a slightly aromatio odour, and an aromatioally bitterish^ rather sharp taste. It dissolves in alcohol, ether, and oils, both fixed and volatile. (Bley, N, Br. Arch, 30, 167.)

FERM£NT-OILS. 407

1 0. FemterU-oil of various tpedeB of Plantago. — Obtained from |>1ant- ain-Ieaves hy fermentation, distillation, and agitation of the distillate with ether, in the same manner as the ferment -oil of Achillea MUlefo* lium. — Yellow, transparent ; has an ethereal odonr slightly resembling that of mnstard-oil, and an aromatic, sweet, burninff taste. — Yerj Tolatile. — With/ummy nUnc add, it turns brown, with rise of tempera- ture and intumescence ; the solution first becomes greenish yellow, with milky turbidity, then clear, smells like artificial musk, and has a disgustingly bitter taste. — With oU ofvUi%ol^ it forms a dark brown-red mixture, from which water separates resinous flocks smellin|( of resin and ferment-oil. —-It diasolres in alcohol, ether, and oiU, (Bley, N, Dr. Arch. 40, 130.)

11. FemimU-oU of Quereue Sobur, Fi^Mb — Obtained from fresh oak-leavee by fermentation, distillation, and treatment of the distillate with ether, in the same manner as the fermeui-oil of Achillea MiUe^ folium. -— Pale green j sp. gr. 0*695, has an agreeably enlivening odour, a sweet, burning taste, and reddens litmus. -* It is easily inflammable, and bums, with penetrating odonr, and with a first bluish, then whitish, non-fuliginous flame. — With /umin^ niirio acid it froths up and becomes very hot, but does not lose its odour. — With oil qf vitriol, it becomes hot and assumes a dark red-brown colour. — It dissolves sparingly in vfaier, readily in alcohol, ether, and oiU, both faed and volatile. (Bley, xV. Br. Arch. 26, 48.)

1 3. Ftrment^U of Salix pentandra, L. — Obtained from fresh willow- leaves in the same manner as the hrmeniroil ol Achillea Afillrfolium. — Yellow, lighter than water; has an aromatic odour, like that of castoreum, and at the same time like that of willow-leaves ; reddens litmus. — Smells strongly when heated, and bums, when set on fire, with a very smoky flame, leaving a small quantity of charcoal. Dissolves iodine abundantly. — With /timing nitric acid, it froths up and thickens, but does not take Are, and if water be then added, deposits light yellow, bitter, resinous flocks. With oil of vitriol, it becomes slightly warm, brown, and viscid, and on subsequent addition of water, deposits resinous flocks smelling of the ferment-oil. It dissolves sparingly in water, easily and in all pro- portions in alcohol, ether, volatile mad fixed oiU, and creoeote. (Bley^ N. Br. Arch. 40, 129.)

18. Ferment-^ of Salvia pratensie, L. — Obtained from the fresh herb, like the fennentK>il of AcMliea Millefolium. — Dark red-brown, with a repulsive, ethereal, sweetish odour, and an aromatio taste. — It dissolves sparingly in water, easily^ and in all proportions^ in alcohol, ether, and oUiy lK>th Jixed and vdaHk. It forms a liniment with aqueout ammonia, and is very sparingly dissolved by aqueow potash, (Bley, A\ Br. Arch. 51, "257.)

14. Ferment-oil of Tiifolium fibrinum, L. — Obtained like the ferment-oil of Achillea Millefolium, from the dried plant, even after it has been well boiled with water and no loneer has a bitter smell, by fermentation, distillation, saturating the distillate with common salt, and shaking it up with ether. — Pale yellow, lighter than water, smells strongly aromatic^ like the ferment'oil of TueeUago farfara; its taste is at first burning and sweetish, afterwards aromatic. When eet on fire, it bums with a blue, slightly fuliginous flame, giving off

408 PRIMAKY NUCLEUS C»HW : OXYGEN-NUCLBUS C»H>*0^

strong-smelling yaponrs wbich excite coughing, and leaves a small quantity of charcoal. It dissolves sparingly in water, easily in alcohol and ether. (Bley, Jahi-h, p\ Fharm. 2, 207.)

15. Ferment'oil of Urtica urens, L, — Ohtained like the ferment-oil of Achillea Millefolium, from the flowering plant, which, during fermenta- tion, emits, first a vinous, then a sharp and intoxicating odour. Resembles the ferment-oil of Echium vulgare, (Bley, N, Br, Arch, 30, 167.)

16. Fei'merU-oil of Viiis vinifera, L. — Fermented vine-leaves are distilled; the distillate is cohobated and shaken up with ether; the ethereal solution is distilled ; and the ethereal, peculiar-smelling dis- tillate is rectified : the ferment-oil dissolved in it then remains behind. Pale yellow, lighter than water; has a peculiar vinous odour, like vine-flowers and mignonette, and a burning, sweetish; aromatic taste. It reddens litmus slightly but permanently. It evaporates in the air, diffusing a strong odour. Heated with fuming nitric acid, it resinises and assumes a grass-green colour. With oil of vitriol, it forms first a white, then a light-red, and ultimately a brown mixture, without losing its odour. It is not deodorised by agitation with chlorine-water. With aqueous potash, it forms a clear mixture, from which the oil after- wards separates, with red-brown colour, but with its original odour. It dissolves sparingly in water^ without alteration in hydrochloric and CLcetic acid. With sulphide of carbon, it forms a milky liquid, from which it afterwards separates unaltered; with carbonate of potasli^ a liniment from which it also separates unaltered ; with aqueous aminonia, a soapy mixture. It dissolves abundantly in alcohol, ether, and fixed oils; in oil of turpentine and oil of lemon, it forms at first a milky solution, which afterwards becomes clear. (Bley, Bepert, 68, 301.)

An oil, different from that just described, may be obtained from wine, by leaving it to freeze, distilling off the volatile part of the remainin^^ liquid, and shaking up the residue with ether. (Bley.)

17. Ferment-oil of diseased Apples, — MuhH, Oil (f Apples, — Produced in cellulostasis, a disease of the apple, which imparts a musky odoar to that fruit It is obtained from the diseased apples by distillation with water. Yellowish grey, lighter than water; boils at 109^. Smells of musk, tastes rough and sharp. Contains 64*15 p. c, C« 20*65 H, 15*15 0, and 0*05 N. It volatilises completely when healed, and bums, when set on fire, with a feeble flame, diffusing a small quantity of smoke. Chlorine decomposes it, with elimination of bydrochlorio acid. With dry hydrochloric acid gas^ it forms a crystalline compound (Chlorhydrate de maldile). It dissolves readily in alcohol and ether, and imparts a mnsk-like odour to Ufoter, (Rossignon, J, Fhaim, 27 y 158; J. pr. Chem. 23, 398 ; Ann. Fharm. 39^ 121.)

THYMOL. 409

Oxygen-nudem (?"H'*0'.

Thymol.

A. E. Arppe. (1846.) Ann. FhatTn. 58, 42; abstr. Ben. Jahresber. 27,

451. DovERi. T. Ann. C7nm* Phys, 20, 174; Ann. Fharm. 64, 374; Compi,

rend. 24, 390. A. Lallemani). Compt, rend. 37, 498; J, pr. CA^m. 60, 431 ; Fhw-m,

Cenlralbl. 1853, 754.— Ciwipi. rend. 38, 1022; J: p?\ Chem. 62, 295;

Fharm. Centr. 1854. 513. Report, by Damas & Bassy, Gcmpt. rend.

39, 723. — Chmpt. rend. 43, 375. Report, 43, 459. — Abstract of tho

preceding Memoirs; Ann. Fharm. 101, 122. — Fully, and with

Emendations, N. Ann. Qiim. Fhy». 49, 148; abstr. Ann. Fharm.

102, 119. Stbnhouse. Ann. Fharm. 93, 269; 98, 307. R. Haines. Chem. Soc. Qu. J. 8, 289; J. pr. Chem. 68, 430; Chem.

Centralhl. 1856, 593.

ThymiaU'Campher. Ajwakaphul of the Hindoos. — First observed by Nenm&nn {Chymia medico^ 21, 282), Brown & Forcke {N. Br. Arch. 17, 178), investigated by Doveri and Lallemand. The stearoptene of monarda^oil examined by Arppe, was recognised by Gerhardt, (Traiiit 3, 610) and by Stenhonse, as identical with thymol. The (partly cUffering) statements of Stenhonse relate to the camphor or stearoptene of Ptychotas-oil, which has not yet been completely proved to be identical with thymol^ and has been twice investigated by Stenhonse, with varying results.

Source. In oil of thyme. — In tbe volatile oil of Monarda punctata (Arppe). In the volatile oil obtained from tbe seed of PtychotU Ajowan (or Ajwan)^ an ^East Indian umbelliferons plant. (Stenhonse, Haines.)

Formation. By tbe oxidation of tbjonene or cymene. A mixture of tbymene and cymene through which 1500 litres of dry air were passed for four months, became viscid and dark red, and yielded to caustic alkali a large quantity of tbymol. (Lallemand.)

Freparation. a. Of crude Oil of Thyme. — Bruised thyme is distilled with water in a large still. — l lb. of the dry herb yields on the average 38 grains ; lib. of the fresh herb, 45*7 grains. (Zeller, N. Jakrb. PAarm. 2, 78.)-^ By repeatedly distilling the seeds of Piyehotu Ajowan with water, a volatile oil is obtained amounting to 5 or 6 p. c. of the seeds, having a light brown colour, an agreeable aromatic odonr, and sp. gr. « 0*8!^6 at 12^. (Stenhonse.)

h. PreparcUion of Thymol. — Oil of thyme is subjected to frac- tional distillation, whereupon it begins to boil at 150°, and if the boiling point be raised quickly to 175**, then slowly to 180**, tby- mene and cymene pass over togetber. Wbile tbe temperature of tbe liquid rises quickly from 180** to 230^ a mixture of thymene and tbymol passes over; then between 230° and 235°, thymol, which must be collected apart. (Doveri.) By tbis process, only an imperfect separation of tbe two constituents is effected, tbe distillate obtained below 225% still Msontaining a considerable quantity of tbymol ; this

1

410 PRIMARY NUCLEUS C^H": OXTOEN-NUCLEUS C»H»*0«.

distillate is therefore shaken up with strong soda-ley to dissolve the thymol, and the liqnid is separated from the undissolved thymene, which floats on the surface, and mixed with dilute hydrochloric acid, which precipitates the thymol. After this portion of thymol has solidified, and the distillate which passed over between 230^ ana 235^ has been caused to solidify by the introduction of a few crystals of thymol, the whole of the crystals are repeatedly pressed between bibulous ]>aper and recrystallised from alcohol (Lallemand.) — Arppe presses between filtering paper the thymol which separates from monarda-oil on standing, and distils it either per se or with water. — Stenhouse leaves the oil of Ptychotis Ajowan to evaporate spontaneously, whereupon thymol gradually crystallises out at low temperatures; or subjects the oil to fractional distillation, collects separately the portion which distils between 218'' and 222% brings it to the solidifying poiot by agitation or by immersion in a frigorific mixture, and crystallises it from thymene or from aloohol. Hainet deoompoies the uma oil by fractional dittiUatum into eymflne (p. 184X boiling at 175°, and thymol boiling at 230**, and promotes the solidification of the latter by introducing a crystal of thymol.

Properties, Thin, rhombic tables, probably belonging to the right prismatic system. (Arppe.) Angles 82'' 30' and 97^ 30', with cleavage

Parallel to the edges of the tables. (Arppe.) Miller, in Stenhonses [emoir {Ann. Pliarm. 93, 269), describes the ^" long crystals as belonging to the oblique prismatio system. In a later Memoir by Stenhouse (Ann. Pharm. 98, 310), two crjrstalline forms of thymol are described as determined by Miller. From the crude oil, thymol crystal- lises in the rhombohedral system. (Fig. 1 43.) Rhombohedrons, having the terminal edges replaced by e-faces. Moreover the middle edges of the rborabohedron W : r*, r* : ?•*, &c., are truncated by a six-sided prism (< in Fig. 145). The faces o and s are very narzow, « : a ss 130°; r : e = 130° 39' ; r : r = sr 22^; r : a = 139° 19'. From aloohol it orvs- talliaes in forms belonging to the oblique prismatic system. Thin rhombic tables (somewhat like Fig. 112), having their edges bevelled by the unequally inclined faces n and A, and their acute summits bevelled by the unequally inclined faces t and // the four-edged summits of A and n are replaced by a pair of m-faces ; — /, i, m are hexaid-faces ; u and n a posterior augite-pair ; t, a posterior oblique terminal face ; h and h the second pair ;»i: * = 90-; i :/= 76*37';/: i» = 90°; t :f=l8T*4S'; t:i= 118° M'i h :/= 130° 39'; A : i» = 139° 21'; A:i = 81° 20'; ^ :i = 130°42'; u:h= 130° 38'; t: h= 118" 49'; « : < = 137° 47'; A : A = 98' 42'. In the crystals separated from the oil, the direetions of cleavage are parallel to the rhombohedral faces r, and therefore intersect one another at angles of 81° 22'; the crystals separated from alcc^ol cleave parallel to i and A ; but as the angles % : K and ^ : A are nearly equal to the former angles, Miller is of opinion that the two kinds of crystals may, in all essential points, be referred to the same form.

Thymol in the solid state is somewhat heavier than water ; in the liquid stote lighter. (Lallemand.) Sp.gr. 0 932 at 25*6'' (Haines), of the solid thymol, 1*0285 (Stenhouse). It melts at 44° (Lallemand, Stenhouse), at 48° (Arppe), at 52*7° (Haines), forming a colourless oil, which may remain liquid for a long time at ordinary temperatures, but solidifies when a crystal of thymol is thrown into it (Lallemand) or when it is cooled or shaken (Stenhouse), the temperature then remaining stationary at 44°. After being melted, it solidiflfs at 38* ; bnt tf H be heated aome- what above iU nielUng point, the solidiffing point falU, so that after heating to 70%

THYMOL.

411

105^ 140^ and 170% ioUdification takes place at 34% 33% 31 }% and 31% the teni- ))eratttre of the thymol rising at the same time to 38*, 37% 35^% and 35*. (Ar|ipe.) It solidifies after distillation pw' m (Arppe), or after the decomposition of its potash- solution by hydrochloric acid (Lallemand), immediately on cooling. It appears to volatilise at ordinary temperatures. (Miller.) Thjmol boils at 220^ (Arppe), at

222° (Stenhouse), at 230'' (Doveri, Lallemand). It does not deflect the plane of polarised light. (Lallemand.) Smells like thyme (Arppe, Haines), has a strong peculiar odour (Stenhouse), faint, different from that of thyme- oil (Lallemand). Its taste is sharp and burning (Arppe), pungent and aromatio (Lallemand). Neutral to yegetable colours. (Lallemand, Stenhouse.) It has an acid reaction. (Doveri). Vapour- density at 275'' =; 5*53 (Doyeri;, 5' 42 (Lallemand).

20 C

14 H

20

120 14 16

Arppe. Doveri.

weofim mean.

8000 78-88 .... 78-7

9-33 9-42 .... 100

1067 11-70 .... 11-3

Lallemand. mean,

.. 79-94 .. 9-46 .. 10-60

C U

o

C»H"0« 150 .... 100-00

Stenhouse. Haines.

79-73 .... 79'5»

9-24 .... 9-55

1103 .... 10-86

10000 .... 100-0 .... 10000

C-vaponr.

H-gas

O-gns

VoL

... 20 .. 14 ... 1

Density.

83200 0-9702 1-1098

100-00 .... 100-00 Thymol-vapour 2 .... 10-3995

I .... 6-1997

Arppe examined thymol from oil of monarda. Dover! and Lallemand, that from oil of thymene; Stenhonse and Haines that from the oil of Ptychotls Ajowan. Sten- house formerly examined crystals from Ptychotis-oil, which contained 69*17 p.c. 0, and 9-51 H {C**H^Hyo » 69-84 C and 899 H, 6i€nkou$t), and formed • peculiar compound with chlorine (p. 442) ; but he afterwards regarded these crystals as iden- tical with thymol from Ptyehotis.

Isomeric with cuminic alcohol, carvol, and carvacrol.

Deeampositums. 1. Thjmol is somewhat altered bj repeated dis- tillation, the liquid which passes over containing less carbon. (Sten- house.) It decomposes when heated considerably above its boiling point, and conse- quently the determination of its vapour-density comes oat too high. — 2. When

mixed with anhydrous phosphoric acid^ it becomes hot, assumes a wine- red colour, and forms a syrup which yields oil by distillation. On rectifyinff the distillate once or twice over anhydrous phosphoric acid, then with water, a light, colourless, mobile oil is obtained, which boils at \15^, contains 841 p. c. C and 10*15 H (whence Doveri deduces the formula CP'^H^^O, requiring 84-5 G and 9*8 H), and, alter being again repeatedly rectified over anhydrous phosphoric acid, finally yields a hydrocarbon which boils at 180^^ contains 80*2 p. a 0 and 1(H) H, and is therefore perhaps C^H^, this formula requiring 90*3 0 and 9*7 H. (Doveri.) By the action of anhydrous phodphoric acid, thymol is con- verted into a green substance, which dissolves in alcohol, and is precipi- tated from the solution by water as a thick, dark green, acid liquid, but cannot be crystallised either alone or in combination with potash. (Stenhouse.) — 3. By oil of vUriol, at 50° — 60^ it is converted into sulphothymic acid ; heated with excess of oil of vitriol to 240°^ it yields wiphodraconic acid. (Lallemand.) — 4. Chlorine in difi'used daylight acts with great violence on thymol, with rise of temperature, and

412 PRIMARY NUCLEUS C»H»«: OXYGEN-NUCLEUS C»H"0.

elimination of hydrochloric acid gas, the thymol remaining liquid and assuming a wine-red colour at the beginning of the action. If too great heat be avoided, the product consists of terchlorothymol (which, when the quantity of chlorine absorbed amounts to f the weight of the thymol^ sometimes separates in needles) ; then, if the passage oT the chlorine be continued in bright daylight, a very viscid oil is formed from which quintichlorthymol gradually crystallises. (Lalleraand.) Thymol from jitychotis-oll absorbs chlorine qaickly» becomes hot, and forms a peculiar chlorine- ctimpoand (p. 442), then, when more chlorine is passed throug^h it, an nncrystallisable resin. (Stenhoase.) Oil of thyme, distilled with 8 pts. chloride of lime and 24 pts. water, yields chloroform. (Chautard, Compt. rend. 34, 485 ; J.pr. Chem. 5G, 238.) — 5. Bromine, in sunshine, converts thymol into white, solid, earthy quintibrom thymol, which melts at a stronger heat, decomposing at the same time and giving off hydrobromic acid, and may be crystallised from ether. (Lallemand.) Oa thymol from ptychoti»-oil bromine acts quickly, forming an uncrystallisable substance. (Stenhoase.^ — 6. Thymol is not altered by hydrochloric acid, (Stenhouse.) When hydrochloric acid gas is passed over thymol, it quickly assumes a brown and, after removal of the excess of hydrochloric acid, a purple-brown colour, but does not increase in weight by more than 2 to 3 p. c. even when heated ; on distilling the product^ unaltered thymol is first obtained,

then a red substance. The latter turns blue when treated with alkalis in the cold, green wlien heated therewith, and recovers its red colour by exposure to the air. It dissolves with blue colour in baryta-water, and may be precipitated from this solution by carbonic add, together with carbonate of baryta, then extracted from the precipitate by alcohol, and remains, after the eyaporation of the alcohol, as an amorphou.«, dark violet, chlorinated mass, which may be distilled and forms red yapours when heated.

(Arppe.) — 7. Thymol is violently attacked by nit}ic acid, giving off nitrous and carbonic acid gases, and forming a soft, brown-yellow, offensive-smelling resin (Doveri), and a large quantity of oxalic acid. (Lallemand.) Nitric acid slowly dissolves thymol, and forms a peculiar, colourless, crystallisable acid, which does not form chloropicrin when heated with chloride of lime. (Stenhouse.^ Respecting the formation of binitrothymol, see page 419. — 8. Thymol is decomposed by boiling with strong €Lcid$ or alkalis, (Stenhouse, Hde it^f.) — 9. Aqueous sulpho- thymic acid (the solution of thymol in oil of vitriol, according to Stenhouse), becomes heated by contact with pei-oxide of manganeie or bicJiromaie ofpokuh and sulphuric acid, and yields a distillate of thymol and aqueous formic acid, whilst a brown acid remains, which is solid and friable at mean temperature, and dissolves in alcohol with dark-red colour. (Lallemand.) — 10. Thymol dissolves in glacial acftic acid, and on subsequent addition of oil of vitriol^ forms sulphaceto thymic acid. (Lallemand.)

ComhinaJtions, Thymol dissolves in about 333 pts. of water, (Lalle- mand.) It is not altered by aqueous ammonia, but takes up a large quantity of gaseous ammonia, and resolidifies after the ammonia has

escaped. (Lallemand.) Oil of thyme digested with aqueous ammonia, first turns yellow, then red, then dark brown. (Lewis, Aim. 1780, 32.)

Thymol dissolves in aqueous alkalis and combines with them. (Lallemand.) Thymol from ptychotis-oil is liquefied by aqueous alkalis, but does not dissolye in them. (Stenhouse.) The compounds are decomposed by the carbonic acid of the air or by aqueous alkalis, with separation of thymol.

Thymol-soda, — When thymol in the state of vapour is passed over soda-lime heated to dull redness^ no gas is evolved, but a crystallisable

OIL OF MYRRH. 413

substance is formeil, wliich has the composition C*^H^"NaO', melts when heated, and, when dissolved in water, precipitates the solutions of mer- curic nitrate and nitrate of silver. The mercury-compound is greyish violet, is not decomposed at mean temperature by dilute sulphuric acid or nitric acid, but is decomposed by hydrochloric acid, with separation of thymol, and, after prolonged washing with acetic acid and alcohol, con- tains 56'8 p. c. mercury, and is therefore C'^H'^HgO^jHgO (calculation = 56*07 Hg). (Lallemand.) Alcoholic thymol does not precipitate alcoholic solution of neutral acetate of lead. It does not precipitate nitrate of silver^ even after addition of ammonia. (Stenhouse.)

Thymol dissolves very readily in alcohol, ether, and glacial acetic acid, (Lallemand.) It is precipitated from the alcoholic sotution by water in drops, according to Stenhouse, not at all according to lAllemand.

OU of Myrrh. C»H"0»

Rdickholdt. N. Br. Arch. 41, 10.

The volatile oil of myrrh, the gum-resIn of Baltamodendron Myrrha and B, Kalaf, The alcoholic extract of myrrh yields by distillation a quantity of the oil amounting to 2*2 p. c of the myrrh. BUy h Diesel (N. Br, Arch, 43, 304), by distilling^ myrrh with water, obtained 1*6 to 3*1 p. c of ▼olatile oil, the quantity being smallest from myrrh which had an acid reaction, and the watery distillate then containing formic acid ; this acid is likewise produced, together with a soft resin, when oil of myrrh oxidates in contact with air and water. PfafT (Mater med, T) mentions a ▼olatile oil of myrrh heavier than water and not distillable therewith. Brandes {Almemach, 1819, 125) describes a mobile, colourless oil of myrrh, likewise heavier than water, and distillable with water bat not with alcohoL The last- mentioned oil resinises when exposed to the air. and forms with nitric add a tarbid mixture, with oil of vitriol a dark red mixture, from which water throws down white flocks. It dissolves in alcohol, ether, and fixed oils, and is extracted from the ethereal solution by hydrochloric acid, imparting to that liquid a dark purple-red colour. — Braconnot (/. Pharm, 15, 288; Repert, 34, 398) obtained from (perhaps impure) myrrh, 3 p. c. of a pale yellow, volatile oil, which turned red when mixed with an equal quantity of cold nitric add, dissolved in 2 — 3 pts. of alcohol or glacial acetic acid, readiljr in ether.

Properties, Light wine-yellow, viscid oil, having the taste and smell of myrrh, lighter than water and heavier than alcohol. It has an acid reaction and becomes viscid and darker-coloured by exposure to the air.

Rttickholdt. mean,

20 C 120 .... 80-00 ........ /9-34

14 H 14 .... 9-33 10- 16

2 0 16 .... 10-67 10-50

C^H»H>» 150 .... 10000 10000

Ruickholdt gives the formula C^Ri^O^; Heldt, {Ann. Pharm. 63, 59) gives C4tH»o^; but Ruickholdt's analyses when recalculated, one of them giving 9-88 p. c. H, agree better with the above formula (Kr.)

Oil of myrrh \» soluble in Qkohol and in tAer.

414 PRIMARY NUCLEUS CPWU OXTOBN-NUCLEUS C»H"0».

Carvol. C»H"0*.

VoLKBL. (1840.) Ann. Pharm. BOS, 308; Ann. Pharm. S5, 246;

abstr. /. pr. Chitn. 60, 120. ScHWBiCBR. J. pr, Ohem. 24, 257. Yarbbnteapp. LiMg, Poggendorf A Wohkr, ffandworterb. d. Chem.

4, 686.

Source. In oil of oaraway, together with oarvene (p. 288). (VSlkel.)

Preparation. The portion of oil of caraway which passes over

between 225^ and 230^ is separated by repeated fractional distillation.

(Volkel.) When hydrosulphate of cairol ii digested ?rith dilate alcoholic potash* and the filtrate ii treated with water, carvol leparatea out, and may he dried and rectified with chloride of caldnm ; it then passes over at 250*. (Varrentrapp.)

Properties, Transparent, colonrless, mobile. Sp. gr. 0*953 at 15°. (Vblkel.) Boiling point above 250^ (Varrentrapp.) Smells like carvene. (Vblkel.)

Volkel. Varrentrapp. 20 C 120 .... 8000 80*17 .... 79-80

2 0 16 .... 10-67 10-36 .... 10-89

r!»H"0« 150 .... lOO'OO 10000 .... 100-00

According to VSlkel, it is C*»H'iO*, and therefore • carvene ((FH^) nrimu 3 At H and phu 8 At. O. Isomeric with cuminic aloohol, thymol and carvacrol.

Deeompositioni. 1. Carvol when heated appears to be transformed into carvaorol, and yields by distillation a strongly coloured, viscid oil. (Volkel.) — 2. By niirie aeid and oU of mtriol, it is violently attacked and resinised. — 3. By distillation with glacial phosphoric acid, it is converted into carvacrol. — 4. It likewise yields carvacrol when distilled with hydrate of potash. (Schweizer.) — 5. With alcoholic hydrosvlphate of ammonia, it forms hydrosnlphate of carvacrol. (Varrentrapp.) —» 6. When hydrochloric add and air are passed snccessively through carvol, hydrochlorate of carvol is formed, which contains 18*79 p. c. HCl, and is therefore C*H»*0», HCl (calculation 19-55 p. c. HCl). (Varrentrapp.)

Carvol absorbs hydrocyanic acid abundantly, and gives it off again completely when air is passed through it for some time. (Varrentrapp.)

CarvacroL C»H"0«.

ScnwBiZBR. J. pr. Chem. 24, 271; farther, 26, 118. Clau& J, pr. Chem. 25, 2G6.

Camphokreosot. (Clans.)

Formation. Together with carvene, when oil of caraway is distilled with glacial phosphoric aeid ; together with resin, when the same oil is

CARVACBOL. 415

diBf illed with pnlrerised hydrate of potash ; and with eyolution of hydro- gen^ when it is distilled with potassium ; also, mixed with carvene, when oil of caraway is repeatedly distilled with iodine, as long as hydriodic acid is evolved, and the dfistillate then decomposed by aqueous potash. (Schweizer.^ — Produced also by distilling campnor with an equal weight of iodine, tne other products of the reaction being camphin, colophene, and camphoresin ^Clans) ; also by beating carvol with fused phosphoric acid or pulverised nydrate of potash. (Voikel, J, pr, Chem, 30, 376.) — By distilling oil of thuja with iodine, being then accompanied by thujone and colophene ; — or, together with resin, by distilling the same oil with pulverised hydrate of potash, (Schweizer, Jr. pr» Chm. 30, 376.)

Preparation. 1. Oil of caraway is distilled over glacial phosphoric acid, till all the carvene has passed over and the difficultly volatile oil which remains is decanted from the hydrated phosphoric acid and distilled per se, — 2. Oil of caraway is distilled with pulverised hydrate of potash, carvene then passing over ; the residue is dissolved in water, poured off from the resin which separates, and mixed with dilute sulphuric acid ; and the thick mixture of resin and carvacrol which separates is distilled per 9e. (Schweizer.) — 3. Common camphor is distilled with an equal weight of iodine, wnereupon camphin first passes over, and when the residue is more strongly heated, a distillate mixed with colophene is obtained. This distillate is dissolved in potash-ley and separated from the solution by an acid; and the resulting oil is distilled over lime. (Clans.)

Properiie$, Transparent, colourless or yellowish, viscid oil. Heavier than wa^r ^Schweizer), lighter than water. (Clans.) — Boiling point almost exactly 332^ ^Schweizer.) — Has an odour like that of creosote (Vblkel, Clans); peculiarly disagreeable; the vapour is punffent and excites coughing ; the taste is persistent, strong and biting (Schweizer), like that of creosote, sweetish at firsts afterwards scratching. (Claus.)

14 H	... 120 ... 14	.... 80*00 .... 9 OO .....1 .... 10-67	Schweiser. a. 5. ,.. 8073 .... 80*35 9 '66 .... 9*42
2 0	... 16	... 9-61 .... 10-23
C»H"0« .....	... 150	.... 100-00	... 10000 .... 10000

«, preiMred with phosphoric acid ; h with hydrate of potash. Its formala is C«H»0S (Schweiser); it is carrol (C»H«0»)— HO - C"H*0« (Volkd) ; isomeric with thymol (Cahonrs, Gerhardt, TVoi/l, 3, 615.) Claus's eampho-ereoiote is identical with carracrol. (Schwdser.)

DeoompotUiofu. 1. Carvacrol when 9el cnftr^ bums with a bright^

very smoky flame. — 2. With nitrio acid^ it forma, with evolution

of nitrons acid, a yellow resin (which is more soluble in water than the resin obtained with carrene (p. 284) ; its alcoholic solution produces deep reddish yellow stains, and is not precipitated by neutral acetate of lead. — 3. Heated with

po(€t$$iumf it gives off hydrogen, becomes dark brown, more viscid, and finally hard, and, if water be then added, carvacrol separates, contaminated with a small quantity of a brown resin insoluble in aqueous potash.

416 PRIMARY NUCLEUS (?*H": OXTGEN-NUCLEUS C*»H"0'.

Acids added to tLe solution, separate an additional quantity of carvacrol and a resin soluble in potash. These resins are produced by the action of the resulting hydrate of potash on the carvacrol. — 4. With hydrate of potash, it becomes warm and immediately assumes a dark brown colour, thickens when heated, and on addition of water, deposits a resin insoluble in potash-ley, while the solution, after addition of acids, yields a resrn

soluble in potash-ley. — Both these resins are identical with those which are pro- duced by the action of hydrate of potash on oil of caraway. — 5. It absorbs anuno^

nia^ becoming more mobile and red-brown, but gives off all the ammonia when heated, leaving a quantity of red-brown resin.

Alcoholic carracrol does not precipitate neutral acetate of lead. (Schweisor.) It coagulates white of egg. (Claus.) — Carvacrol is somewhat soluble in water, and dissolves with Ceu^ility in aqueous potash, in cUcohol, and in ether.

Appendix to Oarvol,

Crude Oil of Caraway.

The volatile oil obtained by distilling with water the seeds of Carum Carvi, is a mixture of carvene (p. 283) and oarvol. (Schweizer, Volkel.) Dry seeds yield 4*37 p. c. (TrommsdorflE), 4*17 (Martius, Reperi,

39, 242), 312 (Rayhaud), 5-12 (Hopff, Jahrb. pr. Fharm. 1299), 4 p. c; Saxon seeds, 3 p. c. (van Hees, Fhami, Centr. 1847, 380.) To obtain the whole of the oil, the caraway-seeds must be distilled with water several times. (Martius.)

Crude oil of caraway varies from pale-yellow to colourless ; it is mobile, of sp. gr. 0-94 (Lewis), 0*938 (Volkel), 091 3— 0-926 (van Hees), 0-91 to 0*97. (Zeller.) It begins to boil at 175^ giving off chiefly carvene at first, then carvol, as the temperature rises to 232"", and leaves a slight viscid residue. (Vblkel.) According to Biaio {Brugn, Giom. 19, 360), it solidifies partially on cooling. Smells of caraway, and has a burning, sharply bitterish taste, less powerful than that of the first portion of the distillate. (Schweizer.) According to Vblkel, it contains from 8610 to 76-80 p. c carbon and 11*09 to 9*22 p. c. hydrogen, according as it consists in greater part of carvene or of carvol. Similar results were obtained by Schweizer, J. pr. Chem. 24, 257 ; Ann, Fharm,

40, 329 ; Rw, scient. 8, 195.)

By exposure to light and air, it becomes darker : the same change takes place spontaneously by keeping, in consequence of the formation of a volatile substance (whidi may he separated by heating the altered oil with half its Tolume of aqueous potash, precipiUting the oil with water, and distilling. (Volkel)

Every time that the crude oil is distilled, there remains, according to

V5lkel, a thick coloured residue (probably from partial decomposition of the carvol), or, according to Schweizer, a reddish yellow, brittle resin, soluble in absolute alcohol and ether, and containmg 75*15 p. o. C, 8-98 H, and 25-87 0, — It dissolves when heated, a mixture of sulphur and phosphorus, formine an offensive-smelling oil volatile after boiling with potash, and probably also spontaneously inflammable phosphoretted hydrogen. (Schweizer.) — It dissolves iodine with dark brown -red colour, rise of temperature and slight detonation (Flaschhoffj Br, Atdh. 33, 225)|

HTDROSULPHATB OF CARVOU 417

becoming thick and resinons. (Winckler, Repert, 83^ 185.) When the dark brown solation of iodine in oil of caraway is repeatedly distilled^ it gires off hydriodic acid^ assnmes first a yellow, afterwards on cooling, a red coloar, and, if then distilled, yields carrene and a residue of caryacrol. ^Schweizer.) — Only old oil of caraway becomes hot and detonates with iodine. (Zeller, Stud, uher. ather. Oele, Landan, 1850.)/ — With fuming nitric <icid, oil of caraway yields a black greasy resin (Hasse, Crdl, Ann. 1785, 1, 422), oxalic aoid (Gren, Crell. Ann. 1786, 2, 151 ; Grotthnss, i\r. GM, 8, 709.) With oil of vitriol, caraway-oil forms a black mass, with rise of temperatare and eyolution of sulphurons acid. (Schweizer.)

— With pulyerised hydrate of potash, it immediately assumes a deep brown colour; the mixture when repeatedly distilled yields colourless earyene, and leayes a thick, strongly intumescent mass, consisting of caryacrol, a resin soluble in aqueous potash^ and another insoluble therein. The resin which is left behind on treating the residue with aqueous potash, is dark brown, brittle, melts at 90^, dissolyes in alcohol and ether, and, contains 80*90 p. c. 0, 9*23 H, and 9'87 0 ; the resin which separates, together with the caryacrol, from the potash-solution on addition of oil of yitriol, is dark-brown, transparent, melts at 100°, is not precipitated from its alcoholic solution by neutral acetate of lead, and contains 77*88 p. o. C, 8*56 H, and 13*56 0. (Schweizer.) — Oil of caraway heated with alcoholic potash, leayes a soft, coloured resin, only partially soluble in aqueous potash. (Volkel, Ann. Pharm. 35, 308 and 85, 246.) — It is not altered by distillation oyer lime and hydrate of potash. (Schweizer.)

— Distilled with aqueous chromate of potash and sulphuric acid, it yields acetic acid and a peculiar acid, the greater part of which is howeyer decomposed by the chromic acid. (Persoz, Compt, rend, 13, 433; J. pr. Chem. 25, 59.) — Heated with finely diyided corrosive sublimate, it turns brown and afterwards black, giying off a large quantity of acid yapours. (J. Davy, FhU. Trans. 1822, 360.)

Cruae oil of caraway absorbs a large quantity of sulphuretted hydrogen gas, acquiring an offensive odour, and depositing after a few days a small quantity of sulphur. (Planche, J. Pharm. 8, 372.) It dissolves sulphur abundantly when heated, depositing it again on cooling ; likewise phos- pliorus; it does not dissolve chloride of calcium. It is somewhat soluble in vxUer, to which it imparts its odour and taste; it dissolves with facility in alcohol and ether. (Schweizer.)

Hydrosulpliate of Carvol-

C»H"0*S =r C?»H'*0»,HS.

Yarreiitrjlpp. LidAg, Poggendmf A W'dhler, Hand. d. Chem. 4, 686. St^fhydrate de earvol. (Gerhsrdt)

When the portion of oil of caraway (principally canrol), which distils above 190% is covered with an equal volume of alcoholic hydrosulphate of ammonia, and left to stand for naif an hour, it yields crystals of hydro* sulphate of earvol, which, after the mother-liquor has been drained off, may be washed with alcohol and recrystallised from hot alcohol.

yoL, ziy. 2 b

418 PRIMARY NUCLEUS C»H»8; OXYGEN-NUCLEUS C»H»*0«.

White eilkj needleSi often more than an inch long and half a line broad, melting when heated| and for th^ mo9t part volatile without decomposition.

20 0	.... 120	.... 71-86 •... 0*90 .... 9-68 .... 9-58	Varrentrapp. 71*9
15 H	• ••■ Av	9-0
2 0	•••• Id	9*4
S	.... 16	9-7
C»H"0»,HS ....	.... 107	.... 100-00	1000

Bwms, when set on fire, with a bright, fuliginous flame, giving off sulphuric acid. — In alcoholic solution it is converted by sulphuretted hydrogen into hjdrosulphate of sulphocarvol. — Treated in the fused state with hydrochloric acid gas^ it gives off sulphuretted hydrogen and is converted into a brown oil, — Digested with dilute alcoholic potash^ It gives off sulphur and is converted into oarvol, which is precipitable bj water. — Mixed with peroxide of lead and heated to 153°, it is for the most part resinised, and when raised to a higher temperature, suddenly takes fire.

It dissolves in alcohol, especially after prolonged boiling, and crys- tallises on cooling, (Varrentrapp.)

Appendix to Hydrondphate of Oarvol.

Hydrosulphate of Sulphocarvol.

(7»H"S»,HS.

Varrentrapp. (1849.) Liehig,Poggendorf d: Wohler, ffandwott. d. Chem. 4, 686.

Preparation. 1. Sulphuretted hydrogen" is passed for a longjtime into hydrosulphate of carvol dissolved or suspended in alcohol ; the viscid slightly yellowish oil, which sinks to the bottom, is dissolved in 3-4 vol! ether; the solution is mixed with 18-24 vol. of strong alcohol, where^ upon, after standing for some time, it deposits white flocks which cake together into resinous lumps ; the whole is heated to the boiling point, and the resin which then becomes soft, is boiled once or twice more with fresh alcohol, the liquid being all the while strongly agitated. 2. Sul- phuretted hydroffen is passed for 10 to 20 hours through the decanted mother-liquor of hydrosulphate of carvol, which still contains oil and hydrosulphate of ammonia (p. 417} ; the viscid oil which separates is dissolved in ether, and precipitated from the solution by alcohol ; and the solution in ether and precipitation by alcohol are repeated two or three times.

Properties. White, brittle, easily friable resin, which melts to a ooloar- less oil at 70"", and at 40"^ may be stirred and drawn out into satiny threads.

SULPHOTHYMIO ACID, 419

Varrentrapp.

20 C 120 ..^ 65-58 ........ 65*68

15 H 15 .... 8-19 ........ 8-22

3 S 48 ..M 26-23 26-76

C»HMS«,HS 183 .... 100-00 100-66

Its ethereal solution forms with an ethereal solution of mercurie chh- fide, a white precipitate containing variable quantities of mercury (18*5 to 70*5 p. c.) and of chlorine (5*6 to 11*1 p. c), according as one or the other solution has been added in excess j the precipitate gives off hydrO' chloric ctdd in drying, but without alteration of external appearance. — Dissolved in a large Quantity of ether, it forms with bichloride of platinum precipitates of variable composition.

Sulphothymic Acid,

C*>H"SW = C»H"Q«,2S0».

A. JjALLBifAND. (1853.) Compt. rend. 37, 498; J. pr, Ohem. 60, 432; abstr. Ann, Fharm, 101, 120. — N.Ann. Chim, Fhya. 49, 150; abstr. Ann. Fharm. 102, 119.

ThymohchwrfehSure, 8ulfbthymn$Uur0»

Formation and FreparcUion. Thjonol dissolves abundantly in oil of vitriol at 50 — 60°, and solidifies on cooling to a crystalline mass, having only a faint red colour. By dissolving this mass in water, and saturating the solu- tion with carbonate of baryta or carbonate of lead, sulphothymate of baryta or lead is obtained, from which the sulphothymic acid may be separated, and crystallised by evaporating its aqueous solution in vacuo. — Thymol from ptychotis-oil dissolves in moderately warm oil of vitriol, forming a red liquid which solidifies on cooling, and when treated with hot water, yields a oolourlesi lolation (only a few red oil-drops remaining undissolved), which crystallises on cooling. The aryytali consist of a conjugated sulphuric acid, which forms crystallisable salts with baryta and oxide of lead ; but the quantity obtained was too small for analysis. (Stenhoqse.)

Froperii^. Translucent, pearly tables or prisms. Does not deliquesce on exposure to the air. Contains 2 At. water of crystallisation, and is therefore C»H»*SW + 2Aq.

Its aqueous solution^ treated with nitric acid, forms binitrothymol ; with sulphuric acid and peroxide of tnanganete oi bichromate of potash^ it forms thymoil.

Very soluble in toater.

With salifiable bases it forms the fulphothpmatea C^H'^MSK)*, which

crystallise in forms of the oblique prismatic system. They decompose

at 120°, with violet-red colouring and volatilisation of thymoL The

ammoniO'SaU, which separates from its aqueous solution in well-developed

crystals, and the potash and soda-salts, leave, when thus treated, anhydrous

bisulphates. TAs however they contain only 13 At. H and 8 At. O, the quantity of HO is too small by I At. for thU transformation t C^H^U&O^ » [(C»Hi«0> - HO)

+ MO.aso^. (Kr.)] — The sulphothymates dissolve very easily in water and in absolute alcohol, somewhat less in ether.

2 B 2

420 PKIMART NUCLEUS €»»«: OXTGBN-NUCLBUS C»H«0*.

Sulphacetothymic Acid.

(?*ff«*0" = OH»0»,C»H»0,2S0«.

Lallbmand. (1857.) y. Ann. Cfhim. Phys. A9, 150; abBtr. Ann. Fharm. 102, 120.

When thymol is diMolved in glacial acetic acid, aud oil of vitriol containing a little anhydrons salphurio acid is added to the mixtare, combination takes place at a gentle heat, and the liquid, on cooling, deposits a crystalline mass, which must be dried on porons earthenware, and freed from excess of acetic acid by leaving it over quicklime in vacuo.

The acid is soluble in water. With bases, it forms crystallisable salts, which become anhydrous without decomposition at 1 10% but are decom- posed, with liberation of acetic acid, when their aqueous solutions are boiled or quickly evaporated. The salts are soluble in water and in alcohol.

SulphacetothifnuUe of Baryta, C**H>%*0',BaO, is obtained by saturating the acid with carbonate of baryta.

Oxygen-nucleus C*H"0*.

Quassiin. C«>H"0« = C»HW0*,0*?

WiNCKi.BR. Beperi, 54, 85; further, 65, 74. WioQBRs. Ann. Fharm. 21, 40.

Discovered by Winckler in 1835, after Thomson (Syitem qf Chemutry, 4, 47), Pfeff, {SffMt. d. Mat. med. 2, 11) and Bnchner {Repert^ 24, 257), had described the behavionr to re-agents of the quassia-bitter which they had obtained as an extract. — Keller, {Repert, 52, 197) by precipitating with basic acetate of lead, the aqneons solutioa of old qnasaia-extract, which had become crystalline by standing, evaporating the filtrate to an extract after removing the lead by snlphuretted hydrogen, exhausting the extract frith alcohol, and evaporating the alcoholic solution to an extract — obtained crystals which he regarded as quassia-bitter, though Wiggers regarded them as nitre or common salt.

Q^ania'bitter, Qiuuritet Quotitn. — The bitter principle of the wood of Qmassm annara and Q. exeei$a, perhaps also of the bark of Qua$na Shnaruba, inasmuch as the alcoholic extract of this bark freed from malic and gallic acids by neutral acetate of lead, and from excess of lead by sulphuretted hydrogen, agrees in character with the quassia-bitter of the older authors (Morin, /. PAarm, 8, 57.)-^By distilling quassia- wood with water, Bennerscheidt, (JBr. Arch, 36, 255), obtained a white tabular mass, his guasna'Camphor, having a peculiar odour of quassia.

Preparation. 1. Three ounces of pulverised quassia-wood are ex- hausted with 2 lb. of 80 p. c. alcohol ; the tincture is evaporated in a water-bath j the residue dissolved in water; and the filtered solution evaporated to an extract. This extract is repeatedly treated with small quantities of absolute alcohol, as long as the alcohol acquires the bitter taste of quassia ; the filtrate is evaporated nearly to dryness ; and the residue is exhausted with hot water^ whereupon a small quantity of dark- brown resin remains, while the light yellow aolution, which most be

QUASSIIN. 421

decolorised by animal obarcoal^ yields crystals of quassia by gentle

evaporation. (Winckler.) From aquecuB extract of qnasBia prepared by himself, Winckler was not able by any prooeis whaterer to obtain qnaasiin, perhaps because the extract had already undergone some alteration. — 2. Eight pounds of onassiar

wood are boiled with water j the decoction is evaporated to 6 lbs. ; the cooled residae is mixed with slaked lime, whereby pectin is chiefly separated ; then left to stand, with frequent agitation ; filtered ; and the filtrate is evaporated nearly to dryness and boiled with alcohol of 80 to 00 p. c, which leaves gum, common salt, and nitre undissolved, and dissolves quassiin, together with brown colouring matter and small quantities of common salt and nitre. The alcohol is distilled off; and tne residue is evaporated to dryness, dissolved in the smallest possible quantity of absolute alcohol, and mixed with a small quantity of ether, which throws down brown colouring matter. The filtrate evaporated to dryness is redissolved in absolute alcohol, precipitated by ether, and this treatment is repeated till a nearly colourless residue is obtained by evaporation no longer containing crystals of quassiin. Lastly, the ether- alcoholic solution is poured upon a small quantity of water, and left to evaporate spontaneously, whereupon quassiin crystallises out If the Bobstanoes precipitated by ether are repeatedly treated with alcohol and ether as above, they yield a little more quassiin. (Wiggers.)

FroperHes. Crystallises by spontaneous evaporation ^m the ether* alcoholic solution mixed with water, or, on cooling from the hot aqueoos or slightly alcoholic solution, in white opaque, shining prisms, whicn lose I'd p. 0. m weight at 100^ in a current of air, and 0-37 p. c. more when heated to fusion. (Wiggers.) Very delicate slender needles, having a silky lustre. (Winckler.) — Melts somewhat less easily than colophony and solidifies to a transparent, yellowish, somewhat brittle mass. From solutions in absolute alcohol or ether, it is obtained as a transparent varnish, which becomes white and opaque when water is poured upon it, but does not crystallise. •—Permanent in the air, inodorous, neutral. Its taste is extremely bitter, like that of quassia-wood, but much more intense. (Wiggers.) According to Winckler, it has a slight alkaline reaction.

20 C . 120 .... 66-67 65-75

12 H ............ 12 .... 6-67 6-89

6 0 48 .... 26-66 27-36

C»H»0« 180 .... 100-00 100-00

So, according to Gerhardt (TVmV^, 4, 330); according to Wiggsn it is C^H^^ios,

Ikeompo9itum$, Quassiin, heated in a tube above its melting point, becomes more fluid, acquires a brown colour, chars, and gives off vapours which have an empyreumatic, rather acid odour, a [slightly bitter taste, and redden litmus. (Wiggers.) In the open fire, it bums like a resin, with a bright very smoky flame, and leaves a loose, easily combustible charcoal. (Wiggers.) — Nitric acid of sp. gr. 1*25 dissolves quassiin, apparently without alteration, and, with the aid of heat, converts it into oxalic acid, with evolution of nitrous gas. (Wiggers.) — Oil of vitriol dissolves quassiin at mean temperature, forming a colourless solution, from irhich water separates the quassiin, apparently unaltered ; on heating the solution, carbonisation takes place. (Wiggers.)

42fi PRIMARY NUCLEUS C»tt"! OXTGEN-NUCLEUS C»H»W.

Qaaflfiiin does not dissolre verj readily in water ^inokler) ; it dis- solves slowly in 222 pts. of water at 12*^, more easily m water containing foreign substances. (Wiggers.)

It does not neutralise acids. The solution in hydrochloric acid leaves when evaporated quassiiii free from hydrochloric acid. (Wiggers.) Ar^cordiug to Winckler, quassiin neutralises acids but slightly.

The aqueous solution of quassiin is not precipitated by iodine^ chlorine^ neutral or basic acetate of lead, or iron-salts, (Wiggers.) According to Winckler, it is precipitated by mercuric chloride; but, according to Wiggers, it is not.

Tannin precipitates quassiin from its alcoholic solution in thick white flocks. (Winckler.)

Quassiin didsolves easily in alcohoh especially in hot absolute alcohol. The saturated solution in alcohol of 90 p. c. is rendered turbtd by- water, but becomes clear again on adding a large quantity of water. (Wiggers.)

It is but sparingly soluble in etkeK

Oxygerirnucleus C*H"0*.

Ot)ianyL

DuBLAiic. (1832.) Anii. Chim. PKys, 49, 17. CouERBB. (1832.) Ann. Chim. Phys. 49, 44. — 50, 337.-59, 148. Regnault. Ann, Chim, Phys, 68, 157.

ANDERsok. R, Soc, Edinb. Transact. 20,847; Ann. Pharm, 88, 190; £. Soc. Edinb. Transact. 21, 204; Ann. Phai-m. 98, 44.

Oiuerb$*i Meemihe.

First observed by Dublanc ; prepared in the pure state by Couerbe.

Source. In opiUm. (Dublanc, Couerbe. "i

Formation. 1* By the slow action of dilute nitric acid on opian (narcotine), together with teropiammone, ootamine, opianio acid, and hemi- pinic acid ; but it csknnot be obtained with certainty* (Anderson.) — 2. By the action of strong caustic potash upon opianic acid, which is thereby resolved into opianyl and hemipinic acid. (Matthiessen & Foster, p. 429.)

Preparation. A. Prom Opium. I. Finely-cut Smyrna opium is exhausted with cold water; the filtrate is evaporated to 8° B. ; and the morphiuni and opian are precipitated by dilute ammonia. The filtrate evaporated to a syrup and then left for several weeks in a cool plao8» deposits brown crystals, which must be pressed and then dried at a gentle heat. The brown crystalline mass contains opianyl, meeonates, and other substances. It is exhausted with boiling alcohol of 36^ and the extracts are concentrated to one-third by distilling off the alcohol : the liquid then on cooling deposits crystals, which are purified by recrystallisation from boiling water, with addition of animal charcoal, then from hot ether. The motber-Uquor from which the crystals have separated, yields an additional quantity ai opidnyl by concentration. (Couerbe.)

2. Aqueous extract of opium dissolved in water, is precipitated at the

OPtANTL. 423

boiling heat with ammonia and then left to cool, wherenpon morphine separates, together with small quantities of opianjl and crystals of opian. The filtrate is evaporated down ; the meoonic acid precipitated with barjta-water ; the excess of baryta removed from the filtrate by car- bonate of ammonia ; the clear solution evaporated to a syrup ; the mother-liquor decanted after some days from the crystals of narceine which separate, then concentrated to a certain extent and treated with absolute ether, which takes up opianyl together with smaller quantities of opian and oil. The ether is evaporated ; the opianyl separated from the residue by water ; the hot aqueous solution decolorised by animal charcoal ; the filtrate brought to the crystallising point ; and the opianyl which separates, is purified by repeated crystallisation from water. (Pelletier, Ann. Okim. Fhys, 50, 252.) — The opUnyl precipiuted hj ammonia may also be extracted by absolate ether and purified like the rest*

3. The aqueous extract of opium is precipitated by chloride of calcium; the precipitated meconate of lime is filtered; the filtrate evaporated to the crystallising point, and separated from the deposited hydrochlorate of morphine ; and the dark mother-liquor is diluted with water, filtered from the flocks which separate, and treated with ammonia, which precipitates opian, thebaine, and a large quantity of resin. The filtrate is mixed with acetate of lead ; the excess of lead is removed from the filtered liquid by dilute sulphuric acid ; and the filtrate is neutralised with ammonia and evaporated to the crystallising point at a moderate heat, whereupon narceine separates out, and then sal-ammoniac by further concentration. The mother-liquor is repeatedly digested with 4- vol. ether at 26°, and the ether is distilled off from the extracts, a brown syrup then remaining. On treating this syrup with dilute hydrochloric acid, papaverine dissolves, and opianyl remains, in the form of a dark grey, crystalline powder, which, to free it from resin and purify It com- pletely, must be several times crystallised from boiling water, with addition of animal charcoal. (Anderson.)

B. From Opian. Opian is heated in the water-bath to 49° with 2*8 pts. of nitric acid of sp. gr. 1*4, and 8 pts. water, wherenpon it melts into a yellowish mass, dissolves slowly without eVolutinn of gas, if constantly stirred, and then gradually deposits crystalline terapiammone. The liquid is filtered through asbestos ; the filtrate saturated with potash- ley ; the solution again filtered from the precipitated cotarnine, and con- centrated to a small bulk ; erystallised nitre is removed, and the mother- liquor freed from carbonate ot potash by precipitation with alcohol ; the alcohol distilled off; and the cooled residue treated with hydrochloric acid, which precipitates opianic acid, hemipinic acid, and opianyl. If this precipitate be dissolved in a large quantity of boiling water, opianyl

crystallises out on cooling (mixed with a little opianic add, if the quantity of water

added was insufficient), and may be purified by reorystallisation from water or alcohol. (Anderson.)

P9'0pertie9. Slender, colourless, six-sided prisma, acuminated with two faces. (Couerbe.) White shining needles. (Anderson.) Melts at 90'', and solidifies again in an unctuous mass at 75°. It does not lose weight by prolonged fusion. Distils without alteration at 155° (Couerbe), not even at 270°. (Reguault, Ann. Chim. Phyt. 68, 158.) Melts under water at 77°, per u at 110°, and solidifies at 104*5°. When cautiously raised to a hiffh temperature, it volatilises, and sublimes in beautiful crystals. (Anderson.) Inodorous. Tasteless at first, but with sharp aftertaste. (Couerbe.) Its taste is bitter. (Anderson.)

424 PRIMARY NUCLEUS C»Hi«i OXYGEN-NUCLEUS C»H«»0«.

Couerbe. Regnault. Andenon,

meam^ mean, mean,

a, b.

6 C 120 .... 61-85 61-01 .... 61-39 .... 61*45 .... 61-64

10 H 10 .... 5-15 5-13 .... 5-34 .... 5-12 .... 5-26

8 O 64 .... 83-00 33-86 .... 33-27 .... 33-43 .... 33-10

C»H'0OS 194 .... 100-00 lOO'OO .... 10000 .... 100-00 ,.., 100-00

Coaerbe, Regnault tnd Anderson (a) analysed opianjl obtained from opium; Anderson (6) that from opian. Couerbe first gave for opianyl the formula CH^O^, tiiea eioHfiO, then C^H^oO^i which last is confirmed by the experiments of Regnault and of Anderson.

Decompositions. 1. Opianyl dissolves withonfc colour in diluU md^ phuric acid, becomes dark green when heated with it, rose-red on addition of alcohol, and green again after dilution of the alcohol. Water added to the green solution throws down brown flocks, which dis8o1>re in sol- phuric acid with green, in alcohol and ether with red colour : the alcoholic solution of these flocks is precipitated bj the salts of oxide of lead, bin- oxide of tin, and alumina. (Couerbe.) — With strong stdphuric acid^ it forms a colourless solution, which becomes purple when heated, brown on addition of water, depositing at the same time a brown precipitate which dissolves with red colour in alkalis. (Anderson.) — 2. With chlorine, it

forms chloropianyl. (Anderson.) Chlorine acts but slightly on opianyl at ordinary temperatures, but is rapidly absorbed by melting opianyl, forming a red and then a dark brown mass, which melts at a higher temperature tiian opianyl, and solidifies in the crystalline form on cooling. It contains mechloic acid, meconin-resin, and 25-54 p. c. chlorine. (Couerbe.) — 3. Opianyl is not altered by iodine, but when treated with chloride of iodine, it forms iodopianyl ; with bromine^ UHiter, it forms bromopianyl. (Anderson.) — 4. Nitric acid, either diluto or concentrated, converts opianyl into meconin-hyponitric acid (Couerbe); into nitropianyl, with evolution of red vapours (Anderson). — 5. With peroxide of lead and dilute sulphuric acid, it gives off carbonic acid, and forms an amorphous substance, which remains dissolved. ^Anderson.)

Combinations. With Water. — A. Hydrate of Opianyl, C»H»«0* -f A^., was once accidentally obtained in the decomposition of opianyl by nitric acid. Resembles annydrous opianyl^ but is lighter and melts at 96*1^« (Anderson.)

At 100* Anderson*

20 C 120 .... 59-11 ........ 58-84

11 H 11 .... 6-41 5-29

9 O 72 .... 35-48 35-87

C»H»0O8 + Aq 203 .... 100*00 . 100-00

B. Aqueous Opianyl, — Opianyl dissolves in 265*7 pts. of cold water ^Couerbe); in 700 pts. at 15-5 (Anderson). It dissolves in 18*56 pts. (Couerbe) ; in 22 pts. (Anderson) of boiling water.

Opianyl dissolves without alteration in hydrochloric add; it is in- soluble in amjnonia, bnt dissolves in potash and in sodorley, and is precipitated therefrom by carbonate of ammonia or by acids (Couerbe). it appears not to dissolve more readily in alkalis than in water ; does not unite with metallic oxides, and is not precipitated by basic acetate of lead*

(Anderson.) It is not precipitated by solution of neutral acetate of lead, but the basic acid precipitates it, forming with it a crystalline oompoond of very variable com- position, containing 8 to 39 p. c. oxide of lead. (Couerbe.)

Opianyl dissolves in alcohol, ether, acetic acid (Couerbe, Anderson), and volatile oils. (Couerbe.)

Other combinatione. With stearic add.

MBCONIN-RESIN. 425

Appendix to OpianyU

Mechloic Acid.

CouERBE. Ann. OUm. Phyt. 50, 343; further^ 59, 148. Meehlorsattre, Acide mSehlofque*

JF\nrmation and Preparation, When chlorine is passed into melting opianyl, the mass becomes red, then dark brown, and solidifies in the crystalline form on cooling. The mass which is nearly insoluble in water, and sparingly soluble in ether, is treated with boiling alcohol of sp. gr. 0*833, whereby a solution is formed which yields crystal- line granules by spontaneous CTaporation. The yellow acid mother-liquor contains the greater part of the absorbed chlorine. The crystalline grannies are colourless, melt at 125*, Tolatiliae at 190*" •— 192** with an odour of jasmin, deoompoeing partially at the same time, and yielding drops of a yellow oil which solidifies on cooling and contains 5*43 p. c. chlorine. This is dissoWed in potash-ley and the boiling solution is saturated with nitric acid, whereupon the mechloic add crystallises in prisms on cooling. The chlorinated crystalline granules may likewise be dissolved in weak alcohol, and Uie solu- tion treated with oxide of silver, the add crystallising as the filtrate evaporatesi la pearly scales which are converted by crystallisation into four-sided prisms.

Long foux^ded needles, which mdt at 160% and have an acid reaction.

Cdlctdatitm according to Couerhe* Conerbe.

14 C 84 .... 49-12 48-63

7 H 7 .... 4-09 406

10 0 80 .... 46-79 47-31

C"H70» 171 .... 100-00 100-00

Volatilises at 165, leaving a small quantity of charcoal. It is not decomposed by ot7 qf vitriol or hydrochloric acidf but nitric acid decomposes itj apparently without formation of oxalic acid.

It dissolves sparingly in cold, more freely in boiling water, Predpitatea lead'ialte but not those of /tme, tron, copper, mercury , or eilver,'^

Dissolves in boiling alcohol and in ether,.

Meconln-reBin.

CouBRBB. Ann, CMm, Phye. 53, 352; fVirther, 59» 150.

When the chlorinated mother-liquor from which mechloic add has separated (vid, eup.) is mixed with water, a brown chlorinated resin is deposited, from which the cUorine may be extracted by boiling with aqneous carbonato of soda*

Coueriie.

10 c ....... 5 H	..... 60 .... 46-51 .... •^ 4*fi7	.... 46-65 .... 8-79
8 0	>•••• 04 •«•■ 4«F Oa ••••	.... 49-56

C>»H»0> 129 .... 100-00 ........ 100-00

According to Anderson, (Ann, Pharm, 98« 68), it is perhaps bichloropianyl. Insoluble in water, soluble in ether.

426 PRIMART NUCLEUS C^H"; OXYGEN-NUCLEUS C»H»0».

Opiansulphurous Acid«

WoHLBR. Ann. Pharm. 50, 10.

Formation and Preparation. Hot aoneons opianic acid absorbs a large quantity of sulphuroas acid gas, and, when the solation cools, no opianic acid crystallises oat, provided the qaantity present is not too great, and a sufficient degree of heat has been applied. The eolation evaporated at a gentle heat leaves opiansulphurous acid, generally some- what moist from adhering sulphuric acid. The lulphuric acid is not pmcDt in the receotlj prepared liquid, and it merdf an accidental product. (Wohler.) Perhaps it is produced bj the redaction of the opianic acid to opianjl, which then unites with the sulphurous acid : C»Ht<^0^ + 4SOS + 2U0-oC»H100B,2S0' + 2(SO>,aO). (Gtr- hardt, TrtUii 4, 86.)

Fi'opertiet, Inodorous, finely-crystalline mass. Has a peculiar bitter taste, with sweetish aftertaste.

Opiansulphurous acid, is, according to WOhler C*H'0^2S0'; according to Ger- hardt, either C>bH"0",2SO> or C*'H"Ob,2SO*, in the latter case, comparable with the acid (and its analogues) whose animonia>saIt maj be supposed to be formed by the com- bination of bitter almond oil with bisulphite of ammonia (zii, 27.) The latter formula (perhaps in itself the most probable) does not however ezplain the resolution of opian- sulphurous acid into opianic acid and sulphurous acid, and is reconcilable with WShler's determination of the water in the lead-salt, only on the supposition that the salt was decomposed at the temperature employed to drive off the water. (Kr.)

Deeompontions. When tcater is poured upon opiansulphurous acid, it becomes milk-white, and dissolves partly unaecomposed, whilst another portion is resolved into opianic acid which separates, and sulphurous acid which dissolves. — It reduces teleniovs acidf after addition of hydro- chloric acid. — With terchloride of gold, it forms metallic gold aud opianic acid.

Combinations. The carbonates of barium and lead dissolve in a solution of opianic acid in sulphurous acid, forming crystallisable salts which are not decomposed by nitric acid, and only partially by chlorine.

OpiansulphUe of Baryta. — Colourless, shining^ rhombohedral tables, which become milk-white at 140°, giving ufi* their water of crystallisatioa and then decomposing. It is sparingly soluble in water. According to Wbhler, it is CJ*H«BaO*,2SO« + 3Aq, according to Gerhardt, C«H*BaOS 2SO« + 3Aq.

Opiansufpkite of Lead. — Colourless, strongly shining, four-sided prisms, with two very broad lateral faces, and acuminated with two faces, whereby six-sided tables are produced. Permanent in the air.

At 100° it becomes milk-white, then yellow by exposure to light It gives off 6*5 p. o. water at 180°, and the rest at 170°, in all 1 3*68 p. c. (C»H7PbO8,2SO* + 6Aq.«l307p. c. A<}.), assuming ft yellow colour and emitting an odour of sulphurous acid.

OPIANIC ACID. 427

OaiekMUtn acewding to Gerhardi, WoUer. 0. ft.

20 C 29-05 20 C SO-23 .... 29*23

13 H 3-15 13 H 3-27 .... 300

17 O 32-93 15 O BO-23 .... 83*00

2 S 7*75 2 S 8*06 .... 810

PbO 27*12 PbO 28-21 .... 2667

C»H?PbO«,2SO« + 6 Aq 100*00 C»H»PbO»,2SO» + 4Aq .... 10000 .... 100*00

According to Wtthlcr, it is C»H«Pb08,2SO* 4.6 Aq. (p. 426). The 4 At. water of fonnula b correspond to 9*07 p. c.

Opianic Acid.

LiBBiQ & WbHLBB. (1848.) Ann. Pharm. 44, 126.

WoHLER. Ann, Pharm. 50, 1 .

J. Blyth. Ann. Pharm. 50, 36.

Laurent. Compt. rend. 20, 1118; iV. Ann. Chim. Phys. 19, 372; J. pr,

Chem. 40, 408; Ann. Pharm. 62, 105; Compt.rend. 21, 1118; further,

24, 219; J^. Ann. Chim. Phy%. 19, 370; Pharm. Centr. 1847. 381. Anderson. R. Soc. Edinb. Trans. 20, 347; Ann. Pharm. 86, 179; J.

pr. Chem. 67, 358. — B. Soc. Edinb. Transact. 21, 204; abstr. Ann.

Pharm. 98, 44; N. Ann. Chim. Phys. 46, 105; Chem. Centr. 1856,

450.

Foj'mation, 1. In the oxidation of opian (narcotine) by peroxide of manganese and salphuric acid (Liebig & Wohler), by peroxide of lead and Bulpharic acid. fMarchand.) — 2. By boiling hydrochlorate of opian with excess of bichloride of platinum and water. (Bljth.^ —

3. By the action of dilute boiling nitric acid upon opian. (Anderson.) —

4. By boiling teropiammone with pot-ash-ley. (Anderson.)

Preparation. 1. Opian is dissolved in excess of dilute sulphuric acid ; finel 7 pulverised peroxide of manganese is added ; and the liquid is heated to the boiling point, whereupon it tarns yellow and gives off carbonic acid ; the boiling is continued, with frequent addition of peroxide of manganese and sulphuric acid, so as to keep both in excess, as lon^ as carbonic acid continues to escape ; and the liquid is filtered at the boiling heat, — the straw-yellow filtrate then depositing yellow crystals of opianio acid as it cools. — These crystals are triturated and thrown upon a filter, then pressed, washed several times with cold water, again strongly pressed, heated to boilinff with hypochlorite of soda till they become quit« colourless, and gradually mixed with excess of hydrochloric acid : the liquid then on cooling deposits crystals of opianic acid, which are washed with water, strongly pressed, and purified by recr^stallisation from boiling water. The mother- liquor yields a little more acid by evaporation. — 2. Opian dissolved in dilute hydrochloric acid is boiled with excess of bichloride of platinum and water for half an hour, whereupon the liquid first assumes an orange then a dark red colour, and the platinum-salt, which has also become dark-coloured, melts. The liquid is filtered hot, and the impure opianic acid, which erystallises from th6 filtrate on

428 PRIMARY NUCLEUS C»H'«: OXYGBN-NUCLEUS C»HM(y».

cooling, is purified bj recrystallisatioii. (Bljth.) The mother.liqaor yields more opianic acid by evaporation. — The mother-liquor of the preparation of opianyl (p. 423, B) likewise yields a little opianic acid by evaporation, (Anderson.)

Froperties, Uoloarless^ thia narrow prisms^ grouped in radiating masses. The presence of an extremely small quantity of zanthopenic acid coloors them uranium -yellow. The acid has a slightly bitter taste and a weak acid reaction. At 140^ it melts, without giving off water. It is not volatile, but creeps up the sides of hot glass vessels, so that it appears to distil over. ( Wohler.) Fused opianic acid remains soft, transparent, and of the consistence of turpentine for several hours after cooling, then begins to exhibit a milky whiteness from the surface inwards, and slowly hardens in the course of a few days, without however exhibiting any crystalline structure under the microscope. If water or alcohol be poured upon this amorphous opianic acid, while still transparent, it becomes milk-white, and if boiled with the liquid, is converted into a white earthy mass, a small quantity of which dissolves, and separates on cooling in white, apparently amorphous flocks. The latter, when examined by the microscope, present the appearance of a mixture of long threads and small four-sided crystals. Fused opianic acid is not dissolved by aqueous ammonia and only after prolonged boiling by aqueous potash.

					Wohler.	Blyth.
m\t \y <.M*.*..**.»*..	120	• •■•	5M4	.. 57*04 ....	d/*A(S .••..*■•	6702
x" aX .....i.. .••...**	10	••••	4*76	.. 4*09 ....	4 Ov *••.••.•	4*86
10 o		80	■ *•«	3810	.. 38*07 ....	3813	38-12
C»Hi»ow.	!•••••«	210	••••	100*00	.. 100*00 ....	100*00 ........	100-00
				Laurent.	Anderson.
					c.	d.
	c. H			. 57-10 .... 4*88 .... . 38*02 ....	.... 57*06 .... 6-00 .... .... 0/ 9O ....	66-96 4-98 38*06
		•••••«
^				100*00 ....	.... 100*00 ....	100*00

Wbhler analysed (a) opianic acid dried at 120^ ; (b) fused opianic add; Anderson {d) opianic add obtained by decomposition of teropiammone.

Wohler originally gaye the formula C>bH*0>®; but from his analyses, Gerhardt {Compi. ehim, 1, 61) calculated the formula above given, which was adopted by Bene- litts (jahresb. 24, 419), and has been confirmed by the analyses of Ijanrent and Ander* son.

Decompositions, 1. Opianic acid when heated in the air, fumes, vola- tilises with an odour of vanille, and bums with a bright, smoky flame.

— 2. In its boiling aaueous solution it is not apparently altered by stUphuretted hydrogen, out when the temperature falls to 70^ it is con- verted into sulphopianic acid, without the formation of any other product.

— 3. With stdphurous aeidy it forms opiansulphurous acid. -^ 4. OU of vitriol converts it into a colouring matter, which produces all the madder- colours with iron and alum mordants, and is perhaps alizarin. (Anderson.)

— 5. When melted in dry chlorine gas, it forms a reddish yellow resin. (W&hler.) — 6. Boiled with peroxide of lead and dilute sulphuric acid» it is converted into hemipinio acid. (Wbhler.)

C»H^io + 20 - CMH»0O»».

7. It is partially converted into hemipinic acid by boiling with aqueous

OPIANIC ACID. 429

bichloride of platinum, (Blyth.) — ^8. Evaporated nearly to dryness with an excess of strong potash, it is converted into opianyl and nemi- pinic acid« (Matthiessen & Foster. Froc, Roy, Soe. 1 1, 57.)

2C»HW0W « C»H»«08 + C»H«>0».

9. Distilled with concentrated hydriodio acid, it yields iodide of methyl and a non-volatile snbstanoei which is easily decomposed by heat, and oxidises readily in the air, especially in contact with alkalis. (Mat- thiessen 8c Foster.)ir

Combinations. Opianic acid is slightly soluble in cold wcUer, much more soluble in hot water, so that the solution solidifies completely on cooling. (Wohler.) — With bases, it forms the Opianates, all of which are soluble in water. — Hot aqueous opianic acid decomposes the carbo- nates of barium, lead» and silver, with e£fervescence.

Opianate of Ammonia, — Opianic acid absorbs ammonia gas, with rise of temperature^ and deliquesces instantly in aqueous ammonia. — The saturated solution of opianic acid in ammonia, mixed with alcohol, and left to evaporate, yields large tables. If the solution be evaporated even at a very gentle heat, a transparent amorphous mass is obtained, which when covered with water, becomes milk-white and dissolves but partially, leaving opiammone in the form of a white powder. (Wohler.)

Opianate of Baryta, Prisms united in radiating groups, which efflo- resce when heated, giving off 6 p. c. water (2 At. = 6 '00 p. c. Aq.), and dissolve very readily in water. (Wohler.)

Opianate of Lead. Obtained either in very brilliant transparent crystals apparently of the form of sphene, or in anhydrous, slender prisms united in tufts. The former crystals contain 5*4 p. c. water (2 At. = 5*44 p. c. Aq.), part of which they give off at 130^ and the rest at 150°, melting at the same time. Begins to decompose at 180°. — Dissolves with some difficulty in water, more readily in alcohol. (Wohler.)

WShlcr. Cryttali. at 100"*.

20 C 120-0 .... 36-27 36-23

11 H 110 .... 3-32 3-34

11 O 88-0 .... 26-61 26-81

PbO 111-8 .... 33-80 33-62

C»H»PbO» + 2 HO 830-8 .... 100-00 10000

Opianaie of Silver, — Short, translucent prisms, with a tinge of yellow, which however appears to be produced in the first instance by the action of light, the colour being afterwards unaffected by light, uives off its water of crystallisation towards 100°, and at 200° becomes opaque and melts into a liqnid of fine dark green colour and metallic lustre, after- wards acquiring a red metallic colour and ultimately leaving metallic silver. (Wbhler.)

20 0 9 H	Dred at 100^ 120 .... 87-86 9 .... 2-84	Wtthler.
9 O AgO...	...•..•.•..... lA .... W4b iX 116 .... 36-59	•I..M.. 22*36 36-69

C*>H*AgOW 317 .... 100-00 10000

Opianic acid dissolves in alcohol and ether.

480 PRIMARY NUCLEUS C^H": OXYGEN-NUCLEUS C»H»0«.

Hemipinic Acid,

WbHLBR. (1844.) Ann. Fharm. 50, 17. J. Blyth. Ann. Pharm. 50, 36, and 43. Anderson. Ann. Pharm, 86, 194.

Formation. 1. In the oxidation of opian (narcotine) by nitric acid (Anderson) j by peroxide of lead and snlphuric acid, or peroxide of manganese and hydrochloric acid. ^Wbbfer.) — 2. By boiling chloro- platinate of opian with aqueous bicnloride of platinum. (Blyth.) — 3. In the oxidation of opianic acid by peroxide of lead and sulphuric acid (Wohler) ; by bichloride of platinum. (Blyth.) — 4. By the action of potash on opianic acid. (Matthiessen & Foster, p. 429.)

Preparation. 1. Opianic acid is heated to the boiling point with water and peroxide of lead ; dilute sulphuric acid added by drops till carbonic acid begins to escape j the liquid left to cool partially ; a onan- tity of sulphuric acid dropt in sufficient to precipitate the whole oi the dissolved lead ; and the filtrate evaporated to the crystallising point.

(Wohler.) Unaltered opianic add often crystallises out first, and the liquid filtered therefrom yields crystals of hemipinic acid, which are easily purified by recrystallisation from the boiling saturated solution. (Wohler.) — 2. The mother-liquor obtained

in the precipitation of opianic acid as described at p. 427, 2, is slowly evaporated, after the whole of the opianic acid has separated from it. Tlie liquid then assumes a deep yellow colour, gives off a large quantity of hydrochloric acid gas, and yields by spontaneous evaporation, large, flat rhombohedrons of hemipinic acid, which, by quick recrystallisation from water, are converted into rhombic prisms. (Blyth.) — 3. The solution obtained as described at p. 423, B, from which opianic acid has separated, is precipitated with acetate of lead, and the precipitate is washed and decomposed by sulphuretted hydrogen. (Anderson.)

Properties. Colourless, oblique rhombic prisms (Wohler), or large flat rhombohedrons. (Blyth.) Has a slightly sour, somewhat astring- ent taste, and a strong acid reaction. (Wohler, Blyth.) Effloresces in the air. (Blyth.) Gives off 13-78 d. c. water (4 At. = 13*74 p. c. Aq.) below 100° j melts at 180^ and solidifles in a highly crystalline state on cooling. May be sublimed between two dishes, in shining lamina, like benzoic acid. (Wohler.)

Sfflorueed. \l'($hler. Blyth. Andenon.

20 0 120 .... 53-14 52-94 .... 61-93 .... 53-17

10 H 10 .... 4-42 4-65 .... 485 .... 464

12 O »6 .... 42-44 42-41 .... 42-49 .... 42.19

C2«H»0O» 226 .... 100 00 100-00 .... 99-27 .... 10000

Wohler formerly regarded hetni(»inic acid as C^^H^O^; it was first recognised as a hihasic acid by Laurent {Compi. rend. 20, 1118.)

Decompositions. Hemipinic acid burns with a luminous flame. (Wohler.) — Heated with peroxide of lead and dilute sulphuric acid, it appears to be completely resolved into carbonic acid and water. ( W ohler.) — Distilled with excess of concentrated hydriodic acid, it is

ACID PRODUCED BY DECOMPOSITION OF HEMIPINIC ACID. 431

completely resolved into carbonic acid, iodide of niethyli and an acid having the composition C^^H'O'. (Matthiessen & Foster, vid tVO

0»H»OW + 2HI » C"H«0« + 2C»H»I + 2C0».

CovnbinaHons. Hemipinic acid dissolves with difficulty in cold water (Wohler) ; more readily than opianio acid. (Blyth.)

Hemipinic acid is bibasio. (Laurent.) It forms hibcuie {nmtral) 9aUs C»H^M»0» and mcno-hasie {acid) salts C«H»MO". (Anderson.) The lead, silver, and ferric salts are insoluble. The last has a fine orange- yellow colour. (Blyth.)

HemipifiaU of Ammonia. — Crystals permanent in the air. (Wohler.)

Uemiphiate of Potash. — a. Mibasic. — Easily soluble ; crystallises with difficulty. (Anderson.) — 6. Monobaiic, — Obtained by half saturat- ing aqueous hemipinic acid with potash, and evaporating. — Forms thick, six-sided tables. Has a strong acid reaction. Contains 14*3 p. c. water of crystallisation (5 At. ^ 14*55 p. c. Aq.), which it gives off at 100^ Easily soluble in water and alcohol. (Anderson.)

AnderBon.

20 C 1200 .... 45-42 4504

9 H 90 .... 3-40 3-46

11 O 880 .... 33-32 33-62

KO 47-2 .... 17-86 17-88

C^H'KQM 264-2 .... 100-00 10000

ffemipinate of Lead, — White precipitate insoluble in water. It dissolves in aqueous acetate of lead and afterwards separates in trans- parent crystalline nodules. (Wohler.)

ffemipinate of Silver, — BibasiCf — White precipitate insoluble in water.

20 C 8 H	120 8	•... *7*«o .... .... A ol ... .... lo'lo ... .... 0^*73 ...	WSbler. Blyth. 27-19 .... 27-98 1*83 .... 2*00
10 O 2 Ago	80 232	1810 .... 17-27 52-88 .... 5275

C*H8Ag20W 440 .... 100-00 100-00 .... 10000

Coatains 53-05 p. c. AgO, (Anderaon.)

Hemipinic acid dissolves more readily in alcohol than in water. (Wohler.) It is easily soluble in ether, (Blyth.)

T Appendix to Hemipinic Add.

Acid produced by the decomposition of Hemipinic Acid.

C"H«0». A. MATTniBssBN & G. C. Foster. Proceedingi of the Royal Society, 1 1,58.

Obtained by distilling hemipinic acid with concentrated aqueous hydriodic acid (vid ntp.) and evaporatiiiff the residue on the water-bath : purified by crystallisation from water. It forms colourless, needle-shaped

432 PRIMARY NUCLEUS C^H": OXTGEN-NUCLEUS C^H»0«.

crystals. Ita aqueous solution has a strong acid reaction to test-paper. At 100", the crystals lose 14*80 p. c. water (8 HO =5 14*92 p. e), and slowly sublime,

Hatthiessen St Foster. Driid at 100*. mean,

14 C 84 .... 54*54 ^ 54-39

6H 6 .... 3*90 3*91

8 0 64 .... 41-56 41-70

C"H«08 154 .... 100-00 100*00

The composition of this acid assigns it a place in the following series.

a^HAQS OU of bitter almonds.

am^O^ Benzoic add.

CMHH)< Salicylic acid.

Ci4H<0> Add from hemipinic acid (M. & F.)

CWH«Ow GaUicadd. ?C"H«0« TannoxyUc add. Its behafionr with ferric chloride {inf,) connects it with salicylic and gslUc add.

Heated for some time to a little above 100°, it gradually becomes brown ; the same change takes place when a pwe aqueous solution is eyaporated on the water-bath, but appears to be prerented by the presence of a trace of hydriodio aoid.

It is moderately soluble in cold water; Tory soluble in hot water.

It has decided acid properties, but none of its salts have yet been obtained pure. Its alkcdine and alkaline'earthy salts are yery quickly coloured brown in the air. The Uad-sdlt is a yellowish white, curdy precipitate; the silvev'SaU decoiuposes almost instantaneously, even in the cold, with separation of metallic silver ; the copper-salt is decomposed at 100°, with separation of suboxide of copper. With sesquickloride of iron, the acid or its ammonia-salt gives an intense indiffo-blue coloration, which is destroyed by strong acids, and changed to blood-red by ammonia. In a clear mixture of sesquickloride of iron with red prussiate ofpotask, it causes an immediate precipitate of prussian blue.

The acid dissolves yery readily in hot alcohol and ether, %

Sulphopianic Acid.

C?^H»«»0« = C»H"0«,S»0*. WoBLER. Ann. Fharm. 50, 12.

Comp. page 428. When washed sulphuretted hydrogen gas is passed into aqueous opianio acid heated to 70 , the solution becomes turbid and deposits sulphopianic acid, the formation of which does not cease till after the sulphuretted hydrogen has been passed through the solution for a day.

Yellowish powder, which, if heated while still immersed in the mother-liquor, melts to a pale yellow, clear oil which solidifies on cooling. The alcoholic solution yields slender, pale yellow transparent prisms, which soften below 100 , melt completely below 100^, and cannot after* wards be obtained in the crystalline form by spontaneous eyapoiation oi their alcoholic solution.

OPIANATE OF ETHYL. 433

Amorpkma, Wdhler.

20 C 120 .... 53-10 53-15

10 H 10 ...* 4-42 ........ 4-19

2 S ;.;...«!. 82 «..: 14*10 .;..;;.. 14*32

8 P.. ;. 04 .... 28-32 28*34

C»H»*S»0« 226 .... 100*00 ^*..m lOOOO

It is therefore opianie add haiinir 2 At O repUloed hj 28| or 2HO by 2HS. W9hler Mriginally gaTe the formula C^H'SH)^, which was altered by Gerhardt {CompU ehim, 1, 61), and Laurent {Compt. rend. 20, 1118, 2\, 1418.)

DecomposUums, When heated abore its melting point, it etnitfi a fttrong sulpbur-yellow yapour, which thickens to fine yellow crystalline needles, insoluble in water, easily soluble in alcohol. — It hums with flame and the odour of sulphurous acid. — In alkaline solution, it decom- poses after a while, with formation of metalJio sulphide.

ConJbinaiionit, It disaolves in alkali$, forming a yellow 8<^tion which, wheti recently prepared, may be precipitated by acids without evolution of sulphuretted hydrogen.

Sulphopianate of Lead. — Ammoniacal sulphopianio acid added to neutral acetate of lead, throws down a copious brown-yellow precipitate which becomes brown-black after a while, under the liquid, and at the boiling heat is immediately converted into black sulphide of lead.

JSidph&pianate of Silver, ^- A solution of solphopianic acid in ammonia forms with nitrate of silver, a brown-yellow precipitate, which, if left under the liquid, changes after a while to black-brown sulphide of silver. If quickly filtered and dried in vacuo, the precipitate may be melted on paper without loss of weight. When burnt, it leaves black sulphide of silver. It contains quantities of silver varying from 28 to 37 per cent. (C»H'AgS*0»= 32-43 p. c. Ag.).

The same precipitates are obtained with lead- and silver-salts, by dissolving the sulphopianio acid in boiling mono-hydrosulphate of am- monia, volatilising the excess of the base, and then adding th& hletallic salts. Sulphopianio acid is therefore not a sulphide, since it combines, not with sulphur-bases, but with oxides.

Bttlphopianic difsolres readily io lUwhU, forming a yelloir eolntion.

Conjugated Compounds of the Opian-icriei.

Opianate of Ethyl,

(?*H"0» = C*H»0,C»HW.

WoHLER. Ann, Fharm. 50, 5. Anderson. Ann. Pharm. 86^ 108.

Opianie ether, Opiannaphtha, Opianidure-dtJar^ Opian^vinefier.

Formation and Preparation. -—yJlieTi a warm alcoholic solution of opianie acid is saturated with sulphurous acid, and the liqnid someifh&t concentrated, opianie ether crystallises out on cooling. ( Wohlet.)^- It

VOL. XIT.

2 F

434 PRIMARY NUCLEUS CPH": OXYGEN-NUCLEUS C»HWO«.

wafl once aocidentaily obtained by mixing alcoholic opianate of potash with hydrochloric acid. (Anderson.) It U not produced by Mturadog alco- holic opianic acid with hydrodiloric acid gai. (Wohler.)

Froperiies. Slender, white prisms united in tafts and spherical masses. (W5hler.) Colourless needles melting at 92-2® (Anderson), without loss of weight. fWdhler.) Under water it melts at 92-2^ (Anderson), near 100° (Wonler), forming a transparent oil which sinks to the bottom, and on cooling immediately solidifies, with great contrac- tion of volume, in white radiating masses, like warellite, — ^but if heated abore the melting point, remains soft and amorphous for a long time, even after cooling, and does not solidify for some time after. When heated between two basins, it sublimes without alteration. It is inodorous, has a slightly bitter taste, probably from decomposition. (Wbhler.)

24 0 14 H 10 0	M 144 .... 60*50 ... 14 .... 5-88 ... 80 .... 33*62 ...	W6hler. 60-50 ..... 5-77 33-73	Anderson. ... 59*86 .... 5*90 .... 34*24

C*H»0,C»H»0» 238 .... 10000 100-00 .... 100*00

Thia is Anderson's formula. WQhler formerly supposed it to be C^H*0,C*<^Ero*.

When heated per $e, it requires a very high temperature to decompose it ; but it is resolved into opianic acid and alcohol by boiling with water, and by distillation with potathrley^ (Wohler.)

It is insoluble in watefj but dissolves readily in aicohol and in ether.

Ethyl-hemipinic Acid.

(?*H"0" = C*H«0»,(?»H*0'*.

Andbbbon. Jim. ]?harm, 86» 195.

Aeid Hemipinic etJUr ; Atikerkemtpintdmrt, WeinhetnipimUure,

Produced by passing hydrochloric acid gas into a solution of hemi- pioic acid in absolute alcohol.

FroperUes, Needles grouped in tufts, which melt to a transparent liquid at 132-2^ when heated alone, and at the boiling point under water. It has a strong acid reaction. Oives off 9*93 p. c. water at 100" (calcu- lation 3 Aq.s=3*60 p. c).

Anderson*

24 C 144 .... 56*69 ........ 56*46

14 H 14 .... 5*51 ........ 5*67

12 0 96 .... 87-80 87*88

C«H»0,HO,C»H«0» 254 .... 100*00 ........ 100*00

Yields alcohol when boiled with potash.

It dissolves sparingly in cold, somewhat more freely in boiling utUer,

The ethvl-hemipinates are difficult to obtain pure. Aqueous hemt- iiinio acid does not precipitate lead or sUver salts, but forms a bulky, brown-yellow precipitate with iesquicMoride of iron.

OPIAMMONE. 435

EihyUhemipinaie of Baryta. — Obtained by digesting the acid with oarbonate of baryta. Small tufts of needles which appear to decompose with great facility.

Opiaminone.

C«H"NO»« = C«H"AdC",0«,

WoHLER. Ann. Pharm. 50, 6.

Bmopiammone (Anderson, Ann, Pharm, 86, 189.)

Formaiion. In the decomposition of opianate of ammonia by heat,

(Comp. ii7, 429.)

rreparaUon. A solution of opianic acid > in ammonia is evaporated to dryness at a gentle heat ; the transparent amorphoas residae is kept at a heat somewhat above 100° and constantly stirred as long as it smells of ammonia ; and the mass, which has now become pale yellow and insoluble in water, is freed by boiling with water from any opianate of ammonia that may have escaped decomposition.

Properties. Pale yellow powder consisting of microscopic, translacent, crystalline lamps ; m the perfectly pore state, it would probablv be colourless. Melts easily when heated, and creeps np the side of the vessel, without subliming.

Wohlcr, fnean.

4U V^ ttMM«.**t*l.MMI* ^4w ••.* V9*od •■••«.•• v9*oo

19 H . 19 .... 4-74 4-88

N...... ... 14 ^ 3-48 3-75

16 0 128 .... 31-93 31-51

C«H>»NOW 401 .... 100-00 10000

WQbler formerlf supposed it to be C^H^^NO^— Opiammone » 2 At. C»H><'0><> + 1 At. NH»— 4 At HO

DecompoBitions. 1. Opiammone somewhat strongly heated in contact with the air, smells like melting opianic acid, and gives off a yellow vapour. — 2. When it is boiled for some time with water, a small portion dissolves, probably in consequence of deoomposition. Heated with water to 150° in a sealed tube, it dissolves completely, forming a clear jpale yellow liquid, which on cooling deposits crystals of opianic acid, while opianate of ammonia remains in solution. — 8. It dissolves in cold oU of vitriol, forming an orange-yellow solution, which is rendered milky by water, but becomes clear again when heated, and deposits crystals of opianic acid on cooling, an ammoniacal salt being formed at the same time. -^ It is not altered by hot dilute acids. — 4. An aqueous solution of pure poteuh or carbonate of potath dissolves opiammone after a few seconds, with evolution of ammonia, forming a uranium-yellow solution. On boiling the solution, j- of the ammonia belonging to the opiammone escapes, and hvdrochloric acid then precipitates yellow flocks of xantho- penio acid, whilst the filtrate on cooling yields crystals of opianic acid mixed with zanthopenic acid.

2 F 2

436 PRIMARY NUCLEUS CMH": OXYGEN-NUCLEUS C»HWO«.

Opiammbne is insoluble in cold water. In boiling alcohol^ it dissolyes slowlj bnt abandftntljr, forlning a certain qnantitj of opianio Aoid^ which crystallises bj spontaneous evaporation. (Wohler.)

Appmiiimio OpUnnmom,

Zanthopenie Acid.

W5BLB&. Asm. Pharm, 50, 9.

Prepared by boilings opiammone with poteth-ley {tid* 'V*)*

Beantifiil y«Uow flocks, forming when dry, a lemon-yellow powder, which appears crystalline tinder the microscope. Fusible. Gitea off ammonia when heated with soda-lime. Dissolves in alkalU with fine yellow colour.

Teropiammone.

AKDfeRSOK* Ann. Pharm. 86, 187.

Produced in variable, but always veiy small quantity, together with many other p)*oducts, when opian is decomposed by dilute nitric acid (p. 423, B); purified by washiug with alcohol and recrystallisation from boiling alcohol.

Small colourless needles.

Anderson. At 100". mean,

60 C 360 .... 58-91 5920

29 H 29 .... 4-74 498

N 14 .... 2-29 212

26 O 208 .... 34-06 33-70

C»H»NO» 611 .... 10000 lOO'OO

Deetympotitioiiu, Cold oil of vitriol dissolves teropiammone with yellow, or, when heated, with fine crimson colour. — Teropiammone is not decomposed by hydrocklorie add or amfnonio, bnt nUriG acid decern* poses it ; it is also decomposed by potash into ammonia and opianio Acid.

It dissolves sparingly in cold, somewhat more in boiling alcohol and in ether, (Anderson.)

6E0MINATED OIL OF TURPENTINB, 437

Oxjfiodchnudeui C*^IH*0'.

lodopifuiyL

C»»IHW = C*IH*0«,0». Anderson. Ann, Pharm, 98, 48.

lodomeeonin, Hydrtere d'iodopianyle. (Gerhardt^ TVaiti, i, 1049.)

FornuUion and Preparation. When chloride of iodine is added to ftqneoufl opianyl, and the miztore left to itaelf for eeveral days in a wann place, long crystals form in it, contaminated hf free iodine. They are purified by recrystallisation frpm boiling alcohol.

Properties. Colourless needles, which melt at 112° to a colourless

liquid.

AnderBon.

20 C 1800 .... 87-48 3716

9 H 9-0 .... 2 81 2-96

I 1271 ...: 39-70 39-48

8 O 64-0 .... 20-01 20-40

C»IH»0» 320-1 .... ipOOO 100-00

Seetm^itmtianf. Mel^ at a temperatore abpye lOff" po a brown

liquid, which decomposes at a stronger heat, with yolatilisation of iodino. -— It dissolves in oil of vitriol, forming a dark-coloured liquid when heated. — It is decomposed by nitrie acid, with separation of iodine. It is nearly insoluble in toaUr, more soluble in alcohol and ether.

Bromine-^ucletu C**Bf*H".

Brominated Oil of Turpentine.

C*Br*H«. Dbyille. Ann. Chim. Phys. 75, 63; /. Pharm. 26, 678.

BromterpentAiiMlp TerpeHthtnoibromOr. (L9wig.) Sromure tTmenee de iiriben* ihme. (Derille.) EtMenee de iir^benthine guadribromi.

Formation and Preparation. Oil of turpentine is gradually mixed with small quantities of bromine, till a dark red, fuming, riacid, heavy liquid is produced ; this liquid is partially decolorised by animal charcoal ; and the free hydrobromic acid and water contained in it are removed by* agitation with chalk and chloride of calcium.

Properties. Sp. gr. 1*975 at 20°. — Dextro-rotatory.

Deyille. mean.

20 C 120 .... 20 W 27-43

4 Br 320 .... 70-79

12 H 12 .... 2-66 300

C»Br*H»* 462 .... 10000 ' ^

Isomeric with bromoterebene.

438 PRIMARY NUCLEUS C»HW^ OXYBROMINE-NUCLEUS C»BrHW.

Bromoterebene.

Dkville. Ann. Chim. Phyn. 75, 51; J. pi\ Ckem. 22, 92; J. Pharm. 26, 666.

When bromine is slowly dropped into well-cooled ierebene, till the liquid acquires a deep red colour, a large quantity of hvdrobromic acid is given off, and bromoterebene is formed, which may be decolorised, though not completely, by treatment with animal charcoal.

Reddish, viscid liquid, of sp. gr. 1-978 at 20^

Deyille. mean*

20 C 120 .... 26-55 27-43

4 Br 320 ..« 70-79

12 H 12 .^. 2-66 2-95

C»Br<H» 452 .... 100-00

Isomeric with brominated oil of turpentine.

When heated, it gives off hydrobromic acid (which yields free bromine, in contact with the air) and leaves a residue of charcoaL

Oxyhramine^tidetu C*BrH*0*,

Bromopianyl.

C»H»BrO« = C«BrH*0«,0».

Anderson. Ann. Phar . 98, 48.

Bromomeeonin, Hydrure de bromopianyle* (Gerhardt, TYaiti, 4, 1049.)

Ibrmatvon and Preparation. When bromine-water is gradually added to aqueous opianyl, crystals of bromopianyl separate out, and may be purified by recrystallisation from boiling alcohol.

Properties. Colourless needles, which melt at 167^, and behave ia other respects like chloropianyl.

Anderson.

20 C 120 .... 48-95 43*81

9 H 9 .... 3-29 3-40

Br 80 .... 29-30 ....... 29*21

8 O 64 .... 23-46 . 23-68

C»H»BrO» 273 .... 100-00 100-00

Dissolves sparingly in tvater, more readily in alcohol and ether.

CHLORINATED OIL OF TURPENTINE. 439

Chhrine^udetti C*»C1»H"^

Bichloroterebene.

C»C1«H".

Detillb. Ann. Chim. Phys. 75, 49; J. pr, Chem. 22, 91; /. Pharm* 26, 665; Pogg. 51, 433.

MonochlortirSb^ne.

When the prodoot obtained, together with hydrochloric acid and hjdrochlorate of terebene^ bj the diatilktion of quadrichloroterebene, is heated with a quantity of potash-ley sufficient to saturate the hydro* chloric acid which is set free;, bichloroterebene is produced, and may be dehydrated by rectification oyer chloride of calcium:

8C«>a<H» - 20C + 2C»CPH" + 8HCL (Derille.)

Colourless oil^ of sp. gr. 1*137 at 20"*; refracting power 1*5186 (Derille), 1*531. (Becquerel & Cahours, Poffff. 51, 427 •)

DevUk*

20 C ................ 120 .... 58*53 .m«.... 58*27

14 H .... 14 .... 6*84 6*83

<?»CPH" 205 .... lOO'OO

It is resolved by hmi into hydrochlorate of terebene (p. 874}| and residue of charcoal.

Chlarine-nudeus C»C1*Hm

Chlorinated Oil of Turpentine.

C»C1*H»

Detille. Ann. Chim. Phys. 75, 57; J> Pharm. 26, 672; J. pr» Ohenu 22,97. — Pogg. 51,433.

Cklorierptnihindl, Terpentmdlehloriir. (LSwig.) Chiaroemmpkim. (DeriUe.) C%/oroeafNpAof«» (Lanrent) Eaence de i^ribenikine qnadricMoH* (Gerhtrdt.)

FartnaHon and Preparation. — When chlorine gas is yery slowIjT passed over artificial camphor (p. 2%5\ a small quantitv of hydrochlorio acid gas is evolved, and there is formed a liquid coloured yellow br chloriue (C^H^'Cl^HCl, according to Deville), which decomposes with explosion, even in the atmosphere of chloriue, but still more in contact with the air, giving off hydrochloric acid gas and chlorine, and solidifying

to crystalline chlorinated oil of turpentine — It if also produced, mixed with qnadrichloroterebene, by passing chlorine into oil of tnq)entine (p. 248).

Properties. Cryatalline mass of sp. gr. 1*5 at 8^, and refractini^ power = 1*5448. Melts without volatilising between 110^ and 115. Has no optical rotatory power.

44Q PHIMARY NUCLEUS C»|I«5 CHLORINE-NUCLEUS C»C1*H«.

Deville. mean.

20 C 120 .... 43-79 43-54

4 CI 142 .... 61-83

12 H 12 .... 4-38 4-80

C»C1*H" 274 .... 100-00

Isomeric with qqadrichloroterebene.

Decompositions. When slowly heated, it gives off a large quantity of hydrochloric acid gas, with separation of charcoal, and yields a distillate consisting of chlorinated oil of turpentine, artificial camphor, a hody ooptaining less chlorine, probably C*^H^^C1'| and a large quantity of bydi;oohlorate of tarebene.

t.

. Quadriohloroterebene.

Dbtille. Ann. GUm. Phys, 75, 48; J. pr. Chem. 22, 90; J. Pharm. 26, 664. — Pcy^. 51, 433.

ChhroiSribhne.

FomuxHon and Preparation- Chlorine gas is passed through terebene well cooled and exposed to diffused day-light, as long as any of it is absorbed, whereiipon hydrochloric aoid gas is abundantly evolved, so that the bottle containing the terebene is liable to burst, unless it be frequently^

opened. — The compound is also obtained, together with chlorinated oil of turpentine, when chlorine gas is passed into oil of turpentine (p. 248).

Colourless viscid oil of sp. gr. 1 36 at 156**, refracting power=l •5294, and no rotatory power. Has a peculiar camphorous odour.

Deville. m€on.

20 C 120 .... 43-79 4367

4 CI 142 .... 61-83

12 H 12 .... 4-38 4-73

0»Cl<HO 274 .... 106-00

Isomeric with chlorinated oil of turpentine.

Qnadrichloroterebene blachens when heated, gives off a large quan- tity of hydrochloric apid gas, and yields a colourless distillate consieting qf aqueous hydrochloric acid gas. bicl^loroterebene, hydrochlorate of t^ro- I^ene, and undecomposed quadrichloroterebene, while charcoal f^mains behipd. If the heat be quickly applied, the distillate is red, |>Iue, and ultimatisly black, and contains a large quantity of hydrochlorate of terel^eae; 2C»Cl*H"=20q + C~H",HCl-7HCl. (Deville.)

TBRCHLOBOTHTMOL. 441

QayMorinMiucUm C*^C1H*0\

GhleropianyL

C«»C1H»0« = C*»C1HW,0» Anderson. Ann. Phai'm. 98, 47.

CMaromteonm^ ffydrur§ de ehloropimKyU. (Gerhardt, TVoiM, 4, 1049.)

FormaHon and Preparation, TV hen chlorine gas Is passed into a cold- saturated aqueous solution of opianyl, an abundant crop of crystals quickly separates, consisting of cliloropianyl, which may be purified by recrystallisation from alcohol. — It is likewise produced when dry chlo- rine gas is passed over melted opianyl.

Properties. Colourless needles, which melt at 175° and sublime un- decomposed at highes temperatures.

Andenoih

20 C 120-0 .... 52-Sl ., 52-45

9 H 90 .... 3-93 4-24

CI 85-5 .... 15-53 15-17

8 O 64-0 .... 28-03 2814

it . ^ ' ' II. ,■» ■ ■ ■

C»CIH«0»..... 228-5 .... iOO-OO 100-00

Decompositions. Dissolves in cold oil of vitriol^ assumes a greenish blue colour when heated therewith, and on subsequent addition of water deposits brown flocks which dissolye with red colour in alkalis. — It dissolves with red colour in nitric acid, and is decomposed by heating.

Combinations. It dissolves sparingly in cold, somewhat more freely in boilinfi; water, — in alkalis to about the same amount as in water, and without decomposition.

It is soluble in alcohol and in ether.

Oxychhrine^ucleuM C?*CI'H"0\

TerpUorothymoL

C»CPH'»0».

LAtLRMAiiB. (1856.) Compi. rend, 43, 876; If. Ann, Ohim. Phys, 49^ )58; Ann. Pharm. 101, 128, and 102, 122.

TJkjpnoUrickhrL Formation (p. 411).

Preparaiion. Chlorine gas is passed into ihjrmol in diffused day- light— cave being taken to avoid too much heating — till the thymol has absorbed a quantity of chlorine equal to «| of its weight. On leaving the

442 PRIMARY NUCLEUS C»H» ; OXTCHLORINE-NUCLBUS C»a<H«0<»

product to staudy long yellow needles are formed, which ultimately cause it to solidify : they may be purified by expressing the remaining Hqaid and recrystallising from ether-alcohoL

Lemon-yellow, oblique rhombic prisms, which melt at 61^ and hare an intoxicating odour.

The compound decomposes at 180*^. — Heated with oil of vitriol to 100^ it is converted into a colourless liquid, which floats on the oil of vitriol, solidifies on cooling, and, after solution in aqueous potash, preci- pitation with hydrochloric acid, and drying, forms silky, talc-like flocks. This substance has at first an agreeable odour of beniEoin, melts at 45% and distils without decomposition at 250** ; it dissolves in ammonia and forms a salt, crystallising in slender needles, — whence it is probably terohlorocarbolic acid ; (xi, 181) with which it appears to agree in com- position.

Oxychlorin&^iudetu C**C1*H'0'.

QnintichlorotliymoL

C»C1»H»0«.

Lallemand. (1856.) Compt. rend. 43. 376; iT. Ann. Chinu Php9. 49« 158; Ann. Fharm. 10, 123, and 102, 123.

Thymol pentachlori ou quinUehlorS. Formation (p. 411).

Preparation. When thymol is exposed for a considerable time to the action of dry chlorine gas in bright daylight, a reddish yellow gluti- nous oil is formed, in which, after a while, crystals of quintichlorothymol make their appearance : they may be purified by recrystallisation from ether.

Properties, Colourless, very hard crystals, having the form of ter- chlorothymol (aocordinr to another statement of Ldlemand, it hu the form of thymol), melting at 98 , and containing 55 p. c. chlorine (oalcnktion « 65-03 CI).

Decomposes at 200^, giving ofl* hydrochloric acid gas and propylene gas (G*H*), while a solid product (terchlorotoluenol) collects in the neck of the retort) and charcoal remains behind t

2C»H»C1«02 - C"H*a»0« + C«H« + 7HCI + 2C0 + ISC

In ODe experiment, in which very pure quintichlorothymol was heated, the carbonic oxide evolved towards Uie end of the process was mixed with marah-gas, and the aolid distillate, melting at 150% and crystallising from alcohol in needles, had the composition Ci^H^Cl^O^, and was therefore qnadrichlorotolnenol : 2C»H«Cro> - C^HK^IH)* + C«H< + 6HC1 + CH* + 2CO + 17C. Impure quintichlorothymol yielded also by distillation a large quantity of liquid product, which, after the solid products had been removed by weak potash-ley. boiled at 265* (or, according to Lallemand's first statement, at 365**), and had the composition of bichlorocumol (xiii, 346V — Stenhouse, by passing chlorine-gas over the crystals from ptychotis-oil (p. 411) previously examined by him {Ann. Pharm. 93, 269), obtained dark yellow crystals, which were less soluble in cold alcohol and ether than thymol, and after recrystallisation from hot alcohol* pressing and drying in vacuo, contained 40*26 p. c. C, 3*99 H, 43*09 CI, and 12*66 O, whence Stenhouse deduced the formula C^Cra^'^^.

MECONIN-HYPONITRIC ACID. 443

OxynUro-mtcUiu C^'XH'O*.

Mitropianyl.

C»H»NO» = C*XHW,0«.

Anderson. E. Soc. Edinburgh Transact. 21, 204; Ann. PAarm. 98, 46.

Niiromeeonin, Hydrure de nttropianyle, (Gerbardt, Traiti 4, 1049.)

Foi'matwn and Preparation. Opianjl dissolves abundantly in cold concentrated nitric acid, the solution giving off red fames wben heated. On diluting with water, bulky crystals separate, which may be obtained pure by washing and recrystallisation from boiling alcohol.

Properties. White needles and prisms, melting at 160^ to a trans- parent liquid, which solidifies in the crystalline form on cooling. Neutral*

Anderson.

20 C ......... 120 .... 50-20 50-11

9 H 9 .... 3-76 3-92

N 14 .... 6-85

12 O 96 .... 40-19

CWLH»08„ 239 .... 100-00

Decompositions. 1. Heated in small quantities on platinum-foil, it volatilises almost without decomposition, leaving only a small quantity of charcoal ; but, if heated ia a test-tube, it decomposes suddenly and leaves a large quantity of porous charcoal. — 2. With oil of vitriol, it turns yellow, and dissolves to a red liquid when heated. — 8. Boiled with ammonia or potash, it forms, without decomposition, a yellow solution which does not deposit anything on cooling or on addition of acids.

Combinations, Nitropianyl dissolves sparingly in cold, somewhat more freely in boiling water : it is insoluble in hydrochloi'ie acid, but dissolves in cold strong nitric acid, separating in flocks when the solution is diluted. In cold ammonia and potash, it is not more soluble than in water. It is not precipitated by metalUc salts*

It dissolves in boiling alcoJiol and ether.

Appendix to NUropianyU

Meconin-hyponitrio Add.

C«H»NOa.

CouBRBB. Ann. Chim* Phys, 50,347, and 59, 141.

Add hyponitromeeoni^ue, MeeoninunterialpetersHvre, MeeoninsaJpelerMaure, Nitromeeonintaure.

Formation and Preparation. When the solntion of opianyl in nitric acid is exposed to dryness in the water -bath, a fused mass remains, which solidifies in the crystalline form on cooling. It is purified by recrystallisation from water and alcohol. —Anderson (Ann. Pharm. 98, 47) did not obtain it by this process.

444 PRIMARY NUCLBU8 C»HWf OXTNITRO*HUCLEUS C»X«HmO».

PropertieM, Coloarless or slightly yellow* long, thin, four-aided prisms with rectangular base. Has a strong acid reaction. Melts at 150^.

Couerbe.

20 C 120 .... 60-20 50-24

9 H 9 .... 3-76 3-98

N 14 .... 5-85 . . 6-36

12 O : 96 .... 40-19 39-42

C»H»NO» 239 .... 100-OQ lOOQO

It is perhaps identical with Anderson's nitropianyl, to which, howeyeri AAdervon ascribes other properties.

Decompoaitiont, Sublimes at 190% with partial decomposition and the odour of bitter almonds. — When thrown on red-hot coals, it takes fire and bums away.

Combinationi, The compound dissolves in water, with light yellow colour.

In concentrated 0pi<it. it dissolves when heated, and crystallises, without alien* tipn, on cooling, or whpn the solution is diluted with water, the liquid then becoming colourless. — It dissolves readily in alkalU^ with red colour, and i^ precipitated nnaltere4 by acids. — With pottuht it forms a very soluble salt. — It precipitates Iron-salts reddish yellow, cojiper-salts ^eeii, but forms no precipitate with the salts of Itme, wMgnma, lead, mercury f or gold.

It dissoWes & alcohol with yellow colour^ and forms jl colourless solution in ether.

Oxynitro-nudew C"X*H*H)».

Binitroihymol.

LaIiLBmakd. (1856.) Oompt. rend, 43, 876; abstr. Ann. Fkarm. 101, 122; If. Ann, Chim. Fhy: 48, 152.

Th}fmol hinitrit Acide kmiirotkifmique, Dimtrotkymm9ihir$,

When nitrio acid is slowly dropped into- salpfaotbymolio amd, or into a solution of a sulphothymatc, the liquid becomes slightly wann and deposits a reddish oil which soon solidifies.

Crystals which melt at 55°.

Nitrosvlphuric acid converts it into temitrothymol. — When heated with alcohol and oil of vitriol, it is easily oonyerted into solid binitro- thymolate of ethyl.

It dissolves sparingly in toater.

With bases, it forms salts which crystallise in silly needles, detonate at 150°, and dissolve sparingly in water, to which however they impart a strong colour.

BinUrothymaU of Potash. — Oraoge-yellow in the [anhydrou8,>nby- red in the hydrated, state. Very little soluble in water.

Binitrothymate of Lead, — Contains 32-7 p. c. oxide of lead, and 18 therefore C*H"X*PbO' (calculation « 32*65 PbO). Dissolves very sparingly in water.

MENTHENE. 445

Binitrothpmate of Silver is very sparingly soluble ia watet. In aldohol and Oher, binitrrttbymol dissolres in all proportions^ separating as an oil wben tbe solrent eraporates.

Oxt^nitro^udeuB C»*X»H"0*.

TemitrothymoL

Lallemand. (1856.) Compt. rend. A3, 876; N. Ann, C^im. Phys. 49^ 162; Ann. Fharm. 101, 123.

Thymoi trinitri, Acid triniirtthymiqtu, TriniirothymintSture.

F&rmcUian and Preparation. Binltrotbymol is dissolred in oil of Titriol, and a small qaantity of nitrio acid is gradually added, witbont allowing tbe mixture to get bot. On diluting witb water, yellowisb flocks of ternitrotbymol are precipitated, Wbich may be recrystallised from boiling water.

Beautiful yellow needles, wbich melt at 100^ and decompose suddenly at a bigbet temperature.

A mixture of oU of vUiid and ah(^ol readily cokiyerts it into solid temitrotbymic etber.

Ternitrotbymol dissolves sparingly in cold water.

It unites witb bases, forming yellow or orange-yellow salts, wbieb detonate at 150^, and dissolve in water more readily tban tbe binitro- tbymates. Tbe aqueous solution of ternitrotbyinate of potasb precipitates tbe salts of tbe beavy metals.

TemUroihpmate tjf Lead contains 28*83 p. c. lead otide, and is tbere^ fore C"X»H*TbO* (calctihtion « 28-86 PbO).

Ternitrotbymol dissolves readily in alcohol and in ether.

Prinka)y Kiideus C3*H".

Menihene.

WALTftlfe. (1839.) C'onipi. rend. 8, 9t3; Ann. Chim. Phys. 72, 87; Poyg. 51, 1, 336; J. pr. Chem. 14, 104; Ann. Pharm. 32, 288.

DiscoTered bj Walter in 1838.

Formation. By distilling peppermint-canipbot witb anbydrous phos- )>boriid afeid or oil of vitriol. — Probably ako by beating peppermint^ campbor with potassium. (Walter.)

/

446 PRIMARY NUCLEUS C»H".'

Preparation, Small lumps of anliydroas pbosphoric acid are gradaally added to peppermint-camphor, as long as heat is thereby produced ; the mixture, which separates into two layers, is distilled ; and the colourless distillate is twice rectified oyer anhydrous phosphoric acid (C»H«0» = 2H0 + C*H").

- Properties, Transparent, coloarless, thin liquid of sp. ffr. 0*851 ; boiling between \6V and 163°. Has an agreeable peculiar odour (which it appears to lose when it contains water, and to recover by boiling with potash), and

a refreshing taste. Vapour-density = 4*94.

Vol. Deosttj.

20 C 120 .... 86*96 86*4 C-vapour 20 .... 83200

18 H 18 .... 1304 12-9 H-gas 18 .... 1-2474

C»HW 138 .... 100-00 99-3 Menthene-vaponr 2 .... 9-5674

1 .... 4-7837

According to Kane (Phil. Mag. /. 16, 418; J.pr. Chem. 20, 439), it is C^W». «- Isomeric with camphin and sebacin.

DecomposUions. 1. Menthene, when set onfire^ bums with a bright, smoky flame. — 2. Dry Morine colours it green, with rise of tem- perature and evolution of hydrochloric acid, finally yellow, and converts it into pentachloromenthene. — 3. With irrominey it acquires a violet, with iodine, a red colour. — 4. It is not decomposed by cold eoneentraied nitric acid; with the hot concentrated acid, it turns green^ with evolutioa of nitrous and carbonic acids, then red, floats at first upon the acid, but nltimatelv mixes with it, forming a peculiar acid (C^H^H)^) together with flocks insoluble in water, and a small quantity of an oil slightly soluble in water. — When menthene is heated with strong nitric acid 10 or 15 times, or as long as nitrous acid continues to escape, the liquid then diluted with water, the precipitated white flocks separated by filtration, the concentrated filtrate repeatedly heated with alcohol to remove undecomposed nitric acid, then dissolved in water, and again evaporated in vacuo, the acid remains in the form of a yellow oil, which contains 42- 77 p. c. C, 6 61 H, and 60'62 0 (therefore C~H>»0"), decomposes by distillation, and is soluble in water and in alcohol. — 5. Menthene is not altered by cold oil of vitriol or by pot(usium^ (Walter.)

Condnnalions, With Hydrochloric Acid, — HydrochloraU of Men- thene, C^R^Cl — CIdormenthose (Laurent, Jiev. Scient. 14, 341). — Chloromentltine (Walter), a. CMormenthen (Lb wig.) — Fused pepper- mint-camphor is distilled from a tubulated retort with pentachloride of phosphorus added gradually and in slight excess ; the cblorophosphoricacid (terchloride of phosphorus, according to Walter), which first passes OVer, is removed ; ana then the yellow oil which passes over at a higher tempera- ture is collected : this oil is washed with cold water, and rectified several times over pentachloride of phosphorus, washed with solution of car- bonate of soda and with water, shaken up with chloride of calcium, and dried in vacuo (Gerhardt, N, J, Pkarm. 1 4, 224) :

C»H»0« h Pa» - PCPO« + HCl + C»Hi»Cl.

It is a very pale yellow oil, lighter than water, boiling at 204^ not however constantly, and with blackening and evolution of hydrochloric acid ; has a peculiar odour, like that of nutmeg- flowers, and a refreshing taste.

SEBACIN. 447

V^ alter.

20 C 120-0 ...• 68-7 63-9

19 H 19-0 .... 10-8 10-5

CI 35-5 .... 20-5 20-9

C»HW Ha 174-5 .... 100-0 100-3

4ceordiag to Walter, it is cUorometheoe, C^H^Cl ; according to Kane (Phil, Mag. J. 16, 418), a^W»C\\ according to Gerhardt {N. J. Pharm. 14, 224). C^HUCl. — It is not yet, however, absolutely proved to be hydrodilorate of menthene, (Schiranert.j

The chlorine-compound when set on Jhf, barns with a smoky green- edged flame. With cold oU of vitriol it acquires a blood-red colour. Heated with potassium, it is yiolentlv decomposed, with formation of chloride of potassium j if the action takes place in the cold, the metal becomes covered with a brown crust; It is not altered hj alcoholic potash eren at the boiling heat.

The chlorine-compound dissolves sparingly in water, easily in alcohol and wood-spirit, very easily in ether and in oil of turpentine.

Menthene is insoluble in vfoter. With a small quantity of alcohol or ether, it forms a turbid mixture ; with large quantities, a clear mixture. It dissolves with moderate facility in wood-spirit, very easily in oU of urpentine.

Sebacin.

T. PfiTBRBBN. (1857.) Antu Pharm. 103« 187; abstr. Chem. Ctntr. 1857, 907; J.fv. Oem. 73, 72.

Formation. By dry distillation of sebate of lime mixed with excess of lime.

PreparatiotL Sebate of lime, mixed with excess of lime is subjected to dry distillation, whereupon a mixture of propionic aldehyde, (Buanthol, and a small quantity of benzene passes over, and finally solid sebacin, which adheres to the sides of the receiver and the neck of the retort : more of it is obtained on leaving the liquid products of the distillation at rest. The product is purified by solution in oil of vitriol, precipi- tation by water, and recrystallisation from alcohol.

Fropeiiies. Solid fatty mass ; crystallises from alcohol in nearly colourless laminie which easily cake together. Melts at 55^ ; volatilises above 800°. Lighter than water. Inodorous. Tasteless.

IMed oter oil qf vitriol. Petersen.

20 C 120 .... 86-9 86-70

C»HW 138 .... 1000 99*98

Dissolves in oil of vitriol with red colour, and is precipitated in its original state by water. Scarcely altered by nitrie actd or caustic potash.

Insoluble in tpoter, easily soluble in alcohol and ether.

448 PRIMARY NUCLEUS C^H".

Camphin.

Glaus. J. pr. Chem. 25, 264.

Formation. "By distilling common camphor with iodine.

Preparation, 'The impure camphin obtained in the preparation of colophene from camphor (p. 280), is agitated with mercury io remove iodine, then distilled per K to remove colophene, camphor, and campho- creosote, then shaken up with potash-ley, and repeatedly rectified over potash-lime, as long as the distillate retains iodine. The last trace of iodine may also be removed by setting it aside over potassium, and rectifying.

Properties. Thin colourless oil of sp. gr. 0*827 at ^5^ Boils at 1 67° — 1 70° under an atmospheric pressure of 28 inches. Odour agree- able, like that of mace> but at the same time recalling that of turpentine.

				ClAttS.
				mean.
20 C	... 120 .... 86-96	18 (y ....«	... 108 .... 87-10 ....	.... 86-06
18 H	... 18 .... 13-04	16 H	... 16 .... 12-90 ....	.... 12-79
C»HW	... 138 .... 100 00	' C»H«	... 124 .... 100-00 ....	.... 99-85

Claus is undecided between these tifo fbrroulie. According to the first, camphin is isomeric with menthene (p. 445); according to the second, with campholene (xiii, 365). — According to Gerhardt {TVaitf 3, 694), camphin is perhaps impure cymene : the formuhi of cymene requires however 89*5 p. c. C and 10*5 H.

Decompositions, li Camphin, when set on fire, bums with bright, very smoky flame. — 2. It absorbs dry chlorine, with rise of tem- perature and evolution of hydrochloric acid gas, and forms chlorinated products, which are thicker in proportion as they contain more chlorine.

When chlorine gas evolved from 4 ounces of common salt is passed through 10 grammes of camphin, and the excess of chlorine is removed by a current of air, a transparent, colourless oil is obtained, of the thickness of olive-oil, sp. gr. 1-19 at 21°, containing 47'25 p. o. C, 5*6 M, and 46*7 CI (press-erron in the memoir render it impossible to recalculate these numbers with the uew atomic weights: Kr.); and^ according to ClaUS^ it is

C^^Ci'H^'. This oil is resolved by heat, like quadriehloroterebene (p. 440), into hydrochloric acid and chlorinated oib ; heated with alcoholic potash, it yields chloride of potassium and a chlorinated oil. In sunshine it absorbs an additional quantity of chlorine gas, forming chlorinated chlorocamphin, which is a colourless, viscid, neutral mass, having the thickness of turpentine, and containing 33*1 p. c C, 3*0 H, and 63*9 CI, whence Claus calculates the formula C^^Cl^H^^

3. By bromine^ camphin is attacked more violently than by chlorine, and is converted, with effervescence, evolution of hydrobromic acid, and brown colour, which soon disappears, into a brominated oil. — 4. It dis- solves iodine with rose-red to brown colour, and resinises after a wfaiie^ with evolution of hydriodic add* — 5« Dilate nUriC add acts slightly on

PEPPERMINT-CAMPHOn. 44 9

campbin j the concentrated acid colours it dark red at ordinary tempera- tures, with efTervescence and evolution of red vapours, and forms after a while, with decolorisation, an azotised oil having an odour of cinnamon. Fuming nitric acid converts camphin into a thick red oil, soluble in potash. — 6. Camphin, shaken up with oil of vitriol, colours it yellow, but otherwise remains unaltered. — Heated with fuming sidphuric aciclj it turns brown and thickens, gives off sulphurous acid, and distils partly unaltered. — 7. Resinises in contact with pentacIUoride of antimony.

Combinations^ Camphin dissolves in alcohol, ether, oU of turpentine, and rock-oil; not in water, weak alcoliol, potash-ley, or dilute acids, not even in strong hydrochloric add* It absorbs a small quantity of hydro- chloric acid gas. (Claus.)

Appendix to Camphin.

CamphoresinC*>H«?

Claus. J.pr. Chem. 25, 264.

The residue left on distilling camphor with an equal quantity of iodine (p. 280), consists of camphoresin with small quantities of charcoal camphin, colophene, camphocreosote, and iodine.

Properties. Solid^ black, very brittle resiu, resembling asphalt, and having a glassy lustre, easily rubbed to a black powder ; fracture con- choidal. Melts easily. Tasteless and inodorous.

According to Claus, it contains, wbea not quite pure, 88*88 p. c. C, 8*39 H, and 2*0 I, and is therefore C^H'^. (Clans.) It probably likewise contains oxygen, and, as it was produced from camphor, it is more probably C^H*^. (Gni.)

Decompositions: Camphoresin when boiled, gives off white vapours smelling of creosote* — It takes lire when heated, and burns with a bright flame, leaving a tumefied charcoal, which colours an alcohol-flame green when ignited therein. — By dry distillation, it yields small quantities of camphin, camphocreosote, colophene, and lastly oil-gas and resin, and leaves a residue of charcoal.

Combinations. Camphoresin is insoluble in water and in aqueous alcohol; but absolute alcohol and ether, oil of turpentine and camphor, dissolve it, leaving however a residue of charcoal : the solutions, after agitation with animal charcoal^ exhibit a light green iridescence ; the solution in rock' oil has a blue iridescence after agitation with animal charcoal.

Feppennint-camphor.

C»H»0« = C»H",2H0.

OuELix. n829.) Eandb. Aufl. iii, 2, 408.

Dumas. Ann. Chim. Phys. 50, 232; abstr. Ann, Pharm. C, 252.

Blanchet & Sell. Ann, Pharm. 6, 293#

Toil. xiY. 2 a

450

PRIMARY NUCLBUS C«HW.

Waltbr. Ann. Ckim. Fhys. 72, 83; Poffg, 51, I, 834; J. pr. Chem. 14^

103] Ann. Pharm. 32, 288. Kane. Phil. Mag. J. 16, 418; J.pr. Cfhem. 20, 439. Laurent. Bev. sdent. 14, 341.

Pfefferminzcampher, Menihencampker, Stearoptene qf PeppemUni'Oil, solid Peppermint 'OU, OaHde de menthine hydraU, (Laurent.)

Oil of peppermint obtained by distilling Meivfha piperita with water, deposits on standing (Blanchet & Sell), or when cooled to — 20"^ (Bizio, Brvgn. Giom. 19, 360), to —27'* (Margueron, J. Phys. 45, 136), crystals of peppermint-camphor. American peppermint-oil solidifies at 0° (Damas) ; when it is subjected to fractional distillation, the last third of the distillate, if collected apart, deposits crystals on standing. (Walter.)

Properties. Transparent, colourless, shining prisms, which melt at 36-5° (Dumas), (at 25^ Dumas, 27° Blanchet & Sell, 34° Walter), and volatilise without decomposition. (Gmelin.) Solidifies at 24^ (Blan- chet & Sell.) Boiling point, 208° (Blanchet & Sell), 213°. (Walter.) yapour-density=:5*62. (Walter.) Smells and tastes like oil of pepper- mint (Blanchet <& Sell, Walter), less burning, less agreeably, more bitter, very cooling. (Gmelin.) Neutral. (Gmelin.)

Aocovding to Kane, it U G^^H^O'.

Decompontions. 1. Peppermint-camphor boiled in contact with the air acqnires a yellowish colour (Blanchet & Sell), brown-yellow. (Walter.) — 2. When set an Jlre, it burns with a smoky flame. (Gmelin, Walter.) — 3. CA^ortne decomposes fused peppermint-camphor, with evolution of hydrochloric acid, converting it into chlorinated peppermint-camphor. ( Walter.) -^ 4. With iroiTitne, it acquires a fine red colour, and evolves hydrobromic acid ; iodine does not decompose it — 5. It absorbs hydrocnloric acid gas abundantly, and becomes viscid. (Walter, Bineau, N. Ann. Chim. Phys. 21, 335.) — The solution, which is red by transmitted light, deposits nearly nnaltered peppermint-cam- phor, when shaken up with water. (Walter.) — 6. Cold nitric acid colours it red, without giving off gas ; with hot nitric acid, it gives oflT nitrous acid, and forms an acid whose solution quickly changes on expo- sure to light. (Walter.) — Fuming nitric acid dissolves peppermint- camphor, without evolution of ga^, forming a layer of oil which floats on the aqueous nitric acid, and when shaken up with water yields pepper- mint-camphor in drops which gradually solidify, (Gmelin.) -s- 7. Tntu-

Damag. 20 C 120 .... 76-9 76-5	Blanchet & Sell. Walter. 76*4 .-- 76-3
20 H 20 .... 12-8 13*1	12-&	12-7
2 0 16 .... 10*3 10-4	11-1	110
C*H»0« 156 .... 100-0 100-0	1000	1000
Vols. C-yapour 20		Dennty. 8*3200 1 -3860 11093
H-eas 20
O-xaa 1
^-^ 6*^
Vapour of Peppermint-camphor 2		10-8153 5-4076

PBPPERMINT^CAMPHOR* 4Sl

rated with 2 pts. o! oil of vitriol^ it forms a semi-fluid mass of fine blood-* red colour^ irom which nearly all the peppermint-camphor separates again on saturation with alkali ; the blood- red mixture heated on the water-bath fields menthene floating on a thick red liquid. On satu- rating this liquid with potash, and precipitating the resulting sulphate of potash with alcohol, the solution yields bj spontaneous eyaporation, an oil, which, after washing with water, solution in ether, and evaporation of the ethereal solution, contains 81*3 p. o. C« ll'l H, and 7.6 0 (corre- sponding to the formula C*'H^'0, according to Walter, and to the formula C^H^^O, according to Laurent, who called it tne7ithase), — also a sbininff salt containing 37 p. c. C and 6*8 H. (Walter.) — When strongly heated with oil of vitriol, it gives off sulphurous acid, first with brown colouring, afterwards with carbonisation. (Gmclin, Walter.) — 8. . Heated with anhydrous phos^phorie acid, it is resolved into water and menthene (p. 445). — 9. PentachloriJe of phosphorw added to fused peppermint-camphor^ produces great heat and evolution of hydrochloric acid, and colours the camphor blue, rose-red, and finally dark red : the mixture yields by distillation, chloromenthene and terchloride of phosphorus (Walter), chlorophosphoric acid and hydrochlorate of menthene. (Gerhardt, iV. j, riiann. 14, 224.) — 10. Potassium oxidises slowly in fused peppermint^ camphor, the mixture acquiring a doughy consistence when heated. — The doughy mass separates, on addition of water, into two layers, the upper consisting of aqueous potash having a red colour, the lower probably of menthene mixed with peppermint-camphor. — 11. It is not altered by hydrate of potash. (Walter.)

Peppermint- camphor dissolves sparingly in watti*, — The solution in boiling water becomes turbid on cooling. (Gmelin.) — It dissolves readily in alcohol and ether (Bumas, Walter) ; easily in volatile oils (Dumas), less easily in oU of turpentine (Walter), in fvood-spiril and bisulphide of carbon, (Walter.) — It does not crystallise from a hot solution in alcohol or ether-aJcohol. (Blancbet & Sell.)

Appendix to Pep^^rmint-camphor,

1 . Claude Oil of Peppermini, — Ksseuee de menihe poivrie, — The oil obtained by distilling peppermint, Mentha piperita^ with water, is a mixture of peppermint- camphor with a liquid oil not well examined. — The crude oil has generally an acid reaction. (Zeller.) — The dry flowering plant yields 1*25 p. c. oil. (Martins, Reperi, 89, 243.) The fresh plant yields the same quantity of oil and of the same properties, whether distilled with steam or over the open fire ; but the dry plant yields 1-^ times more oil by distillation over the open fire than by steam distillation, and the oil obtained by the latter process is specifically lighter and less coloured than that yielded by the former. When the oil obtained from the dried plant by distillation over the open fire, is recti- fied with steam, oil of sp. gr. 0*91 passes over, and there remains a portion, which, after rectification over the open fire, exhibits a sp. gr. of 0*93 ; hence the specifically lighter oil contained in the fresh plant appears to be changed into the heavier oil by dryiug. (Geiseler, if, Br, Arch. 86, 151.)

Oil of peppermint is limpid, pale yellow, yellow-green to brownish (Pfaffj Zeller, Stud, uber, attier. O^/e*, Landau, 1850); it has a peculiar

2 o 2

452 PRIMARY NUCLEUS C»H".

odoar, and a strong borning taste, bat at tbe same time cooling, like tbat of camphor (Pfaff) ; the American oil is less burning. (Blej, Br. Arch, 39, 51.) Sp. gr. 0-92 (PfafT) ; 0*89 to 0*92 (Zeller) ; of the American oil, 0-84 (Blej) j 0*907 (Braudes); 0*9083 (Kane) ; of the oil separated from peppermint-camphor by rectification, 0*S998 (Kane) ; of English oil, 0-9068 at IS"* (Chardin) ; French, 0*914 at 25'' (Chardin) ; German, 0*9098 ; rectified, 0*9024 (Martins) ; 0*86 (Blej) ; 0*908 at 20° (van Hees, N, Br. Arch. 61, 18.). Boiling point between 188^ and 193^. (Kane.) — Contains 75*1 p. c. C, 13*4 H, and 11-5 0 (Gobel) ; mean, 78-5 p. c. C, 110 H, and 10-5 0 (Blanchet & Sell, Ann. Pliann. 6, 293); mean, 76C6 p. o. C, 12-15 H, and 11*19 0; the first tenth which passes over in rectification, perhaps containing oil of turpentine, contains 78*42 p. c C, 11*86 H, and 9*72 0 TKane, Lond. Ed. Mag. J. 13, 440; J. pr. Chem. 15, 159), whence Blanchet k Sell deduce the formula C"H"*0, and Kane deduces the formula C"H»0*.

Oil of peppermint treated with chlorine acquires a turbid, whitish aspect. (Blej.) It dissolves iodine, without evolution of vapour or rise of temperature, acquiring a jellowish to red-brown colour and viscid consistence. (Zeller.) The darker colour disappears on addition of water. The oil does not undergo anj alteration of odour. (Flaschoff, £r. Arch. 33, 225 ; Winckler, Repert. 32, 271.) It forms with iodine, a thick magma (Gujot J. Hist. phys. 5, 230) ; with iodine dissolved in iodide of potassium, it does not form any solid product corresponding to the anisoin of oil of anise. (Will. Ann. Pharm. 65, 230.) With bromine, it assumes a lemon- jellow colour, becoming lighter on addition of water. (Blej.) — With concentrated nitric acid, it forms, with great hissing and rise of temperature, an unctuous mass having an odour of pitch, and depositing a brown resin on addition of water (Blej) ; ordinary nitric acid colours it purple-red to reddish brown, and thickens it, when heated, at the same time giving off a large quantitj of gas. (Zeller.) — With oil of vitriol, it turns brown and acauires the thickness of a balsam (Zeller), without losing its odour. (Blej.) — By chromate of potash and sulphuric acid, it is partially thickenecl, and coloured yellowish brown, ultimately greenish brown. (Zeller.^ — When hydrochloric acid gtu is passed into it, or when it is treated with the aqueous acid, it acquires a purple-red colour. (Davy.) — Mixed with ammonia (alcoholic, aqueous, or gaseous) Om.) it gradually loses the odour of peppermint and of ammonia, and becomes turbid, depositing indistinct flocks. (Boullay, JT. J. Pharm. 5, 336.) — Distilled with chloride of lime, it yields chloro- form ; with hypobromite of lime, bromofomi. (Chautard, Compt. rend, 33, 671 and 34, 485.) — It decolorises finely divided sulphide of lead, and by the action of the ozone contained in it, converts tbat compound into sulphate. (Williams, N. PhU. Mag. J. 5, 536 ; /. pr. Chem. 59, 504.) — Boiled with niiropmsside of copper, it yields a dark deposit and acquires a dark colour. (Heppe, iV. Br. Arch. 89, 57.) With finely divided mercuric ddoride, it turns yellow, and blackens imme- diately when heated, whereupon a somewhat purple-coloured oil distils over, together with acid vapours, while calomel and a little charcoal remain behind. (J. Davy, PhU. Trans. 1822, 360.)

Oil of peppermint is slightly soluble in water. — Fresh peppermint- water, and fresh elder-flower-water mixed in equal parts, form a mixture which soon acquires a blood-red colour, and after two months, deposits a red substance somewhat soluble in alcohol and ether. If the waters

CAMPHOLIC ACID. 453

are more than a month old, thej do not become coloured. (Recluz, J. Chim. m6d, 14, 470.)

It dissolves in 1 — 3 pts. of alcohol of sp. gr. 0'8.5, forming a clear solution ; with a larger quantity, an opalescent solution. (Zeller.) It dissolres in all proportions of alcohol of sp. gr. 0*815, in 10 pts. of alcohol of sp. gr. 0*868. (Bley.) — It dissolves with turbidity in hUuHr phide of carbon. (Bley.)

2. Chlorinated Peppermint-oamphor.

Walter. (1839.) Ann. Chim. Phy$. 72, 99; Compt. rend. 8, 914; Fogg. 51, 1, 344 ; Ann. Pharm. 32, 294.

A. Ojnde of CMoromenthene. (Laurent, Bev. icient 12, 341), C**H"'*CP**0'. — Chlorine gas washed and dried, is passed in the dark through fused peppermint-camphor as long as hydrochloric acid gas continues to escape ; the liquid is then heated on the water-bath to expel free chlorine, then washed several times with water and solution of car- bonate of soda, and dried in vacuo, after being shaken up with chloride of calcium. — Yellow oil, heavier than water, not crystal Usable, having a peculiar odour, and a taste refreshing at first, afterwards bitter and exciting.— It conUins 49'IG p. c. C, 6'52 H, 37*80 CI, and 6'52 0 (Walter) ; it is probably C^H^KHPO'. (Gm.) — When set an Jlre, it burns with a smoky green-edged flame. It is decomposed by heat, giving off a large qnantity of hydrochloric acid gas, and leaving charcoal. — It is not altered by chlorine in the dark, but in sunshine it is transformed into the following chlorinated peppermint^ camphor. With cold oU of vitriol, it immediately turns red. — It dissolves slightly in toater, and in aqueous carbonate of soda, easily in alcohol, wood-epirit, ether, and oiL of turpentine. (Walter.)

B. Oxide of Chloroment/tdane. (Laurent.) C»H»»-»CT-*0*. — Pro- duced by exposing the compound A to direct sunshine in a bottle filled with chlorine, and purified in the same manner as the preceding. — Green-yellow, viscid oil, containing 35'38 p. c. C, 3*88 H, 56*85 01, and 3*89 0. — oil of viti-iol colours it after long contact. — It is slightly soluble in cold alcohol. (Walter.)

Gampholic Acid. C»H'«0* = C»H»»,0*.

Delalandb. (1841.) iV^. Ann. Chim, Phye. 1, 120; J. pr. Chem. 23,

390; Ann. Pharm. 88, 337; ReperU 80, 159. Barth. Ann. Pharm. 107, 249; abstr. J. pr. Chem. 76, 125; Chem.

Centr. 1858, 784.

CamphoUUure, Acide campholiquet Acide boruenipte. (Laurent, Rev. icicni* 14, 366.) Discovered by Delalande.

1

454 PRIMARY NUCLEUS C«H«

Formation and Freparation. Camphor- vapour is repeatedly passed to and fro, under pressure, over heated potash-lime ; the whole is then dissolved in boilins: water; the filtrate saturated with acid; and the white, acid, crystalline mass which separates from it, is washed and dried, aild recrystallised from alcohol and ether-alcohol. — No gui is evoWed when camphor-Tapour is pa<sed over potash-lime. (Delalande.)

FropeHies. White crystals. Melts at 80°, boils at 250°. Vapour- deu8ity=6'058. Slightly reddens litnius. (Delalande.)

Delalande.

20 C 120 .... 70-58 6976

18 H 18.... 10-58 10-66

4 O : 32 .... 18-84 19-58

C»H»0* 170 .... 10000 100-00

Vols. Density.

C-vapoar 20 8-3200

N-gaa 18 1-2474

O-gas 2 2-2186

Vapour of campholic acid .... 2 11*7860

1 5-8930

C»H»«CM - C»H"0» + 2 HO. (Delalande.)

Decompasitioni. 1. Distilled with anhydrous phosphoric acid, it yields campholene (ziii« 265, in which place, read eampholie instead of campJioric acid), carbonic acid gas being probably evolved at the same time (Delalande) :

C»H»0* -2CO + 2HO + C«H>«. (Gerhardt, TVaWl 3, 697.)

2. Fused with excess of hydrate of potash, it forms a frothy, viscid mass of campholate of potash, which no longer melts with the excess of potash, but at a higher temperature gives off an aromatic smoke, with- out forming acetic or capryiic acid. (Darth.) — 8. By the dry distilla- tion of its lime-salt, it is resolved into carbonate of lime and campholene, which, after rectification, contains 81*60 p. c. C, 11*01 H^ and 6*79 O; therefore 0*H**0». (Delalande.) — Calculation 8201 p. c. C, 12-23 H, and 5-76 O.

Combinations. Campholio acid is insoluble in water, but imparts to it a slight aromatic odour. (Delalande.) With bases, it forms the Campholates,

Campholate of Lim^, — Aqueous eampholie acid is supersaturated with ammonia, the boiling solution is mixed with aqueous chloride of calcium, and the white crystalline powder which precipitates is dried. For the decomposition by dry distillatioo, tid ngp,

ft

Delalande.

20 C 120 .... 60*61 59-97

18 H 18 ... 9-09 9*08

5 O 40 .... 20*20 20-82

Ca 20 .... 1010 10*13

C»HVCaO^HO 198 .... IWOO lOO'OO

CAMPHORIC ACID. 453

Ccanpholate of Silver. — Aqueous campbolate of ammonia is mixed with uitrate of silver^ and tlie resulting precipitate is washed and dried* White, curdy flocks.

20 C 17 H	Deklande. 120 .... 43-32 4300
4 O	32 .... 11-66 12-17
Ag	108 .... 38-99 38-60
C»H»7AgO* .	277 .... 10000 10000

Gampholio acid is soluble in (Ueohol and ether, (Delalande.)

Oxygen-nuchui C**H"0*.

Oamphoric Acid.

C««H»0« = (?*H"0«,0«.

KosEGARTEN. (1785.) Dis8, de eamphara et partibui quof comlUuunt,

Gottingen, 1785. D&RFFURT. AbhandL uber den Campher. Wittenberg n. Zerbst. 1793. Bouillon-Lagrakgb. Ann. Chim. 23, 123; 27, 19, and 22lj CrelL

Ann. 1799. 2, 221, and 313. BucHHOLZ. JV. GehX. 9, 332.

Brandeb. Schw. 88, 269; BepeH. 15, 431; 20, 824; Br. Arch. 9, 167. LiEBiG. Pogg. 20, 41; Repert. 87, 470. — Ann. Fharm. 22, 50; Mepert.

40, 131. Laurent. Ann. Chim, Fhy$. 63, 207; Ann, Fharm. 22, 135; J. pr.

Cheni. 11, 287. — Compt rend. 20, 511; J. pr. Chem. 35, 501. Malaguti. Ann. Chim. Fhye. 64, 157; Ann, Fharm, 22, 38; J. pr.

Chem. 11, 294; J. Chim. m^d. 13, 107; abstr. •/. Fharm. 23, 74 and

513. — Compt. rend. 41, 625; J. pr, Chem, 67, 277; abstr. Chem.

Centralbl, 1855, 874. Walter. Ann. Chim. Fhys. 74, 88; Ann. Fharm. 36, 59; J. pr. Chem,

21, 241; abstr. Bepet-t. 80, 113; Ann, CMm. Fhye, 75, 212.—

N. Ann. Chim, Fhye. 5,187; 9, 177; Ann. Fharm, 48, 248; abstr.

iT. JBr. Arch. 39, 75.

Relating eepedally to the liomeric Modijioalioni of Camphoric Acid :

Chautard. Compt. rend. 37, 166; iT. J. Fharm. 24, 168; Jpr. Chem. GO, 139; Fogg. 90, 622; If. Repert. 2, 565; abstr. Chem. Centralbl. 1853. 636; N. Br, Arch, 76, 168.

DestrO'Camphorie aeid, Campkersdure, CtmphonUitre, Reektt^CamphereHuret CamphyUdur^t Acid tampkoriqne, Aeld eamphique, (Laurent.) — Obserted and regarded as camphor by Lemery in 1675 (Coure de Chemte): disoovared by Kosegarten ill 1785 ; regarded as bensoic acid by Dorfl^rt, a Tiew wbich was shown to be erroneoos by Boaillon- Lag range and Buchholz.

Formation. By prolonged boiling of common camphor with nitric

acid. — It was found in an anatomical preparation preserved in oil of tnrpentidti (Henry, Thome. Ann, 15, 117 { 8ehw, 31, 361.)

456 PRIMARY NUCLEUS C»H": OXYGEN-NUCLEUS C»Hi«0».

Preparation, 1 pt. of camphor is distilled from a retort with 1 0 — 1 1 pts. of strong nitric acid (Dbrffurt) ; (with 25 pte. of nitric add of sp. gr, 0-33 ; JLagrango; 12 pis. of sp. gr. 1*25; 4 pts. of fuming nitric acid of sp. gr. 1*55; Buch- holz, 7 pts. of nitric acid: L(5wig, Ory. Verb. 2, 611); the distillate is poured.

back into the retort ten times (Laurent), or till the camphor is completely dissolved and no more nitrons gas is evolved^ fresh quantities of nitric acid being added from time to time, if necessary ; the acid solution is somewhat concentrated; and the crystals which separate after cooling are collected and purified by repeated crystallisation from water, or by solution in aqueous potash and precipitation with hydrochloric acid (Brandos), and recrystallisation from water or alcohol.

Camphor boiled with nitric acid is at first converted, without erola- tion of carbonic acid, into a yellow oil which afterwards disappears : the turbid solution, if not boiled long enough, deposits camphoric acid con- taining camphor, which, by further boiling, is completely converted into camphoric acid. (Liebig.) — The mother-liquor contains free nitric acid and a snmll quantity of camphoric acid ; it becomes syrupy when evapo- rated, gives a precipitate with aqueous acetate of lead, after neutralisation with ammonia, and yields by distillation a peculiar oil, together with camphoric anhydride. (Laurent.) — When the nitric acid solution of camphoric acid is heated in a porcelain dish, till white fumes escape from it, there remains, if the liquid be slowly cooled, a viscid mass, whose hot aqueous solution yields white crystalline grains on cooling. These crystals are not altered by further boiling ; they are difficult to melt, but sublime nndec^mposed, not however in the crystalline form. They have a slightly sour taste, and dissolve sparingly in water, forming a solution which has an acid reaction, — decomposes alkaline carbonates, — gives a slight precipitate with solution of neutral acetate of lead,— copious with basic acetate of lead, sesquichloride of iron, and mercurous nitrate,-— crystalline with copper-salts, — and produces no alteration in solutions of titrate ^>r ammonio-nitrate of silver, nitrate of lime, chloride of barium and lime-water. (Blumenau, Ann, FJiarm. 67, 119.) It is perhaps resinous inactive camphoric acid, (Gerhardt, Traiti, S, 701.)

Properties, White four*sided lamiuas, rectangular and arranged like steps ^Kosegarten); small, six-sided pyramids united in plumose groups. (Buchholz.) Belongs to the right prismatic system. — Rhombic prisms u (Fig. 55), having the obtuse edges truncated by t-faces, and the sum- mits with four-sided acuminations formed by the races i and u (Fig. 53). Laurent.) — Melts at 62*5°, solidifies in the crystalline form on cooling, sublimes at a higher temperature (Brandos), with loss of water (Laurent), as camphoric anhydride. (Bouillon.) — Rotatory power 38*873'' to the right ; weaker after saturation with soda, but increases again on decom- posing the soda-salt with hydrochloric acid. (Bonchaxdt, Compt. rend, 28, 319.) — Camphoric acid dissolved in acetic acid exhibits a rotatory power of 38° to the right ; dissolved in absolute alcohol, 38-6'' to 389'' to the right. (Biot, Compt. rend. 85, 233 ; Ann. Pharm. 84, 160.)

Camphoric acid is inodorous (Brandos) ; has an odour of saffron (Kosegarten); when heated to 37^ it smells like camphor and fat, like- wise sour ; at 100"^ very pungent. (Brandos.) Its taste is bitter, inclining to acid (Kosegarten and others), sweetish, scarcely acid. (Dbrffurt.) When taken internally, it passes unaltered into the urine. (Bertagnini, Cimento, 1, 363 j Ann. Pharm. 97, 248.) Reddens litmus. (Kosegarten.)

CAMPHORIC ACID. 457

Brandes. Malagnti. Liebig. Laurent.

20 C 120 .... 60 61-34 .... 59-49 .... 5973 .... 5943

16 H 16.... 8 5-62.... 8 03.... 809.... 7*96

8 0 64.... 32 3304.... 32-48.... 32-18.... 3261

C»H"08 .... 200 .... 100 10000 .... 10000 .... 10000 .... 100-00

Decomponttons. — 1. Heated in a retort, it is resolved into water and camphoric anhydride, leaving a small quantity of charcoal. (Laurent) When heated above its melting point, it turns brown and froths, and at a higher tem- perature leaves a smaU residae of charcoal, and gives off a small qnantity of acid empyreumatic water, empyreumatic oil> and a white opaque sublimate of unaltered camphoric acid (Buchholz), of altered camphoric acid, whidi no longer reddens litmus and is insoluble in water. (Bouillon.) The acid browned by fusion solidifies on cooling into a brown, transparent, non-crystalline, resinous mass. (Brandes.) When thrown on red-hot coals, it volatilises completely, diffusing a dense aromatic vapour. (Bouillon.) — 2. When heated in the air, it bums with a bright flame^ leaving a small quantity of charcoal. (Brandes.) — 3. By repeated distillation with peroxide ofmanganete and sulphuric add, it yields acetic acid. (Dorffurt.) — 4. It dissolves in cold oil of vitriol, forming a limpid solution from which water precipitates camphoric anhydride ; the solution heated in the water bath to 45°, gives off a small quantity of carbonio oxide, and at G0° a larger quant ity, with violent effervescence, and is converted into sulphocamphoric acid (xiii, 879). In fuming oil of vitriol^ it dissolves with yellow to brown colour, likewise forming sulphocam* phoric acid. (Walter.) — Distilled with alcohol and oil ofvitHol, it yields ethyl-<»mphoric acid (Malaguti) ; with wood- spirit and oil of vitriol^ methyl-camphoric acid. (Loir, iV. Ann, Chim. Phys, 37, 196 j N, •/. Fharm. 22, 288.) — 5. Heated with syrupy p/^MpAom add to 195°, it is resolved into: (1), carbonic oxide; (2), a colourless oil, boiling at 121°, having an agreeable odour with somewhat of a turpentine character, of sp. gr. 0*793 at 25°, vapour-density 4*29, and corresponding to the formula (jiegis . ^qJ ^3^^ ^ pg^i^ yellow oil boiling at 250°, having an agreeably aromatic odour, of sp. gr. 0*889 at 21°, of composition not yet determined. (Galle, Eplst, Communication ») — 6. Distilled with pentacfdoride ofphos* phorus, it yields camphoric anhydride, hydrochloric acid, and chloro- phosphoric acid. (Gerhard t & Chiozza, Compt rend. 36, 1050; Ann. Fharm, 87, 290; J.pr. Chem. 59, 452; Jnstit, 1853, 255.) — 7. Potassium and sodium decompose camphoric acid at temperatures far below its melting point, without emission of light, leaving a residue of alkali and charcoal. (Gay-Lussac & Thenard.) — 8. The lime-salt when distilled yields pLorone (xiii, 842). (Gerhardt & Lics-Bodart, Compt. rend,

28, 506 ; Ann. Fharm, 72, 293.) According to Fittig (Ann, Pharm. cxii, 309), the oil which passes over in the distillation of camphorate of lime, begins to boil at GO**, the greater portion distilling between this temperature and 270% leaving however a rrsidoc. Tlie portion which passrs over in fractional disitillation between 200** and 205** has the composition of phorone (C<'H*'*0'). The portions boiling at lower temperatares did not yield any definite compound. — 9. The soda and potash-salts distilled with an equal weight of perchlorovinic etJier (ix, 26), yield a distillate of camphoric anhydride, water, sesquichloride of carbon, carbonic acid, and combustible gases, leaving a residue of hydrochlorate and carbonate of the alkali. (Malaguti.) — 10. Camphoric acid heated for some time to 200° in a sealed tube with glycerin, forms camphorin, which may be extracted by ether from the mass, after cooling and mixing with excess of aqueous carbonate of potash, and remains, after evaporation of the ether, as a viscid neutral mass^ soluble in ether, and resolved by oxide of lead

458 PRIMARY NUCLEUS C^H": OXYGEN-NUCLEUS C»WKfi.

into caraplioric acid and glycerin. (Berthelot, Compt rend. 37, 398 ; ^. J, Phai-m. 24, 2G6 ; Ann, Fharm. 88, 311.)

ConUnnaiions, With Water. — Aqtifous Camphoric acid. — Cam- phoric acid dissolves in 400 pts. of cold water (Dorffurt), 200 (Kose- farten), 100 (Buchholz), 80 (Lagrange), and in 24 pts. of boiling water Dorffurt), 12 (Kosegarten), 11 (Buchholz), 10 (Bouillon). — It dis- solves in 88*6 pts. of water at 12-5"; in 70 pts. at 25^; in 61*5 pts. at 37-5^; in 40*7 pts. at 50"; in 28-4 pts. at 62 5°; and 7-2 pts. at 82-5°; in 8*9 pts. at 90^; in 8*6 pts. at 96*25'^; — under the ordinary atmospherio

firessnre, the saturated solution cannot be heated above 96*25°. Drandes.)

It dissolves without alteration in nitiic acid, (Laurent.)

Camphoratei. — Camphoric acid forms with bases, bibtuic {neutral) salts = C»H"MK)», and mono^basic (acid) salts = C»H»MO«. — The neutral salts are the most easily preparea. — The oamphorates are in- odorous, have generally a rather bitter taste ; yield when heated, an empyreumatic oil, with a residue of charcoal (the lime-salt yielding phorone^ the lead-salt camphoric anhydride), and burn in the air with a blue, or sometimes with a red flame. They are decomposed by sulphuric, hydrochloric, nitric and acetic acid, and are but slightly soluble in water. Camphoric anhydride boiled with bases, yields peculiar salts isomeric with the camphorates (tfid. inf.)

Campkorate of Ammonia. — Bihasic. — Dry ammonia-gas is passed over camphoric acid, and the excess of ammonia is expelled by passing dry air over the product at 100°. (Malaguti.) Separates from its solu* tion by evaporation as a saline film composed of slender needles. (Bouillon.) Tasteless and inodorous. (Malaguti.) Has a rather bitt<>r taste (Bouillon), sharply saline. (Drandes.) Reacts slightly acid. Melts when heated, giving off ammonia with intumescence, and volatilises partly undeoomposed, leaving a little charcoal (Bouillon, Brandos) ; yields water^ ammonia, and camphoric anhydride. (Laurent.) Dissolves readily in water (Malaguti); in 100 pts. of cold water (in a much smaller quantity, according to Brandos), in 3 pts. of boiling water ; the solution gives off ammonia when heated. (Bouillon.) Easily soluble in alcohol (Bouillon.)

Malaguti.

2 NH^O 52 .... 22-22 22'34

C»n»^0« 182 .... 7778 77'66

C»H»'(NI17"08 234 .... 10000 100*00

5. Four-thirds basic. — By saturating aqueous camphoric acid with bicarbonate of ammonia, small, very white prisms are obtained, which melt somewhat above 100^ have a slightly sour taste, and redden litmus. Dissolves readily in cold water. Dried at lOO*', it gives off 19 p. c. water. (Malaguti.) — (18 At. HO=19-5 p. c.)

Dried at 100^ Malaguti.

60 C 360... 53-89 62-84

60 H 60 .... 8*98 8-98

4 N 56 .... 8-38 8-51

24 O 192 .... 28-75 29-67

3C»H»«0« + 4 NH« Us .... 10000 10000

CAMPHORIC ACID. 459

According to Geibardt, it is perhaps monocamphorate of ammonia, C*^H"(NH^)0* (containiDg in the crystnllised state 6 At. water, by calcalation 19*9 p. c. Aq.)> on which hypothesis, the formula of the dry salt requires 55*3 p. c. C^ 8*7 H, and 6*6 N. (TraiU 3, 702.)

Oamphoraff. of Potash. -^ BUnme, — Obtained by nentralising aqaeon^ eamphorio acid with potash a carbonate of potash. — Small six-sided prisms (Boaillon, BuoDhols); needles grouped in tufts. (Brandes.) — The salt prepared with namphoric anhydride and potash forms broad pearly laminie. (Malaguti, p. 458.) Tastes faint saline, aroroatically bitter. Melts when heated, turns brown^ and at higher temperatures hardens to a white mass having a sharp taste. (Bnchholz, Bouillon.) — It dissolves iu 100 pts. of cold, and In 4 pts. of boiling water; also in alcohol (Buch- holz, Bouillon); deliquesces slowly on exposure to the air and dissolves in a very small quantity of water. (Brandes.) The less soluble salt is perhaps the raonopotassio and the more soluble the bipotassic camphorate. (Gerhardt, 7Vai<i?, 3, 703.)

Brandes*

2 KO ; 941 ;... 34-4 32-5

C»H'<(y 1820 .... 65-9

C»H"K«0» 276-4 .... 100-0

Camphorate of Soda. — Bibasic. — Aqueous carbonate of soda is saturated at the boiling heat with camphoric acid ; the solution is evapor- ated to dryness ; the residue dissolved in alcohol ; and the crystals which separate from the syrupy solution after standing for a long time, are collected and dried over oil of vitriol. (Kemper, Episi. communi- cation,)— Limpid indistinct crystals. (Bouillon.) Needles and cauli- flower-like masses. (Brandes.) Swells up when heated, melts, blackens, and gives off vapours which burn with deposition of soot. It deliquesces in the air (Brandes, Kemper); dissolves in 200 pts. of cold, and 8 pts. of boiling water (Bouillon); in 80 pts. of cold alcohol. (Brandes.)

Brandes. Kemp.

2NaO 62 .... 2511 24-82 24*88

C»H"0« 182 .... 74-59

C»H»*Na20« 244 .... 10000

Camphorate of Baryta, — Bibaiic. — Obtained by boiling camphoric acid with baryta-water. — Thin lamina) or needles. Taste, rather acid, bitter (Bouillon), saline. (Brandes.) Gives off ITS? p. o. water when heated (Brandes) (by calculation, 6 At. = 12-5 p. o. Aq). Dissolves in 1*8 pt. water at 19^ and in 600 pts. of boiling water. (Bouillon.)

Dried at 100^ Brandes.

2 BaO 153 .... 43-67 42*66

C»H"0« 182 .... 54-33

C^H"Ba?08 335 .... lOO'OO

Camphorate of Strontia. — White, translucent, crystalline laminos having a rather bitter saline taste, and still mere soluble in water than the baryta-salt. (Brandes.)

Camphorate of Lime. — a. Polybanc t — White, non -crystalline, slightly bitter, perfectly neutral lamina, which crumble when exposed to the air, are nearly insoluble in cold water, soluble in 200 pu. of boiling water, insoluble in alcohol, and contain 43*6

460 PRIMARY NUCLEUS C»H»: OXYGEN-NUCLEUS ^HWQ*.

p. c. CaO (or CaOtCO' ?), 50 pts. camphoric acid (hyp. anhydrous ?), and 7 p. c. water. (Bouillon.) — The first two determinations cannot be reduced to any probable calcula- tion; the amount of water would correspond to 2 At for bibasic camphorate of lime. (Kr.)

b, Bibasic. — 100 pts. of camphoric acid dissolve 5G pts of carbonate of lime (2 At. CaO,CO^=50 pts.), and yield the following salt, even when neutralised with ]ime- water. (Brandes.) Rhombic prisms. (Bemhardi.) Has a slightly saline, bitterish taste; with astringent after-taste; reddens litmus; and when heated, makes a hissing noise, becomes opaque and brown, giving off water and empyreumatic oil. (Buchholz.) For the decompodtion by dry distilktion, see page 458.

Anhydroui. Brandes.

2 CaO 56 .... 23-53 20-24

C»HWO« 182 .... 76-47 79-76

C«H"Ca*0«. 238 .... 100-00 100-00

CrystaU. Brandes.

2 CaO 56 .... 14-67 14-54

C»H"0« 182 .... 47-64 47-96

16 HO 144 .... 37-69 87-60

C»HWCa«08 + 16 Aq 382 .... 100-00 100-00

Camphorate of Magnesia. — Bibasic. — Translucent bitter prisms, which contain 17 p. c. MgO (C^H^'*Mg^O^»18'0 p. c. MgO), become moist on exposure to the air and dissolve in 6*5 pts. of water at 2*5^. Brandes.) -~ When camphoric

acid is heated with water and excess of magnesia alba, the filtrate yields by evaporation, under apparently similar circumstances, crystals varying in their amount of water, whilst another part of the salt effloresces. — The crystals effloresce in the air, and give off their water of crystallt- sation below 120°, without suffering any further alteration at 200°. Those which contain 15 At. water, dissolve in 2-5 pts. water at 20°. (Kemper, JEpist. comm,) — Camphorate of magnesia dissolves in 54 pts. of absolute alcohol at 3*7° (Brandes); it is insoluble in cold alcohol, and dissolves with decomposition in hot alcohol. (Bouillon.)

•

Kemper, CrysiaU. mean,

2MgO 40 .... 11-20 11-21

C»H"0« 182 .... 50-98

15 HO 135 .... 37-82 3804

C»H"Mg»0» + 15HO 357 .... 100-00

CrytttUt. Kemper.

2 MgO 40 .... 9- 13 9-04

C»H"0« 182 .... 41-55

24 HO 216 .... 49-32 49-82

C»H"Mg»08 + 24 HO 438 .... 100-00

Cfrysials and ejjtoreeced $alt, Kemper.

2MkO 40.... 8-60.. 8-68 ..„ 8-91

C*0H"O« 182 .... 39-14

27 HO 243 .... 52-26 52*48 .... 5358

C»H"Mg«08 + 27 HO 465 .... 100-00

b. Monobancf When the aqueous solution of the bibasic salt is heated, iLe camphoric acid separated from an equal quantity of it, and the solution left to cool, it deposits camphoric add, but does not form a monobasic salt. (Kemper.)

CAMPHORIC ACID. 461

Camplutraie of Alumina, — Obtained by boiling hydrate of alamina with camphoric acid and water, and eyaporating the filtered solution. — White powder, having a harah, soar, rather bitter taste, capable of reddening litmus, permanent in the air, soluble in 200 pts. of cold, and in a smaller quantity of hot water, sparingly soluble in cold^ easily in hot alcohol. (Bouillon.)

Uixmie GamphoraU. — Aqueous uranio salts form a yellowish precipi- tate with camphorate of potash. (Brandes.)

Campkorate of Manganese. — By boiling carbonate*of manganese with camphoric acid and water^ a solution is produced, which, when left to evaporate, yields crystalline laminsa very soluble in water. (Brandes.) Alkaline camphorates do not precipitate manganous salts. (Brandes.)

Camphorate of Zinc, — Obtained by decomposing the aqueous solutions of the alkaline camphorates with zinc-salts. White precipitate. (Brandes.)

Stannous Camphorate, — White precipitate produced by decomposing the aqueous solution of an alkaline camphorate with protochloride of tin. (Brandes.) The aqueous solution of neutral camphorate of magnesia forms with protochloride of tin, a precipitate which disappears at first, bat afterwards becomes permanent. (Kemper.)

Camphorate of^ Lead, — Bibasic. — Obtained by precipitating aqueous nitrate of lead with camphorate of potash (Brandes); or by boiling the aqueous solution of camphoric acid with neutral acetate of lead, and washing the resulting precipitate with hot water. (Liebig, Boucsein.) — White precipitate insoluble in water. (Brandes.) When subjected to dry distillation, it gives off camphoric anhydride, toother with a small quantity of phorone, and leaves oxide of lead, coloured grey or black by separated charcoal. (Boacsein, N, Br, Arch, 83, 277.)

Al 100*. Boncsdn.

20 C 120 0 .... 29*60 29-29

14 H » 140 .... 3-45 3-48

6 O 48-0 .... 11-85 12-55

2 PbO 223-4 .... 55-10 54*68

C»H"Pb>Os 405*4 .... lOO'OO ........ 10000

Contains 54*5 p. c. oxide of lead.

Rrric Camphorate, — Obtained by precipitating aqueous ferric salts with aqneous camphorate of potash. — Light brown, bulky precipitate insoluble in water. (Brandes.)

Camphorate of magnesia does not precipitate nitrate of cobalt, (Kemper.)

Camphorate of Nickel, — By precipitating aqneous nickel-salts with aqneons camphorate of potash. Qreenish white precipitate, sparingly Boluble in water. (Branaes.)

Camphorate of Capper, — Bibasic, — ^ Produced by precipitating aqueous sulphate of copper with camphorate of potash (Brandes) ; with neutral camphorate of ammonia (Malaguti). •— Light green precipitate, which, when carefully heated, becomes sky-blue, and at a higher tem- perature, dark green, then white, and suddenly black, bums with bright flame and waxy odour, and leaves cnpric oxide. It is nearly insoluble in water, and forms a crystalline compound with ammonia.

463 PRIMARY NUCLEUS C»HW: OXYOBN^NUCLEUS C»H"0».

Brandef. HalagntU

2 CuO 79- i ... SO'3 .... 29-6 ,. 3001

C»H"0« 182-0 .... 097

C"H»Khi«0« 261-4 .... 1000

Afercurous Campkorate. — Bibasic f — By precipitating aqueous mer- curous nitrate with camphorate of soda (Brandes), with caiuphorate of potash (Harff, N. Br. Arch. 5, 300). — White powder, greyish white after drying (Braudea) ; has a bitterish taste (Harff). Turns grey in sunshine. When heated in a tube, it sublimes with very slight alteration, leaving a residue of charcoal. It is not sensibly altered by cold oil of vitriol ; but hot oil of vitriol decomposes it, with separation of camphoric acid. Potash separates black mercurous oxide. (Harff.) — It is in- soluble in cold water (nearly insoluble, according to Brandes)* — By boiling water or cold alcohol, it is partly converted into mercuric cam- phorate. — It unites with ammonia, forming basic ammonio-mercurous camphorate. Dissolves iu 1666 pts. of ether. (Harff.)

Harff.

2 HfifSQ 416 .... 69-5 63-9

C^H"0« 182 .... 30-5

C»H"Hg*08? 598 .... 1000

Basic Ammonio-mercurous Camphorate. — Produced by passing ammonia-gas into water in which mercurous camphorate is suspended, — block, nearly tasteless ponder, containing 8 1 '76 p. c. Hg'O. The moist salt rubbed in the hand yields metallic mercury. Leaves charcoal when ignited. When dissolved in nitric acid, it leaves a white powder ; dissolved in glacikl acetic acid, it leaves mercury; gives off ammonia when heated with potash. — Insoluble in water, alcohol, and ether. (Harff)

Mercuric Camphorait. — Bibasic ? — By precipitating aqueous mer- curic nitrate with camphorate of potash. — White precipitate, having a rather bitter taste. — Heated in a tube, it sublimes partly without decomposition, leaving a residue of oharcoal. — It is not sensibly altered by cold oil of vitriol, but is decomposed by hot oil of vitriol, with separation of camphoric acid, and by potash^ wjth separation of mercuric oxide. — It is nearly insoluble in cold, more soluble in boiling, wf^ter ; dissolves in nitric and hydrochloric acid, and unites with ammonia, forming basic aiiiraonio-mercuric camphorate. Insoluble in alcohol^ but soluble in 1G66 pts. of ether. (Harff.)

Harff.

2HgO 216 .... 54-2 488

C»H"0« 182 .... 45-8

C»H"Hg»Q8 .'. 398 .... 100-0

Basic Ammonio-mercuric Camphoi^ate. — Obtained by pasainj; nuimonia-gas into water iq which mercuric canipliorate is suspended. — White, nearly tasteless powder, containing 70*0 p. c. HgO, and leaving charcoal when ignited. Dissolves in nitric acid, leaving a white powder ; similarly in hydrochloric acid. With potash it turns yellow and gives off ammonia. Insoluble in water and alcohol; soluble in 1000 pts. of ether. (Harff)

METHYL-CAMPHORIC ACID. 463

Camphorate of Silver, — Bibasic. — Obtained by precipitating aqueous nitrate of silver with camphorate of potash (Brandes), with camphorate of ammonia (Laurent). — White precipitate (Brandes), electric (Laurent). — Tnms bluish when exposed to light Melts when heated and burns away, leaving metallic silver. (Brandos.)

Brandes. Laorent.

2A|fO 232 .... 56*0 551 554

C»H"0« 182 .... 440

C»H"Ag208 414 .... 1000

Camphorate of Platinum. — Aqueous camphorate of soda forms with bichloride of platinum a white precipitate, sparingly soluble in water. (Brandes.) Camphorate of magnesia does not precipitate bichloride of platinum. (Kemper.)

Camphoric acid dissolves in alcohol, in ether, and in oils, both Jlxed and volatUe^ — It dissolves in |. pt. boiling, and 1 pt. cold alcohol (Bnchholz); in 0'94 pts. alcohol at 8*7^ m 0*89 pts. at 12*5% in 0-79 pts. at 25°, in 0*59 pts. at 37-5°, and in 068 pts. at 62-5°. (Brandes.)

Appendix to Camphoric Acid.

Isomeric Modifications of Camphoric Acid.

1 . Laivo-camphoric acid. — Obtained from the IsBTo-rotatory camphor of Jfati'icaria Parthenium, L. Tp. 850), by boiling with nitric aoid^ in tbe same manner as ordinary camphoric acid from ordinary camphor. — The acid thus obtained possesses Issvo-rotatory power equal in amount to the dextro-rotatory power of ordinary camphoric acid^ with which it agrees in all other properties. (Chautard.)

2. Paracamphoric acid. Adde racintique camphorique. — By evapor- ating an aqueous mixture of equal quantities of ordinaiy camphoric and liBvo-campnoric acid, crystals are obtained, destitute of rotatory power, but agreeing in other respects with camphoric acid. (Chautard.)

Methyl-camphoric Acid.

C«H»0« = C»H*0«,C»H»*0«.

Loir. (1853.) N. Ann. Chim. Phys. 37, 196; N. J. Pharm. 22, 288; N. Ann. Chim. Phys. 38, 483.

MeihyleamphertUure, MeihylencamphersH'ire, Camphermethylerudure, Acide ccmphovMthylique, Acid methyl-camphorique.

Formation and Preparation. By distilling 2 pts. of camphoric acid with 4 pts. wood-spirit and 1 pt. oil of vitriol, cohobating the distillate twice over the residue, mixing the alcoholic solution of the viscid, brown distillate with water, washing the viscid oil thereby separated wit

464 PRIMARY NUCLEUS C»HW: OXYGEN-NUCLEUS C»H«0^

water, and leaving it to stand exposed to the air or under water till it solidifies in the crystalline form. The collected crystalline masses are pressed between filtering paper and boiled with water^ set aside till they have again solidified in the crystalline form^ then collected and dried over oil of- yitriol.

22 C	132 .... 61'60	Loir. .. 61-37
18 H	18 .... 8-41	8*48
8 O	64 .... 29-99	.. 30-15

C2H*03,C»H"0« 214 .... 100-00 100-00

Decompositions, 1 . When Iieated, it forms without loss of weight a viscid oil, which becomes opaque some hours after cooling ; if heated above the melting point, it is resolved into camphoric anhydride, a small quantity of viscid liquid (perhaps camphorate of methyl), and a small quantity of charcoal. — Bui-ns, when set on Jire, with a bright fuliginous name. — 3. By distillation with hydrate of potajsh, it is resolved into wood-spirit and camphorate of potash.

Comhlnations, Methylcamphoric acid is slightly soluble in water, — - Aqueous or alcoholic methylcamphoric acid is not altered by lime-wcUer or dissolved baryta-salts; it is clouded by baryta-water, but becomes clear again on the addition of a small quantity of nitric acid ; with aqueous acetate of lead, it forms a white crystalline precipitate, soluble in excess of the precipitant; with cupric acetate, a crystalline greenisli precipitate ; it is but slightly clouded by nitrate of silver, but reduces oxide of silver,

Methylcamphoric acid dissolves readily in alcohol, ether, or chloroform, and crystallises by evaporation of the solvent.

Camphorate of Ethyl-

C»H«0« = 2C*H*0,C«H^*0«.

Malaouti. (1837c) Ann. Chim. Fhys. 64, 152; /. pr. Chem. 11, 294; Ann. Fharm. 22, 32; abstr. J. Pharm. 23, 75, and 513; EeperU 61, 123.

Camphoric ether, Camphemaphtha, eamphers&ures Aeihyhsydf Campher^ farmeiter, Camphorate d*Myle, Ether eamphoriqne.

Properties. Rhombic prisms belonging to the right prismatic system, having the acute lateral edges truncated, and with 4-sided summits formed by the faces of a rhombic octohedron. Fig. 67 without p. — M : M = 106^ 30' ; u:t= 126° 45' ; a : t* = 135° 50' ; a : ^ = 115^ 25' ; a : a ss over tho obtuse lateral edge of the rhombic prism = 129^ lO' ; a : a over the acute lateral edge of the rhombic prism = 109° 50'. — By rapid evaporation of the ethereal solution, hemihedral cryst^ are obtained : in that case only the faces a and t appear, and, by the predominance of the ^faces, the crystals acquire the appearance of four- sided tables. Cleavage at right angles to t.

Melting point 68^ — !^tatory power 51*4° to the right The alcoholic solution reddens litmus.

STHTLCAMPHORIC ACID. 465

Po)*fnaiion and Preparation. EtHjl-camphorio acid is sabjecied to diy dlBtillation ; the distillate^ which solidifies in the crystalline form, is dissolved in hot alcohol ; the solution is left to itself till it has deposited camphoric anhydride ; the mother-liquor is precipitated by water ; the oil which separates and gradually becomes thicker, is boiled with weak aqueous potash^ washed with water, dried in yacuo, and distilled pej* se j and the distillate is again washed with water, and dried in yacuo.

Properties. Amber-yellow oil, of sp. gr. 1*029 at 16% and boiling at 285*^^-287°. Has a strong, unpleasant odour, and a bitter^ yery disagreeable taste. Neutral.

Malagati.

28 C 168 .... 65-6 641

24 H 24 .... 8-9 9-4

8 O 64 .... 25-5 26-5

2;C<H«0,C»H"0« 256 .... 100-0 100-0

Deeompodtions. 1. Tarns brown when heated aboye its boiling point, and leaves a black residue,- yielding, however, a distillate of pure camphoric ether. — 2. It requires to be heated before it can be set on fire by a fiaming body, and then bums with a quiet, white, strongly fuliginous flame. — 8. W^ith dry cMorine gas, it turns yellow, becomes heated^ increases in volume, gives off hydrochloric acid, and fonns chlorinated camphoric ether. (Malaguti, Ann. Chim, Pkys. 70, 360.) Acetic acid is formed at the same time. — 4. It dissolves in hot oil of vitriol without evolution of sulphurous acid, but does not separate on addition of water : the solution smells like oil of lavender. — 5. It is not decom- posed by nitric or hydrochloric acid, even with aid of heat. — 6. When boiled for a very long time with strong aqueous potash, it forms alcohol and camphorate of potash. — 7. It is not decomposed by ammonia.

Combinations. Insoluble in water, — It dissolves in cold oil of vitriol, and is precipitated in its original state by water. — It dissolves iodine, which can afterwards be only partially separated by heat, without decomposing the camphoric ether. It dissolves bromine, and that sub- stance may oe completely expelled from it by heat.

It dissolves in alcohol and in ether. (Malaguti.)

Ethylcamphoric Acid. C»*H*«0* = C*HW,C«H"0«.

Malaguti. (1837.) Ann. Chim. Phys. 64, 152; J.pr. Chem. 11, 294; Ann. Pharm. 22, 45; abstr. J. Pharm. 23, 75, and 513; Sepert. 61; 123.

Camphomnic acid, WeineamphersUure, Aethyl-eamphersdure, Aeide ean^Ao* vinique, Aeide eampkoiihylique, Acide ethylcamphoripie*

Formation and Preparation. 2 pts. of camphoric acid or camphorio anhydride are distilled with 4 pts. of absolute alcohol and 1 pt. of oil of vitriol ; the distillate amounting to about half the mixture is cohobated ; the residue in the retort is mixed with water; the oil which then separates is washed with water, dissolved in aqueous potash, precipitated

YOL. ziy. 2 H

466 PRIMARY NUCLEUS C»H": OXYOBN-NUCLEUS C»H»H)'.

bv hydrooUorio aoid, and dissolved in alcohol after washing with water ; the solution is left to eraporato ; and the residue is dried at 130^

FroperHei. Limpid, sjrrupy liquid, of ap. gr. 1*095 at 20* d^. Begbm to boil at 196^ but the boiling point soon rises, in consequence of decom- position. Has a rather peculiar odour, disagreeably bitter but not acid. Reddens litmus after some time only,

MalagatL

24 C 144 .... 63-15 62-55

20 C 20 .... 8-77 8-87

8 O 64 .... 28*08 28-58

C*H»0«,C»H"0« 228 .... 10000 10000

Ethyl-camphoric acid is resolved by heat into camphoric anhydride, camphoric ether, water, a small quantity of alcohol, and carburetted hydrogen gas ; by prolonged contact with tmterf or by boiling therewith, it yields camphoric acid and camphoric ether, and by continued boiling with aqueous. a^^i| it is converted into camphoric ether and an alkaline camphorate.

Combinattani, Ethylcamphoric acid unites with bases, forming the ethylcamphorata. These salts dissolve in aqueous alkalxB aud are preci- pitated therefrom by acids. The limey baryta, stnmtia^ magnesia, and manganotu salts are soluble in water; the alumina, iron, zinc, lead, copper and mercury salts are insoluble or sparingly soluble in water.

JBthylcamphoraXe (^ Ammonia, — An alcoholic solution of ethyl* camphoric acid is not quite saturated with ammonia, the unneutralised portion of the acid is separated by water, and the filtrate is evaporated. — The salt has an alkaline reaction, but does not contain free ammonia.

Ethylcampkorate qf Silver, — Aqueous ethylcamphorate of ammonia is precipitated by nitrate of silver, and the precipitate is dried at 100^. When heated, it blackens, melts, gives off a fragrant odour, and leaves 31-9 p. c. silver (C"H«AjeO«=:32-2 p. c. Ag).

Mihyloamphorate of Copper, — By decomposing ethylcamphorate of ammonia with sulphate of copper, a sesquibasic salt is produced, con- taining 4 At. water.

Ethylcamphoric acid is slightly soluble in alcohol and in ether. (Malaguti.)

Chlorinated Camphoric Zither.

C»ff''Cl*0* = 2C*H»CP0,C«H"0«.

Malaguti. (1839.) Ann, Chim. Phys, 70, 360; J. pr, Chem. 18, 45; Ann, Pharm, 32, 33; N, Br, Arch, 12, 150; RepeH. 70, 134,

CAlorcamphemaphtka, Campher-Chlorvinester, Ether can^horique chlontrS, Camphorate d^ethyle hichlori (comp. vii^ 30lf).

Preparation, Camphorate of ethyl is saturated with dry chlorine ; the excess of chlorine is removed by heating the yellow liquid ; and the cooled thickish mass is washed, first with weak aqueous potash, then repeatedly with weak alcohol, dissolved in absolute alcohol, and evapor* ated in vacuo.

CAMPHORIC ANHYDRIDE. 467

Properiies. Limpid, viseid oil of so. gr. 1 *d86 at 14''. Hu an agree- able odour, and a strongs persistently bitter taste.

Ifalaguti.

28 C 168 ... 42*6 .....,.• 42*1

80 H 80 .... 6-1 5-4

4 01 „ 148 .... 36-0 35-3

8 O 64 .... 16-3 17-2

2 C*H»C1«0,C»H"0« 894 .... 100-0 1000

DecompaUumi. 1. When keated, it becomes risoid and then decom- poses.— 2. Aqueous potash acts upon it very slowly, if at all; by alcO' holic potash, it is converted into camphorate and acetate of potash and chloride of potassium :

CfflH»Cl<0» + 8(K0,H0) =r C»H"IC*0« + 2C*H»K0* + 4 KCl + 8 HO.

Combinations It dissolves in 8 pts. of alcohol and in an equal quan- tity of ether, (Malaguti.)

Oxygen-nucleus C*H**0*.

Camphoric Anhydride.

Bouillon-Lagrakgb. (1799.) Ann. Chim. 2B, 153; CrelL Ann. 1799,

2,221. Laurent. Ann. Chim. Phys. 6d| 207; Ann, Pharm. 22, 41, and 135;

abstr. J, Pharm, 23, 513. Malaguti. Ann, Chim, Phys. 64, 152; J. pr. Chem. 11, 294; Ann,

Pharm. 22, 41; J. Chim. med. 13, 107.

Anhydrous Camphoric acid, Ojeyde dc Camyhisc. (Laurent.)

Formation. By the action of heat on camphorio acid. (Bouillon, Laurent.) Also on ethyl* camphoric acid (Malaguti), methyl-camphoric acid (Loir. iV. Ann. Chim. Phys, B7, 196), camphoranilio acid (Laurent & Gerhard t, ff, Ann, Chim, Phys, 24, 191), camphorate of lead (Boue- sein, i\r. Br, Arch, 8*3, 773), ana by heating alkaline camphorates with an equal quantity of perohlorovinic ether. (Malaguti, Comyt, rettd. 41, 625; J, pr, Chem. 67, 277; Chem. Centr, 1855, 874.) —2. By the action of pentachloride of phosphorus on camphoric acid. (Gerhardt & Chiozza, Compt. rend, 36, 1050; Ann, Pharm, 87, 290; J. pr, Chem. 59, 452.) — 3. By dissolving camphoric aeid in oil of vitriol, and preci- ])itating the solution with water. (Walter, jAT. Jinn. Chim. Phys., 59, 177.)

Preparation. 1 . Camphoric acid is distilled per m, and the white sublimate which settles on the neck of the retort is collected. (BouUlon, Lagrange.) — 2. Ethyl- camphoric acid is distilled ; the solidifying distil- late is dissolved in boiling alcohol ; and the crystals of camphoric anhy- dride which separate after the cooling and further evaporation of the solution, are separated from the camphoric ether which remains dissolved in the mother-liquor, and purified by recrystallisation from alcohol. (Malaguti.)

2 H 2

468 PRIMARY NUCLEUS C^H^*: OXYGEN-NUCLBUS C«H"0*,

Properties. Long white prisms. (Malagnti.) — Crystallises from alcohol in long, upright, six-sided, very flat prisms, with rhomhic base and broad faces on the two obtnse vertical lateral edges ; the terminal faces are replaced by acumination-faces, two of which are rhombic and rest upon the acute vertical lateral edges, and two triangular, resting on the two vertical faces which replace the obtuse lateral edges of the prism. (Laurent.) Sp. gr. 1*194 at 20*5°; begins to sublime in long needles at 130**; melts at 217° (Malaguti); at about 220° (Boucsein); distils com- pletely at 270°. ^— Tasteless at firsts but after a while produces irritation in the throat. Neutral. £lectric when rubbed. (Malaguti.)

Malagati.

20 0 120 .... 65-93 66'24

14 H 14 .... 7-69 7-90

6 O 48 .... 26-38 25-86

C»H"0« 182 .... 100*00 100-00

Liebig. Laurent. Walter. Boucaein.

20 C 65-71 64-87 6555 65-70

14 H 7-85 7-87 791 7-76

6 0 26-44 27-26 2654 2654

C»H"0« 100-00 10000 100-00 100-00

The colourless solution of camphoric anhydride in cold oil of vitriol ffives off carbonic oxide when heated to 45°-— 50°, abundantly at 60% and forms sulphocamphoric acid (xiii, 379, Walter, i\r. Ann, Chim, Fhys. 9, 177). Camphoric anhydride dissolves in anhydrous or in fnmine sulphuric acid, with evolution of sulphurous acid, forming a dark-coloured liquid. — Distilled with oil of vitriol and absolute alcohol^ it yields ethyl- camphoric acid. (Malaguti.) — 2. When carefully distilled with anhy^ drous phosphoric acid, it gives off a gaseous mixture consisting of 1 vol. carbonic acid and 4 vols, carbonic oxide, yields a yellowish oil having a penetrating, but not disagreeable odour, and isomeric with oil of tur- pentine or with naphtha (88*30 p. c. C, 11*27 H), and leaves a black acid residue. (Walter, Ann, Chim, Phys, 75, 212.) — 3. Alcoholic camphoric anhydride saturated at the boiling heat with amtnania-gcts (or with ammonia or bicarbonate of ammonia, according to Malaguti), yieldB camphoramate of ammonia (Laurent, Compt, chim. 1845, 141 ; Ann. Phami. 60, 326), and probably also camphoramide. (Laurent, Bev, scient. 10, 123; /. pr. Cfhetn. 27^314.) — 4. It is not acted upon by aniline in the cold^ out when heated with it, yields camphoranilic acid and camphoianil, (Laurent & Gerhardt, JVT Ann, Chink Phys. 24^ 191.)

Comhinations. Camphoric anhydride dissolves sparingly in cold water, somewhat more abundantly in boiling water (Malaguti), though with difficulty, and by prolonged boiling with water, is completely converted into camphoric acid. (Laorent, Boucsein.) According to Malaguti, the hot aqueous solution deposits unaltered camphoric anhydride^ even after two hours* boiling.

Camphoric anhydride does not absorb ammonia in the cold. (Mala- gnti, Laurent, Compt. chim, 1845, 141.) — When ammonia-gas is passed over melting camphoric anhydride, a yellowish liquid distils over, which on cooling solidifies in a transparent mass, easily soluble in alcohol and water, and not giving off ammonia when boiled with aqueous potash.

J

CANTHARIDIN, 469

Salta of Camphoric anhydnde. Alcoholic caxnplioric anbydride does not precipitate metallic salts. (Boucsein.) — Uamphoric anhydride appears to be capable of forming peculiar salts with bases (Laurent, Compt, chirru 1845, 141): it first unites with water, and then forms with bases, salts which have the same composition as the ordinary camphorates, but exhibit different properties. (Malaguti.) — Camphoric anhydride boiled with aqueous potash forms a camphorate of potash which crystal- lises, not in needles like the ordinary camphorate, but in broad pearly laminad. (Malaguti.) — The solution produced by boiling camphoric anhydride for some time with milk of lime, deposits by evaporation, films, which require long boiling with water to dissolve them : alcohol added to the solution throws down small white needles containing 14 p. o. Ca, agreeing approximately with the formula C^H*'Ca'0'^ (calculation = 18*67 p. c. Ca). Laurent (Cbmp^. chim. 1845, 141; Ann. Fkai-m, 60, 830).— The aqueous solution of the potash-salt added to aqueous stdphaU of copper, forma a precipitate containing 80*14 p. c. cupric oxide. — The aqueous solution of camphoric anhydride is not precipitated by netUral acetate of lead. (Malaguti. )

Camphoric anhydride dissolves in cold^ and abundantly in hot alcohol (Malaguti), less easily than camphoric acid. (Laurent.)— It dissolyee in cold Mer, more readily than in alcohol. (Malaguti.)

OxygevrnwUm C**H"0*.

Cantharidin. C»H»0» = C»H"0«,OM

RoBiauBT. (1812.) Ann. Chim. 76, 802; Schw. 4, 198; J. Pharm. 14,

S63; J. Pharm. 21, 123. Thierry. J. Pharm. 21, 44; Ann, Pharm. 15, 314; J. Ohim. mid. 11,

189; J. pr. Chem. 8, 54. Begnault. Ann. Chim. Phyn. 68, 159; Ann. Pharm. 29, 814; J. pr.

Chem. 16, 816. Lavini & SoBRERO. N. J. Pharm. 7, 467; abstr. Sepei^ 100, 562. W. Prootbr, Jun. Pharm. J. Trans. 12, 287; Tiertelj. J. Pharm. 2,

822.

Vmeatmg princ^U qf Cantharides, Canihariden^an^her. Discorered by Robiqaet in 1812.

Source. In Spanish files or cantharides (Lytta vesicataria. Fabric.); in Lytta viUata (Dana, Schw. 30, 247) ; Mylabris Cichorii (firetonneau, J. Pharm. 14, 67) ; in Meloe violaceus, M. aiUttmnaliSf M. fuciOf M. punctattu, M. variegaXus, M. Scahrosus, M. majalis. (Lavini & Sob- rero.)

Preparaium. From Cantharides or Mylabris Cicharii, both of which contain about 0*4 p. c. of cantharidin (Warner, VierUlf. pr. Pharm. 6, 86), more easily from the latter, as they contain less oil. (Robiquet.) — ' 1. Aqueous extract of cantharides is evaporated to dryness ; the residue is exhausted with hot strong alcohol ; the solution evaporated to an extract ; this extract is exhaust^ with warm ether ; and the solution left to evaporate in the air. The residue is treated with cold alcohol to

470 PRIMARY NUCLEUS C»H« : OXYGBN-NUCLEUS C»H»0«.

remoye a yellow substance, and the residual cantbaridin is dried. (Robiquet.) — Larini &, Sobrero boil powdered melo^ with^ water, eva- porate the decoction, exhaust the residue with warm ether, and leave the ether to evaporate. — Direct exhaustion with alcohol yields a lerj oily extract, which does not deposit cantbaridin. (Lavini k Sobrero.) — 2. Powder of cantharides is exhausted in a displacement apparatus, with ether made to run through it very slowly; the nearly pure oil which first passes through is collected apart ; aud only the following tinctures are treated for cantbaridin, by distilling off the ether, and purifying the crystals which separate from the residue, by pressure and recrystallisation from alcohol. (Robiquet.) — Thierry likewise uses ether-alcohol of sp. ffr. 0*82, or alcohol of sp. gr. 0*65, and macerates the cantharides therewith for a few days, before introducing them into the displacement apparatus. He distils off the ether and alcohol from the extracts, separates the oil from the residue, and obtains cantbaridin from the aaueous solution by crystallisation; pressure, and recrystallisation with the aid of animal charcoaL

Properttei. Colourless, rectangular four-sided prisms belonging to the right prismatic system, with four-sided summits resting on the faces of the prism. Faces p, m, t and u of Fig. 53. — t : t =107^ 80'; t : p — 121° 15'; « : w=123°28'; tt:m = 118° 15'; i: tt= 138° 55'. The crystals exhibit a tabular form from predominance of the p- or m- face. Cleavage parallel to p and m. (Mari^rnac, Recherehes sur les fottnes a-yt^ tallineSy Geneva. 1855.) — Rhombic prisms or micaceous laminae. (Robiquet, Thierry.) Generally, four-sided flat prisms, grooved so as to give them a step-like appearance. Separates from ether or acetic acid^ in flat, oblique, four-sided prisms with dihedral summits, and belonging to the rectangular system. (Procter.) — Cantbaridin does not volatilise with vapour of water, nor sensibly in a test-tube at 104°; at 121° it vola- tilises slowly, at 162^ somewhat more quickly ; it melts at 208° — 210" (at 210°, according to Robiquet and others), and then volatilises quickly in white fumes, which condense in fine needles (Robiquet and others), in rectangular prisms having a strong lustre and sometimes iridescent. (Procter.) — Inodorous. !N^eutral. Sinks in nitric acid of sp. gr. 1*88. (Procter.) Placed on the skin, even in extremely small quantities, it raises blisters (Robiquet and others); — not by itself ia the dry state, bat quickly when moistened with oil. (Procter,)

Regnault. Lavini 9t Sobrero.

. 61-22 60-36 61-17

.. 61 2 6-22 6-30

.. 32-66 33-42 32-53

20 C 12 H	120 12
8 0	64

C»H»0« 196 .... 100-00 100-00 IDOOO

According to most authors, ft is C'^^H'O*, bat Gmelin placed it among compoaada eoataioing 20 At. C* (Kr.) — Isomeric with picmtozln.

J)ecompo»itwn§k 1. Heikted on platinum foil, it huf^i with a white flame, leaving an easily combustible charcoal. (Lavini A Sobrero.) — *2, When cantbaridin moistened with oil of vitriol is heated on a watoh- glass to commencing ebullition, and ehromate of potash is then added, brisk effervescence takes place, a splendid green mass is formed, and after some hours, a solution which ultimately beoomee turbid and of a leaf-green colour» (Eboli, M'tuagtro de Lima; i\r. Br, Arch^ t7, 167.)

VOLATILB AORID PRINOIPLBt. 471

Chmbinaiunu, Gantharidin is insoluble in water, whether oold or

boiling. It is however rendered soluble in water by the yellow matter of cantharidea, ao that hot water extracts therefrom the whole of the cantharidiQ. (Robiqnet and others.) — Jt dissolves without colour in hot oil of vitriol, and is preoipi- tated bj water. — It is nearly insoluble in cold hydrochloric add of sp. gr. 1 '18, and \vC aoXd. phosphoric add; a little more soluble in those aoids when hot. — It dissolves abundantlj in boiling niiric acid, searoely at all in hot formic acid, slightly in oold, more easily in hot acetic acid of sp. gr. 1*041; 40 pts. of glaoial aoetio aoid dissolve completely with the aid of heat, 1 pt. of cantharidin. Aocordin|; to Robiqaet, it it insolable in acptic acid. From all these liquids, the canthandin crystallises on cooling. (Procter and others.)

It is insoluble in aqueous ammonia (Thierry), slightly soluble in the hot liquid (Procter). — It dissolves in potash and soda-ley, and is preoipi- taled therefrom by acetic acid. ^Thierry.)

Slightly soluble in alcohol ana acetate of ethyl when cold, more soluble when heated ; less in wood-epirit, more in ether (in 84 pts. of oold ether, according to Warner); its best solvents are aceione and Moroformy which latter abstracts canthamd in from its aqueous solutions. — It dis* solves in hot ot^ of turpentine^ in the oils of dnnamout dovee, and aaeeafrae, also in almond-oU, olive-oil, and lard, and crystallises on cooling. (Thierry and others.) — According to Procter, Cantharadin is extracted from cantharides by glacial acetic aeid, oil of turpentine, and olive* oU, but only the last-mentioned retains any considerable quantity of it in solution after cooling*

Appendia to Oanlharidiv^

Volatile Acrid Prinoiplae.

The irritating action of certain plants on the organs of sensation, is in all probability due to peculiar substances contained in them but not separable, and perhaps allied to the volatile oils or camphors. They were first distinguished as peculiar substances (Frtncipia aera pkmtarum) existing in certain plants by Oren {8yet, HandJb, d, Chem. 1794, 2, 220); they are very volatile, are lost in the drying of the plants, generally pass over in the distillate when the plants are distilled with water, and impart to the distillate their acrid burning taste ; in some cases, how^ ever they are decomposed during distillation. They are often found in the alcoholic extract of plants, and are the cause of the exciting action of such extracts on the organs of sensation : they are especially distin* guished by their easy destmctibility. The most important of these volatile acrid principles are the following :

Volatile acrid principle in Aconitum NapeUus, (Braconnot, Ann. Chim. Phys, 8, 189 ; Geiger, Mag. Pharm. 84, 62.) In the leaves before flowering, in the seeds after flowering ; adheres to the chlorophyll in the leaves. It is not completely extracted by repeatedly pressing the plant with water, but alcohol extracts the whole of it. The fresh herb distilled with water in the chloride of calcinm bath, diflTuses a peculiar odour, irritating to the eyes, but not very acrid, and soon ceasing, and yields at flrst a distillate having a very acrid taste and odour, while the residue is quite destitute of acridity. The distillate loses by rectification mora and more of its odour, which is destroyed at 100^

472 PRIMABT NUCLEUS C»HMs OXTGEN-NUCLEUS C»H»0«.

VolaiUe acrid principle in Arum Dracuncultu. (Landerer, Meperi. 57, 199.) Oocars in the freeh roots, and in the inner blae put of tho flower, bat especiallj in the spadix. The fresh roots, which haye a sharp, burning taste, lose it by boiling or roasting ; the bmised spadioes redden the skin when rubbed into it, but without raising blisters^ and yield bj distillation with water, an aqueous distillate, haying a sharp, tear-exciting odour, and a faint herb-like taste. The fresh spadioes and the blue parts of the flowers yield, after digestion with alcohol, a yeiy fiharp-tasting extract, the most yolatile distillate of which produces i^dening and burning of the skin, while the less yolatile residue goih tains, in addition to wax and blue colouring matter, a sharp-tasting resin soluble in ether and in yolatile oils.

Volatile acrid principle in Arum macidatum, (Stendel, Diu. inaug. de acred. noveU, i^et. Tubing. 1805; J. Dulong, J. Pharm, 12j 156; Tauhenb. 1827j 65.) In the fresh roots, which haye a sharp pungent taste, if pressed during mastication against the sides of the month, bnt otherwise only a slight burning taste : the juice has scarcely any taste. They yield a neutnd distillate which has not an acid but a sickly taste, and an empyreumatic odour ; they yield non-acrid extracts with water, alcohol, acetic acid, and oliye-oil, but neyertheless lose their acridity, which is quite destroyed by the action of those liquids.

Vclatfle acrid principle in Clematis viticeUa. — - The fresh plant yields by distillation widi water, a small quantity of yellow oil which floats on the water, and has a burning taste.

Volatile acrid principle in Clematis Jlammtila. (Braconnot, Ann, Ohim. Phys, 6, 1 34.) The fresh plant yields an aqueous distillate, with- out oiUdrops, which has a sharp caustic taste, reddens the skin, and causes pain, but is not acid. — ^The yolatile acrid principle may be extracted from the plant by fixed oils^ but is lost when the plant is boiled with water.

Volatile acrid principle in HdUhorus foettdus. (Braconnot, Ann. Chim. Phys. 6, 138.) The stems and leayes distilled in the fresh state, yield a distillate haying a yery acrid taste and odour.

Volatile acrid principle in Daphne Mezereum, (Landerer, Repert, 58, 114.) The bark yields by distillation with water, a neutral liquid, haying a sharp burning taste^ and, by exhaustion with alcohol, a deep green solution haying a yery acrid taste, and yielding by eyaporation a thick extract, from which ether remoyes all the acridity. The alcoholic extract, mixed with neutral acetate of lead, filtered, and freed from excess of lead by sulphuretted hydrogen, leayes by eyaporation an extract together with a small quantity of an oil, which has a sharp burning taste, reddens the skin, dissolyes in aqueous potash, and, when separated from the potash-solutiou by distillation with phosphoric acid, is transparent and colourless, and has an acid, acrid, and pungent odour. — The yolatile acrid principle is not extracted from the bark by digestion with pure water, or with water containing hydrochloric acid.

Volatile acrid p>n,nciple in Polygonum hydropiper. (John, dessen. chem. Sckwift, 3^ 14.) The plant yields by distillation in non-luted yessels, a tasteless water, but in luted yessels, a water haying a burning taste : the residue, in either case, is destitute of acridity.

Volatile acrid principle in Banunculus biUhosiu, E.Jlammula, E, lingua, and R. acris, (Braconnot, Ann. Chim, Phys. 6, 138.) The stalks, and more especially the roots of these plants, yield by distillation with water a distillate which has an acrid taste and an odour of radish, becomes turbid after two months^ and deposits white flocks, together with small

PICROTOXIN. 473

shining micaGeonB soalesy without losing its taste or odoar. The residue of the distillation is free from acridity. — Banuncultu lanuginotus^ B, auricomuSf R. phyhanoliSf £. repens, and JB. ficaria, do not yield an acrid-tasting distillate by distillation with water. — The yolatUe acrid principle in Rantmcuhu teelereUtu will be described with Anemanin C^H^'O^.

The volatUe acrid principle of certain Sponges (LeteUier, Mag. Pharm* 16j 187>) is destroyed by distilling them with water^ or by digesting them with vinegar, alcohol, or aqueous potash.

Picrotoxin.

C«H«0* = (?«H«0*,OM

BouLLAY. Fully, BuU. Fharm. 4, 5; Ann. Chim. 80, 209; 8chw. 7, 365; further, J. Pharm. 5, 1; Taschenbuch, 1820, 122; Bepert. 7, 76; abstr. GHh. 63, 319; further, «7. Fharm. 11, 505; abstr. Bepert. 23^ 166; Kaan. Arch. 7, 374; further, J. Fharm. 12, 106.

Merck. N. Tr. 20, 1, 134.

DcFLOs, Schvf. 64, 222.

Pellbtier & CouBRBE. Ann, Chim. Fhys. 54, 181; Ann, Fhai^m. 10, 183.

Menispermin (but different from the menbpermin of Pelletier). (Conerbe.) Coccu/tn. Picrotaxie acid. — DiscoYered by Boidlaj in the seeds of Memtpermum Coceuiut.

Freparation. t. The seeds separated from their husks are boiled with water ; the decoction is evaporated ; the residue exhausted with boiling alcohol of 38° B ; the filtrate left to itself in a cool place for several days, any fat that separates being removed, and then evapo- rated to dryness ; the residue comminuted with a small quantity of water and •}- of its weight of magnesia ,which forms insoluble compounds with any acid that may l^ present and with the fat ; the mixture completely dried, and repeatedly boiled with alcohol of 30^ ; and the solution evaporated to the crystallising point, after decolorisation with animal charcoal. (Bonllay.) The picrotoxin thus obtained may be purified by solution in boiling alcohol of 20*^ B. and spontaneous evaporation. (BouUay.)

The aqueous decoction merely freed from fat deposits, by evaporation, nodules, which, when treated, first with cold and then with hot water, leave colourless picrotoxin, to be purified by recrystallisation. (Meissner, Bert. Jahrb. 1827, 1, 132.) — Casaseca (/. Pharm. 12, 99 ; abstr. Kastn. Arch, 7, 376) likewise exhausts the watery extract with alcohol; evaporates ; removes the fat ; sets aside the remaining extract in contact with magnesia ; and boils it for 24 hours with absolute alcohol, where- upon picrotoxin crystallises from the filtrate on evaporation. — If the aqueous decoction evaporated to a thick syrup be set aside for 24 hours with -^^ of baryta or magnesia, then repeatedly boiled with absolute alcohol, the tincture evaporated to dryness, and the residue again treated with alcohol, — the alcoholic solution, after being decolorised by animal charcoal, yields crystals of picrotoxin by evaporation and cooling. (BouUay.)

2. The decoction is precipitated with subacetate of lead ; the dis- solved lead removed from the filtrate by sulphuretted hydrogen; the residue exhausted with alcohol; the solution filtered and evaporated;

474 PRIMARY NUCLEUS C^^H^: OXYGEN-NUCLEUS C»HttO«.

the residae again exbaasied with alcohol ; and the eolation in alcohol, filtering, and evaporation are repeated till the extract beoomes complete! j soluble in alcohol. The alcoholic solution evaporated to a syrup is then mixed with carbonate of potash, which, by removing the acetic acid, separates the piorotoxin after a while in the crystalline form ; an addi- tional quantity of picrotoxin is obtained by evaporation from the mother-liquor, which likewise contains sugar and colouring matter ; and the entire product is washed with cold water and crystallised from water containing alcohol. (Boullay.) — Crystals of picrotoxin are likewise obtained from the aqueous decoction merely precipitated with subacetate of lead and freed from lead. (Boullay ; Schrader, Br. Arch, 8, 1 47.)

3. Bruised grains of cocculus are exhausted by boiling with alcohol of sp. gr. 0*85 ; the filtrate is distilled till the residue amouuts to about -|^ of the weight of the grains ; the fat is removed after cooling; the residue boiled with half its weight of water ; the solution filtered at the boiling heat ; and the filtrate (after addition of a small quantity of acid, according to Pelletier & Couerbe), brought to the crystallizing pomt. (Vogel, Br, Arch. 20, 250.) The portion of the extract insoluble in water contains menispermiD, para* menispermin, and a brown acid mentioned below. (Pelletier & Couerbe.) The extract

of shelled grains of cocculus prepared with weak alcohol yields by evaporation, brown pici*otoxin, which may be purified by washing with cold alcohol and repeated solution in water. By further evaporation, an additional quantity of picrotoxin is obtained, but in slender needles of difierent aspect. (Gmelin.)

4. Kukle evaporates the aqueous decoction of coccnlus grains nearly to the consistenco of honey; cools; removes the separated oil ; evaporates to an extract; heats the extract in a distillatory apparatus with alcohol of sp. gr. 0'84 till half the alcohol has passed over ; pours oflf the solution ; and treats the residue repeatedly with alcohol, as long as any bitter substance is thereby extracted. The tincture evaporated to the consist^ ence of honey after the distillation of the alcohol, and shaken up with fresh quantities of ether, yields to this solvent, picrotoxin and menispermin, which latter is immediately extracted from the solution, together with the colouring matter, by agitation with hydrochloric or nitric acid. {ZeiUchr. Ph. v, W, 5, 339.) — When grains of cocculus are treated with alcohol and tartaric acid, the solution evaporated, the residue exhausted with water, and the solution shaken up with ether, the ethereal solution yields crystals of picrotoxin by evaporation. (G. GUnkel, K, Br. Arch, 94, 14.)

5. Wittstock {Be^-z. Jahrb, 3 Aufl., 3, 289) frees the shelled grains from fat by pressure; boils the residue several times with alcohol; distils off the alcohol ; boils the solidified residue with water ; separates the oil, and leaves the picrotoxin to crystallize.

Properties, White shining four-sided prisms. (Boullay.) Some- times slender needles, sometimes flexible silky threads, and transparent plates, sometimes radio-nodular and hard granular masses, varying in character according to the concentration and temperature of the solution and the presence of foreign bodies. (Pelletier & Couerbe.) Without action on vegetable colours. (Oppermann, Duflos.) According to tbe earlier statements of Boullay, it has an alkaline reaction. It has a very bitter taste and poisonous action. Ten grains killed young dogs, with convulsions and vertigo.

(Boullay.) Does not contain any water of crystallisation. ^Pelletier 8c Couerbe.) The alcoholic solution tolfns the plane of polarisation

PICROtOXIN.

475

to the left, L»To-rotatory power = 28*1 ^Bouchardat & Boudet, iT. J, Pharm. 23, 288, J. pr. Chem. 60, 1 18. LM>ig u. Kopp's Jahre$ber. 1853, 194).

20 C	a, ... 120 ....	61-22 24 C 6-12 14 H 32-6« 10 O	(	144 14 80	.... 60-50 .. •••< 0*{lo	Oppermann. mean, 60-21
12 H	IS		5-86
8 O	f>A		33-93
C»H"0«		10000 C^W* Pelletier Sl Couerbe. I mean, , 59'77	Qw .... legnault. mean, 59-52 586 34-62	238	.... 100-00 .. Francis, mean, . 60-26 . 570 . 32-74	100-00
	O	6 00 34-23

10000 100-00 98-70

Isomeric with cantharidin. — According to Oppermann (Maff, Pharm. Zh, 2^7 ; Pogg. 23, 446;, it is C*H»0« = \ 0^H»«0« ; according to Pelletier & Couerbe, C»nFO*. Gerhardt {TraiU ^^ 227) adopu the first formula doubled » Ci<^H>0«. *- It is per- fectlj free from nitrogen. (Oppermann, Erdmann & Marchand, /. pr, Chem. 37, 146, and others.) According to Frauds {Lieb. Organ, Chem, 335), it contains 0-75 -^ 1*30 p. c» nitrogen*

Decompositions. 1. By dry distillation^ it yields carbonio acid and com- bostible gas, a small quantity of acid water, a very large quantity of acid brownish yellow, enipyreumatic oil, but no ammonia, and leaves charcoal. (BouUay .) When heated, it melts like wax, takes fire and leaves charcoal. (Merck.) Melts to a brown liquid and gives off aromatic acid vapours (Gniejin.) Decomposes when heated on red-hot coals, without melting or taking fire. (BouUay.) — 2. It is not altered by boiling with iodine and water, and crystallizes by evaporation, free from iodine and hydriodio acid, (Pelletier & Couerbe.) Triturated with ^^ part of iodine, it forms a red- brown mass which yields a reddish solution on addition of water. ( Vogel, Br, Arch, 16, 155.) It is not altered by sulphurous acid, or chlorine (Boullay), or by iodic acid (Dufios), and is not coloured by vapour of bromine, iodine, or chloride of iodine. (Doun6.) — 3. Cold oil of vitriol dissolves it with yellow colour (without colouring, according to Merck) ; warmed oil of vitriol chars it. (Boullay.) — 4. It dissolves without

• •_• • •■«.« B*^ ■ aft MB m. ^

nunc acia converts il mio oxaiic acm. ^Douiiay.; My iin aqua regia \ likewise yields oxalic acid. (Pelletier ^ Couerbe.) It is reddened by nitric acid (Pettenkofer, Repert., 7, 91) ; not coloured (Merck). — 5. ft does not give off ammonia when treated with hydrate of potash. (Boullay.) By strong ammonia, potash, or soda. It is completely decomposed, especially if gently heated, and from the resulting orange-coloured solu- tion; acids throw down a brown powder similar to that wnich is produced from many organic bodies by the action of potash. (Pelletier 8c Couerbe ; see also Comlfinatfom.) — Aqueous picrotoxin changes the colour of bichro- mate of potash to a fine green. (Duflos.) In alkaline solution, it reduces protoxide of copper to di-oxide. (G. Beckers, jV. Br. Arch, 85, 22 ; G. Giinkel.) Hence Ludwig (^. Br. Arth., 82, 139), who examined it only after boiling with aoids^ was led to regard it as a conjugated sugars

476 PRIMARY NUCLEUS Om^: OXYGEN-NUCLEUS C»H»0«.

compound. ^— Solutions of gold, 9ilvei\ and copper^saUs are not altered by aqueous piorotoxin for several hours, provided light be excluded : feme sulphate is verjr slowly reduced to ferrous sulphate. (Duflos.)

Comhtnaiions. It dissolves in 150 pints of water at 14°^ in 25 pt8. of boiling water (Pelletier & Couerbe, BouUay), in 180 pts. of boiling water (Merck)^ in 1 62 pts. of cold, 54 pts. of boiling water (Duflos)^ in 160 pts. of water at 18|^° Abl. {Oesterreich. Zeitschv. Pharm. S, 201).

With Acids. — According to Boullay, picrotoxin unites with acids to form salts, which, however, is denied by Oppermann and others. -— It does not neutralise the smallest quantity of acid. (Oppermann.) Even a very large excess of picrotoxin does not remove the acid reaction from water containing traces of hydrochloric acid. It crystallises free from hydro- chloric acid from a solution containing that acid. (Pelletier & Conerbe ; Regnault, Ann. Pharm, 29^ 214 ; J. pr, Chem. 16, 289 ; Duflos.) Similarly with iodic acid. (Semllas.) Hence the picrotoxin-salts, described by BouUay, are probably merely picrotx)xin with adhering acid. — Picrotoxin dissolves in dilute acids (BouUay) ; not more than in pore water, more abundantly only in acetic acid. (Pelletier & Couerbe.)

With Alkalis. — Aqueous ammonia, potash, and soda dissolve picro* toxin very abundantly. (Boullay.) Acids, even carbonic acid, separate it unaltered from the solution. (Pelletier & Conerbe.) Hence it is regarded by Pelletier & Couerbe (not by Liebig, Ann. Pharm, 10, 204), as an acid : picrotoxic acid. If the alkali is saturated, while hot, with picrotoxin, that substance separates on cooling, and, after washing with cold water, is free from alkali. When a solution of picrotoxin in potash, is placed in the voltaic circle, picrotoxin is deposited in slender needles at the positive pole, while the liquid at the negative pole becomes richer in potash and is no longer bitter. (Pelletier & Couerbe.) — Baryta, sironHa, lime, and magnesia, prevent the crystallisation of picrotoxin in needles. Lime causes it to crystallise in plates or granules, and needles are pro- duced on addition of acids.

Picrotoxin vnth Oxide of Lead. — Oxide of lead forms, with picrotoxin^ a very soluble uncrystallisable salt, which may be obtained by prolonged boiling of picrotoxin with excess of oxide of lead and a small quantity of water^ and evaporating the filtrate in vacuo. Contains 45 or 48 p. c oxide of lead. (Pelletier & Couerbe.)

With Organic bodies. — It dissolves in 3 pts. of hot alcohol of sp. gr. 0*81. The solution on cooling solidifies in a silky mass. It is precipitated b^ a small quantity of water. The finest crystals are obtamed from a mixture of equal parts of alcohol and water. (Boullay.)

It dissolves with difficulty in cold ether (Merck), in 250 pts. of ether of sp. gr. 0*7. (Boullay.) Picrotoxin is not extracted from its aqueous solution by ether, or from the alcoholic solution mixed with caustic potash, but ether abstracts it from the alcoholic solution mixed with hydrochloric acid. ^G. Giinkel, N. Br. Arch. 94, 14.)

Picrotoxin dissolves completely in concentrated acetic acid, but requires 2400 pts. of distilled vinegar to dissolve it, and does not dissolve

f perceptibly in a mixture of equal parts of distilled vinegar and water. Merck.) Acetic acid facilitates the solution of picrotoxin in water. (Pelletier & Couerbe.) The easily produced solution of picrotoxin in acetic acid, which is precipitated by concentrated carbonate of potasby yields by evaporation^ according to Boullay, needles of acetate of plcro*

BROWN ACID FROM THE HUSKS OF COCCULUS-GRAINS. 477

toxin, wHich give off acetic acid when treated with nitric acid, bat not with sulphuric acid, and when washed with water, lose their acid re- action, but not the whole of the acetic acid.

Aqueous piorotoxin is not precipitated by tincture of goLU, (Duflos.) Picrotoxin (containing acid) does not dissolve in Msy either fixtd or volatile. (Boullay.)

Other Compounds. Picrotoxin forms with quinine, dwkonine, imr* phine, strychnine, and hrucine, compounds, which are more soluble than these bodies in the separate state ; thej are crjstallisable, and are decom- posed in the voltaic circuit, the picrotoxin going to the positive, and the alkaloid to the negative pole. (Pelletier is Couerbe.)

Appendix to Pieroioxin.

Brown Acid from the Husks of Gocculus-grains.

Prllstier & CouEBBB. Ann* Chim. Phys. 54, 196; Ann, Pharm. 10, 195.

Acide hypopieroioxiqve.

Preparation, The coarsely pulverised husks of cocculus-grains are exhausted in a Papin's digester with alcohol ; the wax which separates as the tincture cools is removed by filtration ; the solution is evaporated ; and the residual extract is exhausted, firstjwith cold water, then with boiling acidulated water, and finally with ether, which when evaporated leaves a brown extract, a mixture of the chlorophyll and the brown acid. The part of the extract which is insoluble in ether, dissolves in boiling alcohol (or in aqueous potash), forming a solution which deposits wax on cooling, and the nitrate separated therefrom'leaves on evaporation a brown mass, from which ether extracts fat and chlorophyll, leaving the brown acid.

Properties. Solid, amorphous brown mass, which softens at 100^

Pelletier & Couerbe;

22 C 132 .... 63*1 6414

13 H 13 ..,. 6-2 6-09

8 0 64 .... 30*7 29-77

C«H»08 209 .... 100-0 100-00

So according to Pelletier and Couerbe. — The analysis gives ^ p. c. too much carbon, the contrary of that which 'generally takes place ; and as the capacity of saturation was not determined, the formula is altogether inadmissible. Liebig, Ann. Pharm. 10, 297. — It is perhaps^ picrotoxin, contaminated with the brown acid into which that substance is converted by alkalis. (Om.)

It is insoluble in water, even at the boiling heat.

It dissolves readily in alkalis, forming a dark-coloured solution^ whence it is precipitated by acids in brown flocks. Insoluble in ether.

478 PRIMART NUCLEUS C»H»J OXYGEN-NUCLEUS C^H»«Ot.

Oxygen-nucleuB C*H^*.

Oenolin.

Mulder. Ghemie de$ Weins. Leipzig, 1856, S. 44, n. 228. Gle.vard. Compt rend. 47, 468; J, pr. Ckem, 75, 316; ftjMj, N, Ann. Ckim. Phys, 54, 366.

Oenolic add. The colouriDg matter of the akios of red grapes and of red wine. — A. Vogel (Schw. 20, 417) and Ficinus {Br. Arch. 2, 309) were acquainted with the behavionr of red wine to acids, alkalis and lead-salts. — Batilliat's RosUe is, according to Mulder, a mixture con- taiuing oenolin {vide ir^f.) Faure (Analyse chimigue et comparSe des vins de la Gironde, 1844; abstr. Mulder $ Chemiedes Weins, 245,) distinguishes a blue and a yellow colouring matter of wine, both of which, according to Mulder, were impure or products of decomposition.

Preparation. A. From G rape-skim. The skins, after being well washed with water, are exhausted with water containing acetic acid ; the solution is precipitated bj neutral acetate of lead ; and the washed precipitate is suspended in water and decomposed bj sulphuretted hydro«ren. The sulphide of lead, purified by boiling with water, gives up the colouring matter to acetic acid, and the solution when evaporated leaves the colouring matter, which may be purified from adhering fat by boiling with ether. (Mulder.)

B. From Bed Wine. 1. Bordeaux wine is precipitated with neutral acetate of lead ; the dirty blue precipitate is collected and washed, as long as the water runs off coloured, then decomposed underwater by sulphuretted hydrogen ; the precipitated sulphide of lead is freed from apothema by boiling with water ; and the colouring matter is extracted from it by alco- holic acetic acid. The solution when evaporated leaves the colouring matter, which ma;^ be freed from fat by ether, and from adhering lead* oxide by acetic acid. (Mulder.) — 2. Ked wine is precipitated by basic acetate of lead ; and the blue precipitate is washed by decantation, then on the filter, afterwards dried between 100° and 110°, and treated in the state of fine powder in the displacement apparatus, with such a quantity of anhy- drous ether into which hydrochloric acid gas has been previously passed, that the hydrochloric acid contained in it may not completely saturate the lead-oxide in the precipitate. After the ether containing hydro* chloric acid has run oif, the precipitate is washed with pure ether as long as anything is taken up, — tartaric acid, tannic acid, a peculiar crystallisable and volatile acid, fat and wax being thereby removed ; and the washed precipitate is dried by exposure to the air, and exhausted with ether, as long as colouring matter continues to dissolve. The alco- holic tincture freed from the greater part of the alcohol by distillation, and mixed when cold with 4 or 5 vols, water, deposits red flocks which must be completely washed with water and dried. (Glenard.)

Propertiet. Nearly black mass, yielding by trituration a powder of a fine violet-red colour, or red-brown if the mass has been dried between lOO'' and 120°. (G16nard.) Bluish black mass, resembling plumbago.

OENOLIN. 479

i Mulder.) In the moiat state it bus tbe dark coloar of wine-lees, without Qstre. Under the microscope, it appears to be composed of roundish groups of granules. Permanent in the air. (Ol^nard.)

Gl^ard. Ai 120^ mean.

20 C 120 .... 57-U 5702

10 H 10 .... 4-76 4-89

10 O ,.... 80 .... 3810 S809

C»HMO» 210 .... 10000 10000

DeeompositioM. 1. Swells up when heated, giring off a peculiar odour and leaving charcoal. (Gi^nard.) — 2. Bums on platinum-foil. (Gl6nard.^ — 3. When its solution in weak alcohol is boiled for a long time witl] water, it becomes insoluble in alcohol, and iridescent films form on the surface of the water. (Gl^nard.) — 4. The alcoholic solution of oenolin is decomposed by hot, but not by cold oil of vitriol. (Glenard, vid. iitf.) — 5. A small quantity of weak niiinc acid imparts a brighter colour to the alcoholic solution of oenolin ; but a larger quantity gradually decolorises it, more quickly if heated ^Mulder), with formation of a brown detonating resin. — 6. Oenolin dissolred in alcohol is converted by chlorine into a yellow soluble compound (Glenard); when dissolved in a mixture of alcohol and tartaric acid, it is first coloured brown by chlorine, and yellow by a larger quantity. (Mulder.) — With chloiHde of lirMy a yellow-brown precipitate is formed, together with a yellow solu* tion. (G16nard.) — 7. In contact with potask-ley or carbonate of soda, it absorbs oxygen, and turns brown. (Glenard.) — Its solution in alcoholic tartaric acid acquires the colour of chrome-alum on addition of a small quantity of ammonia; a somewhat larger quantity colours it blue; an excess, green, and after a few seconds brown. Tbe green, but not the brown solution, is coloured red by acids. Potash, soda and lime act like ammonia.

Oenolin is insoluble in water (Mulder), very sparingly soluble in cold water, somewhat more in hot. (GUnard )

Oil of vitriol colours the solution of oenolin in alcoholic tartaric acid bright light red, and in excess, violet, the pure red colour being however restored by addition of water. (Mulder.) — Hydrochloric acid does not alter the weak alcoholio solution, even at the boiling heat.

Oenolin dissolves more readily in water containing tartaric or acetic acid. It dissolves in wood-spirit, not in sulphide of carbon or chlorofi/i-m. (Glenard.)

According to Mulder, oenolin is quite insoluble in alcohol; according to G16nard, it dissolves readily, with fine crimson colour, and remains as a varnish when the alcohol evaporates. — According to Mulder, it dis- solves in alcohol containing a trace of acetic acid, with pure blue colour, and if more acetic acid is present, with red colour. (Mulder.) In alcohol containing tartaric acid, it dissolves slowly but completely, with pure red colour. (Mulder.)

The alcoholic solution exhibits the following reactions : Bicarbonate of soda colours it blue ; chloride of calcium forms a blue precipitate ; alum brightens its colour, and on addition of carbonate of soda, forms a lilac lake. — With neutral acetate of lead, it yields a pure blue precipi- tate, which, after drying at 120^ contains 35'67 PbO, and after subtrac- tion thereof, contains in 100 pts. 59*67 p. c. C, 4*49 H, and 85*84 0, and is therefore C»H»Pb0»' (calculation 85-74 PbO, and 59-71 C, 447 H,

480 PRIMAKT NUCLEUS C>i»H»:CHLOIU[NE-NUCLEUS C»C1>H».

85*82 0). With nitrate of lead, it fonoB after a few seconds a violet precipitate, and with the bdsic acetate, blue inclining to brown. It colours ferrous sulphate violet, and then forms a bluish violet precipitate. It precipitates ferric sulphate dark chestnut-brown, ferric chloride yellowish, cupric acetate chestnut-brown, protochloride of tin violet-red^ mercurous nitrate colour of wine-lees, mercuric nitrate light-brown, nitrate of silver brown-red after a while. It does not precipitate mercuric chloride, (GUnard.)

The solution in alcoholic tartaric acid is not altered bj alum; with uoetaie of alumina (acetate and phosphate of soda), and a small quantity of acetic acid, it forms a violet precipitate ; with nUrate of lead, light red ; with neuiral and basic acetate of lead, blue, the precipitate being soluble with red colour in alcoholic acetic acid. It is coloured darker red to violet by bichloride of tin, not altered by m/ercurous nitrate, coloured lighter red by mercuric chlcnide, darker red by nitrate of silverm (Mulder.)

Oenolin is insoluble in ether, benune, olive-oil, and oU of turpentine.

BatilHat (Traiti sur Us vins de la France; abstr. Bull, Soc. d'encour, 1848, 451 ; I>i7igl, pol, Joum. 110, 66) distinguishes two colouring matters of wine, Eosite and Pourprite.

Eosito, — Occurs especially in the sediment of new wines. — The sediment, which remains after the first drawing off of the wine, is collected upon linen, and suspended in alcohol of 85 p. c. ; the liquid is filtered and evaporated ; the residue exhausted with water, which leaves pour- prite undissolved ; the liquid precipitated with solution^ of gelatin ; and the filtrate evaporated.

Colour rose-red. When heated, it leaves slowly burning charcoal and a small quantity of alkaline ash.

Dissolves in water, and without decomposition in oil of vitriol of 66^ ; soluble in alcohol, not in ether. Kot precipitated by white of egg or solvtiofn of jelly.

Pourprite. — Found chiefly in the sediment of old wines, which indeed consists almost entirely of it. Dark blackish red. Has a rough, astringent taste. Leaves, when burnt, an ash consisting of lime, potash, and iron. — Insoluble in toater, — Dissolves in ot/ of vitHol, and is precipitated by water. — Soluble in 150 pts. of alcohol of 80 p. c. ; leas soluble in stronger alcohol, and quite insoluble in ether» With jelly, it forms a compound insoluble in water and in alcohol.

Chlorine-nucleus (?^C1"H»

Qnintichloromenthene.

C«CPH»

Walter. Compt. rend. 8, 913; Ann. Ohm. Phys. 72, 106; Pogg. 51, X, 349; Ann. Pharm. 32, 296.

CAlormenthen (L5wig) ; Chloromenthase (Laurent, Rev. seient. 14, 341) ; Qinii/i. ehlaromenihene (Gerhardt, TYaiiS 4, 359).

^ Dry chlorine is passed into menthene (p. 445) as long as hydrochloric acid gas continues to go off, and the product is washed, first with water and then with carbonate of soda, again subjected to the action of chlorine, washed as before, and dried over chloride of <^ciam| then in vacuo. Yellow syrupy liquid, heavier than water.

CAMPUORAMIC ACID» 481

Walter,

20 C 120-0 .... 38*64 38-24

13 H 13-0 .... 418 4-68

5 CI 177-5 .... 57-18 5730

C»C1»H" 310-5 .... 10000 100-22

Burru^ when set on fire^ with a smoky, green-edged flame. Oil of vitriol eoloQis it deep red.

Soluble in cold alcohol and wood^pirit^ more readily in ether and in oil of turpentine. (Walter.)

Oxyamidogen-nticlens G^AdW^O*

Gamphoramic Acid.

OT&TH"0« = C»AdH»0',0*.

Laubent. (1845.) Compt. Mm. 1845, 141; abstr. «7. pr.\Chenu 35, 501; Ann. Fharm. 60, 826; JReperi. 100, 89/

Camphoramintdure, Camphoranuaure, Acide eamphoramique. — The crystals which form on satnratiiig camphoric anhydride with ammonia were regarded by Malagati {Asm Chim. Phyt. 64, 162) as a peculiar camphorate of ammonia : their true nature was recognised by Laurent. -

Formation and Preparation (p. 468). A boiling solution of camphoric anhydride in absolute alcohol, concentrated as much as possible, is saturated with ammonia-gas ; the crystals of camphoramate of ammonia which separate on cooling (and of which the mother-liquor yields a larger quantity by gentle evaporation), are dissolved in a larger quantity of water and decomposed by hydrochloric acid; and the acid which separates by cooling or by evaporation at a gentle heat, is purified by

recrystallisation from cold alcohol. — When hot concentrated solutions of camphoramate of ammonia are decomposed by hydrochloric acid, the camphoramic acid separates as a syrup, a small quantity only remaining dissolred in the supernatant liquid. (Malaguti, Laurent.)

Properties. Colourless, transparent, rectangular prisms. Fig. 5Q with ^.face. u : u behind = 114^ 30' ; t* : «= 122° 45' ; a : t« = 155°; i : ^ = 138° 20^. — Melts when heated and solidifies on cooliug, partly crystalline, partly as a transparent vitreous mass, which is do longer camphoramic acid.

20 C	... 120 ... 14 ... 17 ... 48	.... 60-30 .. 7-03 .. .... 8-50 .. .... 24-17 ..	Laurent. 60-0
N 17 H	7-4 8-4
6 O	24-2
C»AdH"0».....	... 199	.... lOO'OO .,	100-0

By heating to 150° — 160°, or by distillation, camphoramic acid is converted, with loss of water, into camphorimide.

The acid dissolves sparingly In water. — With hasesy it forms tie Camphoramates, which are crystallisable and all soluble in water. —

VOL, xiv. 2 I

482 PRIMARY NUCLEUS C»H«: OXYAMIDOGEN-NUCLEUS C»A#H"0*,O».

Aqueous camphoramate of ammonia does not precipitate lead, silver, or

copper salts.

CdmpkoraTnaie of Aminonia, Prepared as above, or by dissolving campboramic acid in alcoholic ammonia^ and purified by recrystallieation, washing with absolute alcohol, and drying at a moderate heat. — Slightly- acid, bitter crystals, from the solution of which, chloride of platinam precipitates half the nitrogen as chloroplatinate of ammonium. — The salt melts at 100°, and, between 1.50° and 160°, gives off ammonia and 21-6 p. c. water, and is converted into camphorimide which solidifies in a vitreous mass ; likewise by distillation.

Malaguti. Laurent

20 C 120 .... 61-2 50-1 .... 511

2N 28 .... 11-9 121 .... 11-7

22 H 22 .... 9-4 9-1 .... 9-3

8 O 64 .... 27-5 28-7 .... 27-9

C»AdH"0*,NH*0 + 2Aq 284 .... 100*0 1000 .... 1000

Malaguti regarded the salt which he examined, at a peculiar camphorate of ammonia (comp. p. 468).

Camphoramate of Lead. — The concentrated boiling solution of camphoramate of ammonia in alcohol, mixed with less than the equiva- lent quantity of alcoholic neutral acetate of lead, deposits on cooling small needles, which, when washed with a little alcohol and dried at a gentle heat, contain 33 p. c. of lead, and are therefore C^AdPbH^K)* (calculation = 34*5 p. c. Pb). Dissolves with moderate facility in alcohol.

Camphoi'amate of Silver, — The concentrated alcoholic solution of camphoramate of ammonia, mixed while hot with alcoholic nitrate of silver, solidifies on coolinff to a jelly containing crystals. These aro washed with absolute alcohol and pressed between paper. — Very slender, long, microscopic needles, containing 34*7 p. c. silver (C*AdH"A«0« = 35*1 p. c. Ag.).

Campboramic acid dissolves in alcohol more readily than in water (Laurent.)

Oxyamidogen-nucUm C*Ad*H**0*

Camphoramide.

(?«N»H»0* = C«>Ad»H"0»,0».

Laurent. Bev, scierU, 10, 123; J.pr. Chem. 27, 814; Eepert. 80, 114. Oxyde doomed camphese (Laurent, Rev, seient. 14, 506).

When ammonia-gas is passed through the solution of camphoric anhydride in absolute alcohol, and the saturated solution is evaporated, there remains a thick syrup, which is not decomposed by cold hydro- chloric acid, — gives off ammonia when treated with hydrate of potash, and forms camphorate of potash, — is insoluble in water, but soluble in alcohol. This is probably camphoramide.

CAMPHORAMILIC ACID. 483

\Conjitgated Amides of Camphoric Acid,

Gamphoranilic Acid.

(?»NH«0« == C»(C«NH*)H«0»,0*,

Laurent & Gerhardt. (1848.) JV. Ann. Chim. Phys, 2i, 191; Ann. Fharm, 68, 36; abstr. Fkarm. Oentr. 1849, 74.

Pk^Hyl-eampharamic acid.

Formation, By heating camphorio anbydride with aniline, cam- phoranil being formed at the same time.

FreparcUion, Camphorio anhydride is heated with aniline, and after the yitreously solidified mass has cooled, the camphoranilic acid is dis- solved out of it by hot aqueoas ammonia, camphoranil then remaining undissolved. The solution is precipitated by nitric acid, and the pre- cipitated flocks are washed.

Properties. Flocks which melt in boiling water to a resin, becoming crystalline by continued boiling with water. From dilute, lukewarm, weakly alcoholic solutions, it may be obtained in needles, but from con- centrated strongly alcoholic solutions it separates as a resin :

32 C.

N.

21 H.

60.

			Laurent & Gerhardt.
192	• •■•	69-82 ..	68-6 .... 69'5
14	••••	6*09 ..
21	• >••	7-64 ..	7-7 .... 7'§
48	••••	17-45 ..

C»NH«(y .... 275 .... 100-00

Decompositions.. 1. By distillation^ it is completely resolved into aniline and camphoric anhydride. — 2. When slightly heated with oil of vitriol, it gives off carbonic oxide. — 8. Fused with hydrate ofpotaA, it gives off aniline.

It dissolves sparingly in boiling waier, and solidifies in the crystalline form on cooling.

With boMs, it forms the camphoranilaies* The ammoniansalt does not precipitate the salts of lime or baryta,

Camphoranilate of Ammonia, — The solution of camphoranilic acid in alcoholic ammonia leaves when evaporated, a syrup from which water separates a portion of the camphoranilic acid. It may be obtained, like the acid, as a resin or in crystals, corresponding to the different states of camphoranilic acid.

CamphoranUate of Silver, — Obtained by mixing the ammonia- salt with nitrate of silver, as a white precipitate, which contains 28*25 p. c. silver, and is therefore C^'NA'^AgO* (calculation « 82-27 p. c. Ag), slightly soluble in water.

Camphoranilic acid dissolves very easily in alcohol and in ether. (Laurent & Gerhardt.)

2 I 2

484 PRIMARY NUCLEUS C»H": OXYAZO-NUCLEUS C»NH»*0»,02.

Camphoranil.

C»H»NO* = C»(C'»NH«)H»0*?

Laurent & Gerhardt. (1848.) N. Ann. Chim. Phys, 24, 191; Ann, Fharm. 68, 35; abstr. Pharm. CeniraXbL 1849, 73.

Phenylcampharindde,

Comp. p. 468. Camphorio anhydride is heated with aniline; the vitreons mass which forms on eooling is treated with hot dilate aqueous ammonia to extract camphoranilic acid; the residue is dissolved in alcohol or in ether ; and the solution is left to evaporate :

C»H"0« + CUH^N - C»HWO* + 2HO

Pi'operites. Shining needles, which sublime without decomposition, melt at 116'', and solidify to a somewhat crystalline mass on cooling :

Laurent &Geriiardt.

32 C 192 .... 74-70 74-3

N 14 .... 5*44

19 H 19 .... 7-39 7-4

4 0 32 .... 12-47

C»HWNO* 257 .... 100-00

Decompositions, 1* Camphoranil is not decomposed by a^^ueous potash^ but with hydrate of potash in the state of fusion, it gives off aniline. — 2. It dissolves slowly concentrated aqueous ammonia containing a little alcohol, whereupon camphoranilate of ammonia crystallises on cooling.

Combinations. Insoluble in cold, but somewhat soluble in hMing toate)'. — Part melts in boiling water, while the rest dissolves and crystal- lises as the liquid cools. — The solution of camphoranil in very weak -aqueous ammonia containing alcohol, forms with nitrate of silver a white crystalline precipitate, probably C'H.^AffNO*.

Camphoranil dissolves readily in alcohol and ether, and crystallises on cooling from very weak alcohol, in long shining needles. (Laurent <fe Gerhard t.)

Oxyazo^udetLs C*^NH»*0*.

Camphorimide.

C*NH«0* = C»NH«0*,0*.

Laurent. (1845.) Compt. chim. 1845, 147; abstr. J, pr. Ohem. 33, 503; Ann. Pharm. 60, 326; J^^ert. 100, 89.

Bicamphorimide. (Ltfwig.)

Formation and Preparation. Caraphoramic acid or its ammonia-salt is heated to 150** — 160° (whereupon water and ammonia are given off) or distilled, and the colourless mass, which solidifies in the vitreous form on cooling, is crystallised from alcohol.

CAPRIC ACID. 485

Properties. Colourless six-sided tables. Melts when heated ; solidifies in the vitreous form on cooling; volatilises without decomposition at a stronger heat ; and sublimes partially in white fern-like laminae^ apparently terminated with faces of a rhombic dodecahedron :

Laurent.

20 C ^....o...... 120 .... 66*3 .. . 65*90

N ^, 14 .... 77

15 H 15 .... 8-3 ^. 8-14

4 O 32 .. 17-7

C»NH»0* 181 .... 100-0

Camphorate of ammonia — 2 At. HO and 1 At. NlPy or bicamphoramate of ammonia. — 2 At HO, or camphoramic acid — 2 At. HO. (Laurent.)

Decomponiunu. Hydrate of poictsh boiled with alcoholic camphori- mide eliminates ammonia.

ConibincUums. Gamphorimide dissolves in gently heated oil of viiriot. Water added to the solution throws down white microscopic crystals, consisting of acute six-sided pyramids.

It dissolves readily in boilmg alcohol. — The solution in weak alcohol solidifies after evaporation to a transparent gum, which solidifies in 24 hours to opaque nodules. (Laurent.)

Primary Nucleus C^H**.

Capric Acid.

C»H«0* = C»H» 0*.

Chevrbul. (1818.) Ann. Chim. Phys, 23, 22; 8chw. 82, 170;

Becherehes sur les corps gras. 143. Lerch. Anh, Pkarm. 49, 223. Iljbnko & Laskowsky. Ann. Pkarm. 55, 78. Gottlieb. Ann. Pha)7n. 57, 64. Cahours. TMse presente a lafactdti des sciences a Paris, le 15 Janvier,

1845, 132; Compt. rend. 26, 263. Gbrhardt. iV. Ann, Chim. Phys. 24, 90; J. pr. Chem. 45, 327. GoROBY. Ann. Pharm. 66, 290; Pharm. Centralbl. 1849, 8; iT. Ann.

Chim. Phys. 25, 102. RowNBY. Ann. Pharm. 79, 236; J. pr. Chem, 54, 211; Quart. J.

Chem. Soc. 4, 332; Chem. Gag. 1852, 32. Redtenbacbbr. Ann. Pharm. 57, 150; 59, 54. Fbhliko. Dingier, pel. Joum. 130, 77; N. J. Pharm. 25, 94.

Aeide eapriqne. (Chevrenl.) AeUe rutique. (Cahours.) Diaoovered by Chev- reul in 1828, but according to Lerch, not obtained by him in the pure Btate.

Sources. In the butter of cow's milk (Chevreul) ; in Limburg cheese nijenko & Laskowsky) ; in cocoa-nut oil (Gorgey) ; in train-oil (Wagner, J. pr. Chem. 46, 115) ; in Scotch fusel-oil (Rowney) ; in the perspiration of the human foot (Brendecke, N. Br. Arch. 70, 26 and 34) ; in fusel-oil from maize and rye (Wetherill, Chem. Gaz. 1853, 218 ; J. pr. Chem. 60, 202) ; in the so-called oil of grapes from Leipzig (Fehling) ; in the

486 PRIMARY NUCLEUS C»H».

molasses of mangold- wurxel (Fehlioff) ; in potato faseUoU (S. W. John- son, «7. pr. Chem, 62, 262). According to Wagner, it may be reoogniaed, since it is always accompanied by capric aldehyde, by heating the body under examination with oil of vitriol, and adding hydrate of potash in excess, whereupon the odonr of oil of rue becomes perceptible. (J", pr. Chem. 45, 155.)

FormaHon. In the dry distillation of oleic acid or of fats containing olein. (Gottlieb.) In the oxidation of the following substances by nitric acid : oil of rue (Cahours, Gerhardt) ; oleic acid and choloidic acid (Demar9ays, Redtenbacher). — In the putrefaction of casein and fibrin. (Brendecke.) — Generally, it is formed simultaneously with the other volatile fatty acids.

Preparation. A. From Butter of Cow^e milk, (Comp. x, 80.) — I. When the mixture of caprylate and caprate of baryta obtained in the preparation of butyrate of baryta, is completely dissolved in boiling water, the filtrate, on cooling becomes filled with thin scales of canrato of baryta having a fatty lustre, and the mother-liquor filtered tnere- from and evaporated down to |^, yields an additional quantity (Lerch).

From the baryta-salt thus obtained and purified by recrystallisation, the acid may be obtained in two ways. — 1. To 10 pts. of the baryta- salt is added a solution of 8 pts. glacial phosphoric acid in 32 pts. of water, and the oily layer (still containing a little of the watery solution) which rises to the surface is decanted. — 2. One hundred pt^. of the baryta-salt are decomposed by a mixture of 47 '5 pts. oil of vitriol and 47*5 pts. water, and the anhydrous acid which rises to the surface of the liquid is decanted. (The liquid below the oily layer yields, when neatraliied with baryta-water, an additional quantity of caprate of baryta.) (Chevreul.) — B. FiX/tn

Limhurg Cheese. (Sec xiii, 191.) — C. From Scotch fusel-oil. — The liquid is Bubjeoted to fractional distillation, whereupon water, alcohol, and fusel- oil pass over, and there remains a dark-coloured foetid oil, insoluble in water and in boiling aqueous carbonate of potash. When this oil is digested for several days with concentrated potash-ley, amyl-alcohol is separated, and there is formed a solution of caprate of potash, which, if mixed aifter cooling with hydrochloric or sulphuric acid, yields a dark-coloured oil, to be filtered and washed with cold water. For purification, the acid thus obtained is dissolved in very dilute aqueous ammonia, the solution precipitated by chloride of barium, and the precipitate separated by filtration, washed with cold water, and recrystal- lised from boiling water. Sometimes the precipitate dissolves but slowly in hot water, because it c^kes to a hard mass during the boiling. The nearly colourless baryta-salt obtained by repeated crystallisation is decompo^^cd by boiling with carbonate of sooa ; the liquid is filtered from the carbonate of baryta ; and the filtrate is decomposed by dilute sulphuric acid, whereby nearly colourless solid capric acid is separated : it is to be dissolved in alcohol, precipitated by mixing the solution with a large quantity of water, and purified by repeated solution in alcohol and precipitation by water» The mother-liquor, treated in like manner, yields an additional quantity of eapric acid, oontainingi however, traces of another oily acid. (Rowney.) — - D, Froffi

Oleic Acid and Fats containing Olein (seeziii, 191.)

Propertied. White mass^ composed of small needles. (Chevrenl,

488 PRIMARY NUCLEUS C»H^

gives off olefiant gas, with a small quantity of carbonic acid, and leaves carbonate of baryta mixed with charcoal. (Cheyreul.)

Dissolves in 200 pts. of water at 20^. (Chevreal.) According to Chevreul, the solution decomposes when exposed to air ; according to Lerch, it is permanent in the air. It is but slightly precipitated by carbonic acid. (Chevreul.) It dissolves in boihng alcoboL (Rowney.)

J . IljenVo & Gottlieb. Rowney. ^^^'^ Laskowsky. Dried at 100'.

20 C 1200 .... 50-08 50'26 .... 5005 .... 50-41 .... 49-73

19 H 190 .... 7-93 7-87 .... 7-83 .... 8-01 .... 8-15

3 0 240 .... 10-02 10-17 .... 10*44 .... 986 .... 10-35

BaO 76-6.... 31-97 31-70.... 31-68.... 31-72.... 31-77

C»HWBaO< 239-6 .... 10000 100-00 .... 100-00 .... lOO'OO _ lOO-OO

Contains 36*08 p. c. BaO (Chevreul); 32*07 p. c BaO. (Redtenbacher.)

Caprate of Sirontia. — Obtained by saturating strontia-water with

capric acid, and leaving the solution to evaporate. — When heated, it

melts, blackens, and gives off an aromatic and empyreumatic odour.

Dissolves in 200 pts. of water at 18^ Contains 27*62 p. c SrO.

(Chevreul.) (C»Hi»SrO^ « 24-11 p. c. SrO.) According to Chcvrcul, it is C^SRVSrO^ ; calculation, 26*19 p. c. SrO.

Capraie of Lime, — Crystallises from the hot aqueous solution in very fine shining laminss ; very bulky. (Gottlieb.) Resembles the barytar salt, but is more easily soluble in hot water and in alcohol. (Rowney.) Contains 14*79 p. c. CaO (Gottlieb), and is therefore C**H"CaO* (calcufaitioii = 14-66 p. c. CaO).

Caprate of Magnesia, — Crystallises like the baryta-salt and resembles it in other respects ; but dissolves more readily in hot water and in alcohol. Contains 11-37 p. c. MgO (C»H»MgO* « 10-92 p. c. MgO.)

Caprate of Lead, — The combination of capric acid with oxide of lead is attended with evolution of heat. (Chevreul.) The salt is insoluble in water, and very slightly soluble in hot alcohol, whence it crystallises in rounded grains on cooling. (Rowney.)

Caprate of Copper, — 'Insoluble in water and in alcohol ; soluble in ammonia. (Rowney.)

Capraie of Silver, — The solution of capric acid in a slight excess ot ammonia is precipitated by nitrate of silver. — The salt is insoluble in cold, sparingly soluble in boiling water, and crystallises in needles from the solution on cooling. It is very soluble in ammonia, and crvstallises from the solution when left to stand in a warm atmosphere. (Rowney.) It dissolves more readily in boiling alcohol than in water, and the solution yields darker-coloured crystals. (Rowney.) — It blackens when exposed to the air in the moist state, but not when dry. (Rownoy.)

Dried in vacuo over oil qf vitriol, Rowney.

20 C 120 .... 43-01 42-43

19 H 19 .... 6-81 6-77

AgO 116 .... 41-57 41-64

3 O 24 .... 8-61 9-16

C«0Hi9AgO* 279 .... 100-00 10000

Capric acid mixes in all proportions with ahsoltUe alcohol, (Chevreul.) It dissolves in ether, (Rownoy.)

OIL OF RUE. 480

Caprate of Ethyl.

RowwEY. Ann. I^harm. 79, 236.

Capric ether, Caprineauree Aeihylojcyd, Capritunnetier.

When a solution of caprio acid io absolute alcohol is saturated with hydrochloric acid gas and precipitated by water, capric ether separates on the surface of the liquid, as an oil, which must be removed, washed with cold water, dehydrated by chloride of calcium, and rectified.

Oil of sp. gr. 0*862.

Insoluble in cold water j easily soluble in alcohol and in ether.

Appendix to Capric Acid.

Oil of Rue.

Will. (J 840.) Ann. Fhaim. 35, 235.

Cahours. Thise presents a la facultS des sciences, le 15 Janvier, 1845,

132; Ckmipt. rend. 26, 262. — Further, Qiem. Soe, Qu. J. 3, 240. Obrhardt. Hf. Ann. Chim. Phys, 24, 96; J. pr, Chem. 45, 327; Compt.

rend. 26, 226. R. Waonbr. 46, 155; farther, 52, 48. Ohiozza. Compt. rend. 35, 797; J. pr. Chem. 58, 216. Bbrtagnini. Ann. Fharm. 85, 283. C. Grevillb WiLiiiAMS. Fhil. Trans. 1858, 199; Chem. Cenir. 1858.

734. H ALLWACHS. Ann. Pharm. 1 1 3, 1 07.

Capric aldehyde, Caprol, Hydride qf JRu/y/.— Hrst examined by WilL

The volatile oil of rue, obtained bv distilling garden rue, Suta graveolens, with water, was long regarded, according to the results of Cahours <fe Gerhardt, as capric aldehyde, C**H*®0* ; but according to the more recent investigations of G. Williams, which have been confirmed by Hallwachs, it is chiefly = C«H»0*, and is regarded by Williams as enodic aldehyde mixed with a small quantity of lauric aldehyde ; by Hallwachs, as a compound not belonging to the class of aldehydea

Fresh rue yields 34 grains of oil per ponnd ; dry rue, 18 ; the dry

flowers, 15 ; the seeds, 17 grains. (Zeller, N. Jahrh. Pharm. 1, 30.)

Crude oil of rue is greenish yellow, has a strong unpleasant smell of rue, and a sharp bitterly aromatic taste. Sp. gr. = 0*837 at 1 8®. It con- tains 77-5 p.c. C, 12-87 H, and 9*56 0 (Will.) ; 7765 p.c. C, 12-80 H, and 9-55 0. (Gerhardt.) — Oil of rue is supposed by Wagner to exist : in train-oil, in butter, in rich cheese, and in herring, inasmuch as train-oil heated with oil of vitriol, and then mixed with excess of hydrate of potash, gives oflT an odour of oil of rue, and the alkaline mixture yields by distillation drops of oil smelling of rue.

490 PRIMARY NUCLEUS C»H».

Preparation, 1. Gerhardt obtained his caprol or oapric aldehyde by sabjecting oil of roe to fractional distillation^ setting aside the small quantity of non-oxygenated oil which first passed over, and collecting the principal portion which distilled at 233°. — Cahours likewise isolates his capric aldehyde, — which, according to him, passes oyer from 228° to 230°, — by fractional distillation of oil of rne. — 2. Williams agitates oil of rue with aqueous bisulphite of ammonia, and obtains thereby a crystalline mass, regarded by him as a mixture of the compounds of enodic and laaric aldehydes with bisulphite of ammonia, — which mass, after being separated from the other constituents of the oil of rue (a substance isomeric with oil of turpentine and another homologous with borneoH, yields by its decompo* sition, enodic and lauric aldehydes. These two oodics may be separated, though not completely, by fractional distillation, enodic aldehyde which boils at 213° passing over first, and afterwards the small quantity of lauric aldehyde present, which boils at 232°. (Williams.) — 3. Commercial oil of rue, subjected to fractional distillation, yields (probably from admixture of turpentine) a considerable quantity of products, which pass over between 160° and 205®, and do not form solid compounds with bisulphite of ammonia. The portions which distil between 205® and 240° (amounting to nearly the entire residue), solidify when shaken up with bisulphite of ammonia, and then left to cool quickly, into a crystalline mass, which, after being washed with alcohol and pressed, yields an oil by decomposition with potash-ley. When this oil is once more shaken up with bisulphite of ammonia, and the resulting compound is again decomposed, the oil thus obtained passes over between 213 and 216°. (Hallwachs.)

Properties. Colourless, oil having a faint agreeable odour of rue (Will, Hallwachs), solidifying completely, in shining laminae between — 1° and — 2°. (Cahours.) Boiling point (vidsnp.). Sp. gr. of the portion distilling between 218° and 245® = 0-838. (Will) — Vapour- density 5-83 (Gerhardt), 7-822 (Will), 5*87 (Williams).

Calculation according to Cakoun Sc Gerhardt.

20 C 120 76-92

20 H 20 12-82

2 0 16 10-26

C»H»0* 156 100-00

Calculation aecordinff to Willianu, a. 6.

22 C 132 77-64 24 C 144 78-26

22 H 22 12-94 24 H 24 13-04

2 O 16 9-42 2 O 16 870

C«H«0* 170 100-00 C«H«0» 184 100-00

Will. Gerhardt Cabouri. Williams.' Hallwachf.

a. b*

C 76-67 .... 76-82 .... 76-74 .... 77-71 .... 78-1 .... 77-66

H 12-62 .... 12-86 .... 12*83 .... 1307 .... 12 9 .... 12-96

O 10-71 .... 10-32 .... 10-43 .... 9-22 .... 90 .... 9-39

100-00 .... 100-00 .... 100-00 .... 100-00 .... 100-0- .... 100-00

OIL OF BUB. 491

Vol. Density. Vol. Density.

C-Tapour 20 .... 8*3200 22 .... 9" 1520

H-gM 20 .... 1-3860 2 .... 1-6246

O-gas 1 .... 1-1093 2 .... M093

Ctpric Aldehyde .... 8 .... 10-8153 Enodio Aldehyde .... 2 .... 11*7859

1 .... 5-4076 1 .... 5-8929

Vol. Density.

C-vaponr 24 .... 9*9840

H-gae 24 .... 1*6632

O-gas 1 .... 1-1093

Laurie aldehyde 2 .... 12*7565

1 .... 6*3782

All the analytical resolta are mean nnmbers. Will originally gave the formula C^^H^O^. The oil a analysed by Williams is his enodic aldehyde ; I his lauric alde- hyde. Hallwachs found the portion which passed over between 205* and 240^ to be of uniform composition throughout.

DeccmpotUionB, 1. Slightly heated oil of rae (prepared by S), is easily inflammable and burns with a bright, slightly colourea flame. (Hallwachs.) •^- In contact with iodine, oil of rae becomes viscid and brown-red (Flaschhoff^ Br, Arch. 33, 225), but does not form any product analogous to anisoin. (Will, Ann. Fharm. 65, 230.) — 3. It absorbs dry chlorine gas abundantly, becoming hot, giving off hydrochloric acid gas, and thickening. (Will.) — 4. Alcoholic oil of rue (prepared by 1), through which hydrochloric acid gas is passed, is converted, without change of composition, into metacaprol. (Gerhardt.) — 5. Oil of rue is attacked by fuming nitnc acid, with evolution of nitrous gas (Will); strong nitric acid converts it into capric acid, or, according to the duration of the action, likewise into pelargonic (xiii, 369), caprylio (xiii, 189), and oBnanthylio acid (xii, 451), with which also may be mixed acids containing a smaller proportion of carbon. (Cahours.) Nitric acid diluted with an eoual quantity of water forms pelargonic acid ; more dilute nitric acid forms capric acid (Gerhardt); the more dilute acid likewise forms pelargonic, and after prolonged boiling, ultimately alto suberic and sebacic acids. (Wagner, J. pr. Chem. 57, 435.) Under circumstances not yet thoroughly understood, nitroso-pelargouio acid Txiii, 371), may also be produced. (Chiozza.) — 6. With alcoholic hydrosulphaie qf ammonia, oil of rue tornis, after a few days, white shining crystals which are decomposed by recrystallisation. They are probably (j^NH'^SS a^nd rek^ted to capric aldehyde in the same manner as thialdine to acetic aldehyde, inasmuch as, when boiled with potash- ley, they yield ammonia, capric aldehyde, and hydrosulphate of potash. (Wagner.) — 7. When oil of rue is heated to the boiling point with potaih^lime, it resinises, without giving off gas, and leaves a yellowish residue, from which hydrochloric acid separates resin and a large quantity of unaltered oil. (Gerhardt.) — 8. Oil of rue distilled with 8 pts. of chloride of lime and 24 pts. of water, yields chloroform. (Chautard, Compt. rend. 34, 485; J. pr. Chem. 56, 238.) — 9. By the passage of its vapour over melting chloride of zinc, it is converted into a hydrocarbon. (Gerhardt.) — 10. Ammoniacal silver-solution is quickly reduced by boiling with oil of rue. (Gerhardt.) If the boning with excess of ammoniacal silver-solution be continued as long as any reduciion of silver takes place, the filtrate yields with aqueous potash, a precipitate of oxido of silver, which, when dissolved in dilute sulphuric acid, leaves a small

492 PRIMARY NUCLEUS 0»H».

quantity of metallic silver, while the alkaline liquid filtered from the oxide of silver contains a little capric acid. (Wagner.) — From these experiments^ Wagner infers the existence of an acid corresponding to aldehydio acid (viii, 181), viz., caprinyloTis aarf=0*H"0', or in the hyp. anhydrous state = C*H"0'. — 11. In contact with dry nitr<hprus$ide of copper, oil of rue hecomes brownish yellow and forms an ash-grey deposit. (Heppe, N, Br. Arch. 89, 57.)

Combinations. Oil of rue dissolves m oil of vitriol, with a fine brown- red colour, and is separated again colourless by water. (Will.) — It is scarcely altered by hydrochloric add gas, merely acquiring a brown colour, which it loses by agitation with water. (Will.)

With Jmmonta. — NH«,0»H>^0«1 When oil of rue dissolved in alcohol is saturated at a low temperature with ammonia, a white crystal- line mass is formed, which melts at about 0°, and is resolved into ammonia and oil of rue. (Wagner.) Wagner regards these crystals as a com- pound of ammonia with oaprie aldehyde. — For the deoompontion of c^ric aldehyde-ammoiua, by sulphuretted hydrogen see page 491.

With Biwlphite of Ammonia. 1. When sulphurous acid gas is passed through an alcoholic solution of ammoniacal oil of rue, and the solution left for several days in a very cold place, ciystalline laminaa are deposited. (Wagner.) — 2. Oil of rue is shaken up with aqueoos bisulphite of ammonia of 29^ B., till the mixture, which is buttery at the commence- ment, becomes solid, and the product is recrystallised from warm alcohol. — - The compound is likewise obtained in crystalline laminao, by passing ammonia and sulphurous acid gases into an alcoholic solution of oil of rue. (Bertagnini.) — White shining laminaa. (Wagner.) Aggregated, transparent s^es, unctuous to the touch, and having somewhat of the odour of oil of rue. (Bertagnini.) It is decomposed by heat, without previous fusion. (Wagner.) By heating its aqueous solution, it is readily decomposed, with separation of oil of rue, but not in presence of sulphites. With bromine in aqueous solution, it forms snlphuric acid, and a heavy brominated oil ot peculiar odour. (Bertagnini.) — It is insoluble in water, but dissolves readily in boiling alcohol. (Wagner.) It is soluble in water and in alcohol. (Bertagnini.)

Calculaiion according to Bertagnini. Bertagnini. Wagner.

20 C 120 .... 43-96 N 14 .... 5-13 27 H 27 .... 9-89	44-12 •».••... .... 9-71 11-41 ....	5-00
2 S 32 .... 11-72	13-83
10 0 80 .... 29*30
C»H»0»,NH»,2S0« + 4Aq .... 273 .... 100-00 Caleulation iiccordinff to Wd§ 20 C M.t*. 120 .... N „ 14 ....	mer. ...• 50»63 .... 5-91 .... 9-71 .... 13-50 .... 20-25
23 H 23 ....
2 S 32 .... 6 O 48 ....
C«>H»«0s,NH»,2S0« 237 ....	.... 100-00

Wiih Bisulphite of Potash. — Prepared by agitating oil of rue with aqueous bisulphite of potash of 28*^ — 30° Bm, a crystalline mass then forming after the action has been continued for several hours. — The

SBBACIC ACID. 493

compoand dissolves with tolerable facility in boiliog alcohol^ and the solution deposits scales on cooling. (Bertagnini.)

^ With JBimlphiie of Soda, — Oil of rue in contact with aqueous bisul- phite of soday of 27^ Bm. fonns a buttery mass^ which after a while becomes crystalline. — Shining crystalline scales, unctuous to the touch, having the smell of oil of rue and a fruity taste. — The concentrated, but not the dilute solution of the compound in boiling alcohol, solidifies on cooling to a gelatinous mass, changing in the course of 24 hours into delicate laminae, arranged concentrically in spherical crystalline masses. (Bertagnini.)

Metacaprol.

Oerhabdt. N. Ann, Chm. Phyi, 24, 105.

When oil of rue (prepared as described at p. 490, 1) is dissolved in 3 or 4 vol. alcohol and excess of hydrochloric acid gas is passed into the solution, the brown and fuming mixture, if mixed with water after the most volatile portion has been distilled oflT, deposits metacaprol.

Oil having a highly agreeable fruity odour. Solidifies, after a while, at a temperature at which oil of me remains liquid, and melts again at 13°. Boils between 230"^ and 235^

20 C

20 H

20

			Gerhard t«
120	•••.	76-92	7710
20	•••.	12-82	••..M«« 12*90
16	••••	10*26	9-95

C»H»03 156 .... 100-00 100-00

Isomeric with capric aldehyde. (Gerhardt.)

Dissolves in oil of vitriol almost without colour. On heating the mixture, a conjugated acid is formed, the baryta-salt of which is soluble in water. It is not altered by caustic potash or by nitrate of silvei\

Oxygm-nudeus C^^H^O*.

Sebacic Acid.

C»H»0* s= C»H»0»,0*.

TH^iARD. (1802.) Ann, Chim. Fhys. 39, 193; 8ckw. J. 8, 127. V. Rose. A. GM, 275, 3, 170.

Berzelius. N. GM, 2, 275; Lehrlmch. 3, Aufl. 8, 667. Dumas & Peligot. Ann. Chim. Phys. 57, 332; Ann. Phamu 14, 73. Redtenbachbr. Ann, Pharm, 35, 188.

St. Evre. N. Ann. Chim. Phys. 20, 93; J. pr. Chem. 41, 144. Schlieper. Ann. Pharm. 70, 121; Pharm. Centr, 1849, 459. Bouts. Gompt. rend. 33, 141. — JT. Ann. Chim. Phys. 44, 100; 48, 99; Ann. Pharm. 80, 303; 97, 34.

494 PRIMARY NUCLEUS (^H»: OXtOBN-NUCLEUS C»H»0».

W. Matbr. Ann. Pharm, 88, 143; 95, 160.

RowNBY. Chem. Soc, Qu. J, 4, 334; Ann, Pharm. 82, 123; J.pr, Ohem.

55, 825. Carlbt. Compt rend, 37, 129; /. pr. Ohem. 60, 181; N. J. Phartm*

24, 176.

BrenzoUic acid, Pyroleie acid, SebacyUaure, Fkttidun. Diteoverad in 1802 by Thenard, who at the same time showed that the product of the distillation of aalmal fat, to which the name of Fettsdure or Acide yra^ had been applied by Crell (OrelL cAcas. /. 1, 60; 2, 112; 4, 47), and Gayton Morveau, consisted partly of acetic, partly of hydrochloric acid. Th^nard's experiments were confirmed by V. Rose. Berzeliiift regarded Th(Snard's sebacic acid as identical with benzoic acid, an opinion which was shown to be incorrect by the experiments of Dumas & Peligot

Mayer's ipomaiic acid (not Sandrock's, N. Br, Arch, 64, 164), agrees with sebacio acid in most of its relations, but melts at a different temperature and exhibits a differ- ent behaviour to bases : for this reason, the statements respecting it are given separstdy.

Formation. 1. By the dry distillation of hog's lard (Th6nard), fat oil (Berzelias), and other fats, in so far as they contain oleic acid: henoe also by the dry distillation of oleic acid* (Kodtenbacher.) — 2. When ricinolate of potash or castor-oil is distilled with excess of potu^h-hvdrate, hydrogen is given off, caprylic alcohol (p. 1 83) passes over, and sebate of potash remains behind. (Bonis. ) — The largest amount of sebacio acid IS obtained when a large excess of alkali is used and the mixture is rapidly heated to the melting point, whereas bj slow heating to at most 225° — 230°, neither sebacic acid nor caprylic acid is obtained, but the acid C*H"0* and caprylic aldehyde. (Bonis.) — Limpricbt {Private communication) hj using an excess of alkali, alwajs obtained sebacic acid, whether caprylic alcohol or caprylic aldehyde was produced ; simi- larly Malaguti (Cimento, 4, 401; Liebig u. Kopp*i Jakresber, 1856, 579). According to Dachauer (Ann. Pharm. 106, 270), the products obtained with excess of alkali^ are caprylic alcohol, methyl-OBuanthyl (isomeric with caprylic aldehyde), and sebate of potash; (according to Stadeler^ J, pr. Chem. 72, 241), oenanthylic alcohol, and sebate of potash (see ziii, 587). — 3. By continued boiling of oil of rue with dilute nitric acid, (Wagner, J. pr. Chem. 57, 435.^ — 4. Convolvulio acid, conyolvulinolio acid, jalapin, jalapic acid, and jalapinolic acid, treated with moderately strong nitric acid, or with the fuming acid, yield ipomaeic and oxalic acids. (Mayer.)

Preparation, Method II. is the most advantageous. — 1. From Olive oU, Hog's lard, or other fats containing Oleic acid. Crude oleic acid from the stearin manufactories is best adapted for the purpose. (Redteubacher.) 1. The fat

is distilled per se, and the distillate is repeatedly treated with hot water, then filtered, and evaporated to the crystallising point — Or the solution obtained by treating the fat with hot water is precipitated with neutral acetate of lead; and the precipitate is collected and decomposed by heating with dilute sulphuric acid, whereupon the sebacic acid rises to the surface as a melted mass, which is taken off, washed with cold water, and recrystallised from boiling water. (Th6nard.) Redteubacher like* wise obtains sebacic acid from the products of the distillation of fats by repeated boiling with water, and purifies it by recrystallisation, till it becomes white and scentless. — Berzelius washes the distillate of fat oil with cold water to separate acetic acid^ and then boils it with coarsely powdered carbonate of lime, whereby only the sebacic acid is converted

SEDACIC ACID, 495

into a lime-salt^ not tbe other acids. After loug-continned boilings the fiolotion is filtered, deodorised with charcoal, and mixed with nitric acid, whereby sebacic acid is precipitated : It may bo purified by washing with cold water, recrystallisation from boiling water, and finally by sublima- tion, in the apparatus used for the subliming benzoic acid.

2. The distillate of crude commercial oleic acid is repeatedly boiled with water; the extracts are saturated with carbonate of soda, and evaporated to dryness; and the residue is freed from caprylate and caprate of soda by means of hot absolute alcohol. The undissolved sebate of soda is dissolved in water and precipitated by hydrochloric acid, and the sebacic acid thereby separated, is purified by recrystal- lisation from boiling water. The still yellow sebacic acid obtained by this and other methods, is obtained pure by once boiling it with 5 to 6 pts. of nitric acid, and pouring the solution into a lar^e quantity of boiling water, whereupon it crystallises on cooling. (Scluieper.)

II. From Ooitor-oil, The residue left in the retort in the preparation of oaprylio alcohol (xiii, 183) is decomposed by hydrochloric acid, an*d the sebacic acid is extracted by boiling water £rom the mixture of in- soluble acid which separates. (Bonis.) — Petersen boils the residue with water ; strains ; precipitates the other fatty acids by adding a small quantity of hydrochloric acid ; then, after separating these by filtration, precipitates the sebacic acid by excess of hydrochloric acid, and purifies it by recrystallisation from hot water with the aid of animal charcoal. {Ann. Gh, Pharm. 103, 184.)

Propeiiies. White, pearly needles, very much like those of benzoic acid. (Redtenbacher.) Under certain circumstances, it may be obtained in long, large, strongly shining laminse. (Thenard.) Bulky and of a feathery lightness. (Berzelius.) — Ipomteic acid is dazzling white, of feathery lightness, and presents under the microscope the appearance of thin colourlesa needles, some of which are united in tufts, while others lie separate, sometimes in very thin flexible laminsB. (Mayer.) Sebacic acid melts at 125'' (St. Evre), ^t 127** (Redtenbacher, Mayer, Bonis), to a colourless oil which solidifies in the crystalline form on cooling, and sublimes at a higher temperature, partly pulverulent, partly in minute laminae, generally with some decomposition and separation of charcoal. (Berzelius, Redtenbacher). Ipomieic acid melts at 104° to a colourless oil, lighter than water, and solidifying in the crystalline state. It some- times sublimes between two watcWlasses in very small, proportionally short needles radially grouped round a point, leaving a small quantity of charcoal, whereas sebacic acid sublimed in like manner, forms larger and more definite crystals. (Mayer.) — Sp. gr. of melted sebacic acid =^ 1*1317. (Carlet.) Scentless (Th6nard); has a faint empyreumatic odour (Berzelius). The vapours, both of sebacic and of ipomseic acid, produce a scratching sensation when inhaled. (Redtenbacher, Mayer.) Has a faint, rather acid taste (Thenard), pungent, but not exactly. sour (Berzelius). Reddens litmus strongly (Thenard), slightly (Redtenbacher). Ipomseic acid is scentless, has a pungent, sour taste, with irritating after- taste, a slight acid reaction, and becomes strongly electrical by friction. (Mayer.)

496 PRIMARY NUCLEUS C»H»: OXYGEN-NUCLEUS C^H^'W.

20 C	.. 120 .. 18 .. 64	Dumas & Peligot. Redtenbacher. mean. .... 69-40 69-62 59-62 .... .... 8-91 908 8-90 .... .... 31-69 31-40 30-90 ....	StEvre. 59-30
18 H	9-04
8 0 ..........	31*66
C»H"08 G .... H.... O....	.. 202	.... 100-00 Mayei mean a, 59-44 .... 9-01 .... o^-oo ....	100-00 Bonis. 59-20 .... 60-62 8-97 .... 8-97 31-83 .... 30-51	99-32 .... Carlet. .... 59-25 .... 9-07 .... 31-68	100-00

100-00 .... 100-00 .... 100-00 .... lOO'OO

Bouia and Carlet analysed sebacic acid prepared firom caator-oU; Mayer analysed ^mteicacid: a obtained from eonvolvnlic and conTolYolinolic acid ; b from jalapin, ^Suipic acid and jalapinolic acid. The formula C^H'O, given by Mayer, is here doubled in accordance with the principles of the Handbook.

DecomposUiom. 1. Ipomieio acid heated ou platiDum foil; Yolatilises in white fumesy which burn slowly and with a feebly luminooa flame. (Mayer; see also ti^-a.)

2. Nitric acid of ep. gr. 1-4 dissolyee sebacic acid with the aid of heat, giving off red vaponrs and acquiring an orauge-red colour, and if the boiling be continued^ and the exhausted nitric acid removed, slowly con- verts it into pyrotartaric acid (Schliesser, xi, 83); into succinic acid (Carlet) ; into a mixture of succinic and oxypyrolic acid CH'O' (Arppe, Ann, Pharm. 95, 242) ; of succinic, pimelic (xii, 463), and perhaps also adipic acid. (Wirz, Ann. Pharm, 104, 280). After two or three hours boiling with nitric acid, the greater part of the sebacic acid remains unaltered, the decomposition not being completed in less than a week. (Scbliesser.) — Ipomseic acid is not altered by being heated with nitric acid on the water-bath for many days, and separates out unaltered when the nitric acid is evaporated. (Mayer.) — 3. Sebacic acid is attacked by pentachhrtde of phosphorus, with formation of hydrochloric acid gas, chlorophospboric acid and sebacic anhydride. (Gerhardt & Chiozza^ Compt rend. 30, 1050; Ann. Phaitn. 87, 294.) — 4. Chlorine acts on sebacic acid only in sunshine, forming two yellow substitution* products, Cr»ClH"0« and C*»CPH"0*, which are pasty at mean tem- perature. (Carlet.) — 5. The lime'Salt of sebacic acid, subjected to d7'y distillation, gives off hydrogen gas, and yields an oil boiling between 80^ and 200^ — On rectifying this oil, a liquid passes over between 85° and 90% which has a pleasant ethereal odour and appears to be propionic aldehyde, — then, between 156® and 200**, oenanthol (xii, 446) distils over, (dalvi.) When sebate uf lime is distilled with excess of lime, sebacin (p. 447) is obtained, together with an oil boiling between 80® and 280®. The latter, when rectified, first yields a product which, when treated with nitric acid, forms nitrobenzene, and is therefore probably benzene, — then, between 90® and 100®, propionic aldehyde, — and at 160®, oBuanthol, inasmuch as the portion which distils at these temperatures forms, with nitric acid, propionic and cBnanthylic acids. (Petersen, Ann. Pharm. 103, 184.) By distillation with excess of baryta, sebacic acid yields carbonate of baryta and a hydrocarbon, C**H'^ boiling between 126'' and 130% chiefly at 127®. (A. Riche, Par. 8oc.

SEBACIC ACID. 497

£uU. 1, 88 ; Fep, Chiiru pure, 2, 127.) — 6. WLen (dcoholie sebacic acid is treated with hydrochloric add gas, an oil is produced which with ammonia forms sebamide and sebamic acid, and is therefore probably a mixture of sebacic ether and ethylsebacic acid. (Rownej^ see page 502.)

Comhinations. Sebacic acid dissolves sparingly in cold water. It dissolves abundantly in boiling water (Th^nard); in all proportions (Berzelius), so that the solution solidifies on cooling. Jpomffiic acid is slightly soluble in cold, very easily soluble in hot water. (Mayer.)

Sebacic acid is Made, Its aeminicid or bibasic (neutral) salts are C^M'H^'O^. The mono -add or monobasic {acid) salts are, excepting the ammonia- salt, easily decomposible. (Carlet.) It decomposes alkaline carbonates, forming with them, easily soluble salts^ whose solutions precipitate the salts of the alkaline earths and heavy metallic oxides (not ferrous salts, according to Berzelius). Acids separate sebacic acid from them and cause concen- trated solutions to solidify. Aqueous sebacic acid does not precipitate baryta-, strontia-, or lime-water. It precipitates lead-, silver-, and

mercuric-salts. (Thenard.) Sebadc acid obtained from marrow does not precipi- tate lead- or silTer-salts, or only if prepared from marrow having membranes or blood- Teisels adhering to it. (Berzelins.) Berzelius likewise found that sebate of potash is divided by absolute alcohol into two parts, and that only the acid of the insoluble, not that of the soluble salt, precipitates lead and silver -salts. Redtenbacher, however, did not succeed in separating from his sebate of potash by absolute alcohol, a salt whose acid did not precipitate mercurous and silver salts.

The iponueates^ excepting those of the alkalis, are sparingly soluble or insoluble in water. Ipomssate of ammonia forms a white precipitate with lead-salts, flesh-coloured with ferric chloride, bluish-green with cupric salts, and white with silver-salts. With bichloride of platinum, it forms a yellow precipitate which dissolves in boiling water, separates again on cooling, and then becomes crystalline after long standing. — The ipomffiates become electrical by friction. (Mayer.)

Stbate of Ammonia. — a. Bibasic. — Indistinct crystals, which are easily soluble in water, and in drying, give off ammonia and turn acid. (Redtenbacher.) Yields sebamic acid by dry distillation. (Kraut.)

6. Monobasic, — The easily prepared solution of sebacic acid in excess of ammonia gives off ammonia when evaporated, and leaves the monobasic salt, sparingly soluble in water. Crystallises from boiling water by slow cooling, in pointed feathery crystals ; by rapid cooling, in small grains. Dissolves with difficulty in alcohol. (Berzelius.) — Ipomseic acid, saturated with aqueous ammonia, continually gives off ammonia by spontaneous evaporation or on the water-bath, and yields a white cauliflower-like salt, probably C*H"O^NH*0, therefore ipomadate of

ammonia.

Sebate of Potash. — Bibasic. — Obtained by neutralising the acid with carbonate of potash. Small granular nodules. (Redtenbacher.) Docs not deliquesce on exposnre to the air. (Th6nard, Redtenbacher.) Easily soluble in water, sparingly in absolute alcohol. (Redtenbacher.)

Redtenbacher.

20 C 1200 .... 43-11 43-00

2K0 94-4 .... 38-91

16 H 160 .... 5-74 5-94

6 O 48-0 .... 17*24

CSOK'H^^O* 278-4 .... 10000

VOL. XIV.

2 K

498 PRIMARY NUCLEUS C»H»: OXYGBN-NUCLEUS C^HWQs.

Redtenbacher did not obtain an add lebate of potash by treating the nentral aalt with aebacic acid.

S^HJJte of Soda resembles the potasb-salt, but is somewhat more soluble in water. (Redtenbacber.) Insoluble in absolute alcohol. (Scblieper.)

Sehate of Lime, — Bibasic. — Chloride of calcium solution precipitates sebate of ammonia. The precipitate, which dissolves with some difficulty in water, is obtained, by spontaneous evaporation of its dilute solution, in white, shining crystalline scales. (Redtenbacber.) The precipitate obtained with sebate of ammonia and chloride of calcium is crystalline when formed ; but that which is produced by ipomaeate of ammonia becomes crystalline only after standing for some time. (Mayer.) — For the decomposition of the lime-salt by dry distillation, see page 497.

Redtenbaeher.

20 C 120 .... 50-00 49-49

2CaO 56 .... 23-33 22-91

16 H 16 .... 6-67 6-76

6 O 48 .... 20-00 20-84

C»Ca«H»«08 240 .... 10000 100-00

Sebate of Lead, — The white precipitate insoluble in water^ which sebate of potash forms with solution of neutral acetate of lead, is con- verted by ammonia into a basic salt. ^Berzelius.) — The precipitate obtained by treating acetate of lead witu ipomaeate of i^mmonia, is a white powder, insoluble in water, which, after drying over oil of vitriol, contains 54*70 p. c. oxide of lead, and is therefore G^Pb'H^^O' (calcnlation = 5400 PbO). (Mayer.)

Ferric Sehate, obtained by double decomposition, is a flesh- coloured precipitate, which^ when treated with aqueous carbonate of ammonia or caustic potash, dissolves partially, with red colour^ leaving a highly basic salt. When heatedi it melts, swells up, and decomposes. (Berzelius.)

Sebate of Copper. — The precipitate which soluble sebates produce in aqueous sulphate of copper is bluish, and redissolves at flrst, but becomes permanent on addition of a larger quantity of sebate, and exhibits a fine

freen colour when dry. The filtered liquid, when left to evaporate, ecomes covered with a green crystalline crust and deposits green granules* (Berzelius.) — Cuprio acetate is precipitated by ipomsBate of ammonia, and the precipitate is dried in vacuo over oil of vitriol. (Contains 20*92 p. c. cupric oxide, corresponding to the formula C^Cu'H^O' (calculation 30*30 CuO). (Mayer.)

S^ate of Silver, — Bibasic, — Nitrate of silver is precipitated by sebate -of ammonia (ipomseate : Mayer), and the precipitate is washed, and dried in vacuo at 120° (Dumas & I*eligot)j over oil of vitriol. (Mayer.)

White curdy precipitate (Redtenbacber). White, rather light powder. (Mayer.) Heated in a glass tube, it yields metallic silver and a subli- mate of sebacio acid (Redtenbacber), of ipomseic acid (Mayer.) Dissolves with difficulty in water (Redtenbacber), not at all (Mayer). Dissolves with difficulty in alcohol and ether. (Mayer.)

SEBATB OF ETHYL. 499

Redtenhacher, Mayer*

20 C 120 .... 28-84 29-19 .... 29'U

2 AgO 232 .... 55-76 55-45 .... 54-89

.16 H 16 .... 3-84 3-97 .... 4-02

6 0 48 .... 11-56 ^ 11-39 .... 11-95

C*«Ag3H»«08 416 .... 100-00 100-00 .... 100-00

Contains 54*9 p. c. oxide of silver. (Damas 8t Peligot.)

Sebasio acid dissolves readily in alcohol, in eiber, and in oilsi both fixed and volatile. (Berzelius.) — Ipomfeic acid dissolves readily in alcohol and in ether. (Mayer.)

Sebate of Methyl.

C»*H«0» = 2C»H«0,C«>H"0*.

Henry Carlbt. (1B58.) Conipt. rend. 87, 129; i\r. J. Fha^^m. 24, 176; J. pr. Chem. 60, 181; Fkarm, Oentr. 1853, 669; Chem. Gaz. 1853, 324.

MethyUehadc ether. Sehaeylformesfer.

Formation and Freparation. Sebacio acid is dissolved in oil of vitriol, wood-spirit carefully added, the liquid being agitated and cooled to prevent too great heating ; and the resulting ether is precipitated by water, washed first with alkaline, then with pure water, and crystallised from alcohol.

fieautiful needles, which melt at 25*5°, and boil without decomposition at 285^. In the solid state, it dissolves in water with comparative difficulty, in the fused state mol'e readily. Has a very faint odour.

By ammonia it is converted into sebamide and wood-spirit, by hydrate of potash, into sebate of potash and wood-spirit.

Sebate of Ethyl.

C^H^O* = 2C*H»0,C«'H*«0«.

Redtenbacher. (1840.) Ann. Pharm. 35, 193.

Sebacic ether yfetteaurea Aethylojeyd, Fettnaphta^ Sehaeylrineaier.

Foinnation and Freparation. Sebacic acid is dissolved in a small quantity of alcohol ; hydrochloric acid is passed into the solution to saturation; and the chloride of ethyl thereby produced is volatilised by gentle heating. The residue is washed with water, then with aqueous carbonate of soda, dehydrated by chloride of calcium, and rectified. (Redtenhacher.) — Alcoholic sebacic acid, treated with hydrochloric acid gas, yields a mixture of sebacic ether and ethylsebacic acid. (Bowney, Ann. Fkaim. 82, 124.)

Froperties. Colourless oil, lighter than water. Solidifies in the

2k2

600 PRIMARY NUCLEUS C»H»: NITRO-NUCLEUS C»XH».

crystalline fonn at — 9°. Boils above 100° ^Redtenbacher), at 308^ (Carlet^ Compt. rend, 37^ 130). Has an agreeable odour of melons.

28 C

26 H

80

	Redtenbacher.
168 .... 65*12	64-45
26 .... 10*08	10-24
64 .... 24-80	25-31

2C<H»0,C*H»»0« 258 .... 10000 100-00

By hydrate qfpotash, it is resolved into alcohol and sebate of potasli (Redtenbacher) ; amvumia, after long continued action, converts it into sebamide. (Rowney.)

le is insoluble in cold uniter, but dissolves very easily in alcohol. (Rowney.)

Sebin.

M. Bertbelot. N. Ann* Chim. PhyB. 41, 293.

Formation, 1. Sebacio acid, heated with glycerin to 200° for some time, forms a small quantity of neutral cry stall isable sebin :

C»HWO« + 2C«H80« = CafiWO" + 4 HO.

2. By the action of hydrochlorio acid gas on a mixture of sebacio acid and glycerin heated to 100°, a considerable quantity of liquid sebin is obtained, mixed with chlorhydrin, C^H'^CIO^ which, after strong drying at 120°> solidifies partially after a few days, and completely at — 40°.

Bertbelot.

32 C 192 .... 54-85 52-7

30 H 80 .... 8-57 9*6

16 O 128 .... 36-58 37*7

2C«H70»,C»H'«0« 350 .... 100-00 100-0

Forms acrolein when heated, — Oxide of lead converts it into sebacic acid and glycerin ; with alcoholic hydrochloric acid, it yields sebacic ether and glycerin. (Bertbelot.)

Nitro-nucUus C*^XH".

Nitrocapric Acid.

Wmz. (1857.) Ann, Pharm. 104, 289.

Obtained by the process described at page 217, vol. xiii, but mixed with nitrocaprylic acid, from which it cannot be completely separated.

SBBAMIG ACID. 501

When the solution of this mixtore in ammonia is fraciionallj precipitated in three portions by nitrate of silver, the precipitate first produced con- tains 28*89 to 29*3 p. c. silver, the second portion 32*8 to 33*3 p. c, and the last 37*4 p. c, corresponding to nitrocaprjlate of silver.

Niiroci^ate qf Silver. Win.

20 C 120 .... 37*0 33*67 to 35*97

N 14 .... 4-3

18 H 18 .... 6-6 5-14 „ 6*30

Ag 108 .... 33*3 34*04 „ 31*90

8 O 64 .... 19-8

C»AgKW»0* 824 .... 1000

Amidoffeti'nueleus C*AdH".

Capramide.

C»NH"0» = C«AdH»0«.

RowNEY. Ann, Pharm, 79, 236. Rutamide.

Caprate of ethyl dissolved in alcohol is precipitated by strong aqaeoos ammonia, till the ether disappears and is completely converted into crystals ; and the crystals are collected,— an additional quantity being obtained from the mother liquor by evaporation to dryness, solntion of the residue in alcohol, and precipitation by vater, — and recrystallised from warm dilnte alcohol.

Colourless shining scales, acquiring a silvery lustre when dry. Melts below 100°.

20 C N

21 H 20

		Rowney,
120	.... 70-17 ...	70*62
14	•«.. o'lo ...	■ •«■•
21	.... l£ £o ...<	12'17
16	.1.. «F tit ...

C»AdH»0« 171 .... 10000

Insoluble in water and in ammonia.

Dissolves readily in cold alcohol^ and is precipitated therefrom in needles by water. Easily soluble in ethers but does not crystallise therefrom.

Oxyamidogen-nudem C**AdH*^0*.

Sebamic Acid.

C«>NH»0« = C*»AdH"0«,0^

Rowney. n851.) Chenu Soc. Qu. 7.4, 334; Ann. Pliarm. B2, 123; J. py. Chem, 55, 325.

FettamiuMduret Sebamintduref Sebacylamintdnre,

502 PRIMARY NUCLEUS C»H»5 OXYAMIDOGEN-NUCLEUS C^AdH^O^.

FarmatUm, 1. Bj ibe action of ammonia on etbjisebamic acid. (Rowney.) — 2. By the dry distillation of neatral sebamate of ammonia. (Kraut.)

Preparation. 1. The oily mixtnre of eobacio ether and ethyl-sebacic acid obtained by the action of hydrochloric acid gas on an alcoholic solution of sebacic acid, is digested with strong aqueons ammonia for several weeks in a closed vessel, or till the oil is converted into a granular mass, the sebamide which separates from the liquid containing sebamic acid, being removed by filtration, and washed to free it from mother- liquor. The several portions of liquid are then united and concentrated over the water-bath ; the sebamic acid is precipitated by hydrochloric acid, washed with cold water, and dissolved in dilute aqueous ammonia, which still leaves a small quantity of sebamide undissolved j the solution filtered therefrom is again precipitated by hydrochloric acid; and the resulting precipitate, after being washed, is purified by recrystallisatioii from water. ^Rowney.) — 2. Neutral sobate of ammonia yields by simple distillation, first a colourless, then a yellowish empyrenmatic distillate, which is to be dissolved in ammonia, filtered from a small quantity of oil which separates, and precipitated with hydrochloric acid. The precipitate is washed with cold waCer, and recrystallised from boiling water. (Kraut.)

Propei^ties, Rounded granules. (Rowney.) White, crystalline, pul- verulent mass. (Kraut.) Has an acid reaction. (Rowney.)

20 C.

N

19 H

60

			Rowney.	Kraut. Dried over oil
			mean.	qf 9itriol.
120	■ •■•	59-70 ...	59-65	.... 59-98
U	• •■•	6-97 ...	6-70	.... 7-09
19	• ••1	9-45 ...	9-53	.... 9-81
48	• •••	2.^88 ...	2412	.... 2312

C«AdH»'0« 201 .... 100-00 10000 .... 100*00

Decompositions. 1. Gives off ammonia when boiled with potash^ (Rowney.) — 2. The soda-salt brought in contact with chloride of benzoyl, yields chloride of sodium and an oil, which may be dissolved out by- ether, is left behind when the ether evaporates, gives off ammonia whea fused with hydrate of potash, is insoluble in water and ammonia, and, when washed with ammonia, gives up to it only a small quantity of free acid. (Kraut.)

Combinations, Sparingly soluble in cold, easily in warm water. Easily soluble in ammonia, (Rowney.) Boiled with carbonate of limey it gives off carbonic acid, and forms 'a lime-salt slightly soluble in water. (Kraut.) The solution of sebamic acid in ammonia does not precipitate the alkaline earths ; it precipitates acetate of lead, and forms with nitrate of silver^ a precipitate soluble in ammonia and in nitric aoid. (Rowney.)

Sebamic acid is easily soluble in alcohol, (Rowney.)

ANISOIC ACID. 503

Oxyamidoffen -nucleus C*Ad*H^O".

Sebamide.

RowNRY. 0851.) Chem. Soc. Qu. J, 4, 334; Ann. Fhatnn. 82, 123;

J, pr. Chem. 55, 325. H. Carlet. CompL rend. 37, 128; iV^. J.Pharm. 24, 176; J.pr. Chem,

60, 181; Pharm. Centr. 1853, 669; Chem. Gaz. 1853, 324.

Feth&ureamid.

Formation and Preparation, 1. Sebamide obtained in the manner just described (p. 502). is purified by two recrystallisations from alcohol, (Howney.) — 2. It is produced by the action of ammonia on sebate of methyl. (Carlet.)

Properties. Hard rounded granules composed of microscopic needles. Neutral.

Rowney. mean.

20 C 120 .... 60' 59-94

2N 28 .... 14- 13-85

20 H 20 .... 10- 10-01

4 O 32 .... 16- 16-20

C*Ad2H«0< 200 .... 100- lOO'OO

Decompositions. Water gradually converts it into sebate of ammonia. (Carlet.) It is not attacked by potash-ley in the cold, but gives off ammonia when boiled therewith. (Rowney.)

It is insoloble in cold, moderately soluble in boiling tvater. Insoluble in ammonia. Dissolves very sparingly in cold alcohol^ very easily in boiling alcohol. (Rowney.)

Primary Nudeus C^H** : Oxygen-nucleus C"H^'0'.

Anisoic Acid.

LiMPRiCHT & RiTTEB. (1856.) Aim, Pharm. 87, 364; abstr. «7. pr. Chem. 68, 160; CJiem. Centr. 1856, 446.

Formation and Preparation. When oil of star-anise is heated with nitric acid of sp. gr. 1*2, as long as it floats on the surface of the acid, and the product is shaken up with a warm ac^ueous solution of bisulphite of soda, anisoate of soda crystallises on cooling. This salt is recrystal- lised from a small quantity of hot water, mixed with a quantity of dilute sulphuric acid exactly sufficient to decompose it, the solution evaporated

504 PRIMARY NUCLEUS 0»H«: OXYGBN-NUCLEUS C»H»0».

to dryness ou the water-batb, and the residue exhausted with absolute alcohol, whereupon anisoic acid passes into solution and may be converted into a baryta or silver-salt^ by digestion with carbonate of baryta or carbonate of silver. By decomposing the baryta-salt with dilute sul- phuric acid, or the silver-salt with hydrochloric acid, a solution of anisoic acid is obtained, which may be brought to the crystallising point by evaporation.

Properties. Separates from warm solutions by concentration In small laminsD, by spontaneous evaporation in small thick tablets, which melt at about 120 and have a strong acid reaction.

Decompositions, Heated on platinum-foil, it turns brown, gives off an empyreumatic odour, also that of anisylous acid, and burns with a bright name. It cannot be distilled without decomposition, and by dry distillation appears to yield a sublimate of anisic acid (vid. Ann, Pnarm. 97, 366).

CornUnations, Anisoic acid dissolves very easily in water.

With bases it forms the anisoates,

Anisoate of Soda, — Preparation (p. 603.) By recry stall isation from hot water, it is obtained in white crystalline nodules. Dissolves readily in water. Dried at 100°, it contains 8*9 p. c. sodium, and is therefore C»NaH"0» (calculation = 8*9 p. c. Na).

Anisoate of Baryta, — Preparation (sup.). Easily soluble nodules resembling those of the soda-salt.

Limpricht St Ritter. mean.

20 C 1200 .... 39-78 89*44

Ba 68-6 .... 22*74 22*39

17 H 17-0 .... 5-65 5-44

12 O 960 .... 31-83 32*73

C-»BaH»70« 301*G .... 10000 10000

Anisoate of Silver, Obtained as above described, or by decomposing the baryta-salt with sulphate of silver.

Crystalline nodules, which in the moist state blacken on exposure to light.

Dried over oil of vitriol, Limpricht k Ritter.

20 C 120 .... 35*19 341

Ag 108 .... 31*67 32-2

17 H 17 .... 4*98 4*0

12 O 96 .... 28*16 29-7

C»AgH>'0»2 341 .... 100-00 100-0

Anisoic acid dissolves very readily in alcohol and ether.

DERIVATIVES OP SULPHONAPIITIIALIC ACID. 505

Addenda to compounds containing 20 At. Carbon. Product of the decomposition of Amalic Acid.

RocTiLEDEa & Schwartz. JVien. Akad, Ber, 12, 190.

Amalic acid (xi, 433) dissolves with pale yellow colour in warm concentrated bisulphite of ammonia, the solution when heated becoming darker and depositing needles, which, after boiling for some time, cause the liquid to solidify. The whole is' left to cool, and the needles are collected, washed, and pressed.

White, silky needles, free from sulphur.

[ Bochleder & Schwarfie. In vacuo. mean.

20 C 120 .... 431 7 43-24

4 N 56 .... 20-14 20-27

14 H 14 .... 504 5-38

11 O 88 .... 31-65 3111

CaoN<H"0" 278 .... 10000 10000

The compound acquires a rose-colour by exposure to moist air (containing ammonia). — It decomposes when heated, giving off colourless and purple smoke, con- sisting of crystalline spangles. — Left for some time in contact with bichloride of platinum, it decomposes, yielding light yellow crystals which contain 58-77 p. c. platinum, and are probably therefore Reiset's ammonio-platinous chloride (vi, 300 ; calculation 58*79 p. c Pt.). Perhaps formed in this manner :

C»N*H"0" + HO + PtCP = N«H6PtCl + C»H«N«OW + HCl.

(Rochleder & Schwartz.)

The compound dissolves very readily in acide, but not in other liquids. The hydrochloric acid solution does not precipitate bichloride of platinum^ even after addition of ether-alcohol.

f Derivatives of Sulphonaphthalic Acid.

KiMBEBLT. Ann. Fharm. 114, 129; abstr. JRep» Chim. pure, 2, 258.

Sulphite op Chloronaphthalin. C"H^C1,2S0*. — XaphthyUulphurous Chloride, ChlorUr der naphtyltchwefiigen Saure, — Produced by the action of pentacliloride of phosphorus on sulphonaphthalate of soda (p. 17) :

C?»H«,2S0' + PCP - C?»H7C1,2S02 + PQW -f NaCl.

1 At. of the soda-salt dried at 100° is intimately mixed in a slightly heated capsule with 1 At. pentachloride of phosphorus ; and the solidified mass is triturated and washed with water, till the oxychloride of phos- phorous is completely decomposed and the chloride of sodium dissolyed: the residue consists of sulphite of chloronaphthalin. It is purified by drying on filtering pnper, dissolving in ether free from alcohol, filtering, evaporating, and drying at 100°.

606 ADDENDA TO COMPOUNDS CONTAINING 20 AT. CARBON.

White, iDodorous solid body, which melts at B5° and solidifies at a lower temperatare in rounded lamellar masses. Partially volatile without decomposition^ but begins to decompose, even at 120^

20 C	120-0 .... 62*95
7 H	7-0 .... 3-14
01 2S	35-5 .... 15-67 .... 320 .... 1412 ....	.... 15-62 .... 14-03
6 0	32-0 .... 14-12
C»H7C1.2S0» .	226-5 .... 100-00

May be regarded as /naouA' r CI* ^•"^*°S ^^^ *^* mixed type A jjqj .

The compound is decomposed by tDcUer and by the aqueous and alco- holic solutions of potashf especially with the aid of heat, yielding hydro- chloric acid and sulphonaphthalic acid :

C»H7C1,2S0> + 2H0 = HCl + C»H8,2SO»:

With absolute alcohol, it forms hydrochloric acid and sulphonaphthalate of ethyl :

C»H7Cl,2SO« + C<H«02 » HCl + 0»H^(C<H«),2S0».

Sulphite of chloronaphthalin is insoluble in water, but dissolves in tidphide of carbon, oxychloride of photphorua, e^er and benzene; likewise in alcohol, but not without alteration.

Sulphonaphthalate of Ethyl. C«*H"S*0«= C"H'(C*H»), £S0». —

Sulphonaphihalie ether. Ether naphtyUulfiireux, Naphtyhchto^liffeawee Aethyl. (Kimberly.) — Produced by the action of absolute alcohol on sulphate of chloronaphthalin {vidtup.) — In preparing the ether, it is best to use 2 At. alcohol to 1 At. of the sulphite. — The excess of alcohol is expelled by distillation, and the residue is washed with water. The hydrochloric acid produced at the same time, acts upon the alcohol, forming chloride of ethyl and water, which then decomposes a portion of the snlphite of chloronaphthalin.

Sulphonaphthalic ether, recently prepared, is, at ordinary tempera- tures, a viscid liquid, which does not solidify, even at — 8® or — 10^. If care has been taken not to heat it as high as 50° during the preparation and purification, it crystallises, after a few days, in aggregated laminsd ; but if it has been more strongly heated, it does not crystallise for a much longer time.

Kimberle.

24 C 144 .... 61-01 60-77

12 H 12 .... 5-09 519

2 8 32 .... 13-56 13-77

6 O 48 «.. 20-34 20-27

C»H7(C*H»),2SO> 236 .... 100-00 100*00

It is decomposed by distillation, with formation of sulphurous acid, naphthalin, and carbonaceous matter. — Heated with tMiter to abont 154>" in a sealed tube, it yields alcohol, naphthalin^ and sulphuric add, witkoot any secondary products, according to the equation :

C»H7(C^H5),2S03 + 4H0 = C^H'O^ + C»H« + 2(H0,S0»). PotaA transforms it into alcohol and sulphonaphthalate of potash. ^-

NAPHTHTLTHI0NAHID8. 607

With pentachloride of phaapliorus, it yields sulphite of chloronaphthalin^ chloride of ethyl, and oxychloride of phosphorus.

It is insolohle in water, but mixes in all proportions with alcohol and ether.

NAPHTHYLTHioNAMtDB . C»H*NS'0*= C*°H' Ad,2S0l — pToducod by the action of ammonia on sulphite of chloronaphthalin. The sulphite triturated in a basin with aqueous ammonia, becomes heated and melts to a yellow oil, solidifying in a light yellow amorphous mass, which may be purified by washing with water^ solution in alcohol, and crystallisation. — It forms microscopic crystals apparently belonging to the right prismatic system, peyish yellow when dry, light yellow when moist, and becoming reddish by exposure to the air. In boiling water, it melta to a viscid mass, without decomposing. It is soluble in hydrochloric acid, ammonia, glacial acetic acid, alcohol and ether. Potash decomposes it into ammonia and sniphonaphthalic acid :

Kimberly.

20 C 120 .... 57-96 57-58

9 H 9 .... 4-36 4*55

N 14 .... 6-77 ■ 6-64 .... 6-36

2S 32 .... 15-45 15-57

4 O 32 .... 15-46 15-66

C»H7Ad,2S02 207 .... 10000 lOO'OO

May be regarded as (C»H')' >q2> deriving from the mixed type gjgj Y

m

Argento-naphthyUhiorumide. C'°H«AgNS«0*=C~AdH«Ag,2S0*. — A slightly ammoniacal alcoholic solution of naphthylthionamide is not pre- cipitated by nitrate of silver, but as the ammonia evaporates in the air, argento-naphthylthionamide is deposited in small radiating needles, which alter by exposure to light. They are soluble in ammonia, alcohol, and ether, and likewise, without apparent alteration, in glacial acetic acid.

— Contains 34*10 p. c. silver, the formula requiring 34-89 p. o.

BenzoyJrnaphthylthionamide, C^H^NS'O* = C»AdH«(C"H»0»),2S0«.

— Obtained by melting naphthylthionamide with chloride of benzoyl. It is soluble iu alcohol and in glacial acetic acid, and crystallises from its solutions in prisms apparently belonging to the oblique prismatic system. Potash decomposes it, yielding ammonia, benzoate of potash and sulpho'- naphthylate of potash. — Contains 4*36 p. c. nitrogen and 10*41 sulphnr (calcuktion ss 4*50 p. c. N and 10*28 S).

Argento-henzoyl-mphthvlthumamide. C*»AdH»Ag(C"BL*0»),2S0*. — The solution of the preceding compound in absolute alcohol forms, with ammonia and nitrate of silver, as the ammonia evaporates, an amorphous flocculent precipitate, sparingly soluble in alcohol and decomposed by boiling. By precipitating its ammoniacal alcoholic solution with a slight excess of acetic acid, and raising the temperature for a few seconds to 30^ or 40^, the compouud may be obtained iu shining microscopic crystals.

— Contains 24-94 p. c. silver and 7*75 sulphur (calculation =: 25*83 p. c. Ag and 7*66 S). (Kimberly.)

608 ADDENDA TO COMPOUNDS CONTAINING 20 AT. CARBON,

Cumylamines.

A. Rossi. Compt. rend. 51, 570; Bep. Chim,pure, 2, 465.

Cuminaminet, — - Tbese bodies which are EDalogoas to the ethylamines, methylamines, <&c., are produced by the action of ammonia on chloride of cumyl (p. 165). When a mixture of chloride of cumyl and strong alcoholic ammonia is heated for some hours in a sealed tube placed in thd water-bath, and then left to cool, sal-ammoniac separates, together with a few drops of oily tricumylamine. The liquid filtered and evaporated, leaves a crystalline residue consisting of the hydrochlorates of cnmyla- mine and bicumylamine, mixed with oily tricumylamine, which may be dissolved out by ether, and remains after evaporation of the ether as an oil, which may be made to crystallise by agitation. — The hydrochlorates of the other two bases are separated by fractional crystalline from water, the hydrochlorate of bicumylamine being much less soluble in water than the cumylamine-salt. The bases are separate from the hydrochlorates by distillation with potash.

Gumylamine, C»H«N = C*»H"Ad,H» = N.IP.C^H". -- Ommamn*

primaire. — Isomeric with bietfaylaniline (xi, 307). — Colourless oily liquid, which does not solidify in a mixture of ice and salt. — Volatile at ordinaiy tem- peratures, and produces white fumes in the approach of a rod moistened with hydrochloric acid. Begins to boil at about 280^, with partial decomposition sparingly soluble in water, soluble in alcohol and ether. Absorbs carbonic acid, forming a solid compound. — The h^^drochlorats crystallises in nacreous, rhomboidal laminsd. — The chloroplcUinaU is slightly soluble iu cold water, whence it crystallises in small yeUow plates.

Bicumylamine, C^^'H'^N = C»°H"(C»H»)Ad,H» = N.H(C«»H»)». — Cuminamine tecondaire. Dense, colourless oily liqnid, beginning to boil, with decomposition, above 300^ Insoluble in water, soluble in alcohol and ether. The hydrochlorate crystallises in needles slightly soluble in cold water. — The chloroplatinate is sparingly soluble in cold water, and crystallises from alcoholic solution in small roseate needles.

Tricumylamine, 0»H»»N == (P°H«(0«>H»»)»Ad,H« = N.(C»H^)».— Cuminamine ieriiaire. Crystallises in small rhomboidal laminse, which melt at 81° — 82^ Insoluble in water, very soluble in ether and in boiling alcohol, slightly in cold alcohol. It does not affect the colour of litmus. The hydrochlorate^ which crystallises iu needles grouped in crosses, is nearly insoluble in water, very soluble in alcohol. — The chloroplatinate crystallises with difficulty ; the alcoholic solution deposits it in a viscous mass which solidifies in drying.

Oxidisiny properties qf Oil of Turpentine (comp. p. 256). — Berthelot has exanuaed the oxidation of various substances in contact with oil of turpentine which has been exposed to the air. 5 cubic centimetres of oil of turpentine, rectified a few weeks previously, were introduced into a 10-litre bottle, together with 50 grammes of water and 100 cub. cent, of a standard solution of indigo (requiring for decoloration 50 cub. cent, of chlorine »25 cab. cent, oxygen). The whole was left to itself at 20* to 30* for

VOLATILE OIL OF CITRUS LUMIA. 509

eight months, the indigo-solution being added by portions of 50 toIs. at a time. The quantities of oxygen absorbed by 1 toL of the oil of turpentine were as follows :

In 7 days 20 vols, oxygen.

„ 16 f, 40 „

,» 25 „ 60 „

ft 3« If 80 If

II 63 fi 102 „

„ 77 „ 108

II 160 „ 135 „

„ 182 „ 146 „

II 220 „ 168 „

At the end of the time, the oil of turpentine was found to be completely resinised, and had lost all its characteristic properties. The quantity of oxygen absorbed by the indigo amounted to 12 times as much as would be sufficient fur the complete com- bustion of the oil of turpentine, that is to say: 1 At. oil of turpentine, C^U>", determines the absorption of 4'7 At. oxygen by the indigo. — The rate of absorption varied considerably during the experiment.

The oxidation of pyroffollate of potash by active oil of turpentine takes place immediately, attaining its extreme limit in a few seconds. — Mercury shaken up with active oil of turpentine is quickly killed; at the same time a black powder is formed, which appears to be the suboxide. — A solution of eane'Sugar left for seven months in a large bottle, together with a small quantity of slaked lime, the whole being covered with a layer of oil of turpentine, yielded a considerable quantity of oxalic acid.

Oil of turpentine acquires the oxidising power when merely left to itself in a vessel containing air ; sunshine accelerates the action, but is not necessary to it. The time required for the development of the oxidising power is not very long : for oil of turpen- tine cannot be absolutely deprived of it, unless very carefully excluded from the air. — Active oil of turpentine retains its power for several years, probably till it is completely resinised. The oxidating power may be destroyed by boiling or by agitation in a close vessel with deoxidising substances, such as indigo or pyrogallate of potash. — The oxygen absorbed by oil of turpentine may be partly displaced by a stream of carbonic acid ; but the quantity thus displaced does not exceed the -j^ pt. of that which is absorbable by indigo. The amount of this active oxygen is also much greater than that which is merely soluble in the oil of turpentine, amounting in fact to half the volume of the oil of turpentine, whereas the portion simply dissolved does not exceed one-fifth of the Tolume of the liquid. — From these phenomena, Berthelot concludes that the active oxygen of oil of turpentine is in a state of combination, similar to that of the transferable oxygen of peroxide of nitrogen. {N. Ann. Chim, Phya% 58, 426 ; Rep. Chint. pure. 2, 269.)

Volatile Oil of Citrus Lumia.

S. DK LucA. Compt. rend. 51, 258; Eq>. Oiim, pure. 2, 462.

Obtained by expressing the rind of the fruit of Citrus Zumia, a plant which grows abundantly in Calabria and Sicily, and yields a fruit very much like the lemon, the greater part of the oil distils between 180° and 1 90°, yielding a limpid colourless liquid.

The portion boiling at 180"* is isomeric with oil of turpentine, and has a density of 0*853 at 18**. It possesses a dextro-rotatory power = 34"* for the sensitive tint. It is slightly soluble in alcohol, very easily soluble in ether and in sulphide of carbon. It is resinised by nitric acid. — Mixed with alcohol and nitric acid, it produces after a while, a crystal- lised hydrate. With hj/drocIUoric acid, it yields both a liquid and a crystalline compound. The crystallised compound, which has a peculiar odour and melts at a low temperature, is a hihydrocfdorate C^H",2HC1.

510 ADDENDA TO COMPOUNDS CONTAINING 20 AT. CARBON.

Amber-camphor, C«»H"0»

Berthelot & BuiGNET. Compt. rend. 50, GOCj Bep, Chim. pure, 189.

Obtained by distilling powdered amber with a fourth of its weight of potash and a large quantity of water; it then passes over with the vapour of water, a kilogramme of amber yielding 3 grammes of the camphor. — It resembles common camphor in its physical properties, excepting in having a more penetrating and persistent odour. It is isomeric with borneol (p. 832), but is distinguished therefrom by its smaller dextro-rotatory power which is only 4 '5®, whereas that of natural borneol is 33-4°, and that of artificial borneol, prepared from common camphor by the action of alcoholic potash is 44*9°.

It unites with hydrochloric acid (with elimination of water), forming the compound, C*H"C1 ; similarly with stearic acid. The latter compound distilled with an alkaline hydrate, reproduces the amber-camphor with its original rotatory power and other physical properties. The camphor probably exists in the amber in the form of a compound ether.

Oil of Cajeput.

Max. Schmidl. Tramactiona of the Royal Society of Edinburgh, 22, 369; abstr. Proceedings of the same, 4, 326 (Session 1859-60).

This oil consists mainly of the bihydrate of a hydrocarbon (cajputene), isomeric with oil of turpentine. It has a green colour, even when puri- fied by distillation from the copper-salts, which it generally contains (see page 335). Its specific gravity is 0 926 at 10^ On submitting it to fractional distillation, bihydrate of cajputene, which constitutes about two-thirds of the crude oil, passes over between 175° and 178°; smaller fractions, perhaps products of decomposition, are obtained from 178° to 240° and from 240 to 250°, and at 250° only a small residue is left, con- sisting of carbonaceous and resinous matter mixed with metallic copper. On treating this residue with ether, a green solution is obtained, which, when evaporated, leaves a green resin, soluble in the portion which boils between 175° and 178°, and capable of restoring its original colour.

Cajputene. C^H*^ — Obtained, together with two isomeric hydro- carbons, {isocajpviene and paracajpttlene) by cohobating bihydrate of oajputene with anhydrous phosphoric acid tor half an hour, and then distilling off the liquid, whereupon cajputene passes over at 160° — 165**, isocajputene at 176^ — 178°, and paracajputene at 310° — 316°.

Cajputene is perfectly colourless, and has a very pleasant odour resembling that of hyacinths. Sp. gr.=0'850 at 15°. Vapour-density 4'717.

Schmidl.

20 C 120 .... 88-24 88-29 .... 8834

16 H 16.... 11-76 11-91.... 11-78

C»HW 186 .... 100-00 100-20 .... 100-12

CAJPUTENB. 51]

Vol. Density.

C-Tiponr 20 8*3200

H-gas 16 11088

Vapour of cajputene 2 9*4288

1 4*7144

Cajputene is permanent in the aii\ — • It is not affected by iodine at ordinary temperataree, but at a higher temperature, hydrogen is evolved and a black liquid is formed. — Bromine acts quickly on it, producing a dark viscid oil. — With gaseous hydrochloric acid, it forms a beautiful violet liquid, but no crystalline compound, even at — 10°. — A mixture of ordinary nitric and tulphwio <icid9 act upon it with violence, forming a yellow brittle resin.

Cajputene is insoluble in alcohol, but dissolves in ether and in oil of turpentine.

liocajpiUene C^H^'. — Obtained : (1.) as above. •— (2.) By distilling the bihydrate of cajputene with oil of vitriol.

Oil boiling between 176^ and 178°. Has an odour less agreeable than that of cajputene, and becoming more pungent and aromatic by exposure to the air, the oil at the same time acquiring a yellow colour. Sp. gr. = 0-857 at 16°. Vapour-density of (1) = 482; of (2) =4-52.

SchmidL

Prepared by {I) Prepared by (2)

20 C 120 .... 88*24 8816 .... 8818 88*05 .... 88*23

16 H 16 .... 11*76 11*64 .... 11*68 11*90 .... 11-83

C20H" 136 .... lOn-00 99-80 .... 99*86 99*95 .... 100*06

Iodine, bromine, gaseous hydrochloric acid, and a mixture of nitric and sulphuric acids^ act upon isocajpetene in the same manner as on cajpu- tene. With oil ofvitrioly and with dilute sulphuric hydrochloric or nitric acids (neither of which acts upon cajputene), it forms dark viscid liquids.

Isocajputene is insoluble in vniter and in alcohol, but mixes in all proportions with ether and with oil of turpentine.

Paracajputene C^'^H*'. — Obtained as above mentioned by distilling bihydrate of cajputene with anhydrous phosphoric acid; passes over between 310° and 316°. It is very viscous, has a lemon -yellow colour, and in certain directions exhibits deep-blue fluorescence. Vapour- density 7'96.

Schmidl. Vol. Density.

40 C 240 .... 88-24 88*30 C- Vapour .... 40 16*6400

32 H 82.... 11-76 1206 H-gas 82 2*2176

C^^H® 272 .... 100-00 100-36 Vapour 2 18-8570

9*4288

The differenoe between the experimental and ealcolated vapour-densities is probably due to deoompositioii, taking place at the high tempenitare required for the determina- tioD.

Paraoajpnteno oxidises rapidly in contact with the air, acquiring a red ooloQ? and resinous consistence. — A mixture of nitric and sulphwic

512 ADDENDA TO COMPOUNDS CONTAINING 20 AT. CARBON.

aeids does uot act so violently on it as on cajputene and isocajputene. — With hydrochloiic acid gas, it forms a dark viscid liquid which does not yield crystals, even at — 10^

Insoluble in waiei*, alcohol and oil of turpentine ; soluble in ether.

Hydrates op Cajputene. — a. i/bwo-A^yefro^, C^H",HO.— Obtained by the action of oil of vitriol on oil of cajeput. When the crude oil is raised to the boiling point in a deep open vessel, and oil of vitriol con- tinuously dropped into it, violent ebullition takes place, accompanied, after a while, by a peculiar crackling sound. As soon as this is observed, the flame must be lowered and the acid very cautiously added till the liquid suddenly assumes a dark colour, extending in an instant from the surface throughout the whole depth. — The vessel must then be imme- diately removed from the fire, otherwise further decomposition will take place, attended with evolution of sulphurous acid. The upper oily liquid is separated from the acid on which it floats, well washed, and distilled, and the portion which passes over from the 170° to 175^ is collected and rectified.

Oily liquid, having a vapour*density of 5"19 to 5*27.

Schmidl. Vol. Density.

mean,

20 C 120 .... 82-75 82.71 C-Tapour .... 20 8*3200

17 H 17 .... 11-72 11-77 H-gas 17 1-1781

0 8 .... 5-53 5-52 O-gas \ 0*5548

C^OH'^O .... 145 .... 100*00 100-00 Vapour 2 10*0529

1 5-0264

The yapour-density is anomalous, inasmuch as the molecule C^^H'^O, which occupies two yolumes of Tapour« contains but 1 At. oxygen. Probably the true formula of the body is C«H»*02 = C^H** + H»0«, this molecule splitting up at high tempera- tures into C^H^ and H^O^, each of which occupies two volumes of vapour, and conse* quently the two together occupy 4 volumes (compare xiii, 487.)

6. Bihydrate. C^H^O' = C«'H",2H0. This is the chief constituent of oil of cajeput (p. 510), and passes over in the fractional distillation between 175° and 178^ After rectification, it is a colourless oil which boils constantly at 175°, has a specific gravity of 0*903 at 17^^ and vapour-density == 5*43.

Schmidl. Vol. Density.

20 C 120 .... 77-92 7784 C-vapour .... 20 8-3200

18 H 18.... 11-68 11-91 H-gas 18 1-2465

2 0 16.... 10-40 10-25 O-gas 1 1-1093

C»Hi802 .... 154 .... 100-00 10000 Vapour 2 10-6758

1 5-8379

JDecompoiitions, 1. Exposed to the air for a considerable time in the moist state, it changes to a reddish liquid which ultimately exhibits a rather strong acid reaction with litmus. — 2. Iodine dissolves in ttie oil, and under certain circumstances forms crystalline compounds (p. 515). — 3. Bromine acts quickly upon it, and forms crystalline compounds under similar circumstances (p. 514). — 4. Chlorine gas "psLSSod into iho oil raises the temperature, but does not appear to act upon it further ; but nascent chlorine (evolved by passing hydrochloric acid gas into the oil mixed with dilute nitric acid) converts it into bichloride of cajputene C**H*®CP. — 5. Anhydrous 'phosphoric acid heated with the bihydrate,

BIHYDRATE OF CAJPUTENE. 513

takes away the whole of its water, coDverting it into cajputene^ isocaj- piitene and paracajputene (p. 511). — 6. Chloride of tine likewise dehy- drates it, but less completely. — 7. Oil of vitnol acts but very slowly on the oil at low temperatures ; but if the temperature be allowed to rise, sulphurous acid is given off, and the oil blackens and ultimately suffers complete decomposition. If the action be checked at a certain point, a sulpho-acid is formed, which yields a soluble baryta-salt. Oil of vitriol dropped into the oil at the boiling heat, in the manner described at page 512, takes away half the water, forming monohydrate of cajpu- tene. — Dilute sulphuric cuyid on the ^contrary causes the bihydrate to take up 4 At. more water, converting it into C^H^+BHO. — Fuming oil of vitriol converts the bihydrate into a thick brown liquid, which boils above 360**. — 8. Fuming nitric acid rapidly oxidises the oil, even at ordinary temperatures, forming a large quantity of oxalic acid. Ordi- nary nitric acid produces the same effect at the boiling heat, but at ordinary temperatures, it acts very slowly, converting the oil into a red liquid. — 9. Distilled over permanganate or hichromxxte of potash in presence of sulphuric acid, it forms a thick resinous liquid. — 10. It does not appear to be altered by digestion with peroxide of lead, — 11. In contact with aqueous poiash, or when dropped into melting potash, it forms a soluble salt, the acid of which is precipitated as a resin by hydrochlorio or sulphuric acid. — 12. Heated with sodium, it forms a crystalline mass, soluble in water and alcohol, and consisting of soda and an organic sub- stance, which is separated by strong acids in the form of a fragrant resin. — 13. When the vapour ot the bihydrate is passed over red-hot soda- lime, a yellow oil distils over, having a peculiar odour quite different from that of the bihydrate* and at the same time the soda-lime becomes blackened by deposited charcoal, and when treated with acids, gives off a

large quantity of carbonic acid. The yellow oil thus formed yielded by distilla- tion a fraction boiling between 180** and 185% which gave in two analyses, 79*76 and 8003 p. c. C, 12*20 and 12*07 U, agreeing nearly with the formula C^IF^O^ which requires 79*59 p. c. C, 12*44 H, and 7*97 O.

ChmbinaHoiu. Bihydrate of cajpntene dissolves in all proportions in alcohol, ether, and oil of turpentine.

c. Hexhydraie, C*»H*K)* = C»H",eHO. — Produced hj the action of dilute sulphuric acid on the bihydrate, or on crude oil of cajeput. — Two pis. of dilute sulphuric acid are added to 1 pt. of the crude oil ; and the mixture is well shaken for several days till the watery layer acquires a yellowish colour, and then left to itself for about ten days, whereupon it deposits crystalline tufts of the hexhydrate, adhering to the sides of the vessel.

The crystals melt at 120^ and solidify again at 85^ On submitting them to dry distillation, au oily liquid passes over and condenses again in the colder parts of the apparatus, apparently as the unaltered hex- hydrate. The crystals dissolve sparingly in cold^ easily iu boiling alcohol :

Schmidl. nuan,

20 C 120 .... 63-15 63-20

22 H 22.... 11*57 11*96

6 O 48 .... 25*28 24*84

C»H«0« 190 .... 100-00 100*00

VOL. XIV. 2 L

514 ADDENDA TO COMPOUNDS CONTAINING 20 AT. CARBON.

CrysUls having the same composition were deposited from a Mcondaiy fractioa of crude cajeput^oil, which distilled at 210*' — 230°t &nd was left for a very long tiioe moist and exposed to the air. The crude oil mixed with nitric acid and alcohol changes, in the course of seven or eight months, into a black heav; liquid in which crystals are suspended, perhaps consisting of the hexhydrate. The same compound appears like- wise to be formed in beautiful long prisms, when the crystalline mass produced by passing hydrochloric acid gas into rectified oil of cajepat b thrown into water or alcohol.

Chloride ofF Gajputene. C'H^^GP. — - Produced by tbe action of nascent chlorine on the bihydrate. When the portion of cajeput-oil, distilling between 175^ and 178^ is mixed with very dilate nitric acid, and hydrochloric acid gas is passed into the liquid, a violent action takes place in a few minutes, yellow and red fumes of chlorine and nitrons gas being evolved, and if the passage of the gas be continued, chloride of e%)putene ultimately sinks to the bottom, as a limpid brown oil, which may be freed from adhering nitric and nitrons acid by distillation over strong potash-ley. It has a fragrant odour, and may be kept for any length of time without alteration, but is decomposed by distillation. Boiled with nitrate of silver, it detonates in a peculiar manner and forma ehloride of silver.

[ Schmidl. mean.

20 C 120 .... 57-97 57-46

16 H 16 .... 7-73 8-09

2 CI 71,... 34-30 34-39

C»H"C1« 207 .... 100-00 99-93

Crystals were onoe obtained by keeping the oil at a low temperatoK, bnt not in sufficient quantity for analysis.

MoNOHTDROCHLORATE OP Cajputene. C*^H",H01. — Obtained by distilling the bihydrochlorate, and collecting apart the fraction which boils at 160*" :

Schmidl. mean. 20 C 1200 .... 69-76 69-70

17 H 17-0 .... 9-88 10-00

CI 35-5 .... 20-36 2053

C»Hi7Cl 172-5 .... 100-00 100-23

A product having the same composition is obtained by treating the bihydrochlorate for several days with aqueous or alcoholic potash ; but its odour is different from that of the product obtained by simple distilhition of the hydrochlorate, and resembles that of pelargonic ether.

BiirrDROcnLORATB OP Cajputene. C*»H'«,2HC1. — Obtained by passing hydrochloric acid gas through rectified cajeput-oil, mixed with a third of its volume of alcohol or strong aqueous hydrochloric ^cid. Crystallises from alcohol in beautiful radiating tufts. Melts at 55^, and solidifies again at 30°. It has no taste or smell. — By dry distillation, it gives off hydrochloric gas at 00°, and splits into several fractions, one of which is the monohydrochlorate. — It is also deprived of half ita chlorine by heating with aqueous or alcoholic potash. It dissolves sparingly in cold, easily in boiling alcohol or ether.

HYDRIODATB OF CAJPUTENB. bli

Schmidl.

20 C 120 „.. 57-41 57-67

18 H 18 .... 8-61 8-94

2 CI 71.... 33-98 34-49

C»H»8CP 201 .... 10000 101-00

When hydrochloric acid gas is passed through rectified oil of cajepat« kept at a low temperature, a violet liquid is formed which in 10 or 15 minutes solidifies in a crystalline mass. This crystalline compound is eitremely deliquescent, liquefying rapidly eren when pressed between blotting paper cooled to — 25* : the resulting liquid rapidly gives off fumes of hydrochloric acid, and is completely decomposed by distillation, if the crystalline mass, immediately after its formation, be thrown into water or lUcohol. beautiful long prisms are formed^ after a few days, apparently consisting of hexhydrale of cajputene (p. 513).

Bromidb of Cajputbnb. G*^H^Br*. — Obtained by the action of bromine on oil of cajepnt. When dry bromine is dropped into tbe rectified oil, a yery brisk action takes place, and tbe sides of the vessel become covered with yellow needles, which however soon disappear ; but if the addition of the bromide be continued till the reaction almost ceases, a dark, thick, viscous oil is formed, which, after several weeks, deposits a granular substance. By boiling the mixture with alcohol, the granular substance is extracted ; a heavy oil is left behind ; and the alcoholio solution, on cooling, deposits bromide of cajputene as a soft crystalline substance, having a fatty lustre and much resembling cholesterin.

Bromide of cajputene melts at 60^, and solidifies again at 32^ By dry distillation, it yields a liquid which crystallises again in the cooler parts of the retort. It is nr)t altered by boiling with aqueous potash. It dissolves in ether and in boiling alcohol.

	on p	..... 120 .... 26*31	Schmidl. ... 26-32 .... 25-97
	16 H		4-24 .... 4-15
	<K M^f •••••••■•«•«	.... 320 .... 70-17	70-03
	C«>H»Br* ....	.... 456 .... 100-00

Rectified oil of cajepnt shaken up with bromine-water forms a red resin, from which a solid substance separates in small white prisms extremely deliquescent and rapidly decomposing.

Another crystallised bromine-compound (probably a hydrobromate analogous to the hydriodate), is formed in the same manner as that compound {vid, ir^.), dissoWed in bisulphide of carbon.

Hydriodate op Cajputene. — a, Anhydt^us, C**H",HI. — Obtained by adding a solution of phosphorus in bisulphide of carbon to a solution of iodine and oil of cajepnt in the same liquid. Brisk action then takes place, the vessel becoming very hot ; red oxide of phosphorus is precipitated ; and the oily liquid becomes reddish, giving off vapours probably containing phosphuretted hydrogen^ and if left to itself for 10 or 12 days, deposits crystals of the hydriodate. The reaction probably takes place as repre- sented by the equation :

3C»HW + 3P1 + 6HO - 30»H>U + PH» + PO + P0»

The crystals of the hydriodate are deposited in cells like those of beehives, and possess a black metallic lustre. They are soluble in alcohol and in ether, and are very stable, not being altered, even by boiling with potash :

2 L 2

516 ADDENDA TO COMPOUNDS CONTAINING 20 AT. CARBON.

Schmidl.

20 C 120 .... 45-45 45-29 .... 45-36

17 H 17 .... 6-43 6-31 .... 635

I «. 127 .... 4812 48-85

r ■

C*H>7I 264 .... 100-00

b. HydraUdy C»H»IO = C»H",HI + HO. — When iodine is added in small quantities to cajeput-oil, crude or rectified, at ordinary tempera- tures no visible action takes place (if external heat be applied, the action goes too far and nothing bat a ▼iscoua maaa ia produced which doea not crystaliiae) ; bat on

stirring rather constantly, the action is assisted, partly by the heat resulting from the friction of the glass rod, partly by the mechanical distribution of the iodine, and the temperature of the liquid soon rises from 10® to 40^ The addition of iodine must then be discontinued, and the vessel immersed in cold water. A black crystalline compound tbea separates after a short time ; and on separating this substance from the oily liquid by filtration, pressing it between blotting ^aper, and when it is nearly dry, dissolving it in alcohol or ether, a solution is obtained, from which the hydrated hydriodate crystallises in prisms having a fine yellow- green colour and metallic lustre. They are very deliquescent, and melt at 80° into a liquid which does not recrystallise in the cold. Potash-ley liquefies the componnd, abstracting part of the iodine^ and with the aid of heat abstracts the whole.

mean.

20 C 120 .... 43-95 43-11

18 H 18 .... 6-50 6-90

I 127 .... 46-52 46-51

O 8 .... 2-04 3-48

C«H»IO 273 .... 5901 10000

Regarded by Schmidl aa hydriodate of monohydrate qfetyputtM » C^H^O^HT.

It is insoluble in water, and is not decomposed thereby ; very soluble in alcohol and ether.

GRAPHITIC ACID. 517

COMPOCTNDS CONTAINING 22 AT. CAEBON.

Graphitic Aeid«

B. C. Brodie. Ann. Pharm. 114, 6.

Formation. ' By the repeated action of chlorate of potash and nitric acid on graphite.

Preparation. Graphite carefallj purified hy boiling with acids and fasion with hydrate of potash in a silver crucible, is intimately mixed with 3 At. chlorate of potash ; the strongest nitric acid is added in sufficient qnantitv to render the mixture fluid ; and the whole is either exposed to sunshine or heated on the water-bath to 60° for three or four days. If at the end of this time, no more yellow vapours are evolved, the mixture is to be shaken out into a large quantity of water, the undissolved portion completely washed by decantation, then dried on the water-bath, and again brought in contact with the same quantities of nitric acid and chlorate of potash, and the same treatment is to be repeated four times or as often as any further alteration of the substance appears to be produced. — Graphite cannot be completely converted into graphitic acid by one warming with chlorate of potash and nitric acid, even for a long time. — Graphitic add obtained as above contains about ( p. c. ash, probably derived from the glass vessels.

Properties, Perfectly transparent, thin crystaU| belonging either to right or the oblique prismatic system..

Brodie. At 100* or in vacuo. a* h.

22 C 132 .... eill 60-74 .... 6104

4 H 4 .... 1-85 1-85 .... 1-85

10 O SO .... 3701 37-41 .... 37- 11

C»H*Oi» 216 .... 10000 10000 .... 100-00

a, mean of eight analyses; h, mean of the same analyses after dedacUng ( p. c. ash. The formula should perhaps be doubled, inasmuch as Brodie, from the analysis of the baryta^salt, is inclineil to regard the acid as bibasic

Decompositions. 1. The acid decomposes when heated, with explosion, incandescence, and evolution of gas, and leaves a black finely divided residue. — - When graphitic acid is suspended in Rangoon naphtha

S18 PRIMARY NUCLEUS CaH»: OXYGEN-NUCLEUS C«H<0«.

(rectified over sodiam and boiling at 270^) and heated, a large qnantitj of water distils over between 100^ and 200°, whilst at first a small and afterwards a larger qnantitj of carbonic acid escapes, the naphtha acquires a deep red colour, and a black residue is left having the appearance of charcoaL This residue, collected after 3 — 4 hours heating of the g^phitic acid with the naphtha to 250% weighed 60*77 to 66*98 p. c, but still contained traces of transparent crystals; after 14 hours heating, it weighed 65*77 p. c, and had then the composition C^H'O*. — Brodie gives the following decomposition -formula as probable :

7C«H«0» = 3C«H«0» + 12HO + 12 CO* + 10 CO.

(Bot this equation gives no account of the disappearance of 10 At. H; JTr.) Tlie formation of 3 At. C^H^O^ from 7 At. C^H^O^^^, should give a residue of 65*48 per cent.

The black residue obtained bj heating graphitic acid with Rangoon naphtha, after being washed with ether and a1a>hol, contains on the average 80*13 p. c. C, 0*58 H, and 19*29 O (after heating for a short time, it is comparatively poor in carbon, bat becomes licher after longer heating). Calculation 80*00 p. c. C, 0*60 H, and 19*40 O. The residue obtained by heating graphitic acid per se, contained 80*36 p. c. C, 0*71 H, and 18*93 O. Heated for some time to 250** in nitrogen gas, it gives off 2*26 to 2*30 p. c. water and traces of carbonic oxide, leaving a residue amounting to 97*16 — 97*38 p. c. The latter residue contains, on the average, 81*82 p. c. C, 0*44 H, and 17*74 p.c. O: it is therefore C»»H*on (ralcuUtion 81*48 p.c. C, 0*41 H, and 18*41 O), and is forihed as shown by the equation 3 €"««()» = C>«H*0« + 2 HO. — If it be again strongly heated, carbonic acid and carbonic oxide are evolved ; but eveD after several honra exposure to a red heat, it still retains hydrogen and oxygen.

2. When hydrosulpkate of ammonia or sulphide ofpoiamnm is poured npon graphitic acid, it decomposes with decrepitation, forming a graphic toidal substance faavinff the metallic lustre.

8. It is decomposed in like manner by boiling with acid solutions of cuprous or tCannous chloride.

Combinations, Graphitic acid is somewhat soluble in pure water, not in water containing acids or salts.

It unites with aucalis. Shaken up with aqueous ammonia, it is transformed Into a transparent I'elly, without dissolving, and on addition of acids, is precipitated as a jellj, like silicic acid, which after drying in vacuo, has the same weight as the graphitic acid originally employed.

Graphitate of Baryta. — Moist graphitic acid, shaken up with baryta- water, washed and dried at 1 00% yielded a compound which contained 21*19 p. c. Ba, and after being suspended in water and decomposed by a stream of carbonic acid, still contained at 100% 13*80 p.c. Ba. Hence Brodie regards the former salt as essentially containing CH'BaO*^ (calculation 24*13 p. c. Ba), and the latter as C^H^BaO'*' (calculation 13*73 p. c Ba), and graphitic acid probably as bibasic. — The baryta-salts are hygroscopic and detonate with violence when heated. (Brodie.)

LIMBTTIC ACID. 6] 9

Azo-nucleug C**NH».

Gryptidine.

C«NH" = C«NH»,H».

Gr. Williams. Trans.'^ Jioy. Soc. JSdinh. 21, Pt. iii. 377; CTiem. Gaz. 1856, 261 and 283: abstr. 69, 355: Lieh. Kopp. Jahrulvr. 1856, 537.

Known only as a pladnum-talt.

Found, together with many other prodacts, in coal-tar, and obtained in the preparation of chinoliue (xiii, 243) amon^ the products boiling at about 274^ As however these products still contain chinoline and lepidine (xiv, 103), from which the cryptidine, on account of its small quantity, cannot be completely separated by fractional distillation, the hydrochloric acid solution of the portion which distils at 274° is mixed with bichloride of platinum ; and the platinum-salt, which precipitates as a jrellow pasty mass, soon becoming crystalline, is recrystalliised from boiling water, and washed with ether alcohol ; — or the portion distilled between 270" and 274® is treated with nitric acid, whereby an insoluble powder is separated, and this is converted into a platinum-salt.

Williams. Platinum^iali. mean,

22 C 1320 .... 36 31 35*89

N 14-0 .... 3-85

12 H 12-0 .... 8-30 3-37

Pt 990 .... 27-24 2717

3 CI 106-5 .... 29-30

C»NH»,Ha,PtCl« 363-5 .... 10000

Cr3nptidine is isomeric with ethyl-chinoline and metbyl-lepidine.

Pnmarjf S'udeus C"H" : Oxpgenrnudetu C"H*0*.

Limettio Acid.

C«H«0» = C"H*0*,0«.

H. VoHL. N. Br. AnA. 74, 16; abstr. Pharm* CnUr. 1853, 818.

Formation, Produced, together with formic and acetic acids, by the action of bichromate of potash and sulphuric acid on oil of lime (p. 304), and oil of rosemary (p. 396).

520 PRIMARY NUCLEUS OSH": OXYGEN-NUCLEUS C»H"0^.

Preparation. Oil of lime is added by small portions to a mixture of bichromate of potash and sulphuric acid ; and the portion of the oil which is volatilised in consequence of the great heat developed, is collected and poured back. As soon as the action is finished, the liquid is diluted with water^ and the limettic acid which separates as a resin is washed, and purified by repeated solution in aqueous carbonate of potash, precipitation with nitric acid, and recrystallisatiou from alcohol.

Properties. White, crystalline. Volatilises when heated, and forms a crystalline deposit on cold bodies. It has neither taste nor smell.

Vohl. fMMm* At 100*»- a. b.

22 C 132 .... 55-93 55*79 .... 55-97

8 XI 8 .... 3*39 ..M.... 3*46 .... 3*43

12 O 96 .... 40-86 4075 .... 40*60

QOHK)" 236 .... 100-00 10000 .... 100*00

a, from oil of lime ; b, from oU of roflemary. According to Vohl, it is monobasic and - C"H*0«.

Limettic acid is sparingly soluble in water.

Limettate of Silver. — Obtained by adding nitrate of silver to the acid neutralised with ammonia. Powder sparingly soluble in water, and blackening on exposure to light. Contains 51*44 p. c. oxide of silver (C«H«Ag20W«51-56 p. c. AgO.)

Limettic acid dissolves readily in alcohol.

Oxygen-nuclem C**H"0*,

Bottlerin.

C«H"0« = C«H"0*,0'.

Anderson. Edinh. New Phil. J, (new series) 1, 300; abstr, Pharm. Centr. 1855, 372; Lieh. Eopp, 1855, 669.

The stellate hairs and glands which cover the fruit of Rottleria tincioHa, and are used in the East Indies as a dye, contain rottlerin, together with a flocculent substance, C«H«08, and a resinous colouring matter, C«H»0".

Preparation. The colouring matter is exhausted with ether, and the greater part of the ether distilled off, the rottlerin then crystallising from the residue.

Properties. Yellow, silky crystals.

Anderson.

22 C 132 .... 69-47 69-11

10 H 10.... 5-26 6-55

6 O 48 .... 25-27 25-34

CS2HW0« ISO .... 100-00 10000

\

SINAPIC ACID 521

Melts when hetsied, giving off pungent vaponrs and leaying charcoal. — By bromine, it is quickly decolorised, with formation of a non-crystal- lisable substitu tion- product. »- With cold oil ofvUrioly it forms a yellow solution, but hot oil of vitriol chars it, giving off snlphurous acid. — Nitric acid first converts it into a yellow resin, and then decolorises it.

It is soluble io water, and with red colour in alkalis. Its alcoholic solution is not precipitated by neutral acetate of lead.

It is slightly soluble in cold alcohol, more soluble in boiling alcohol^ easily soluble in ether.

Primary Nucleus CH** : Oxygen-nucleus C*H"0*.

I

Sinapic Acid.

C«H"Ow = C«H>»0*,0«.

V. Babo & HiRSCHBRUNN. (1852.) AuYi. FharM. 84, 19; abstr. Pharm. Centr. 1852, 916; J. pi: Chem. 58, 283; N. Ann. Ohim. Phys. 38, 108; N. J. PJiai^m. 33, 293; Chem. Gaz. 1853, 81.

Formation. Hydrosulphocyanate of sinapine is resolved by boiling with potash or baryta-water into sulphocyanide of barium, sincaline, and sinapate of baryta :

C«NH»Ow,C2NHS2 + 3 BaO = C?NBaS? + C«H»08,2BaO + CWH"N03,H0.

By exhausting aqueons mustard-paste with ether, distilling off the ether, and treating the residual ccrid extract with cold water, Simon {Pogg. 44, 601) obtained his Setifsaure, which is perhaps identical with Babo's sinapic acid. It remains behind when the aqueous solution is cautiously evaporated (if too much heat is applied, sul- phurous acid escapes), and may be freed from soft resin by washing with ether and crystallised from alcohol. It Joes not colour alkali* yellow, but reddens ferric aalt$, like hydrosulphocyanic acid ; it dissolves easily in alcohol, slowly in eMer, and is not easily converted into hydrosulphocyanate of sinapine. (Simon.) i

Preparation. Hydrosulphocyanate of sinapine is boiled with potash- ley; the liquid is supersaturated with hydrochloric acid; and the resulting precipitate is purified by recrystallisation from boiling alcohol of 60 p. c. If the solution be left for some time exposed to the air, it becomes red-brown and suffers partial decomposition, but the unaltered portion may be recovered by treatment with animal charcoal. — The acid is obtained as an insoluble baryta^salt, in the prepara- tion of sincaline bj boiling hydrosulphocyanate of sinapine with baryta- water.

Properties. Small prisms which melt between 150° and 200°, and solidify in the crystalline form.

At 110^. V. Babo & Hirschbmnn.

22 C 132 .... 58-93 58-67 .... 5892

12 H 12 .... 5-35 4-87 .... 5-67

10 O 80 .... 35-72 36-46 .... 35-41

C»H«OW 224 .... 100-00 100*00 .... 100-00

622 PRIMARY NUCLEUS C«HW: OXYGEN-NUCLEUS CbH««0«.

DeeompoiUiont. 1. When heated above its melting point, it giree off a coloarless oil, and leaves a brown residue, which tarns red after some hoors, and chars at a low red heat. Ammonia-gas prodnoes from the oil and the residue, crystalline yellow substances, which dissolve with difficulty in water, and scarcely turn red. — 2. The acid neutralised with potcuh or soda turns red on exposure to the air, then brown. The other sinapates likewise alter quicklj (see below). — 3. By Morine^wUer, espe«> cially when warm, it is colonred rose-red and then purple-red, but not dissolved. — 4. It dissolves in nitric acid with red colour changing to orange -yellow, apparently with formation of oxalic acid and a nitro- compound.— In the form of potash-salt> it immediately reduces ffold from the terchloride.

CoTnhinations. Sinapic acid dissolves very slowly in cold, somewhat more readily in hot water. — It unites with hoses, forming salts, among which those of the alkalis are easily soluble and crystallisable, while the rest are difficultly soluble.

Sinapate of potash forms white precipitates with chloride of calcium and with solution of alum; the latter precipitate treated with chlorine- water, assumes first a rose-red and then a dirty red colour. With sesqui- chloride of iron, it forms a rose- red or sometimes a purple-red precipitate, with formation of ferrous oxide. — From solution of copper and lead-salts, it throws doirn precipitates which soon turn blue-green ; with mercuric and silver salts, white precipitates which decompose^ with separation of metal, especially on addition of more alkali.

Sinapate of Potash, — Precipitated from the aqueous solution by absolute alcohol, in iridescent laminse, which soon change after the alcohol has been poured off.

Sinapate of Baryta. — (Yid. p. 520.) Sinapic acid is boiled with excess of baryta- water out of contact with the air, and the precipitate is washed with water free from carbonic acid.

V. Babe & HirBchbrnnn. fiMmi.

22 C 132 .... 36-80 3645

10 H 10 .... 2-78 2-90

8 O 64 .... 17-82 18-12

2 BaO 153 .... 4260 42*53

C22HWO«,2BaO 359 .... 10000 100-00

Sinapic acid is sparingly soluble in cold, easily in hot alcohol, inso- luble in ether.

SINCALINE. 623

Interpolation: Sincalilie. CioNH»0« = C^<^NH"0»,H».

y. Babo k HiRSCHBRUNN. Ann, Pharm. 84, 22.

Formation. By boiling hjdrosalphocjanate of sinapine with baryta* water or potash-ley (p. 520).

Preparation. Hydrosalphocyanate of sinapine is heated with baryta- water till the sinapate of baryta is completely separated ; the filtrate mixed with a slight excess of dilute sulphuric acld^ is freed from hydro- snlphocyanic acid by precipitation with aqueous sulphate of iron or copper ; the liquid is filtered from the precipitated sulphocyanide of copper ; the filtrate precipitated with baryta-water ; carbonic acid passed through it ; and the solution filtered from the carbonate of baryta is evaporated on the Krater-bath : carbonate of sincaline then remains behind. By neutralising the carbonate with aqueous faydrochloric acid, digesting the hydrochlorate with oxide of silver, and evaporating the solution filtered from the chloride of silver and excess of oxide, in vacuo or on the water-bath, sincaline is obtained as a colourless crystalline mass.

Sincaline, according to v. Babo, is C'^NH^^O' ; the formula here adopted, which is that proposed by Gerhardt, contains 1 At. hydrogen less.

Sincaline chars when heated, giving off an odour of methylamine and a combustible vapour.

Combination 8. Sincaline exposed to moist air, deliquesces and becomes heated. — It dissolves sulphur, with formation of (pentat) sulphide and sulphate of sincaline, and on adding an acid to the solutions, sulphuretted hydrogen is evolved and milk of sulphur is precipitated.

Sincaline is a strong base. Its aqueous solution acts upon metallic salts like potash, precipitating the oxiaes, even from the salts of baryta, lime and mercuric oscide. The precipitates formed in solutions of alumina and chromic salts dissolve in excess of sincaline, the chromic precipitate being reprecipitated on boiling. — The sulphate, hydrochlorate and nitrate of sincaline are deliquescent.

Carbonate of Sincaline. — Aqueous sincaline absorbs carbonic acid from the air, and forms a deliquescent salt.

Chloro-aurate of Sincaline is precipitated as a yellow crjnstalline powder, on adding terchloride of gold to aqueous hydrochlorate of sinca- line, and may be obtained in plumose crystalline needles and lamin» by washing with cold and recrystallising from boiling water.

IOC ....	At 110*.	V. Babo & Hirschbrnnn. .... 600 .... 13-55 13-63
14 H ....		.... 14-0 .... 3-16	3-38
N ....		.... 14*0 .... 3-16
2 O ....		.... 16-0 .... 3*61
An ....		.... 196-6 .... 44*42	44*54
4 CI ....		.... 1420 .... 32-10
C"H«N(	)2,HCl.AixCl» ....	.... 442-6 .... 100-00

624 CONJUGATED COil POUNDS OF SINAPIC ACID.

So accordinf? to Gerhardt (Traiti, 2, 431); according to t. Babo & Hincfalvninn, jt is CWH»N02,HCI.AuCR

Chloroplatinate of Sincaline, — Crysiftllises on mixiDg hydrochlorate of sincaline with bichloride of platinum and evaporating, in splendid orange-coloured prisms ; by slow evaporation, it is obtained in six-aided plates half an inch in diameter. — At 1 10°, it gives off 5*32 p. c water (by calculation, 2 At. =5*50 p. c. Aq).

IOC	T. .... 60-0 ... 19-40	Babo & Hiitchbrmm. 19-65
14 H	.... 14-0 .... 4-53	5-13
N 2 O	.... 140 .... 4-53 .... 16-0 .... 5-18
Pt 3 CI	.... 98-7 .... 31-92 .... 106-5 .... 34-44	31-30
C«>H"NO»,HCI,PtCl»	... 309-2 ,... 100-00

Conjugated Compounds of Sinapic Add,

Sinapine.

0. Henry & Garot. J, Pliarm. 17, 1. — further, 20, 63.

Pelouze. Ann, Chim, Phy$. 44. 214; Fogg, 20, 358; N, Tr. 23, 2, 253;

Schw. 60, 468; J. Chim. med. 6, 577; fnrtiier, /. Pharm, 17, 271;

Schw, 63, 93. BovTRON & RoBiQUET. .7. PiMrm, 1 7, 279. Faur4 J. Pharm. 17, 279.

0. Henry & H. Plisson. Ann. Chim. Phys. 46, 198. Winckler. Bepert 41, 169; further, 67, 257. Simon. Pogg, 43, 651; further, 44, 593. BouTRON & Fremy. J. Pharm, 26, 50. y. Babo k Hirsghbrunn. Amu Pharm, 84, 10; abstr. Pharm, Centr,

1852, 916; J. pr, Chem, 58, 283; iV. Ann. Chim. Phys. 38, 108;

j^. J. Pharm. 23, 294; Chem. Gaz, 1853, 81.

O. Henry & Garot described, in 1825, a peculiar sulphuretted acid of white mus- tard, Acide mlphosinapique, which .they extracted from the fixed oil. These experi- ments however partly relate to hydrosulphocyanic acid, which was obtained from white mustard at the same time by Hornemann {Berl. Jahrb, 29, 1, 29), and afterwards by Pelouze, according to the process given by Henry & Garot. Pelonse likewise poiRted out certain discrepancies in the statements of Henry & Garot, who thereupon discovered hydrosuIpUocyanate of sinapine. Von fiabo & Hirschbruun, starting apparently from some observations of Will {Ann, Pharm. C5, 213), first recognised the true nature of this body, and studied its products of decomposition. — Hydrosulphocyanate of sinapine is synonymous with the tulphoHnapUinCj or sinapine of Henry flc Garot, the sttlphO' sinapic acid of Henry & Plisson, the sinapisine of fioutron & Fremy, the sulphotimapine of Boutron & Robiquet and of Winckler, the sulphocyanide qf sinapine {Sekw^<slcyan» tinapin) of v. Babo, and exhibits certain reactions in common with the (not isolated) acid of mustard {SenfsSure) of older authors. — Different from this u the sinapisine of Simon {Pogg. 43, 652), a solid fatty acid from black mustard {Pogg. 50, 379).

Source. In white mustard, the seed of Sinapis alha, as hjdrosulpho- cyanate of sinapine (v. Babo & Hirschbrnnn). Also in the seed of Twriiis glabra and Sinapis nigra. (Henry & Garoi, Faur^.)

8INAPINE. 525

Known only in aqueons solution and in combination with acids.

Preparation of Hydromtphoeyanate of Stnapine, 1. Dry mustard powder, exhausted with ether and thereby freed from fixed oil^ is treated with cold absolute alcohol as long as the alcohol acquires a reddish- yellow colour^ whereby a small quantity of sinapine is taken up, to be recovered as described farther on J the residue is boiled with alcohol of 90 p. c, then pressed, and the boiling and pressing are repeated twice more. The hot- filtered tinctures yield, after half the alcohol has been distilled off, colourless crystals of hydrosulphocyanate of sinapine, an additional quantity of which may be obtained from the mother-liquors by further evaporation and addition of sulphocyanide of potassium. Snlphocyanide of potassium likewise precipitates hydrosulphocyanate of sinapine from the above-men- tioned extracts prepared with cold alcohol.

2. Mustard-flour, freed from fixed oil by pressure in the oil-mill, is exhausted with cold and then with hot alcohol of 80 p. c. ; about f of the alcohol is distilled from the united tinctures in the salt-bath, or so much, that a sample of the residue separates on cooling into two equal layers consisting of oil and aqueous hydrosulphocyanate of sinapine. If the con- centration is carried too far, the hydrosulphocyanate of sinapine no longer crystallises ; and, on the other hand, if a sufficient quantity of the alcohol be not distiUed off, part of the sinapine remains dissolved in the alcoholic oily layer^ and is somewhat difficult to obtain in the form of crystallised hydrosulphocyanate : the best way of effecting this is to add a small quantity of alcoholic sulphocyanide of potassium. — The upper layer

is remored, and the lower watery liquid is either left to itself for a week or as long as hydrosulphocyanate of sinapine continnes to crystallise from it; and the crystals are collected on linen, separated from the viscid mother-liquor by means of a centrifugal machine ; moistened with alcohol ; strongly pressed between filtering paper, and recrystallised from alcohol of 90 p. c., then from a small quantity of boiling water, with addition of animal charcoal; — or belter, the lower watery layer is mixed with alcoholic sulphocyanide of potassinm, and the crystals which separate are purified as above. The mother-liquors also yield an additional quantity of hydrosulphocyanate of sinapine on addition of sulphocyanide of potassinm. (v. Babo & Hirschbrunn.)

d. Bruised white mustard-seed^ freed from the greater part of the fixed oil by pressure at 50^, is exhausted with ether; the residue is digested with 7 pts. of alcohol of 80 p. c, then with 2 pts. more ; the alcohol is distilled off from the tinctures till the residue is reduced to one- fourth of the weight of mustard-powder used ; this residue is set aside for 1 4 days to crystallise ; and the crystals^ after being freed by ether from a red-brown matter, are purified by repeated crystallisation from water and alcohol, with addition of animal charcoal. ( Winckler.)

Winckler also digests white mustard with 3 pts. of alcohol of 80 p. c, evaporates the tincture to -}- of the weight of mustard used ; treats the residue^ which is covered with oil drops, with ether, as lon^ as the ether is thereby coloured; and purifies the residual hydrosulphocyanate of sinapine by solution in water and recrystallisation as above. — A similar process is adopted by Simon, who, however^ at each extraction of the mnstard-flonr, uses only enough alcohol to moisten the mustard-flour^ and subjects the whole to strong pressure : by this treatment, the ex- haustion is effected more quickly than when a larger quantity of alcohol is used.

Oldir Methods, 0. Henry & Ghu*ot boil mustard-flour for a few seconds with water ; strain the liquid through cloth ; press the residue ;

526 CONJUGATED COMPOUNDS OF SINAPIC ACID.

evaporate the decoction to the consiBtenee of honey ; and shake it vp with 6 to 8 vol. aleohol of 40°. The alcoholic tincture freed from alcohol by distillation is set aside to crystallise j and the crystals are pnrified by pressure, recrystallisation from alcohol, washing with ether (to remove a volatile red substance), and another crystallisation from alcohol The mother-liquors become acid, in consequence of the continual liberation of hydrosulphocyauic acid. — This process does not easily yield hydrosul- phocyanate of sinapine in the crystalline state, (v. Babo & Hirsch- brunn.) — Faur6 evaporates the decoction of black mustard, boils the extract with alcohol, evaporates to the consistence of honey, and dilutes with water, whereupon hydrosulphocyanate of sinapin is precipitated. This product is purified as above. ()r he first exhausts black mustard with hot ether, then boils it with alcohol, and suspends the alcoholic extract in water, whereupon the greater part of the hydrosulphocyanate of sinapine is precipitated, part however remaining dissolved in the water.

Sinapine cannot be obtained in the free state, because it quickly decomposes when separated from its salts. If baryta-water be added from a burette to aqueous bisulphate of sinapine, till the colourless sola- tion turns yellow in consequence of the conversion of the acid sulphate into a neutral salt, a second quantity of baryta-water then added equal to the former, and the liquid filtered from the sulphate of baryta, an aqueous solution of sinapine is obtained, having a deep yellow colour aod distinct alkaline reaction. This solution added to the solutions of many metallic salts precipitates the oxides (forming a green precipitate with copper-salts, yellow with mercuric salts and ^rey-brown with silver- salts), and, on standing or heating, reduces the metal, (v. Babo & Hirschbrunn.) — Sinapine is not separated from its solution by alcohol or ether. Neither can it be obtained by treating the sulphate or hydro- sulphocyanate with oxide of lead, the product thence resulting being a gelatinous compound containing lead, and somewhat soluble in boiling water, (v. Babo & Hirschbrunn.)

Sinapine is, according to ▼. Babo & Hirschbrunn, CH^NO^« according to Ger« bardt, it is C^^HSNOio, which formula is here adopted.

DecomposiHons. 1. The aqueous solution of sinapine acquires by- evaporation first a green, then a brown, and then a red colour, and does not leave a crystalline residue. — 2. Aqueous sinapine reduces ffold from the terc/iloride. — 3. When its salts are mixed with aqueous alkalis or baryta-water, it instantly turns yellow, and is resolved on boiling into siucaline and a salt of sinapic acid. (v. Babo & Hirschbrunn.)

JDecomposiHons of Hydroeulphocyanaie of Sinapine, — 1. When heated, it melts to a yellow liquid, which then decomposes, giving off stinking products — among which are a brown oil, carbonate of ammonia and hydrosulphate of ammonia^ — and leaving charcoal. (Henry & Garot.) Combustible gases are evolved in this decomposition. (Winckler.) The vapours do not smell of sulphuretted hydrogen, sulphide of carbon, or hydrocyanic acid. In the course of the decomposition, volatile bases are evolved, together with gases and empyreumatio oils, which burn with luminous flame and formation of sulphurous acid. (v. Babo & Hirsch- brunn.)— 2. It dissolves readily in oU cf vitriol, with greenish yellow oolour and slight rise of temperature, turns brewn when the aolution k

SINAPINE. 527

heated, and then chars. (Winokler.) Hydrosnlphocyanio aoid is likewise evolved, (v. Babo & Hirschbrunn.) — 3. With iodic add, it acquires a light reddish brown colour and separates iodine (Winckler); probably because it contains free hjdrosulpboc3ranic acid. (Kr.) — 4. In contact with iodine, it immediately assumes a light yellow-brown colour, and when heated, melts, gives off iodine, and leaves a brown-red brittle resin. (Winckler.) — 5. Its aqueous solution is coloured by chlorine, first brown- red, then red, and finally yellow, with formation of sulphuric and evolution of hydrocyanic acid. (Henry & Garot.) According to T. Babo & Hirschbrunn, no formation of hydrocyanic acid takes place in this and similar cases. — G. With nitric acid of sp. gr. 14, or weaker, it immediately assumes a deep red colour, giving off red vapours, and when heated, turns yellow with formation of sulphuric acid. (Henry & Garot, and others.) — 7. When hydrosulphocyanate of sinapine is boiled with peroxide of manganese and dilute sulphuric acid, the distillate contains hydrocyanic acid (jnd, sup.), and the residue contains a substance which dissolves in water with dark brown-red colour. (Winckler.) — 8. With alkalit {vid, tup.). It is likewise coloured yellow by the alkaline earthe (Henry & Garot); and by ammoniay strydinine^ morphine, and quinine (but not by narcotine or ealidne), (Winckler.) A trace of tobacco- smoke is sufficient to produce this colouring, (v. Babo & Hirschbrunn.) — The behaviour of hydrosulphocyanate of sinapine to dilute acids and saline soliUions is the same as that of other hydrosulphocyanates (oomp. Henry & Garot, J. Fharm. 17, 10 and 11 ; Winckler, JRepert. 41, 88.) — For iU behaviour with tesquichloride qf iron, see Hydrosulphocyanate of Sinapine. According^ to Henrj & Garot, oil of mustard is given off in many of the decompositions of hydrosulphocyanate of sinapine; but according to Boutron & Robiquet, v. Babo & HirBchbmnn^ and others, this statement is erroneous.

Compounds of Sinapine, With water. — Aqueous Sinapine (Wd. tup.) With Acids. — Salts of Sinapine. — Sinapine unites with acids, form- ing colourless salts, which are less decomposable than free sinapine (v. Babo & Hirschbrunn).

Sulphate of Sinapine. — a. Nevi^ral — Half the acid of bisulphate of sinapine is precipitated by baryta-water, and the colourless filtrate is evaporated. — Colourless crystalline mass easily soluble in water (v. Babo & Hirschbrunn).

b. Add. — When a small quantity of oil of vitriol is added to a hot concentrated solution of hydrosulphocyanate of sinapine in alcohol of 90 p. c, the liquid on cooling deposits rectangular laminoB, which may be purified by washing with absolute alcohol, and repeated crystallisation from water and alcohol. — Contains 4 At. water, which are given off at 110° (Will ; Babo & Hirschbrunn).

At 100''. V. Babo & Hirsdibrann.

32 C 192 .... 47-19 ....... 46-99

25 H 25 .... 6-14 6-87

N 14 .... 3-44

12 O 96 .... 23-57

2 SO» 80 .... 19-66 19-82

C»H2^NOao.2SO»,2HO 407 .... 100-00

ffpdroehhraie of Sinapine. — Slender very solnble needles, obtained by decomposing snlphate of sinapine with chloride of barinm (v. Babo^A Hinehbrnnn).

]

528 CONJUGATED COMPOUNDS OF SINAPIC ACID.

Nitrate of Sinapine. — Obtained by decomposinjr tbe salpbate with nitrate of baryta, or the hydrocyanate with nitrate of silver. — Colourless, very soluble needles, (v. Babo & Hirschbrunn.)

Chloroplaiinate of Sinapine. — When hydrochlorate of siuapine is mixed with bichloride of platinum, a resinous precipitate is formed, which turns brown when heated, and yields flocks, (v. Babo & Hirsch- brunn.)

Uydromlphocyanaie of Sinapine, — FormaHon, Preparation, and Synonymes (pp. 523, 524). — White needles having a pearly lustre and loosely aggre- gated in tufts. (Henry & G^rot.) Colourless, nearly transparent, glassy prisms, mostly rectangular, truncated, grouped in stars or thin nodules. (Winckler.) Melts when heated (at 130® according to v. Babo), form- ing a yellow liquid, which solidifies in a gummy mass on cooling. (Winckler.) Scentless, tastes bitter, then like mustard. Neutral. (Henry & Garot.) — Hydrosoulphocyanate of sinapine for tbe most part reddens ferric salts immediately, like other hydrosulphocyanates ; some* times, however, it is obtained in such a condition that it does not redden ferric salts till heat is applied. (Will ; v. Babo & Hirschbrunn.)

BoatroQ & Robiquet obtained hydrosulphocyanate of sinapine not possessiog the power of reddening ferric salts, by treating mustard-floar with alcohol after it had been exhausted with ether. This variety of the compound contains, according to them, lest nitrogen than that which reddens ferric salts, and is less soluble in alcuhol. But Winckler, following their directions, obtained hydrosulphocyanate of sinapine which did possess the power of reddening ferric salts. — Hydrosulphocyanate of sinapine dissolves with yellow colour in water and in alcohol, — in greatly increased quantity when the liquid is hpt, and crystallises on cooling. — A drop of scid renders the solution colourless (v. Babo & Hirschbrunn). — It likewise crystallises without alteration from acidulated water (Henry & Garot). — It dissolves in ether

sulphide of carbon and oil of turpentine. (Simon.) According to Boutron & Fremy, hydrosulphocyanate of sinapine is decomposed by emulsion, with formation of the acrid principle of white mustard. Accoro- ing to Simon, and v. Babo & Hirschbrunn, on the other hand, emulsin has no effect on it.

Henry Boutron v. Babo & ' & Oarot. & Robiquet. Hirschbnma.

1MMSI*

34 C 204 .... 55-43 57-92 .... 54-06 55-42

24 H 24 .... 6-53 7-80 .... 10-65 6-84

2 N 28 .... 7-61 4-94 .... 2-84 721

2 S 32 .... 8-69 9-66 .... 9-37 8-97

10 O 80 .... 21-74 19-68 .... 2308 2156

C«H»N02,(?NHS3.... 368 .... 100-00 10000 .... 10000 ........ 10000

So, according to Gerhardt {Traiti^ 2, 426); ▼. Babo's formula contains 1 At. H more. Boutron & Robiquet's hvdrosulphocyanate of sinapine did not redden ferric salts.— Comp. Henry & Garot (/. Pharm. 17, 1 and 20, 63); Pelouze (/. Pharm. 17, 271); Henry (/. Phdhn, 17, 273); Henry fiU (/. CMm. mid. 6, 582).

Appendix to Sinapine,

1. Acrid principle of White Mustard, — White mustard owes its sharpness, as appears from the preceding, not to hydrosulphocyanate of sinapine (neither can volatile oil of mustard be obtained from it by any treatment whatever), but to a non-volatile, easily decomposable substance.

APPENDIX TO SINAPINE. 529

perbaps containing sulphnr. — Tbis acrid principle is produced, according to Boutron & Fremy, by tbe action of emulsin on b jarosnlpbocyanate of fiinapine ; but Simon and Babo & Hirschbrunn could not perceive tbat any decomposition of bydrocyanate of sinapine was produced by emulsiii. — Winckler, on tbe otber band, tbinks it more probable that bydro- sulpbocyanate of sinapine is a product of tbe decomposition of tbe acrid principle. (Repert. 67, 257.)

Wbite mustard stirred up with water, yields a milk wbicb has a mild odour, but sbarp taste, and yields by distillation witb water^ not a trace of mustard-oil, but only insipid water, the residue also losing its acridity. (Boutron & Robiquet.)

Alcohol of 94 p. c. or absolute alcohol does not extract any acrid principle from wbite mustard \ tbe residue no longer becomes acrid when moistened witb water. (Simon.) Tbe alcoholic tincture has a sharp taste at first, but loses its sharpness by evaporation, and then yields crystals of hydrosulphocyanate of sinapine. (Winckler.)

Ether does not extract any acrid principle from the seeds, after they have been freed from oil.

The acridity of aqueous mustard-paste is destroyed by beating, even below the boiling point, and without evolution of acrid vapours ; also by addition of alcohol or of dilute carbonate of potash, and is not restored by acids. It is destroyed by drying the paste, even by quick and careful drying in vacuo, and remains in the residue when an aqueous emulsion of mustard is filtered, tbe filtrate being insipid. (Simon.)

When wbite mustard is moistened with water, the acrid principle thereby developed may be completely extracted by cther^ so tbat the ethereal liquid, if allowed to run over the band, produces a roseate inflammation, attended with pain which lasts for several days. (Alcohol extracts from the residue very pure hydrosulphocyanate of sinapine, which therefore is not the cause of the acridity.) The ether, when distilled, leaves a very acrid and acid extract, tbe alcoholic solution of which separates on standing, into two layers, with evolution of sul- phuretted hydrogen and separation of resin. Tbe lower resinous layer is witb difilculty deprived of all its acid (Simon's Senfidure p. 523) by cold water, more easily by warm water (but with evolution of sulphuretted hydrogen) or by alkalis. At tbe same time it loses all its acridity. The acrid and acid resin contains sulphur ; that which has been deprived of its acridity is free from sulphur. (Simon, Fogg. 43, 651, and 44, 593.)

When a pressed cake of wbite mustard is exhausted with ether in the displacement apparatus, a mild fixed oil first runs away, then an acrid ethereal tincture. The latter leaves on evaporation an acrid oil, which, when repeatedly agitated with cold alcohol, gives up to tbat liquid its acrid principle, together witb a small quantity of oil, which may for the most part be separated by repeatedly evaporating the alcohol and redissolving tbe residue in alcohol. In this manner, the acrid principle is obtained as a thick reddish oil, scentless, with a biting taste of horse-radish, soluble in alcohol and in ether. This oil bums when heated, without leaving any fixed residue, and does not yield any volatile acrid principle by distillation with potash or ammonia. (Boutron <& Robiquet, «/'. Fharm. 17, 279.)

2. Erucine, — When wbite mustard-flour is moistened with water and then exhausted with ether, tbe ether distilled ofi* frcm tbe acrid extract, and the acrid residue left to itself for some time in an open dish,

VOL. XIV. 2 M

530 PRIMARY NUCLBUS C?»H«

small bard points are produced in it^ consisting' of enicine. This sab- stance may be freed from soft resin bj sprinkling with aqneoas alkali^, then dissolved in ether containing alcohol; the solution left to evaporate in the air ; the alcoholic mother-liquor poured off ; the emeine on the filter freed from the last traces of sinapine by sprinkling with ammoniaoal water, then dissolved in ether; and the ether left to evaporate* — Fine, non-crystalline, yellowish white powder, free from sulphur. It does vot dissolve in toater, in aqueous ammonia, or in aqueous ^eti aUtalU, which do not even colour it yellow. It does not redden ferric salts. It dissolves easily in sulphide of carbon, ether, and oil of turperUine, sliglitlj only in boiling alcohol. (Simon, Pogg, 44, 600.)

Unknoum Primary Nucleus C*H*.

Enodic aldehyde.

This body is, according to Williams, tho chief constituent of volatile oil of rue (p. 489.)

Digitaloic Acid.

C«H»0* = C«H» 0*.

Walz. {iS5S.)N. Jahrh, Pharm, 9, 310; further, 10, 324.

Respecting Kosmatia's fatty scid from DigUalU and Morin's digitalie acid, DiyitaUn.

From commercial digitaline {pid. inf.) ether extracts Walz*6 digitalacrin or digital icrin, which, by the treatment presently to be describetl, yields digitalin-fat, the acrid principles of digitalis, A and B, and digitaloic acid. — Walz*s digitalin {vid, it^.) is digested with absolute ether; and the residue left after the distillation of the ether is washed with water as long as the water which runs away from it has a bitter taste, and then dried. (The product thas obtained waa formerly described by Wals. Jakrbr. pr. PAarm. 21,40, as digttalicriD.) On digesting the brownish, crumbling mass thus obtained with alcoholic solution of subacetate of lead, that substance takes up the colouring matter, and the wine-yellow filtrate leaves on evaporation (ufter rftnoTnl of the lead ? Kr.) a gold-yellow resin. The reeio is freed by agitation with water from admixed digitalin and its products of decomposition ; the undissolved portion (Walz's dtgitalacria, N. J^Ukrd. Pharm, 9, 311) is digested with water containing a few per cent, of ammouia ; and the white flocks which separate are filtered from the brown solution and completely washed with ammoniacal water. (The unmoniacal solution contaios the acrid priociple ^A ; vid. iff/*.) The Undissolved

white flocks, containing digitaloic acid and the acrid principle B, are washed with cold alcohol, and the residual shining white mass is diaaolved in boiling alcohol. The solution thus formed yields, on cooling, white

DIGITALIN-PAT. 531

pearly lamina of digitaloic acid, an additional qaantity of which is obtained by concentrating the mother-liquor, and likewise by precipitating with water the cold alcohol which has been used for washing. Part of the digitaloic acid still remains in solution, together with the acrid principle B : to separate these substances, the liquid is evaporated, and the residue, which solidifies to a white jelly, is digested with potash-ley and thoroughly washed. Digitaloic acid then remains behind, while the acrid principle B dissolves. The latter is precipitated with dilute sulphuric acid, dissolved in alcohol, and treated with animal charcoal (which however exerts a decolorising action), and obtained in the solid state by spontaneous evaporation of the solution.

Fropertie*, Oblique truncated prisms^ scentless at first, afterwards ameliing of fat.

Wall. mean,

22 C 132 .... 70-96 7086

22 H 22.... 11-82 1190

4 0 32.... 17-22 17-24

C»H»0* 186 .... 10000 100-00

It ia not easy to see why Walz designates this body as an acid, inasmach as it Is insolnble in alkalis.

Insoluble in ammoniaf or in potash^ but soluble in alcohol.

Jfpendix to DigUaloio Add.

1. Digitalin-fet.

Walz. N. Jaht'h. Pharm. 9, 312; further, 10, 324.

Extracted by ether from orn^e digitalin, together with the sobgtanoes above mentionea, and remains — in the preparation of digitaloic acid as above described — dissolved in the aqueous ammonia, together with the acrid principle A. — When this ammoniacal solution is neutralised with dilute sulphuric acid, a copious white precipitate is formed, which soon unites with the resin. The resin is dissolved in alcohol; the solution precipitated with alcoholic subacetate of lead (the acrid principle A then remaining dissolved); and the precipitate is completely washed with alcohol and decomposed under alcohol, with sulphuretted hydrogen. The solution filtered from the sulphide of lead leaves, by spontaneous evaporation, digitalin-£Ett in white scales, which melt to an oil at a gentle heat :

Walx.

dried.

Calculation according to Walt. metm.

25 C 150 .... 73-17 73-41

23 H 23 .... 11-21 11-33

4 O 32 .... 15-62 15*26

C»H»0^ 205 .... 10000 10000

Walz calcnlates his analyses incorrectly. He regards the fat as consisting of an add C»H^O and Berzelins's oxide of lipyl (ix, 487) CH^O; or perhaps also as

2 H 2

532 PRIMARY NUCLEUS COHa

a^BJiQa^ produced from 3 At. C^H^Q^ and 1 At. C8H»0«. According to the firrt of these formulae, the acrid principles A and B of digitalis consist of digitalin with 2 and 3 At. oxygen added to it.

2. Acrid Principle of Digitalis, A.

Walz. iT^ Jahrh. Pharm. 9, 314; 10, 324.

Extracted by ether, together with other Buhstances, from crade di^- talin, and remains, in the preparation of digital in- fat, as above, in solution J on the evaporation of which it is left in the form of a resin. Separates by spontaneoas evaporation from alcohol, at the, bottom of the vessel, in yellowish red oil-drops, on the edge in warty resinous spherules, and appears, after complete evaporation of the alcohol, as a yellowish mass having the consistence of honey.

	Calculation according to Walz,		Walz. stMon.
25 C .... 23 H .... 6 0 ....	... 68-33 32 C 67-60 40 C .... .... 10-40 28 H 9-85 34 H .... ... 21-27 8 0 22-55 10 O ....	.... 67-80 9-60 .... 22-60	... 68-18 ... 9-61 ... 22-21

0»HaO«.... 100-00 C«H»08.... 100-00 C^m^O^o.... 10000 100-00

Walz is undecided between these formuls: the relations of this body to the other constituents of digitalis may be seen under Digitaliretin and JMgitalin-fat (p. 530).

Decompositions, 1. When heated, it gives off a smoke having a pecu- liar odour, and at a higher temperature burns away without residue. — 2. Blackens with oil of vitriol; dissolves with brown colour in fuming nitric acid, whence it is precipitated by water ; and with green colour in warm hydrodhloric add.

It is insoluble in water, but imparts to the liquid its acid reaction and very sharp taste. Sbluble in alcohol and in etiier.

3. Acrid Principle of Digitalis B«

Walz. (1858.) K Jahrh, Pharm. 9, 314; further, 10, 324.

Preparation, (See Digitaloic Acid, p. 529.)

Uniform, yellowish mass, friable at ordinary temperature, melting at 100°, and solidifying again but slowly. Its aqueous solution has a burning taste and slight acid reaction.

Walz.

Calculations according to Walz, mean.

25 C 65-5 32 C 65-54 40 0 66'14 ., 66-89

23 H 100 29 H 989 85 H 9-64 9-73

7 0 24-5 9 O 24-57 11 O 24-22 24-38

CSSH«07 .... 100-0 C«»H»09 .... 10000 C«H»0" .... lOO'OO 10000

Walz is undecided between these form alae : the relations of the compound to the other constituents of digitalis may be seen under Digitaliretin and Digitalin-fat (p. 530).

VOLATILE OIL OF ARISTOLOCHIA CLEMATITIS. 638

Turns brown in contact with oil of vitriol, and olive-green with hydro^ eUorie acid, which partially dissolves it. Dissolves with yellow colour in nitric acid.

Scarcely soluble in water, easily in ether. (Walz.]

4. Digitalosmin.

Walz. (1852.) iT. Jahrb. Fharm. 24, 86.

The odorous principle of foz-^love {Digitalis purpurea).

On subjecting 80 pounds of dry foz-^love a year old to slow distilla- tion by steam, 15 to 18 lbs. of slightly acid distillate were obtained, with fatty scales floating on the surface. By agitating the distillate with ether, removing the ethereal layer, and leaving the ether to eraporate, the substance composing these scales is obtained as a yellowish white, pearly residue, having a strong odour of infusion of digitalis, and a nauseating, scratching, very persistent taste.

Heated on platinum, it melts and volatilises in vapours, which bum with a non-smoking flame. — Softens when triturated with oil of vitriol, and is decomposed by heating. — It is slightly altered by cold fuming nitric add, and coloured yellow by hot nitric acid, with evolution of nitrous gas.

It is insoluble in cold toater, but imparts to it the odour of digitalis j in warm water, it melts and separates in scales on cooling. It dissolyes in alcoholic pciaek, and is precipitated apparently unaltered by water. In aqueous ammonua, it softens without dissolving.

It dissolves readily in alcohol, with slight coloration, and is precipi- tated therefrom by water, — Dissolves with great ilMility in ether.

Oxygen-ntickus C?*H"0'. Volatile Oil of Arietolochia Clematitis.

G. P. Walz. Jahrb. pr. Pharm. 24, 65.

The volatile oil of Ariitoloehia was previously observed by F. L. Winckler (JaAr5. pr. Pharm. 19,71) and by FTXckhinger {If . Sepert. 7^ ]). — Winckler obtained about 0*4 p. c. by distillation from the dried roots ; Walz obtained the oil from the dried plant by vapour- distillation.

Viscid, gold-yellow oil, having a sp. gr. of 0'903 at 15° and a strong add reaction (arising probably from adhering acid : Kr.).

Wak. fueoH.

22 C 132 .... 67-34 66-51

16 H 16.... 816 8-65

6 O 48 .... 24-50 2484

196 .... 100-00 100-00

634 PRIMiLRT NUCLEUS C"HB: OXTGBN-NUCLEUS CBH»0«.

WiJs heated the oil tbat he analjssd to 100® for aome time preneuly, whiok tam- peratiure was ^^robabljr not sufficient for dehydration* The calculationa of h.is analfjo^ which vary from 65'18 to 67*18 p. c. in the carbon, and from 7'98 to 9'26 p. c. jn tha hydrogen, are partly incorrect. (Kr.)

By exposure to the air, the oil becomes more viscid, bat does not resinise. — According to Winckler, it resiniaes when exposed to the air. — It colours oil of vitriol liver-brown when cold, black when heated, and finally becomes carbonised. — It dissolves iodine with rise of temperature, forming a yellowish brown, tough mass, which resinises when heated. — By nitfie acid of sp. gr. 1*5, it is violently attacked, with evolutioii «f nitrous gas, becomes brown-red and resinises. — With alcoholic potash, it forms a deep red liquid, becomiqg red-btown when boiled, and remains in red dro|»s when the aleohol evapmntes. — With etnuiie emmouia it hama an orange-yellow emalsion. With aqaeois bieknmak o/ pgimA uti. snlphurio aoid it aequires a yellow-green colour.

Dmoii<eB in 1&— £8 pts. alcohol of ap. gr. 4>'BS»

^ND OP TDL. XIV.

ERRATA.

VOL. XIII. P^ 576, lines 9 — ^20 belong to page 577 where thej ahonld follow line 9.

		VOL.	XIV.
Page.	Line.
139	9 from bottom	for	2BaO,HO	read	2(BaO,HO).
140	5 from top		3BaO,HO	»»	3(BaO,HO).
tt	1 1 from bottom		3CaO,HO	>f	3(CaO,HO).
158	21 from top		c»«	t»	C".
176	U M		C»NHVO<	t»	C«NHWO«.
268	17 „		UQ	»t	HCL

REPORT

OF

THE THIRTEENTH ANNIVERSARY MEETING

or THB

CAVENDISH SOCIETY.

The Anniversary Meeting of the Cavendish Society for the year 1860^ was held at the rooms of the Chemical Society^ in Burlington House^ on Thursday^ the 1st of March^ at three o'clock in the afternoon.

The Chair was taken hy Thomas Graham^ ^sq.^ F.B.S.^ President^ who called upon the Secretary to read

THE REPORT OP THE COUNCIL.

" In the last annual report the Connoil stated that the thirteenth volume of Gmbltn's ' Hand-book of Chemistry' was then in progress, and was intended as a book for 1859. The completion of this volume has oeonpied a longer time than was antioipated, partly in consequence of the Editor having to wait for a portion of the German edition which 18 comprised in it, and partly in conisequence of the extensive additions of new matter which had to be made in the form of appendix. It is now ready for distribution^ and the large amount of matter it con- tains will, it is hoped, compenaate in some degree for the unavoidable delay that has occurred in supplying it to the members.

''The Council are unable to hold out the prospect of any other Tolume being supplied for 1859, and must refer to the statement made in the last report for an explanation of the causes which have contri- buted to limit the issue of books during the last two or three years.

*' The propositions, originating from sereral sources, which hare been made with reference to works thought to be suitable for publica- tion by the Society, and some of which were referred to in the last annual report, have r^eiv^ the attention of the Council, and haVe been fully discussed on repeated occasions. The conclusion to which the Council hare arrived, after mature consideration, accords with the opinion expressed in the report of last year, which is, that the whole of the resources of the Society should be .concentraled upon the com- pletion oFthe'fbw remaining volumes of QwSLnfs ' Ohemeiry^ before any other work is undertaken. This opinion, they have reason to believe, is also in accordance with that of the majority of the members of the Society. In the present state of the Society, the attempt to bring out any other work in conjunction with the * Hand-book of Chemistry' would necessarily retard the completion of the latter, as the means at the disposal of the Council are insufficient for the pro- duction of more than one large volume a year j while an apparently insurmountable obstacle is presented to the extension of the number of subscribers, by the necessity imposed on new members to provide a large number of the preceding volumes of the work now in progress in order to make their sets complete. Attempts have been made to overcome this difficulty, but without success ; and even if, in other respects, it were possible, the small stock of the early volumes left on hand would so far limit the power of enlarging the Society in tllkt way, that no sufficient increase could be derived to justify any material auginie'ntation in the expanses of j^nblication.

'' The present income of the Society, if maintained, will be saffi- cidtit to enable the Council to bring out what remains to complete die Work of LttopoLD Omblik as fast as it Is produced by the German editors ; and at the same dme to add, in the form of appendix, all new matter relating to those parts of organic chemistry treat^ed of in the preceding volumes. The matter thus added to the volume now Til course of distribution, occupies two hundred pages. These addi- tions, which are nikade to each sacceeding volume of the work, may be regarded as ' Antiual Abstraeta of Piq^rs on Chenrieal Seieii^' whleh

some of the members of the Society suggested to the Comioil^ in a oommanication noticed in the last annual report, as suitable for publi- cation. The Council are glad to be enabled thus far to meet the wishes expressed by members, without retarding the progress of the Work which all seem desirous to expedite, or inrolying the Society in liabilities beyond the current income.

'^A new part of the German edition of the Hand-book has just appeared, the translation of which will at once be proceeded with ; and there is every reason to believe that the supply of matter will be kept up so as to admit of the publication of a volume, with the usual additions, or abstracts of Papers, every year, until the completion of the Work.

" The preparation of an Inde^ to the whole of the volumes is now occupying the attention of the Council.

*'When Gmelin's Work has been brought to a conclusion, a suitable opportunity will be presented for considering the course to be pursued with reference to the future. The obstacle to the extension of the Society, to which allusion has been made, will then cease to exist. New works may be undertaken, for the selection of which ample time will have been afforded. These may resemble in character the works previously produced, or it may be thought desirable to undertake works of a different description, which would attract a new class of members, and the extension or reconstruction of the Cavendish Society would be the probable result.

" The Council feel, however, that they cannot too strongly impress upon the members the importance of retaining the support of all the present subscribers to the Society, nntil the Work on which they have been so long engaged is brought to a satisfactory conclusion.*'

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It was moved by Db. Roscoe, of Manchester, seconded by Daniel Hanbttbt, Esq., and resolved unanimou8ly--->

"That the Report just read be received, approved, and adopted.*'

The Meeting then proceeded to the election of Officers for the ensuing year, and the following Gentlemen were declared to have been didy elected : —

^rnrOrnit.

Thokas ObahaIc, F.B.S. 9ice«9re4Clrfntir*

PsovESSOB Bbandb, F.R.S.

EaBL OT BUBLIlfOTOK, F.B.S.

Wambb Cbum, F.R.S. John Davy, M.D., F.R.S. ChablebG.B.Daitbbny, M.D., F.R.S. Hiohabl Fabadat, D.C.L., F.R.S. John Obaham^ F.C.S.

A. W. HoncANir, Fh. D., LL.D.,

F.R.8. Hbnbt Bbavkobt Lbbson, M.D.,

F.R.S. W. A. MiLLEB, M.D., F.R.S.

ROBEBT POBBBTT, F.R.S.

William Shabpbt, M.D., F.R.S.

CnundL

Rev. J. Bablow, F.R.S.

G. B. BroKTON, F.R.S.

DuQALD Campbell, F.CS.

P. J. Chabot, M.A, F.R.A.S., F.CS.

Fbbdbbio Claudet, F.CS.

Wabbek Db la Rue, Ph.D., F.R.S.

W. FEBarsoN, Esq.

J. H. QiLBEBT, Ph.D., F.CS.

Daniel Hanbvbt, F.L.S. Chables Heisoh, F.CS. N. S. Maskeltne, F.CS. William Odlino, H.B., F.R.8. Tbenham Reeks, Esq. J. Denham Smith, F.CS. R. D. Thomson, M.D., F.R.S. Colonel Philip Yobke, F.R.S.

Obobob Dizon Longstatt, M.D., 9, Upper Thames Street

J^tttftxrs* Tkeophiltts Rbdwoop, Fh. D., 19, Montagne Street, RtuseU Sqiuoe.

CoIIeftor.

Mb. Thomas West, Burlington House, Piccadilly, W.

9itittd (or t^t Biitxibtdian at SSoo&iT, ^

Mb. F. Habbison, 69, Pall Mall, S.W.

It was resolved —

'' That Dr. Fbakkland and Messes. Thomas Htdjb Hills and Alfbed Smex be appointed Auditors for the ensuing year.*' The following Resolutions were unanimously adopted:—-

'*That the thanks of the Meeting be given to the Pbs- BiDEMT, CoxTKCiL, and Officebs, for their services to the Society."

*' That the thanks of the Meeting be given to the Hokobaxy Local Secbetaries for their services to the Society."

*' That the thanks of the Meeting be given to the Chemical Society for the use of their rooms."

THEOPHILUS REDWOOD, Secbetart, 19, Montague St., Russell Square, & 17, Bloomsbury Square.

March, 1860.

OBJECTS, &o., OF THE CAVENDISH SOCIETY.

The Cavendish Society was instituted for the promotion of Chemistry and its allied sciences, by the difiusion of the literature of these subjects.

. The subscription, constituting membership, is one guinea a-year, to be paid in advance; and the subscription becomes due on the Ist of January of each year. . A member is entitled to a copy of every book published by the Society for the year for which he has subscribed, but no member can receive the Society's publications until his subscription has teen duly paid.

^p-^^^"

WORKS OF THE CAVENDISH SQCIETT.

1848.

l.--OHfiMIOAL REPORTS AND MEMOIRS. Edited by Toomas Geaham, P.R.S. (Out of Print.)

8.— HAND-BOOK OF CHEMISTRY. By Lsopold GxKUir. Trans- lated by Emsly Wavts, B.A., F.O.S. Vol I.

1849.

3.— HAND-BOOK OP CHEMISTRY. By Leopold Gmblth. VoL II. 4.— HAND-BOOK OF CHEMISTRY. By Lbopold Gmblin. VoL III. 6.— THE LIFE AND WORKS OF CAVENDISH. By Dr. Gbobm Wilson.

1850.

6.— HAND-BOOK OF CHEMISTRY. By Leopold Gmblik. Vol. IV. 7.— HAND-BOOK OF CHEMISTRY. By Leopold Qkblw. VoL V.

1851.

8.^PHYSI0L0GICAL CHEMISTRY. By Pb^pbssob Lbhhavit.

Translated by Geobob E. Day, M.D., F.R.S. VoL L (Out of

Print.) 9.— HAND-BOOK OP CHEMISTRY. By Leopold Gxbuk. VoL VL

1852.

10.— HAND-BOOK T)F CHEMISTRY. By Leopold? Gkbliit. VoL VIL (Organic Chemistry, VoL I.)

11.— PHYSIOLOGICAL CHEMISTRY. ByPBOPEBSOB LEHMAinr. VoL II.

la— ATLAS OF PLATES belativo to PHYSIOLOGICAL CHEMIS- TRY. By Db. Otto Fu»ke. (Supplement to Lehhaitii's Phtsiolooioal Cheiostbt.)

1853. 18.^HANI>-B00K OF CHEMISTRY. By Leopold Gmelib. VoL Vm.

(Organic Chemistry, VoL II.) .—BLBMF

14.— ELEMENTS OF CHEMICAL AND PHYSICAL GEOLOGY. By Pbofessob BiscHor. Vol. I.

1854.

15.— THE LIFE AND SCIENTIFIC RESEABOHES OF DALTON.

By Db. W. C. Hehby, F.R.S. 16.— PHYSIOLOGICAL CHEMISTRY. By Pbofessob Lehxam.

VoL III. 17.— LAURENT'S CHEMICAL METHOD. Translated by Wx. Oduvo,

M.B.

1855.

18.— HAND-BOOK OF CHEMISTRY. By Leopold Gmblih. VoL IX.

(Organic Chemistrj, Vol. III.) 19.— ELEMENTS OP CHEMICAL AND PHYSICAL GEOLOGY. By

Pbofbssos BiBOHor. Vol. II.

1856. 20.— HAND-BOOK OP? CHfflWISTRy, By LHOP^LDiQioiLW. YoL X.

(Organic Chemistry, VoL IV.) 21.— HAND-BOOK OF CHEMISTRY. By Leopold Gmblif. Vol. XII. (Organic Chemistry, Vol. VI.)

1857. 22.— HAND-BOOK OP CHEMISTRY. By Leopold Gmeliit. Vol. XI. (Organic Chemistry, Vol. V.)

1858. 23.— ELEMENTS OP CHEMICAL AND PHYSICAL GEOLOGY; By Peofesbob Bischop. VoL III.

1859. 24.— HAND'BOOK OP CHEMISTRY. By Leopold Gif Bim. ^M. XIIL (Organic Chemistry, Vol. VIL)

CHEMIGAL REPORTS AND MEMOIRS. Edited by Pbopessoe Gbaham. This work is out of print.

GMELIN'S HAND-BOOK OF GHEMISTRT. Translated and* Edited by Hi^&t Wattsj B.A., P.CS.

The first Volume of this Work treating of Physics, is out of print. The Five Volumes, from VoL II to- VoL VI, com^ prising the Inorganic Chemistry, may be obtained for £L 5> 0.

The 7 th and 8th Volumes, being the first two volumes of the

part treating of Org^c Chemistry, for 110

The 9th and 10(^ Volumes, for 1* r (^

The 8ub9ec|[nent volumes can only ba obtained by' sobecribing; for th» years for which they are issued.

LEHIIANI^S PHYSIOLOGICAL CHEMISTfiY. Trspslated aod Edited by Ds. G. E. Day,. F.R.S.

The First Volume of this work is out of print. There stilL remain. a few copies of the Second' and Third Volumes, anct of Dr. Otto Funke'S Atlas of Phymologioal Pistes, which, together, may be- obtained for £1 U.

BISGHOFS elements OF CHEMICAL AND PHYSICAL GEOLOGY.

The First and Second Volumes of this Work are supplied for a sub- scription of £1 Is,

THE LIFE AND WORKS OF GiAVENDISH. By Dr. Geo. Wilsoit.

THE LIFE AND BCISNTIFIC BESEAECHSS OF DALTON. By Dr. W. C. Hbhbt, F.R.S.

LAURENT'S CHEMICAL METHOD. Translated by Dr. Onuvo. These three Works are supplied for a subscription of £1 It,

%* Applications for the works of the Cavendish Society, are to be made to the Agent, Mr. Harrison, 59, Pall Mali, S^W.

^onotatp Hocal $e(tetatie0.

Aberdeen — Dr. B« Rsttray. J9an6ufy— Thomas Beesley, Esq. BcUh—J. P. Tylee, Esq. BtUhgate^Jtaaw Young, Baq. Becdea—yf, E. Crowfoot, Esq. Bet(fard^Yf. Blower, Esq. BelfoH—lh, J. F. Hodg«8. Birmingham — George ShAW, Esq. BoUon^B., H. Watson, Esq. ^ra<{/^or(f^Robert Parkinson, Ph. D. BrighUm — F. Basse, Esq. Bristol — Wm. Herapath, Esq. Cambridge— W. H. MiUer, Esq.,

A. A.., F.A.0.

Cheeter—Ji. D. Qrindlej, Esq. <nift<m—0. F. Schacht, Esq. Cork — Thomas Jennings, Esq. DubUn — Dr. J. Afgohn. Bdinburgh^1>r. Qeo. Wilson, F.E.S.E. jBbeter— Qeoige Cooper, Esq. I'aimham — W. Newnham, Esq. Oaltoay^Dr. T* H. Bownej. G^2<u^oto— Walter Cnun, Esq., F.B.S. Goepm—J>t. W. Lindsay, B.N.

Ouemeey^Dr. E. Hoekins, F.B.S. Hali/ax- John W, Garlick, M.D. J7tf/^— Thomas J. Smith, Esq.

Leede—Yf. S. Ward, Baq.

r . V ( Dr. J. Dickinson.

Liverpool — J

1 J. B. Edwards, Ph. D.

LlandHo—B. Moigan, Esq.

/John Qraham, Esq.

■»^'»"**'''*^{H.B.Roeooe,Ph.l>

Newport (Monmouthahire) — Ebene- zer ISiogen, Esq.

Norwich — Edward Arnold, Esq.

i\roMin^Aam-^oBeph White, Esq.

Oirford-^K, J. Smith, 1^.

SL Andreufa-'DT, G. E. Day, F.B.S.

St, Hden*a {Lancaekire) —Zvaim Shanks, Esq.

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Stockbridge — George Edmondson, Esq.

Swansea — Dr. Thomw Williams.

Woltferhampton—B, Walker, Esq.

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For*— W. Q. Procter, Esq.

UNITED STATES.

New Fori— Henry BiOlliere, Esq., 290, Broadway. Philadelphia— Wimam Procter, jon., Esq.

Haerison ako Sons, Primtbrs, St. Maktim's Lani, W.C.

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