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Si

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\^

.^^

WORKS

OF THE

CAVENDISH SOCIETY.

FOUNDED 1846.

HAND-BOOK

OF

CHEMISTRY.

BY

LEOPOLD GMELIN.

VOL. XII.

ORGANIC CHEMISTEY.

VOL. VI.

OBGAMIC COUroUNDS CONTAIKINa FOURTEEN >itOM8 OF C&BBOM,

h^

TRAN8LATKD BY / ^'

HENRY WATTS, B.A., F.C3^

LONDON:
PRINTED FOR THE CAVENDISH SOCIETY.

MDCCCLVIII.

CONTENTS OF VOL. XII,

(VOL. VI. OF ORGANIC CHEMISTRY.)

COMPOUNDS CONTAINING 14 AT. CARBON.

Primary Nucleus C"H< ; Nitro-nucUut, C^X^H*.

Page

Chry«ammic acid, CMNSHao^a = C"X2H2,0< 1

Chryiammate of Potash, C^X^HKO^ ... 3

Chrysammatc of Soda, C"X«HNaO^ + 3Aq .... .... .... 4

Chryaammate of Baryta, C^^XmBaCH + 2Aq .... .... 4

Chrysammate of Strontia .... .... .... .... .... 4

ChnrBammate of Lime, C^^X'HCaO^ + 6Aq. — Chrysammate of
Magnesia. — Chromic Chrysammate. — Chrysammate of Man-
ganese, C'^X^HMnO* + 5Aq. — Chrysammates of Zinc and Cad-
minm. — Chryiammates of Lead, CWX'HPbO* and Ci*X«HPbO^

+ PbO,HO 5

Ferrous and Ferric Chrysammates. — Chrysammate of Copper, C'^X'HCuO^
and 4- 4Aq. — Mercuroos Chrysammate. — Chrysammate of

SUw 6

Chrysammates of Gold and Platinum .... .... .... 7

Chrysammide,C><N»H<0"=:CWHAdXW,HO 7

Lead-compound, CMN»H»0>o,2PbO + 4HO 9

Appendix to ChryeamnUc acid :

Aloereticadd, CMNH»0>3 9

Aloctic acid, C"N«H<0>3 ? 10

Aloetamide, C"N2AdH«OW 12

Chrysatric add .... .... .... .... .... 12

Chryiodin.... .... .... .... .... .... .... 13

Hydrochrysammide .... .... .... .... .... 14

39

vi CONTENTS.

Bknzylknk Sbribs.

Primary Nucleus : Benzylene, C*^H«.

Bensylicether^Cim^O^Ci^HSHO ^ 16

Bthylo-benzylk ether, C»H>30» = C^HSC"HSHH)» 17

BeittjHc Alcohol, C"HH)« = C»^H«,HK)« 18

Bitter Almond «1, C"HH)» = C»^H«.0» W

Bitter Almond oil with Bisolphite of Ammonia. — Withftsnlplute of

PotMh. — With Bisulphite of Soda, C"H«0» + NaO,2SO» + Aq 27
Bitter Almond oil with Bichloride of Tin. — With Hydrocjanie add,

C"HH>»,C?NH.— With Cyanic add 28

AfgteiUUjp t9 BUier Almond oil: Laurel-oU, Peach-leaf oU, OU of the
Purtn^ Leard, Bitter Almond water. Laurel- water, Cherry- water ..^ 29

ValnatioD of Bitter Almond water, Lanrd water, Bcc .... 50

Piatinctioo between Bitter Almond water and Lanrd water ... 31

,C»H*0* 52

i of Ammonia and Potash .... ...• — ••« •^

B«iao«t««or Soda, Lithia, BaryU, C"H*BaO* + Aq., Strontia, Lime,

C**M*CaO« + 2Aq, and Magnena

BeuMWtet of Cerinm, Yttria, Gludna, Alumina and Zirooniaj—
QiroHioas Beaxoate .... .... .... •••• •••• ^

t'nmic Bensoate; Manfranous Benzoate, C"H*MnO* + Aq., Ben-
SMrtei of Bismuth, Cadmium and Tin ; Trihadc Bensoate of
Lead. ZPbO.C»*H*PbO< 41

MiiooUdc Bensoate of Lead, C^m^PbO^ + Aq; Aoeto-bensoate of
Lead, 2PbO,C»*HK)» + 2(8PbO,C"H»0») ; Ferrous and Ferric
Beiisoctes ... .... .... .... .... • ^2

BeikSMdes of Cobalt, Nickd and Copper; Mercorous Bensoate,
C**H*Hf'0* ... .... ... ... • 45

Mercttric Bensoate, basic and normal. — Ammomo-mcrcnnms and
Ammonio-mercaric Bensoates .... •• * •••• 44

Bensoeir of KQtct, C^H^igO^. ^ Bensoates of Gold, Flatinnm and

Palladium . . .... .... ..• 45

Jk/^tmdi* iv Bemsoic meid :

AjBurpbons Bensoic add, C^MIH)* . . 46

C«rtiobenaairadd,C»HK)« . 47

CarMbtssoato of Baryta, Ume, Lead and Silver : C»H*MO« 47, 48

HyppiiiBinrloM acid.. .... .... — ••.. 48

boipni^ of Bei^kmr, C>«H«S2 49

Hvuriuoau of B^rrteDe. C^HH - C*H«.HI *0

tiyim^cniifrBe of BensTlrne. C^H'O - a«H«,HC1 ^

f_W«r If* bcnrr^ne, C»*H«CF — *!

•.?«iuir a* l#oar- CMH- - C^\C»H? ..- W

^uruic tf! lievT^. C»T1*0* - C»irO.OH*0» . .... — W

*s^LO««SiW - CHll«a»,28C>» ^ w

■Me«f rrtHh; Nrvtraland Acid ... &4

CONTEf^TS.

VI

u

I

Prtge

SulphobenKoatcof Baryt*: Neutral C"B*Bn?CH .2 SD^ 54

Add, C'^HSBaO\2SO> ... 35

Sttlphob(!iiaoateof Lead»C'm*Pb*0*,2S0* .... ... „„ B5

SulphobenKoatc of Silver, C^^H^Ag^0*,2S(>" .... 55

! of Metliyl, anisQ* = O^H*0,C'*H*0» .... ,,.. ..., 56

MtDdelk acid, O^H^O'' - C^trO^C^H'W 57

Mandelates tif Ammcmia and Potjish ,,„ ... 5S

Mai^dates of Baryta, Ma|^««ta and Lead .,. .... 59
Maaddfttc of Copper, C^'^H^CuO*. — Mercuric Mandeliite. — Mao*

delate of SiWer, D«H'AgO* ... ,. 59

E&nxmts of Ethyl, C'^H'^^O* = cmsO.C"H*0» .., 60

SulpboWnaoat* of Ethyl, C^^H'^S-O^t* ^ 2C*H5O,C**H<S?0« .. 62

Ethjbswlphobenzoic add, Cn-t^^S^O'** =Cm^O,llO,C'ni*r-0« . 63

Amrooma-salt, C'«H«(NH^)S^OJ" 63

Soda-salt, C^'H'NaS^Oitf _ Bgryta.aalt, C^^H^BaS^O^". — SiW«r-

salt,,. * .... .... .-,. 04

BfiMoglyCTlic add, C>»H«a* = Cim*0«,C*H30* 61

Benioglycolates of AtDtnooia, — Potash, — 8odi, C^H^aO*. —

BaryUt am'BaOS fi6

BeDzoflrcoktes of Liroe, C^H'CaO",— M«ftieaia,— Zinc, CnVZnO^ 67

B^mioglycolate of Lead : a. SejE-basir, 5PbOX**H?PbO» .... 6S

A. Sesquibaaic, Pb0.2C'«mPb03, — c. Mfmobosic, Cni'PbO* fi8

Feirifi Benzoglyr^olate, 2FcS03,3C«HW ... .... 68

B«tiKogly(!oliite of Copper — Benioglycolate of Silter, CWH^AgO" 68

HippDric acid, C^^NIPO* = C"*AdH7(y ,... . . ,..- 69

flipparate of Ammouia.— Normal.— Acid, CWNH«(NH<}0",Ci*NH»0«

+ 2Aq .... .... ,.. .... rs

Hippurmte of Potash, — Normal, C^-*'KKH'*0'*. and with 2 Aq . 75

Add, a^NH*'Ka*,Ci^H'(y + 2Aq , 76

Hippurate of Soda, 2C»'*NH'T^aO« + Aq „.. ..„ 76

Hippnrate of Baryta, — Basic. — Normal, C'*NH*BaO" and with

lAq , 76

Hippurobenzoate of Baryta, C"^H*BaO<,C'8NH«BaO^ + Aq 77

Hipptirate of Strontia, C^^'NH^SrO** and with 5Aq .... .,„ 78

Hippurate of Lime, C^^H^CaO^ and with 3Aq ,... .... 76

Hippurateof MagncBia, C^'NH'*MgO«' + Aq .... . 78

Hippuratc of Zinc .... .... .... 78

Hippurate of Lead, — Ba»ic. — Nonaal, C^^NH'^PbO* - 2Aq and

+ 3Aq .... ».. „.. ... 79

Ferric Hippnrate ,.« .... .... 80

Hippnrate of Cobalt, C'^NH'CoO^ and + hAq „.. .... „.. 80

Hippwnite of Nickel, CWNH^NiO^ and + 5Aq , 80

Hippurate of Copper, C"*NH'*CuO'' and + 3.Aq .- .„. 80

MercurouB Hippurate,— Hippvi rate of Si Iter, C^sNH^AgO* and 4- lAq 90

Htppurateof Ethyt, C^NH'W = C^H*0»C'^NH«0» 81

Appendtj- to Hippuric add: Hipparaffin, C^'^NH'O^ 82

Benaoate of Allyl, C»Hi°0* ^ C*H*O.C'*H O^ Hi

^m i^ii CONTKNTR, ^^^^^|

■

Pk?«

^M Benaoate of hmyl, C^^H^W = C^H^OX^HK)* »»

.. «i

■ Beowtie, Ca"H^W = C^MI^CF.Ci^H*

15

■ BentoAte of Phenyl, C^Wm* ~ €PWO^0*BKSi^ ».

» 86

■ BeniMte of BromopIiTOjK C^H^BrO* ,

SS

^^1 BeniMteofCUloropKei.yl. C^rPClO*

.. 89

^^H BcDioate of BinUroplienjl, C^Xm^r,.,

90

^H Bervaoate of Terijitropbenyl, C^X*H^O*

. ^l

^1 TVnTfibcticadd, C^H^l)'* - (Ci*H*oa)5C»m»"0«

92

^^^^^ Seemditiy Nueiti ^ B^zylen^,

^H^ 0^ff€n-mmt^ C^mK).

^m Anbjdrau* Benzole wnd, C**HK>» - C»<HK),C^

,. 03

^1 Anhfdroui BcmwMeUc «:id, O^H**©* = C^H*0*,C'*H*0>

9a

, 96

^H Ajipemli^ io Amkfdrota B^nzmt Add:

■ Oieo«?lorifl,C'*H'0* ..

96

^H Couipflund obtaincHi from llydrocUlorate of Athtmintiii, C^UH)^ ,.

.. n

98

^^H Kitropeuceditniin C>*NIP''0'

100

^^^ Nitrop€iic«damide. C^^N^H^ao* ^,^,

100

^K Athammiitiii, CS^II»*0? - C»H*0»,C»'H»0*> ,

101

^^^ Hjdrocbbnite, C«HiK)T.HCl?

103

^^H O^fim^fiuctem, Ci«HK^<

^^^V D?ivii?<i/<?(i dmpmtHd*.

104

■ Bensmhlorhydrin. C?"H"ClO* ^ C**HK:1,C«H<0»

105

H Trfbeuioloin, L«U»0»> « (C»*H«OJ)',C«H«0*

105

H Shif^Aiir-Mifi^^M Cm*B.

H Sulplxide (if Beiuorl, C^H'SO* - rMH»0*,R

108

^H fttdine^niicUfu C*<IH*.

^^^ Iodide of B«i«»flC»lH*.CF-C«HW,t

107

^^^^V J9romiBt.iiiidff«w C'^fifll**

^F Bromidf ofBfDfojl. C»*BrHVO' - 0*H*OS.Br ,„

107

107

^^^ 8iH«iwMt,C^BrH*Hf><

107

^^^P rA/oriit#.iiiiir/#«i#. C'tlHt

^^H

^V Chlorfd* <»rfiti«07l, C**aH\0* - r'n!Hl«,C 1

lot^^l

^^^ ConiUhiiUciii with B*. bloroflnic ctber, C*C!'M»a,a*nHHV

iii^^H

^^^^^ Comblii*hoii *itb Biifri nlmoml ml< f^»*H*O',C"ClH*0'

m ^^B

CONTENTS. ix

Page

Chlorobcnxolc acid, Ci*ClH»,0^ .... 112

Chlorobeiuoates of Ammonia, Potash and Soda .... .... 114

Chlorobenzoate of Baryta, C"ClH<BaO< + 3Aq .... .... 114

Chlorobcnzoate of Lime, C**ClH*Caa» + 3Aq .... .... 114

Chlorobenzoates of Lead and Copper .... .... .... .... 114

Chlorobenzoate of Silver, C"ClH*AgO* .... .... .... 115

Chlorobenzoate of Ethyl, C"H»CiO< ^ C*H»0,CMH*C10» .... .... 115

Appendig to CMorobemoic acid: Nitrochloromichmyl.-^Chloromichmyl 116

Chlonne^nucUus C^^H^Q'.

Chloride of Chlorobenzoyl, C»*H*C1«,0« » C"H*C10«,Cl .... .... 116

Cblurosulphobenzoic add or Chloride of Sulphobenzoyl, Ci^H^CP,2S0'

- CMH*(S«0*)02,C1« 117

Cyanogen-nueleut C"CyH».
Cyanide of Benzoyl, CMNH»0« ^ C"CyH»,02 118

Nitro-nueieus 0*XH\

Nitrobenzaldide, C"NH40» = C"XH»,02 119

Compound with Bisnlphite of Ammonia, C»<NH*0« + NH<0,2S02
+ 2Aq.— With BUulphite of Soda, C»^NH»0» + NaO,HO,2SO«

+ lOAq .... 121

Nitrobcnzoic acid, CMNH»0« « C"XH»,0* 122

Nitrobenzoate of Ammonia. — Neutral C"XH\NH<)0*, — Add

C"XH<(NH<)0* + C»*XH»0< 123

Nitrobcnzoates of Potash, Soda. Baryta, C*<XH*BaO* + 4Aq.... 124

Nitrobenzoate of Strontia, 2(C"XH^SrO*) + 5Aq. — Of Lime
C"XH<CaO^ + 2Aq.— Of Manganese C"XH<MnO^ + 4Aq.—
Of Zinc : Quadribasic 32nO,C>-*XH^ZnO<. — Monobasic

C^XH^ZnO* + 5Aq 12«

Nitrobenzoate of Lead: — Basic, PbO, 5 C»^X H^PbO^. — Normal

C"XH^PbO< 126

Ferric Nitrobenzoate, Fe»0>,3C"XH^ 126

Nitrobenzoate of Copper, C^*XH*CuO* + Aq. — Nitrobenzoate of

SUver, C"XH<AgO* 127

Nitrobenzoate of Methyl, CWNH^O" = C«H»O.C"XHH)« .... 127

Nitrobenzoate of Ethyl, CWNH'O* « C^H«O.C"XH^O» 128

Nitrohippuric add, CmWHH>w> = C»XAdH«,0« 129

Nitrohippurates. C»N«H7MO>« .... .... 130

Nitrobenzoate of Bibromophenyl. C^NBi^HW = C»2BraHK).C"XHK)» 132
Nitrobenzoate of Binitrophenyl. C»N»H70i« = CWX2H«0,C"XH<0> .... 133

Sulphide of Nitrobenzylenc, CMNH»S«0< = C"XH»,S« 134

6

CChllTEirTS.

C"XH^.

«^^

•^ 134

_ tss

»- IM

mc add C»NH*0» =* CWXH*0*X"H*0» _

CKaXlPAgO' ^ Aq?

itrol Elliot

^ C**XH^D» = C**AdHVO* _. _ _

rTmt^ i^ Bemwnic) Mad. C'^NttW « C»AdH>,0* „„
^**5^^,af Aoiidoben«jic«dd»C'*NIFO,SO*H + 2A<|

i^idab«i«^ c^f S^*^ Ct-KH'N.O'

j^jjjljobrfWO*tis <rf LonJ sftiJ Gikfifaer. — Amidobenfciite oT SUf«r
C«Nll*AfO«

*-iJ^bfliuw»*« '^^ *''***^ "

CONTENTS. XI

Page
Amidochloro-nucletts C^^ClAdH^

Chlorobeniamide, C"NH«aO» = CMa.\dH^O» 151

Amidonitro.nucleus C^^AdXH^.

Nitrobenwunide, C"N2H«0« » C"AdXH<,C)» 152

AnUdonitro-nucletu C^^AdX^H'.

Binitrobcnxamide, Ci<N»H»OW - Ci<AdX'H»,0» .... .... .... 153

Conjugated Amidet qf the Benzylene Series,

BeMoyl-urca, C^N'HW !. .... 154

Benxanilidc, C«NH"0» - 155

Bibcnianilidc, C«NH»0* 156

Bcnxosulphophcnamide, C^NH^SK)* .... .... .... .... 156

Silver-salt, C»NHWAgSK)». — Ammonio-silver salt,

NH»,CMNHWAgS«0« 157

Solphophcnylbenxamic acid, C^NH^^S^O^ .... .... .... 158

Benzacetosalphophenamide, C^NH^SH)^ .... .... .... .... 159

Bibenzosulphopbenamide, C«NH'*S«0* .... .... .... 159

Saccinylbisnlphophenylbibenxamide, C^'N^IP'S^O** .... .... .... 160

SulphobcnraniUde, C»N«H»«S»0« 160

Azo^nueleus, C^NH*.

Bcnxonitrile, Ci^NH* 161

Appendix : Sulphocyanobcnxylenc, CWH»,C?NS« . ., .... 163

Benzosylanilide, C«NH" « C»NH«,CMH» 165

FlaTine, C»NH»*0» 166

Compounds containing two or more Atoms qfC^*W, or qf Nuclei derived
therrfrom,

Stilbenc, C»H" 167

Sulpbide of StUbcne, C»H>«S< .... 168

Hydrobromate of Bromostilbene, C^BrH^^HBr .... .... .... 170

Chlorostabcne, C»C1H" 170

Hydrocblorate of Chlorostilbene, C»C1H",HC1 171

HydrochlorateofBichlorostilbene, C^CPH^^CIH .... .... 172

Nitrostilbic add, C»NH"0M « C»XH"OW 173

Bciuoln, C»H»*0» 173

Aoetyl-beMoIn, C«HM0« - C»H"(C<H»0»)0* 175

Bcnxoyl-bcnxoin, C^W^Cfi = C»H"(C»<H»0«)0* 176

Nitrobenxoyl-benioln, Ci^H»»0« 177

Stabousacid, C»IP20«? 178

Stawte of Potash, C»HMKO« 180

52

XH

CONTENTS.

Stilheaicaciil, C^H'°0? .... ,,. .... 181

StilbcAileofsilTer, C^H»AgSO' .... _. .... ,_ 181

BcMilicAcidC^H^^O* = CS'Hi-W^O* _ .,„ 182

BeniJktf^ of Potaah, Lmd aad Silver^ C»H"MO* .... .... 18S

CMorobenwle. C^CllPiO^ ... .... 184

Ben^ile, C^'H^^'CH „ _ 184

Hydrocjaaale, C2«»HW^»,2C*NII.., „.. .... ... 185

Appendix i& EenzUe :

Hydfobtn«ile, 0»H»05 .... 18G

Picril, C^NHi^O*orC*JNH»0* .... .... .... ,. 186

NUropicnl C«NXm^iO* or C^'NXSH^^O*.,. .... 188

TyiHi«««iiU c«H«s = om^s.c^m* ... »*. .., ... iss

BromottioneMal, C«Bf=H?S .... 189

NitrathionesMt, C»«X»H7S . .... ..* .... 189

BtbeDioylimide, C«^Hi»0> = C*AdH^SO« .... 190

Hydrobcnwrnidc, C^^N^H'^ = C«NAdH«? 191

Appendix 1o Hydretbfnxamidt i

Benxolone, C^B'O' ? _ .... ..„ 103

Benao»£ilbm, C«H»0* ? .-.. .,. .... ... .... 193

Amarine, C«N'H» = C«N^HW.H3 ? . 194
Sulphate.-Hydrochlontte, C^N'H^^.HCI.— Nitmli!. C^N^w NCH 198

ChbropUtmate, C«H=H« HCKPtCl^— AreUte ... .... 19?

TemitrohjdrobeDMmide, C«Nni»'0>3 =. C^N^^Qii _ ^ 197

Terai^rDftrine, C«N*H'*0^* =C*^N^xm^»,H=.^ ... .... 198

Lophittf, C*N*H" or C*^Nm*«; or r*2Nr*Hi? ; or C^^N^I^* 199

SyKphate ind HydHodftle of Lophme .. .... 201

HydrochbrAte.— Nitrate ..,. .... .... .... ,».. 202

LciphinB with Nitrate of SilTCf , .... .,.. 203

Lopbine with Bichloride of Piatinam ,.., .... ..it .... 203

Chlomplatmate of Lopbine .... .*.. 203

Apptmdi^c U L4>phinf i Pyrobentolioe, C^^N^Ri* ... .„. .... 204

Kit«)lophitie .„ .. .. .,.. .... 20&

Aaob*njoilidei C»«N»H" .... ... .... „.. 205

B«n*orluMidr, C^N^H"* 206

QiMdmt'i Campouiid rftaismbUiif Betiioykiotidep C"N*H'*? ,,, 207

AwMWie, C«NH^* ... .... 208

AsohBitoylp C^N^ll" ... 208

Bcnihydraffiid^C^N'H'*©* = C*^CYAdH^*,OS? ... 209
Appfndix t^ Bmthydramide :

Bf ti^.miU C**N'H^V .... 210

AtobcnKOlde, C^NMl^ or D**N«B" 211

AMbtrtioidin, C**NMI^? . ,. 211

Bwdmid^.C^Nni^O*- c^cyniwo^ .... il2

Thlobeniaidin, C«NH»»S* - C*2AdH'^5^ 2U

App^adir : Hydrwfuljihftte of Axobmioyl. C*»N'H«S» ? . 215

Ben>«ylttrc»d*, C*"K*H*0* 2lfi

Beiiiflinsm, C»KH*0 - C»AdH«»0? ,. ... 216

CONTENTS,

im

ImBbenzile, C»NH*"OS = C»AdH«,0* ..
Betifiliw, C«NiHEO< - C*«Ad»H^<

Aiobraiik, C«NH**Oa

Addends ia

Methykte of BcniyleDC, C^H^CH
ECiivkte of Benzylcne, C»H*H>< =
AnijfUte of Bcnzjlcne* C^tP»0* =
AreUte of Benxylene, C^H^^W ^
Valermte of Beitiyboe, C«H»*0» =
BeiuoBle of BeniyJcRe, C*^H*«0» =
Sulphftteof Benarykne, CfHSS^O*
Sacciiate of BcatyUne, C=^H*"0« .

ike Bentyiena-*erMt,

217

219
220

22]
221
222
223
224
225
225
225

Frimaiy nueleut C^^H*.

Totueae or Toluol, a^Ha , 226

Ujdrmte of Crcsyl, CJ*H*0* .. ._ .... 22i

SulphotoSak acid, C'*tFS=0* = C"H",2SO* .,.. .., ,.., 230

SalphotoluflUt, C"H7M,28(F .,, .... ..„ »» 231

Saltfetin,a*H'^0=.... 231

Saiigtoin, D^H*0* = C"HW,HSfO' .« ... 233

Sttlicybui idd, Cini*0< » C'*H»03,OS 235

Siiieyilteof AmtDOoia! n. Noraial,Cim*tNH*)0* .... .... 23t

h. Add .„ „ _ 240

S*licylite of PoUfh. ^ a. Normal, C^*H'KO*. — *. Acid,

C"H^KO*,Ci*H*0^ .. 240

Sulicylous add with BUulphite of Potasb, C'ni«CH,K0/2SO* + Aq 2-il

Acid SaUcylite of Sodft, a^H*NH0^C^*H«O^ + Aq .... ,... 241

SalicylDua acid with Bisulphite of Soda, C"H«O^NftO,2SO^ .... 242
SalicjUte of Bftr|tJJi, C'^H*BiiO' + 2Aq.— Salicylite of MBpifsia.^

SalicyUtff of Zinc .... . 242

Sdicylite of Lead, C"*HSO*,2PbO.— Salicylitea of Iron.— Salicy lite of

Copper, Ci^H*CuO* .... 245

S«licytite« of Mercury and Silver .... . .*.. ,.» 244

Eectoate of Salicylous acid, C=H'«0« = C"H"0*,a*H'0* „,, S44

kcttMtt of SaUcylooB acid. C^^HW = C^H^O»,C"K^O= ..,. „.. 245

SilicyUc add, 0^H*0^ = C»H*0^0* ^46

Sdkflite of Ammontap C^4H\NH')0'^ .... .... .... 25Q

uv

CONTENTS,

S«Iic7lmtc of PPtiuih* C'*H*KOfl ¥ Aq . „

Sdkjbte of B*rj to :— Neutral, C^+H^Ba^CF + 2Ai|. — Acid,

C»H5BaO* + Aq .,. »

Salicylate of Lime : — NcotraU C»*H*CaSOi + 2Al. — Add.

a*H*CftO* -*■ 2Aq.— Salicylate of Magnetic
Salicylate of Lead: — Pentabasic, C^^H* Pb»0«, 3 PbO. — Neutral »

C**H^P1^D» ..

Acid, C^*H'PbO» + Aq ,„

Sriicylate of Ci^pper i Neutzml. C"H*Cu^ + 2Aq. — Add,

C"H*CuO* + 4Aq
Salicylate of Co|jper and Potft^jiiim, C'*H*KCiiO« + 4Aq. —

Salicykte of Coppw and BAriain, C**H*B«CuO*.— Salicylate of

surer, C»il*As(>* ,

Mcthylaalicylicacid, C"'HH>« = Cm'0,C"H^O*

Potash-salt, C"iH'KO^"S<ida.iaJt.-^Biiryta-iBlt, C^«H^BaO» + A^

Neutral Sdi^jrliites of MvlbyU Etbyt and Amyl

Snocm*t€of Methyl-aalicyU C«H "0'« = 2a*H-0»,C«H*0«. — Ben*

loatc of MetbyUsalicjl, C^uUiHF » C**H?0*,Ci<HH>»
Ethylialicylic add, C'^H'^O* = C*a*O,C"H*0»

Bcniofttcof Etbyl-iilicyl, C^WHy^ - C»*H'0*,Ci*H*0»....
AmylsalicyUc add. 0**H*H>* ^ C"^H^'0,C'^H*0*

Page
260

252
252

2'4Z

2M

255
257
258

258
259

zm

260

D«fivaHve§ {behn^mff to ike Bmsenv^serieM) q/ike Acid SttUc^tk Eik€r§*

Aoiiol, O^KP ^ aa^OjC^H'O .... .„, „„ _,. 261

Sulph«iwolide, C'*H*SO^ ^ C^*H^(SO*)0» „.. 2G2

Broomiiiol. C^'H'BK^ .„. 2G2

Bibrotoaoiao!. a*H«BrW .... .« ... ... .,„ 263

Nitranbol, C>*XH'09 ..„ „ -- 253

BitraniHol, C**Xm<0= _ _ „ 264

Teriiitraniiol. C"X»H*CF ..„ »,„ „.. .... ^,. 265

Amiidiiie, C'^NH'^' - C»*AdH*OMl^ 286

Nitraniiidme,C**N'H1l« ^ C'*AdXHW.HS ., 266

SuLpKilP. C'^NH'KJs.SOnL — Hydrobmtiiate, C'*N*H»0»3rU 267
Hydrocbbrau-, C'*N*H^O^,ClH. - N!tr4te, Ci^N*li«0«,NO*ti, —

Cliloroplati!i.ti5. C^N'UHJS^HCl.PtCF 268

Bmitranbiditic, C'WH'O* =- C'<AdXni»OM|J _ _ 26«

Phcnrtol, t^'lP'^ • C*a»O.C^*H*0 .... .... .,., 270

Biinlmiitiet»rtal, U«WH*0»» « C"ri*0,C«X'HH> 271

Kiii^P**«^i«^*^**'"*'**-*'"^'H"'C>* =^ Ci^NXIlww *... _, ,_ 272

P!Mii*ro|lol.C^UW = C'"H=i0.C'^H*O .... 212

J^f^mMm i& Saiieyiic acitif

Aiiipfilkaeid,Ci(|l«0« .... ., „„ _ .., 272

OiybeaiLolc «eld. C'Hf'O* ^ _, .., ..,, 273

^ulp}u>»lico]. anrCpSS „„ .... .^ .., ,,„ 274

CONTEEfTS,

Tf

Sulphosalicylates; Neutral, C^H^M^S^^^ . _ ^cid, CWH*MS«>1* 276

+ 4Aq. : and Ci^H^KaS^O^ C^'H*K^O»= + 2Aq

Soda-ealta, O^tt*NR^S?0^' + 6Aq., and C^< H^NaS^O*^ + 4Aq,

PQt«ah.«>dA-«alt, C^m^KNaSSQ^' + SAq .„.

Baryttt-wltB ; Ci*H^Ba-&^0«^ + GAq. — and C*^H*BaS^O*= + 4Aq

27B, 279
Limc.fl4lt, C**H^Ca3S30'3 + 2Aq

276, 277

277, 278
27a

279

Zinciftlti, C"H*Zq3S20^ + GAq. — Ltt^-ialt, C"H*PIP&^0^\ —

Copper^salts, 2CoO,C^*H*Cii*S=0" + 4Aq,— aad Ci^H^Cu-S^O*^ 280

SilTer^ialt, C'*H»Agi2S?Oi* .... _ .... 281

Snlphosalicjbte of Ethyl, 2C*HK>.Ci<H^^MJi* ..„ 281

AnhydroiK Sniicyilc add, C^HPCP.O*.. »,. ..,. ..,. 2^2

Acetic Sulieylate, Cim*0*,Cni^^ ,. „^ $|»2

Bgnzoic Salicylate, Dni^0*,a*H^O' .... „ ^83

Appmidix. SalicjUde, C'^H^O" „., „., .,.. „., 2^3

Tbiotolaol, or Solphitoluol, C"H^(S03) .... .... .... ..., ^d

Os^iodme- n utleui O * I E^O^.

lodosaUejlouJiacid, a*IH*0=,0^ ,». „ 283

Bromosalicybiu add, C'^BrMH)5,03 .... _ .,,, .,„ 284

Bromaftalicylic acid, C^BrHWpO^ .... ..*. -■' „., 285

MethylbromoBalicjlic ncid, C?H50,C'^BrH<0* .... „» .„. 286

Ethf IbromosalicyUc add, C'*H*0,C'^Bi'H^O* .... ..» ,„. 28fi

Snlplude of Bromoaalicetie, C^+BrH^O^jS^ .... ^ ,.„ .... 287

Osgbrommt-mucteut C**Bi^H^O^,

Bibrotaosalkylouj acid, a^Brm*0^(F _ „„ „„ 2«7

BibromosflUcyUc acid, O^Br2H*03,0* , „ 2§a

Motliylbibromosalicylic ucid. C^^'BrH''0« „.. ,.., ,„, 289

Etbylbibromosalicylic acjd, C^'*Br=H'^0* .... .... .... .„, 290

Sulphide of H/dfOgeo and BibromoHalieede, C'*Bi^H*03.S= + gHS 200

Ttrbrotnoialieylic icid, C^*fli'HW,0* ^. .^, .... 2«Jl

Evi

COKTirCTS-

ChLomtaluoi, 0<€lW «„ ^,. ,_

B^drifchlortta of Tenjblorotolaol, C"Cl»HSHCl ....

Bihjdroehbratl! of Qdoiictilorotoluol, C^^l*H\2HCl ....
Terfaydrocbtonite of QoiiitichlorotoluoU C'^CPH*,5HCI ^

J5«iichbrx)toltnir, Ci^CJ^H* .„

Chloride of BmXicfU C»*C1H'0^

CWo«*Uicyloi« acid, C^*C1H*0J,0« _

fniloTOMlicylic Acid, CJ*CIH*CF,0* ....
Methylcyorosalicylic add, a*CIH70*

BicWofwttligemn, C»*CFH*0^2H0

iiciibfii»lic|louindd,Ci^CPH*05,<y'

Bidhtorotdkylic ftcid, Ci^CFU^tJ^.O^
Metiijtbii;liloronlic;Lb add, C'^Cini^O*
Etb|lbidiloro»iiejlicicid, C**Cl=a«0* -„

Nitrotolttol, C'^NH'O* - C^XW

Dialtrotoliiol, C"^»H*0« = U^XHi* .*.,

Clir7«niiic Kid, 0*7^H*O^* m C»*X»H*.03

CbrjMiiiiMle of Ethji, C^N»H*0»* ,

NitroMlicjIoui wld, G»NII'0" - C**XH»0>,0» ...

Ammctmii, Futa«H, urid ^kidi-iAlU. — BArjU-SAlt, Ci^NH^Uim-
Uid.iil|pO^NUW.9PbO.«

291
292

292

2tS

293

293
294
294

29T

297

297
298
299
299

^00

aut

303

341
30S

CONTENTS.

xvu

Nitrosalicylic arid, C>*NH*OW = C^^XHHiS^CH 305

Htdratedadd, C>^NH*0"^ + 2Aq .,.. 308

AmmonU-iAlt, C»*NHXNH^)0^". — Potnsh-Mlt, Ci<NH<KO»n .,.. 308
Soda*fuilt. — Baryta*ialU i Neutml, C'*NH^Ba^'» + 6^q ; Add,

CWNH^BflO'" + Aq und + 5Aq .... , 300

Uad-Mlta I Neutral, C"<NHSPb*Oi" + Aq ..„ .... _. 309

Seiqui^basic, 3PbO,2C'*NH^O0. — Acid, C'^NH*PbO^" + Aq 310

Iron Mill Copper-aalti.— McrcarouB aalt, C'^NH^Hg^Q"* + IQAq 310

SiWer-salt, Ci*NH^AgO^« 311

Mcthylnitrosalicylicarid, C^*^NH'0"' .,„ _. .„. .... 311

Etbylnitrosalicjiic Hdd, Ci*NH'0'" », „.. ^.. ,„. 312

Appendix lo Niiro^alicyiie Acid:

Kitrojybenzoicadd, a^NH*OJ<> .... .„, ..,. .,,, 3I3

Bbitroialicylic add, C»*N2H*0" ^ C"X=H^O',CH

Ammonia'salt, 0*X-H3(NH*)0«.— Potash -salts, Ci*Xm-K=0« + Aq

anda^Xm^KO''
Soda-Bait, C'^X^H^N&O*. — Raryta-saita, C"X«H>B«?0* + Aq, md
C'*X»H^BaOfl, — Silver.salt, C'^Xm^gO"
MethylbinitroafllicyHc add, C"Nni»0'* - ad'O^Ci^X^IPO^ ....

Amtnonia^ialt, a^N^H^CNH^jQi' ; — SUver-aalt, Ci^N^HMjO"
EthylbmitromlicyUo acid, Ci«N^H«0« - cqi*0,Ci*X-H5K3*
MethyltcnutroMlierlic ftdd» C^'^N^H'^O** -= CH'O.C^^X'H^OS ,...

313

315

sie

317
318
319
319

OxyGmidtf^m-nucievMt C^'^AdH^O**

SftlicyUmic add, C»NBTO^ - CWAdHW^O^ ..,, ..,. .. 320

SalicylainatCB of Baryta, Strontia, T.ime, Magnesia, Copper and

Silver, C'^NtH»M)0^ ..,. ..„ ..,. ,... 322

Salicylimidc, a*NH*0* ..» .... „„ 323

Ethjl»alicylflraic add, CJ^^NH"©* , 323

BeHMylsaltcjlamtcarid, CPNH^W »., .... .... .... 324

BcQfoylsalicylimide, C»NHW *.,. *... 325

Anthrauilicadd, C"NH*0< .,., ..., .... 326

S«Ipb«te, C^^NHW,SHO*. — Hydrochlorate, C><NmO^,ClH, —

Nitrate, CWNHR>*,NHO«. — OiaUtc (C^*NHW)-,C*H=^0« 328

Anthranilale of Lime— Anthranilate of Silver, Ci*N H^AgG* .... .... 329

Appendijr (q AnikrunttU acid .-

Chrysanilic add .... .... .... «... .... 329

SdicylisHfi add, Ci«NH"0« = C^AdlFO* .... .„ 331

NitrG-o£yamido$m'nucifm9 C^AdXH^O*.

Nitroaalicylamk acid, C»*N'H«0« =- CHAdXH*O3,0»

333

xfm

CONTENTS,

TQloidme, 0»NH* = G^'NH7,H> ^

Sulphate, C**NH»,8HO*. — Hydrochlorate, C^*NH%CIH.— Cbbro-
aurate, C»*NHi»Cl,AuCl3.-^ Cyorot>Utbate, CWNH^^Cl.PtCl*,

Chbropalladiatc.^Oxslate, Ci*NE^C*Hi'Oa + Aq

LutidmoC'^NH" - C^*AdH*,H^? ... ,„

Mercury^compound* C"NH»t2HgCl. — ChlofopUtinate,
C**NHJ*Cl,PtCl3

Page

3sa

33^
337

Vonjuffaied C&mpoundM contmnmg C**NH^ or Mimlar nmtieL

MethjMutidme, C«NH» - C»AdH^(tFH3),H^

EthylMuidine, C»NH" ^ CJ*(C*H*)NH«,W' ...

Bietliyluiluidjne, CPfiW^ = C»*(C*H*f NHSH' ,

TriethyltolQiiiine» C»N1P^ - Ci*(C*HS)*NHSH«
Metoluidine, C*WH*^ = a»CyNAdH« U^
Cyiootoluidinc, C*N*H'» ^ <FCy2Ad*H»,H* .*,*
ThiotolimiciMTid, C^*NH»S?0« = C**AdH^2SO" ....

ThiotoUmatci of Fotaah, Soda, and Baryta, C»*N(H»M)S?0* ....
Salhydramidc, C^^Nm^W

Lead -coin pound, — Tron*compouad, C'*^N^H''H>*,Fe*0'

Copper-compoand, C«N»HiK:u»0» ....

Bromowihydramide, U<*N=Br*H»*0* .,, „

CUoroaalbydramide, C^NK^mi^W

S«lkjl0Mzullde, C»NH'i03 = C"{N.UX •H*)H*,Oa

^ 339

339
340
341
341
342
343
343
344
345
34$
347
348
34S
349

UnJkmften PHmaty nudeut C^*H"*.

Pyrog aaiaciti. C'^H'CP ? ... .... ..„ ,„, „„ 349

Pyroguaiacicacid, C**H»CH - C"H«03,03> .... _ .... 330

Lead.aaU,Ci*H«O*,2Pb0 .... .... .... .... .... 331

Orcia. C'^H-^O^ « CiniW.Oa? _ „., 353

aydmud Oreio, C**H'^ + 2Aq _ , ,,„ 353

L^-c@mpouiidpC<'II*Pb^0^.2PbO .... ..^ _ 356

Tcrbrefflorcittt CWBr*li*0* ., 33fi

Chbfordn, C"CI*H*0* ..., ,,„ 357

Ororfn* C»<NH^O» or Ci''NEi»0»> ... _ .. ,„. 358

EfyUiroMc acid, C»H»0', — Leul*corapotmd, C«H»0*,PbO 339

hvewjtkrin, C»NH^«0» ,„ „,, 359

L«>wl-GDwpmiad,I^NU*K3P,3PbO .... ..» „., 369

Zioc Mid Ltad omnjiottiMia or Orcein ... ,.,, ,,., ..,, 3@1

Clipper aad SilTer oootpoimda of Onodn .««. ^.. ,.^ 3$3

CONTENTS,

XIK

CLIoforcciii, a*NCIH»0*,HCl ? , ,« ^. 362

L«ocoi-ceto,C'*NHi'0»? ..„ .„, „ 363

AioUtnim, C^*NHioOii? .... .... _ ._ ,... 3^4

Lend-compouad. D^VH«Oi»,3PfeO ,„. .... 365

Tm^comptiiitidfl, C^*Nll'^X>i^4SnO,~C»^NH«0^i,2SaO 4 2A^» and

OaNH»'»Oi»,2Sn03 + 24q .», „„ 356

ChlorftioUtmin, C^NCltl'O" .,.. «.. 360

Lettcuditmin ...^ ,... .... «... >.» «..* 357

SpmnipUtmrn, C»»H^Oi» .„. .... .... .... .... 367

Lead-componndi, C»«HW«,5PbO, ami C^H^OW^iaPbO- — Silver-

compound, Omm'^MgO .... .... 368

AEphA-«»rceui, C^NH«*0^ ... .„. _ ^.. ... 368

Lead-<:ompound, Ci^H^^O^.SPbO .... .... «.. 369

Erythroiem, C^H^O^ .... .... „„ ,„ 369

Erythrolitmin, G^^H^O^ + HO „ „ , 370

Lead-compound, C^H*»Oi«,2PbO « 370

OtveUk: add, C«H»0» = C^H^O^SCOa
Bsryta^Mlt, C'^^BaOS

Onw-llnte of Methyl. C-H»0,Ci«H7(F ,.

OfBdbite of Etbjl. U<H'^0,C4170^

LcBd-coitiptiuiid , C^H^O", 7 PbO....
AppendiJ' to Orsetlate qf Etk^l i
Amarythriii, C^Hi^O'* ?
Tckfjtiirio, C»H^"0*' ?
L*c»iM3fic auid, C=H^<0" - C^nVO^.V^^WO^

BaryU-salt, C^^ll^BaOi*."- Lead -salt
Picroerjthrin, C?*H**0** = CWH?0^C9H»0?
Efythrid Add, C*H^O»

jlj?|»«wlw: Krytlirylm, C:^H^«0»

Erythrogluciu nr Phyeite, C'^H'«0«
NitTO-erythrogltidii, C«X''H*0»

371
... 372

372
... 373

375

... 376

376
.,., 377

379
.... 380

5B1
.. 381

385
..*. 387

Cmtcehin, C*m'0» - C^m*0*,0» .... .... 367

Hjdrfttcd Cftttcbio .... ..-- — *-.- *... 391

Lead -com pound .... .... ,*.. »« ».*. 392

ji|»^«wf«» (o CflfecAm .* RiiMc acid.— Japonic acid ,., .... .»». 394

Gallic idd, C**H»0"» = C*JHHJ*.0* or C'^irO^O^ 396

GiiUjitMi TribaMic, C^nPHKi^* I — Bt*«*V, a^H*M20i" ; ^ and

3foi»o*(!#i<:, Dni*MO^^;— also ^c»^»flit» ,. i04

Gailate of Araruomn, C'^tPfNH')©"*, — GaUate of Potaah,

2C^H*£0^,C^^HS0i^ + 2Aq. — Gallate of Soda, C**ii*NaO'* 405

XX

CONTENTS.

Page

Giillaie of Biiryt*, C"H*BaO'" + ^Aq.— G&tlate of Strorvtit,

aWSrO'" + 4Aq.— Galliteof Lime, C"H*C*0» + 3Aq ... 406

GiiUatii of Magne5i*.-'Ci^H^MgK)i» + 6Act, ; ~^2C>*HmgK>» -*-
a*H*Mg30"» + iSAq,;— 0<H'Mg^"* + 2C^<H<Mg«0"> 4-

l4Ai|.;— »ndC»H^\fg*OJ" + 4Aq , 407*408

Gallrite of Aliimina. — Gallate of Munganeic, CMU'Mn^O^" +

2C'*H'Mi.=0'« + UAq.. 408

Galkte of Antimony. - G«U Ate of Bismuth, — GalUtt? of Zfnc,

C"H*Z»"-0^lZfiO.*^Stiitioous GnJUte. a*H*SllW^2SnO .... 409

GftlUle of Lead, Ci^H^PbaQ^PbO i^»&d C'*H*Fb^O«' + 2Aq 410

Gatlatei of Iron and Copper .. ... .,,. ... 410

Gttllate of Cobalt, 3C»HK:oK)W CoO + UAq|-Mid C"H*Co*0*»

+ 6Aq .... .... 410

G*llat« of NickeJ, 2C»lPNTOi(^ + a*H^NFO"' + 6Aq .... 411

Mercuroas GaQate, 2C>*H^Hg*0" + a*H^Hg3()W + 7Aq .... 411

Mercuric Gallate, 2C*M1»Hk*0'* ^ C»*H*H|»OW + 12Aq ..., 4U

Aronaonio-gallatet of Mercury ... .... .... .... 41)

A^mdir t<t Gatlic add - Bnfig^lUc acidf C^^H^O^. — TuinoEoelanb acid 4 1 2

O^ytfen^ucie^ Om*Ofi.

Chelidonlcttdd. 0^H*O'a ^ C'<H<0*,0* .... 413

CbelidoimlPi : Monetonic, C» K*MO» ^ — Bi *«»> or Nfnirai,

Chclidonatc of Ammooi*, C^^ H% N Wj^O^ ....

Cbclidoiiabej of Potash ; — Trlbaslc and Bibatio ,...

CbeliJooatc of Soda.— Tnba«ic*— iSibatk, C^'H^'aW* + Aq.—

MotiobaBic, D*H»N«0»' + lAq -Acid, C"H'NaO« C"H*0«

+ 3Aq ....
Cbelidomite of Birjim, C'^H^Bi'OW.BmO + 5Aq j^ind C^H'Ba'O'^

■f 2Aq

Cbelidonste of Scmtitla

CMMonttff of Ume, C**fPCa*0».CiO + &Aq j— C»*lTO^OW ? ilio

wm lAq mnd 6Aqj— and C»^llKaO^C'ni*0*^ + .^^q.—

Cbr lido Mate of Lime and PotiiBh. — CboUdonaf« of Maftiftia 4 17, 4 IB
ChdidonalB of Lead, Ci*HW*,6PbO( — Ci4FPb»0^,PbO and

cMiimm^

Ferroui Clieridoriate. -- Ferric Cbeltdonate, C^MKl^.PeH)*. —

Chelidonat^ of Copper
CheUdonate of Silw.— C"HA|H>" and C'ni<Ag*0«;— Cbdidoiiat*

of SUtrr Mnd C-krom, C»IlCa.\rO»
Utieoftwmdd, C^<H*0"* ^ C"ni*0*.0"
CP7itiim*edadd,r**HW^ -<- 6Aq
Mm>ii«lri, t'^H M*0'* : 0Htm'O^* and C^H'MO'*
Wfe«n4te of Ammoniap C'*H»(NH*)*0** and C>*H»tNH*)0'^

414
41$
416

416

417
417

419

42§

421
421
426
42@

CONTENTS.' XXI

Page

Meconates of Potasb, Soda and Baryta .... .... ... 427

Meconates of Lime, Magnesia, Yttria, Zinc and Tin. — Meoonate of

Lead, C"HPb«Oi< + 2Aq 428

Meconates of Iron.... .... .... .... .... .... 429

Meconates of Copper and Mercury. — Meoonate of Silver, C^^HAg'O^

andC"HUg20" 430

Ethylmeconic acid, CWH80»< = C*H»0,C"H»0» 431

Baryta-salt, CWH«BaH)»< and CWR^BaO" 431

Silver-salt, C^H^AgO^^ — Meconate of Ethylmeconic add,

Ci8H7oa CMHK)« + 2H0 432

Biethylmeconicacid,caH»20i< *« 2C<H»0,CMH«0M 433

Ammonia-salt, C2H»(NH<)0M— Baryta-salt. G«H»BaOM ... 434

Meoonamidic add, C«N7H»078 or C"NH»Oi2 > 434

Oxyamidogen-nucleuM C^^Ad^H^Cy^.
Biamidomeconic add, C"N»H«OW «* CMR^Ad^O*,©* 485

Oxyamidoffen -nucleus, C^^AdH'CH*
Gallaraic acid, CWNH70» * Ci^AdH»0<,0* 435

Primary Hucleut 0*W^.
Damaluric acid, C"H>2,0< 436

Oxygen-nucleus C"H«0«»
TannoxyUc add, C»*H«0« ^ C"H«0«,0« 437

Primary nucleus C**H".

Naphtha (Rock-oil), C"H" 438

CEnanthylene, C"H" .... .... .... ..u .... .... 445

GEnanthol, C"HW 02 446

Hydrate of (Enanthol, C"Hi*0« + Aq 448

CEnanthol with Ammonia

CEnanthol with Bisolphite of Ammonia, C"H"02,NH«.2SO* .... 449

CEnanthol with Bisulphite of Soda, C»^Hi^O»,NaO,2S03 + 3Aq 449

Met(Bnanthol, C"HWO> or C«H«0* ? 450

xxn

C1NTENT3

The io-dilled Hydride of (Enantbyl, CMH"0 or C»H«0> ? .4 50

CEQadthjUc«cid>C"H'rO* ... « 451

Ammonia and PoUsb-i»lt», — Baryta- salt, C^H^BaO*, — Lead and

Copper iaits —SUTcr-iiilt, C'^H"AgO* .-. 453

tEnanthykte of EthyU C^H*O.C**H^*0* ..,. ,.,. .... .... 454

CEmnthylate of Phenyl, C^H*0,C»H'^0* .... .... .... 454

Appendu: to CEnanthyiic acid:

_ CEnanthic acid „.. .... .... ,., .... 454

CEoanthie £tb«f ... .... ..„ .... .... 457

So-called AohydrouaCEnantbic Acid .... .... .... 459

ChlonsnAiitliJc add. — ChloreenMiUiic ether... ..,. .... 460

Chloride of CEoarvthylcJie, C^H " Cl« ... 461

Anhydfotii CEnanthjlic add« C'^H^O^CP .... .... .... 4G2

Anhydrotu BenKO-oenmChyllc acid, Benioie (Enuilhylatei or (Eiuuithylic

Benaoftte, C»HH)a,CWH«0» ... 462

Hmelic acid, C»tHi3CF.t>' ... ._ .. _ ._ 463

Baryta-salt, C'^^^Bi^O*. — Copper-talt, Cl*H»lia«0». — Siker-ealtt

C'*H«Ag=0«

Pimelate of Ethyl, 2C^HK>,Ci^H^"0*
PimelaU of Amyl, 2C"H"0,C^H»»0«...,

465
465

Terebilic acid, 0*W>0*,0* ,

Silier-ialt, C»H»AfO»

TenbiUtu of Methyl, Ethyl and Amyl .„.

467
469
469

Oilonenanlhytetie. C^K:IR>>

Chloride of (Enanthyl, C^^CIH^.O* or C»<H"0»,a

.... 469

4ro

Tiwhlomn*tttlsoU C'Kn^H'VO"

470

Amii^g^-ntititmt a*Adirw

€71

OONTBNTS. xxiii

Page
Oxyazo-nuelew CMN<H«0<.

Theobromine, C><N<H»0« - C"N<H«0<,H« ? 471

Hydrocblorate, C"N<H«0,C1H. — Nitrate, C"N<H»0<,NO«H .... 472

Nitrate of SUver and Theobromine, CWNH8CH,N0«H + NO«Ag 473

Chloroplatinate, C"N<H*CH,Ha,PtCP 473

Primary nuclPUi 0*W\
Oxygen^nuelew 0*W^Ky^.

Boheic add, CMHi0O«,O< 473

Baryta-Balt, C"H«Ba*OM + 2Aq 474

Lead-nlts, CMH»Pb»OJ« + 2Aq and C"H»PbK)tt,2PbO .... 474, 475

ADDITIONS TO VOL. VIT.

Formation of Organic Compounds Arom Inorganic Matprialt .... 477

Synthesis of Methylic Alcohol .... .... .... .... 477

Preparation of Formic acid .... .... .... .... .... 478

Thiofonnic acid, (?H»S*0» .... .... .... .... .... 479

Action of Heat on Chloride of Methyl .... .... .... .... 480

Methylophosphorons acid, P(C»H»)H«0« .... ^.. .... 481

Methylophosphoric adds, P(C«H5)H«(y» and P(C«H»)«HO« 482

Bisnlphometholic acid, C^H^S^O^ .... .... .... .... 484

Methylobithionic add, C«H<S20< 488

Iodides and Chloriodides of Tetramethylinm .... .... .... 490

Trimethylphosphine, (C»H')«P .... .... .... .... .... 491

Tetramethylphosphonium, {C^1V)*P .... .... .... 492

Nitroform, C«N»HO« = C*X3H 493

Binitrometholic add, C*H*N«0* .... .... .... .... 494

Cyanides and Ferrocyanides .... .... .... .... .... 495

ADDITIONS TO VOL. VIII.

Cyanides and Ferrocyanides .... .... .... .... 497

Platinocjanides .... .... .... .... .... .... 498

Snlphocyanides .... .... .... .... ... .... 499

Hydrate of Ethylene, or Glycol, C<H«0< 501

Acetote of Ethylene, C*H\C*HH)2)*0* 602

Glyoxal, C*H«0* 603

GlyoxyUc add, C<H<08 or C*H»0«,2H0 505

GlycoUc add, C^HW 508

XJDT CQHTE!fTS.

GljwhiVif , CqiHHy. .. ^ _ — _ _ 511

Glf«o6^C<H>0«^ _____ 511

Amie add; Acetate of Lmdbanam _ _ _ _ 512

U^de ttmd Bmuae of Ethjl _ ^^ _ _ 512

BOTateoTE^l ^. _ _ _ 513

EdiyloCritlMwkadd,C«H«S^O« _ .... _ _ 513

RwrpWflinKr add, C*gSH>" _ _ _ 516

ADDITIONS TO VOL. IX.

*

MoityloOTlpkvieada 518

AACal or Ediybte of Ethyleoe, C^H«(C«H*)SO« _ 519

Mcthylate of Ethylene, C«H«(C>H')>0« _ 520

Metbykdiylate of Etbyleoe, C«HXC>U'XC«H*)0« 520

f wpTatioe of Tricthylaiine .... _ .... _ 521

TrfalliylplMMpluiie, (C'H*)>P ..^ ^ .... 521

TctndiylplKMphoiiini, (C«H>)«P _ .... 526

McdiyltrietliylplKMphoiiiiuD, (Cm>)(C<H<)*P 528

TrfMCtkylet]qrtplioq>boiihiin, (C>H>)S(C«H*>P 528

TfiMChylaaylplKMipboiiiiim, (Cni>)>(C>*HU)P 529

TricCliyUmylplKMiplioDiam, (C«H*)*(C>*HU)P 529

Cadama-cthyl .... .^ .... .... .... .... 530

lodMe of acetyl, C«H>0>I 531

BroMoetie add, CH^BrCH ^ 532

BibnmmBetiemdd,C*WBiK)* 535

AetioB of Chlorine on Aldehyde ... .... .... .... .... 585

MoBOchlorometaldehyde, C^ITCIO .... .... .... 636

Monochlonnated Chloride of Acetyl, C^HKJPO* .... _ .... 536

Monocfaloracetic acid, C«HK10« .... .... .... .... 537

IfoBOchlo.aeetiite of Ethyl, C«H'(C^H*)C10« 540

Mooochloracetamide, CK:1H<0*,NHS 541

AcetoeyUmtne, C<H',NH« .... . .. .... .... 541

Preparation of Acetaniide and Acetonitrile .... .... .... 542

Hydrocfalorate of AceUmide, (C«NHK)>}>,HC1 543

Conponndi of Aoetantde ... .... .... .... .... 543

Biaeetamide, 0*NH70« 545

Accdiamihe, C«H«N' ... .... .... .... .... 545

Temitracetomtrile. C<(N(y)*N ... ... .... .... .... 547

Binitnunmonyl. C*(NO*)a(NH<)N 548

Bibromonitracetonitrile, C*(NO«)Br»N .... .... .... .... 550

Constitation of Fulminic acid .... .... .... .... 551

Mrtb)l.thtaldinr, C»NH»(C«H») 554

Binitro-ethylic acid, C^H^NH)* .... .... .... .... 555

ERRATA IN VOL. VII.

Page.

Line.

49 ..

27

from top, for

85 56

read

55-86.

51 ..

13

from top, , „

950 950

it

975 975.

ERRATA IN VOL. XII.

1 ..

5

from top, for

C"H2X2,02

read

C^^H'X^O^.

7 ..

14

from top, „

H»*

It

H*.

44 ..

18

from bottom, „

•Hg

»»

Ag.

47 ..

15

from top, „

H8

ti

H«.

76 ..

11

from bottom, „

OS

It

0«.

96 ..

18

from top, „

CM

tt

C«.

114 ..

15

from bottom, „

lead

tt

lime.

132 . .

22

from bottom, „

C"XH<0

C"XH*0».

189 ..

6

from bottom, „

cw

it

C».

246 ..

16

from top, „

H^

>»

H«.

262 .

9

from bottom, „

C"BrH70»

It

C"BrH702.

272 .

2

from top, „

HW

tt

Hio

291 .

1

from top, „

Br

tt

Br3.

291 .

10

from bottom, „

0^

tt

W

297 .

20

from bottom, „

CIH*

t»

C12H*.

298 .

2

from top, „

C"C12HW,02 „

C"C12H*02,0<.

313 .

. 11

from top, „

o«

o>».

313 .

. 12

from top, ,,

o«

0».

4U0 .

. 13

from top, „

H«

H«.

406 .

6

from top, „

018

o»».

465 .

4

from top, „

CIO

Q>\

COMPOUNDS CONTAINING 14 AT- CARBON.

Primary Nucleus C"H*.

Chrysammic Acid.

Bbaconnot. Ann. Chim, 68, 28.
Cheyrbul. Ann, Chim. 73, 4G; aLso Gilh, 44, 159.
LiEBio. Schw, 49, 387; Pogg, 13, 205.
Boutin. J. Phai-m. 26, 184; also N. Br. 23, 294.
ScuDNCK. Ann, Pharm. 89, 1; 65, 234.
RoBiQUET. iV. J. Pharm. 10, 178.

Mulder. Scheik. Onderz. 4, 516; 5, 173; abetr, J, pr. Chem. 42, 250;
48, 1.

From xpv<roc and a/i/ioc (sand).

Aloetic acid, Polychromatic acid. Artificial Bitter of Aloes, Aloet&ure, Aloe^
iimaure.

Formation. By tbe action of hot nitric acid npon aloin. (Stenhouee,
Ann. Pharm, 77 1 208.) Apparently also by the action of nitric add npon aporetin,
one of the constitnenta of rhnbtirb. (Do la Rue & MUller, Chem. 8oc, Qu, J. lOj
306.)

Preparation. 1 pt. of aloes is gently heated in a capacions flask
with 8 pts. of strong nitric acid, till gas begins to escape. In this action,
according to Boutin, a peculiar substance is iriven off, which he calls cyanyl^ which,
however, according to Robiquet, is a mixture of hydrocyanic and formic acids in
Varying proportions. The liquid begins to boil violently after being removed
from the fire. As soon as the evolution of gas has ceased, the mixture is
introduced into a retort and the nitric acid distilled off, 3 or 4 pts. more
of strong nitric acid then added, and the distillation repeated; the
residual liquid mixed with water till no further precipitate is thereby
produced; and the precipitate, consisting of small shiniog scales, is
washed with cold water till the water acquires from it no longer a yellow

VOL. XTI. B

2 PRIMARY MClEUS C-rl- : XmiO-NrCLEUS C"X«H*.

but a faint purple~r*?'l oi-zr. T'l^ r:?.:!::::? cHrysammic acid, still con-
taining alo^tic acM. s ::::.::j.:cI wiil i^^-•;•:•us caruonate of potash; and
the geiatinoua: nia^* wh:o>. :s :h-:r: j tormeii. with evolution of carbonic
acid, is wa^htvl w.;!i c:M \^a:cr ::/. :^e is'liole of the carbonate of potash
is renioTeJ, iht-^^n d:A5»->t I in coi"/:2^ waier, and the solution filtered; as
the liquid coo!?, tho i "rj? p^^rasli-sil: jopouraies in golden yellow laminie.
These crysiaU are •i:j«?i. Ived in l«. lire water, and decompoesed bj nitric acid;
and tho chryai;in:r.::c aoid. whx'h ?<:: antes in the form of a yellow pow-
der, is washovl i»i:h v*. li waiter. ;:I1 ibe nitric acid is completely remoTed,
and the water i< vvl.;i:rtf>i n.^ L-cj^:? yellow, but light pnrple-red. In
treating the chrysduimi.- acid wiih carbcuate vt potash, an excesa of tho
latter must be avoided as far as rcs«ible. becaase it prodnces a decom-
position and red.;er.:n^ e: tbe >al: ■ frxai admixture of aloelic acidt).
The same dewrajvsi::-.:! oveur? wl:e:: the acid, as Schnnck recommends, is
boiled with carbenate ot Jvul;^■3.

Pn-^pertUs^ Ye'^^w ponder, ofien li^L: yellow or (^reeniab yellow,
consisting of ^n;all shir.i::^ scales, t^^hunck.) B>ra;in*s polychrooMtic add
was dArk rt-d i^rv^wiK A r.*.:\:unf of il,*::* or i!>.rx*i;.* a.'ii si^es to cbrjmnmie add
an oninge i::ut\ l>\ Vo;I'v: ir: '•. <-■.' ; -v.-:.: :; iscoaT^rteu ir.ttaereen modificatioD.

(Mu^!n•.^ Tho aoM when slowly l;or.:evi in c* uuio: with the air, melts to
a brown liquid, .c'>^i:>^ % d* a lar^v ^^^uancity of gas. and diffnsing a small
quantity of grivui>h vaivur. . Sv*l.r.r.oi. i I: mehs when heated and
gives ort* rovl vajvT:rs. (Muld;r.^ T:;stes v^fry bi.ter and astringent;
reddens litmus. ^Bnuvuno:, Ku:::-. Sctunok.)'

P,'u::-'. Scharok.

Mulder.
a. h.

UC _ <t . 4i^.o . TM 39:7 .•»9*80 .... 40-C9

2N 1'^ . 1 ;•.» ... r: 2 . lJ-44 .. 1300 .... 13-5!l

2H 2 0,-> 11 l-2«) . 105 .... 1-06

12 o . _ ?.;. .. -i:»:j . 4:3 . 4359 . 4615 .... 45-26

C'N-HW- 210 HOiO . hOO . lOKO lOOOO ...100-00

Dfc&mpcfitiMkf, 1. The acid, heated in a glass Ube aealed at the
bottom, molts with copious ovoliitien of cas, but detonates immediatalj
afterwards with a br-ght fla>h, t'Uir.j: tie tulv completely with soot
and emitting a ttrong odonr of hvdroi'vauie and nitrous acids. (Schnnck.)
It detonates when ^uddenly heated ^ Praeo'.inot. Cheneul), between 300^
and 400', according to PoutiiK givin- crT carbonic oxide, carbonic add,
nitrogen, olefiai.t i::i>. l.v.In eyanic a.id, and oharet<il ^Chevrenl, B«>ntinX
emitting the o^liir if t. nnie/hvun ev;iKio:;nd n-.trcus .icids, and vieldinif
a larjc ijuiiniity ..f c urcva!. * ,Mui.ier.) — i\ When quickly heated in
contact with iLc air, it iuto;:aio* violeutiv. aud bums with a bright, vciy
fcooly flauio, leavin- a very diii!eu:;ly combu-iiblo cliareoal. (Schnnck.)

3. Dry ch'-u-.u^ i:x- dt»e.- v.v\ net up<.:i tho aiid at or»:inarv tempeia-

ture.*, but cii::.m:.!(., hydrodil-rie acid on the application of heat.

(Shunrk.)- 4. It i.< .!i>M>lvvMi Iv >.ni:j ;,./,... acuK e.^ivcially by the

fmiiii.z ari.l. lindoii iH.ilinir. i< slov.lv ci.nver:od into picric acid. — 5. By

•hatdUiion «:th chon.h rf /,^,. ,r,^\ ^.^.^^^ j^ ^i^KU chloiopicrin.

ienh..ii.f.;- 6. Oil .f v:iri.d d.»o^ n.tt act u|K>n the acid at oidiaary

efatun'i|; hut at a boilin- heat it eliminates hvponitricacid,tiilpbar>

nd, cartofiic oxnie, and carUnic acid, and 'separatca Tiolet cfciy-

N

*C11ETSAMM[C ACID.

iodin. — 7. Chrysammfc acid dissolves in 3 or 4 pU* ofjiiute sulphnrio
acitl; water a*Me<l to tbo brown solution throws dowa a green powder
(llobiqucfs chr^mmtneUde) consisting of pure cbrysaramic acid, which lias J
inerely asstttnod a dlt!ereiit eUte of aggregation, as shown by Mulder'*'^
analyaia h, Chrysaramic add ia not altered by boiling with very dilute
hydrochloric or enlpbiiric acid.

8* When chry^^mmic acid b boiled with 'poimhA^f^ carbonate of
potash, baryta- water, or lime-waterj a black-brown liquid ia produced
containing chry&utric acid. — 0. Hydromlphntf of amtymnmim^^vU tQ itj
o beautiful violet colon r, which changes to indigo-hlnc when heated^]
from formation of chrysindamide and a compound of chryeindiu witii 1
oxide of ammonium. — 10, When suiphurom fwid in oxcesg is paaset^j
into ft eolation of eh rysam mi 0 acid in ammonia, the hqutd turns brown»|
and does not yield any precipitate when treated with hydrochloric acid J
if an excess of sulphnrona acid he avoidedj the liquid aeon ires a fina
violet colon r, and hydrochlono acid tlirowa down from it a brown jelly*
(Mulder,) — 11. ProtmMorkie of tin colours the aqueous acid viol el
after a while, the colour changing to Indigo -blue when the liquid ia
heat'cd*

Combintitiona. Chrysaramic acid dissolves spariogly in cold water
(in 12j pt«. according to Braconnot, in more than 80Q pts. according to
iiehig}j forming a light red solution; more aljundantly in hot water
(in 850 pts. of water at 100"^, according to Boutin), forming a purjde-red
solution; the solution is coloured yellow by nitrie or hydrochloric acid*
In nitric acid and other minenil acida it is somewhat more soluble than
in water. In saline solutions, also, it diasolves more abundantly than in
cold water. (Mulder.)

Chrysaronnc acid ha^^ for aalifiable bases, as strong an affinity as
oitaiio acid. The chn/samiHaUa are all yellow^ mostly crystallise in small
needles or scales, and exhibit on the crystalline faces a gold -green
metallic lustre; the nmor]>hous chrysanj mates exhibit the same lustre
when rubbed with a hard body. They detonate violently when heated,
but less so than the picrates. They are all, even those of the alkalies,
but very sparingly soluble. In acetates they dissolve more readily
than in pare water, but Icm when heated than in the cold*

Chi'ygammnte of amfnania does not appear to exut, inismuch as cbryiammic add
and Aiumoiiia immediately fbrni chr^-satnmide*

Chrymmmate ofPotush. — Frepamiinn^ P* I* ^ Crystallises on cooling
from a hot solutiouj in gold -green laminrc exhibiting the most splendid
iridescence ; when quickly cooled, it separates as an amorphous red
powder. The powder is easily burnished upon glass, and then exhibits
a remarkable dichroTsm, both ty transmitted and by refiectcd li^ht. By
transom itted light polariard in the direction of the streak, its colour varies
from flesh-red to blood-red; at right angles to the streak, from rarmJuo
to crimson; by reflected light jjolansed in the direction of the streak:
steel -jfrev, pasdng into violet, or at greater angles of incidence, violet
to deep indigo; at right angles to the streak, brass-yellow, or at gre.ilcr
angles of incidence, metallic green to dark steel- hi ue» (Brewster, Hai-
dlnger* Wien. Akad. Ber. 8, 97.) — -Heated to 120° in a current of dry
air, the salt gifci off 0^5 per cent, of water (3 At. calculated quantity
8 '8). Mulder.

PRIMARY NUCLEUS C"H<: NltRO-XUCLEUS C"X5H^.

KO

14 C

.. 47-2 .
.. 840 ..
1-0 ..
.. 280 ..
.. 88-0 .

... 19-02 ...
... 33-84 ...
,.. 0-40 ...
.. 11-28 ...
... 35-46 ...

Sclmnck.

17-88 ..

34-65 ..

0-95 ..

10-69 ..

3593 ..

Mulder.
.. 18-9
.. 341

11

2N

0-8
.. 11-2

11 O

.. 350

C'^N^HKO" ..

.. 248-2 .,

... IGOOO ...

100-00 ..

.. 100-0

Scbunck dedaced from his own anulj'sisi the formula KOyC'-^N^U-O^y bat OTcr*
looked the water.

The salt detonates when heated, emitting the same odour as the
acid — It dissolves sparingly in cold water (in 1250 pts. acoordiog to
Schunck); in boiling water it dissolves pretty easily, forming a fine red
solution.

ChryMmmaie of Soda, — TIic aqueous acid immediately forms with
acetate of soda, a red jelly, which, after washing with cold water, dissolves
in boilin;^ water, and the solution, if quickly cooled, deposits the soda*
salt, in the form of a red, or sometimes a greenish yellow powder; by
slow cooling it is obtained in crystals. — Gives off 11-6 p. c. (3 AL)
water at 155°. (Mulder.) It is as sparingly soluble in water as the
potash-salt.

C»-N-HO"

;c-2

Mulder.
76-11

K»0

12-2

11-97

3 HO

11-rt

11-92

C»N-HNaO'^ + 3 A.

n ... ICOO

100-00

Chrysammatc of JJan/tn, — Formed ly mixing a solution of chloride
of liarium, drop by drop, with a boiling solution of chrysammate of potash.
Heavy precipitate of a fine vermillion colour. When rubbed with a hard
substance, it acquires a yellow golden lustre. Insoluble in water. Deto-
nates when heated. (Schunck, Mulder.) Contains 13-9 p. c. (5 At.)
water, of which only 3 At. are given off at 1 10"*; to render it auhydrouf,
it must be heated for a long timo to 154°. (Mulder.)

BaO

14 C

25-9 ...

28-5 ..

S<. hunck.

25-55 ...

30-38 ...

9-51

1-24 ...

33-32

iviuiaer
at 110^
. 25-91
. 23-30

2 N

9-5 ...

3 H

10 ...

1-41

13 O

35-1

C"N3IIBaO»-*

+ 2Aq ...

.... 1000 ...

10000

CImjRammaie of Strouiia, — A solution of a nitrate of strontia is
adiled by <lrops to a warm aqueous solution of chrysammio acid or
chrysammate of pota«h. Ijght purple salt more soluble than the Wyta-
salt. (Mulder.) ^ i f J

^^^rysammaU of Lime. — Obtained by decomposing a warm solution
ammato of potash with chloride of calcium, or by heating acetato

CHRYSAMMIC ACID. 6

of potash with cbrysammio acid. Park red, somewhat crystalline
powder. (Schonck^ Muhler.) — After drying in the air, it gives off
20 p. 0. (6 At. water) at 145°. (Mulder.)

Mulder.

CiWHO" 7M 70-4

CaO 9'9 9*4

6 HO 190 20-2

C»iN2HCaOW + 6Aq .... 1000 1000

Chrt/sammate of Magnesia. — Prepared like tbe baryta-salt. Light
red powder, soluble with tolerable facility in hot water. After drying in
the air, it contains 19*6 per cent of water^ tbe whole of which is ^ven
offatl54^ (Mulder.)

CAromie Chrytammate 13 of a dirty brown colour, and sparingly soluble.

Chri/sammaU of Manganese, — Obtained by decomposing acetate of
manganese with chrysammic acid. Has a fine red colour; dissolves in
water with tolerable facility. After drying in the air, it contains 16 per
cent. (5 At.) of water, which goes off at 145^ (Mulder.)

Mulder.

C»N2HO" 2010 .... 7J-3 7116

MnO 35-6 .... 127 12-29

5 HO 450 .... 16-0 16C5

C»*N2HMnO'- + 5Aq.... 2816 .... 1000 10000

Chrysammate of Zinc, — Chrysammate of potash forms with sulphate
of zinc a very sparingly soluble precipitate of a fine purple-red colour.
(Mulder.) SmaOl dark-red needles having a golden lustre. (Schunck.)

Chrysammaie of Cadmium, — Aqueous chrysammic acid is not pre-
cipitated by nitrate of cadmium. Chrysammate of potash forms with
nitrate of cadmium a dark purple precipitate soluble in water. (Mulder.)

Chrysammate of Lead. — a. Monobasic. — Obtained by double decom-
position of chrysammate of potash with a soluble lead-salt, or by
treating neutral acetate of lead with a warm solution of chrysammic acid.
(Mulder.) — Brickred powder. (Schunck.) Insoluble in water. Gives
off 12*6 p.c. (5 At.) water at 155^ (MuMcr.)

Schunck.

Mulder
at 155**.

PbO 111-8 .... 3574 34-19 .... 356

14 C 84-0 .... 2C-85 26-82

2N 280 .... 8-95 8-40

H 1-0 .... 0-32 0-78

11 O 880 .... 28-14 29-81

C»*N2HPbO».... 312-8 .... 10000 100-00

h, Bihaslc. — Obtained by dropping a hot solution of chrysammate
of potash into an aqueoos solution of neutral acetate of lead. Dtuk

5rcxxi3

1 ?rf> 223 « _ Sl-51 51-«

:*c ?4-ii ... if-3r nr»

ly ^ _ 2sii ... <-4* ^-m

1 a 1^ ... ♦►4» •^i

ISO «^ .- 2M5 il-3»

r y copper. — Bt Jfijyyiag a ^
4^ firiA isto a iolstkiQ of sulpkut of copfcr. a dnk ic4 powder
m ftimfGaSisd- SA^aek^ Mulcer.) It dssolTes im ksc Bore rmdilj
cIbk a eiU waler. and crj^stAliised from the boiixac solatiom cm coolii^
m 4aA pujpfa-ied aeeile/ karmf a t«IIow gofcieai lutie. (Sc^aack.)
If a* jnaaiL ail «-» aac &« &QmakieaB«r mcbebc ac»i» tkri
(Urn

MaUrr

<f Lar.

C^N^OP .. _

.-. 201-* -

. S3 34

CoO

35«

- u-u -

— !€-«

C'VHCwO^ 2l^y-S . 10»K«

THnkfirvied €%tipawtm4Mi€ ^' C.pptr^ — Pare ciursaaaue aeid it
trxtantcd vTth acetate of copper, aod tbe mixtare «lifestVd for «oaM tiaio
at »C^'. At 150% or vkea dried for a cuosidenbie tiiiw al 100% tko salt
prca «C 13^4 per ceat. <^ va:er. (Mulder.)

4 HO PC 0 U 4 . 15-7

C**X^HC»0^ -r 4Aq . 276 S lOO-O

M^rmrous Ckrymma^tc — Poiple-red, sparinglj solablo ia water.
A »xitkn of caxT— ■Iff of pDUsh if boc predpititcd by sdMmi of corrostre

/>i — aai^^*^ ^y SilfKr. — Dark brown, somewhat onrstalfiBe. Streak
ow. (Schanck.) Dark riolel crvstailine iieedles, ^larioglj
lid water, readilj ia kot. (Boaiia.) Dark Tktel» aearij
vlw. (Maidtr )

CHRTSAMMIDE« 7

C^rywaummaU qf Gold. — Prebipitated from gold solations by chr^sftin-
mate of potash ; yellowish brown. Dissolves in hot water without
•hange of colour, bat is nearly insolaUe in cold water. (Mulder.)

ChiymmmaU cf Flaiinum. — Yellow. — Obtained by dropping a
platinum solution into a warm solution of chrysammie acid, or hy
double decomposition of chrysammate of soda with chloride of platinam.
(Mulder.)

In alcohol and in eiher, chrysammie acid dissolres more readily than
in water. (Schunck.) It dissolves in 70 to 80 pts. of cold alcohol of
36^ (Boutin.)

It imparts to silk and wool a very fine and permanent crimson, violely
or blue colour, according to the mordant used. (Boutin.)

Ghrysammide.
C^*N»H^*0" = C^*HAdX«0',HO.

Schunck. Ann, Pharm, 39, 22; 65, 236.

RoBiQUBT. N. J, Pharm, 10, 177.

Mulder. Scheih 4, 486; 5, 184; abstr. J, pr, Chem. 48, 5.

Chrysammamsduref Chrysamminamide,

Preparation, 1. Dry ammoniacal gas is passed over dry chrysammie
acid at 100°, the acid then giving off water and assuming a deep violet
colour. (Mulder.) — 2. Chrysammie acid is dissolved in boiling ammo-
nia, and the dark purple solution left to cool, whereupon the chrysammide
crystallises out. (Schunck.) — Chrysammie acid is treated with excess of
ammonia, and %he resulting violet-red jelly washed with water and dried
at 100°. (Mulder.) The chrysammide obtained by boiling chrysammie acid with
ammonia, is contaminuted with cbrysatrie acid. (Mulder.)

Properties, Green needles having a metallic lastre, reddish brown
by transmitted light. (Schnnck.) Dark violet amorphous powder;
crystallises from solution in hot water in violet-gold-green laminn.
(Mnlder.)

14 C

3 N

4 H

.... 84 .

.... 42 .

4 .

... 38-53 ...
... 19-27 ...
... 1-83 ...
... 40-37 ...

Schunck.

37-21 ...

19-81 ...

2-28 ...

40-70 ...

Malder.
. 37-81
.. 19-15

207

11 o

.... 88 .

. 40-97

C^WHH)" ....

.... 218 ..

... 100-00 ...

100-00 ...

. 10000

According to this, the formation of chrysammide would be attended,
contrary to the general rule, with the separation of only 1 At. water :

CMNSHSQW + NH3 = C»WH*Oi* + HO.

8 TJZhVZ i : l-m : •*£- -. JC3C-3 *CLC3

OML tilt f^L*^! mjTtrm«» uciL jJjt^ -t * l»*r wwn? jjl '

br c&arxjicjia i^n^r i 'I — yr-KTivr js^^^f z: mma^Bl ■tttlim kit
ctijBMui-i.-* juiULiL ia-* ^i»» J I rim:" t .^> jl^jI^ «p C^XVC^, Ai

Z^ici'ikp-^^.^LL I ifinax IjfL.^ua^ir'M: aai Lam bcc act €■ ehrf-
Busrajei^ iz irLns^ i*TiTencg"& 21c -noL icued vith it, pvodneei
al-aa=k:=i:.r uli iIj^-sijilzlj: x«n>L — ^ ^ J *^^*''^'"*^ scuon c^ strong
nitn-r acil, iz. L>t r^:.*!. :r ~3 j :*:i"Hr i3a? &;wc«s w3mo« vhh nitiio
acid. chnr9aai3ii<5e ^ 7£e:ji^srse*£ in.: cajisMue acid. (SdiUDck,
Mulder.)'— S. C:li rJ ./ : :=-i.t £Lssi>** :2Jj9Ba5&.iDiHiBga jdlow
fiolntion; ani = ills K-lmfi :« iiQZ2«>^i^-T ssixed vitk a laige qoan-
tity of water, zz* 2 :xJ£ i^rrnsz* l ligarrrTiI t>:!«( coloor, and depositi
the greater pan :f :ii rlrrsi-^' i^ ii. ii* saaliesred fflate. If the
yellow soluuvn iz :€. :f -Kir-:! ••;: ti1x« w:ia a small qaaatatj of water
and heated, it loses lis e:':c^ 2^i^^*:i^i« cutwbbk add in the fora
of a jrroeaish jellvw r.:»^i=r- V. :_*z. til :f rlaiol has acted npon chiy-
sanmiic acid for a '':*=^ ;=.?- il*f'i:'.zi a:', zrls not reprodneed by water;
and on heating the I::^^I. :irjsss — '< icii s«fara;ei out. (Moraer.)

AcconliD^ to N:L::=ck J&x. FIc-^t^ i^, 5*7 vbea Krdrodibrie or nlphaiw
«rul U atideil to a b?t ftqz^:'L^ s-l .-::=. .f :l.-7Kcs>ae, the liijsfi oa cooliiig, yicMi
dark (tlive-grv*en neevilet ci cm. i.-rir? »:»>.." cri^. vbr^ss oossposldoa is either

Ctthuhiijm I.
14 (• 84 .

1?3
19*2:
40-3;

15 C 90 ....

4H ..- 4 ....

3 X 42 ....

120 96 _

3d-74

1-72

18-27

41-27

38-72

4 II 4 ....

1-88

3 N 42 ....

18-26

n 0 8S ....

41-14

C"N»11H)».... 218 ....

10000

C-N'HH)^ .... 232 ..-

100-00

loooe

/'According to Mulder, these crrstils s;« a mixture of chrymmnkle with a imaH
/|U«iiliCy of cbrys-imniir crid.) — fh? sabstanoe dusolres in water, fbnniiig a d«rk
f/urtde solulioiit and is not reprecipiuted by strong acids. It unites with saUfiaUe
Lftke*, forming wits, which Terr much resemble the chrysammates, bat may be dis-
tinguished from the latter by their^roperty of giving off ammonia when treated with
/»fj>tic noiatih. ^AtMidoehrj/sammote 0/ pctasA, prepared by treating the add with a
#/,:d fc/Jution of carbonate of potash, s^rparates when recrystallised from boQing water,
J*j:i fhr ixccss of carbonate of potash Las been remoTed by washing, in small needks,
r/^,^»iMK the metallic green luttre of chrysammate of potssh.— .^fmiiioeAprMnMMfe
*/ /S^ryta ueparatcs as a dark red crystalline powder, when a solotion of chrysammids
J; v/.M fur some time with chloride of barium, and is immediately precipitated oa
it £i»^ ti*c s'jlutiou of chrysammide and chloride of barium with ammonia.

8chund[.
, I r . 84*0 .... 28-53 29-93

4 ii ::.;.. 4o .... i-ae 177

3 X 420 .... 14-29

110 " 88-0 .... 30-05

B,0 ;*;. 70-6 ... 25-77 2511

C-*N'H«0»,B«0.. 291-0 ... 10000

▲LOERBTIC ACID. 9

According to Mulder, the precipitate formed by boiling ohryMmmide with chloride
of barium, consists of chrysammate of baryta, the Uqnid, as Schanck also found, con*
taining sal-ammoniac; when ammonia is added to a solution of chrysammide and
chloride of barium, a compound of chrysammide and baryta is deposited.

4. Strong potash-ley decomposes chrysammide at ordinary tempera-
tares^ with evolution of ammonia. (Mulder.) When the aqueous solu"
tion of chrysammide is hoiled with potash, baryta, or lime, ammonia
escapes and the liquid turns brown, yielding the decomposition -products
of chrysammic acid. (Schunck, Mulder.)

Combinations, Chrycammide dissolves readily in water, forming a
violet solution. It combines with salifiable bases. Its compounds with
soda, baryta, lime, manganoos oxide, zinc-oxide, cupric oxide, and silver-
oxide, are soluble in water.

The compound of chrysammide with lead-oxide is produced on mixing
neutral acetate of lead with a warm aqueous solution of chrysammide,
which has been freed from ammonia by continued boiling: it is nearly
insoluble in water. (Mulder.)

Mulder^ at 100%

14 C 84-0 .... 17-9 18-25

3 N 420 .... 8-9

7H 70 .... 1-4 1-56

14 0 1120 .... 24-1

2 PbO 223-6 .... 47-7 46-42

C"N»H»0^2PbO + 4H0.... 468-6 .... 100-0

When heated above 100®, it gives off ammonia, and leaves a mixture
of chrysammic acid and oxide of lead. (Mulder.)

Chrysammide dissolves in alcohol and ethfi' more readily than in
water.

Appendix to Chrysammic Add,

X

Aloeretic Acid. C^*NH»o»

E. ScHUNCK. Ann, Pharm, 89^ 24.

G. J. Mulder. ikheiL 5, 188; J. pr. Chem. 48, 14«

Foitnation, By treating aloes for a short time with nitric acid. (If
the action be longer continued, the only products are aloetio and ohiy-'
sammic acids.)

Preparation, 1. The alcoholic mother-liquor obtained in the prepa-
ration of aloetio acid (C**X*H*0*) is neutralised with chalk; the liquid
filtered from the precipitate (containing oxalate of lime, <S:c.) is precipi-
tated with neutral acetate of lead; and the precipitate is suspended in
water, and decomposed b^ sulphuretted hvdrogen: the livpid filterec^
from the sulphide of lead yields aloeretto acid by evaporation. (Muldei

8

PRIMARY NUCLEUS C*W: KITEO-KUCLEUS C**X*J

Mulder fonndj that, iu the preparatioD of cUryeammid© by the first |a#-

ces«, tbe chrysammic acid lost 4^4 per cent, of water, the quantity retjuircni
W calculation being 4 -3* — Schunck leaves it undecided whether hia
chrysammide shonld have the formula C^NIH^W^ or C»N'H»«0» As
ehiyiamo^de cotnhmes with basea, Mulder b of opinion that Schiinck*»
piep&ration contained ammonia.

3ee€mpo»iiiQm, 1 * Strong hjdrcehlQrk add does not act on chry-
amide at ordinary tempo rati! rc3> but when heated with it, prodnoii
»l*ainiiioniac and chryeammic acid. — 2. By continued action of atityog
fuirk aeidj in the eoldj or by Lolling the aqueous solution with nitric
ttcidj chrysammide id reconverted into ehrysainmic acid (Schnnck,
Mulder.) — 3. Cold oil of vitriol dissolves chrysammide, fomiiog a yellow
Bolution; and if this aoltition be immediately mixed with a large quan*
tity of water, the liquid assumes a beautiM violet colonr, and de^posiu
the greater part of the chrji^imiindo in the unaltered state. If tho
yellow sulutiun in oil of vitriol be mixed with a small quantity of wattf
and heated, it loaes its colour and deposits cbrysanimic acid in the fono
cjf a greenish yellow powder. When oil of vitriol has acted upon chry*

LAamuiic acid for a long time, the violet col our is not reproduced by water;

Iftod oa beating the liquid^ chrysammic acid se|>arated out, (Mulder*)

According to Sf^lmnck (Ann. Fhurm, 66, 237) when hydmcUlaric or tuliilmrlft

I ftdd i« add^ to a hoi ttqaeoUD Koliitiou of chr^t^mtiildc, the lU\nid on cf^oUng, Tieidi

[ dark (ilive-groeti adfidlM of amidrf*chrifmmtnic urid^ whis&t compofiilion b iiiltlicr

C^*N*U*0" (th« Mmo u thmt of chryfciuimiilO or C'-N^U'«D^^

CaicuMUm I

Caltuhiiott //.

Scliuick.

14 C

. S4 ..

. 38*ft3

15 C,,

. 90 ..,

3B^74

- 38-71

4H .

Urt^it,*ti

, 4 .,

. 1'8S

4H

*.■>«»■, i»

.. 4 ,...

1-72

„..». I'fS

SK ,

. 42 .„

. 10*27

3H

^^^ ^

.. 4a ....

18^27

...... I8'2i

410

1-

. es .

,. 40*37

12 O

. n ....

41 27

il-U

C*WH*Ow.,

21B

. 100-00

C*»N^H*0^ ..

.. 232 ...,

100*00

...... 100 M

I

(Aeeordiag to Mulder. iht» cryBtaU btv m mixture of chrysatiimitle with a tm«U
quMititj of cl^mmmic acid.) — llie Biibftanc^ disicilvf* in water, foming & dtrk
iurpi* lobitigru, and !■ not reprectpiuted bj strong acid a. It DuitcA with HOiSabl*
Piaif, forininf mJU, whtch Terf much reaemble the ehrjsam mates , but m»j he di»« h
|lBfiii*h«d from the latter bj their^ropertT of givitif ofi' aiumonin ^hen treated withfl
oaaitk potash. — Amidoehrjfs&mmah ^ pQtatAt prepared by treating I tie add with a '
told iolutian of earbonate of potash, is^pamtca when rccrjitalliied from bailing w».ttT,
after the exceti of carboiiate of potash has hctn removed by Krufhing* in small tieedi»,
poaaeaaing tbe m«Ul1tc grt^en lu&ire of cbrytammate of potiifli. — Amid9eJ^r^»amm€i*
^Msiyiii Mparatet «a a dark red cryitalliue powder, when a aolution of chrytaioiiiid*
ii boikd for aome time with eLIortde of burmin, and b immediiitifly precipitated on
mM^ the folatloa of cbrjaamuude and chlori<le of barinu tvith atnuionia.

14 C ..„...*«»......., 84*0 .... 2$-53

4 H , 4*0 ... 1-36

tN 4i*0 ..^ 14 29

11 n ,;,.. ti'O .,. 3o-*i5

B»Q ?6'e .. 25*77

C»<N»H*0»\lJaO., 29t*a ., 10000

Schunck,
. 2903
. 177

2^-11

▲LOERKTIC ACID. 9

According to Mulder, the precipitate formed by boiling chryMmmide with chloride
of bariom, consists of chrysammate of baryta, the liquid, as Scbunck also found, con*
tuning sal-aramoniac ; when ammonia is added to a solution of chrysammide and
chloride of barium, a compound of chrysammide and baryta is deposited.

4. Strong potash-ley decomposes chrysammide at ordinary tempera-
tnreS; with evolution of ammonia. (Mulder.) When the aqueous solu*
tion of chrysammide is hoiled with potash, baryta, or lime, ammonia
escapes and the liquid turns brown, yielding the decomposition -products
of chrysammic acid. (Schunck, Mulaer.)

Combinations, Chrycammide dissolves readily in water, forming a
violet solution. It combines with salifiable bases. Its compounds with
soda, baryta, lime, manganous oxide, zinc-oxide, cupric oxide, and silver-
oxide, are soluble in water.

The compound of chrysammide with lead-oxide is produced on mixing
neutral acetate of lead with a warm aqueous solution of chrysammide,
which has been freed from ammonia by continued boiling: it is nearly
insoluble in water. (Mulder.)

Mulder, at 100%

14 C 84-0 .... 17-9 18-25

3 N 420 .... 8-9

7H 70 .... 1-4 1-56

14 0 1120 .... 241

2 PbO 223-6 .... 47-7 46-42

C"N»H30^2PbO + 4U0.... 468-6 .... 100-0

When heated above 100®, it gives off ammonia, and leaves a mixture
of chrysammic acid and oxide of lead. (Mulder.)

Chrysammide dissolves in alcohol and Hha* more readily than in
water.

Appendix to Chrysammic Acid,

Aloeretio Acid. C^*NH»0".

E. ScHUNCK. Ann. Pharm. 89^ 24.

G. J. Mulder. tScheik, 5, 188; J. pr, Chem, 48, 14«

Formation, By treating aloes for a short time with nitric acid. (If
the action be longer continued, the only products are aloetio and chry-*
sammio acids.)

Preparation, 1. The alcoholic mother-liquor obtained in the prepa-
ration of aloetio acid (C'^X^U^O^) is neutralised with chalk; the liquid
filtered from the precipitate (containing oxalate of lime, <S:c.) is precipi-
tated with neutral acetate of lead; and the precipitate is suspended in
water, and decomposed by sulphuretted hydrogen: the livpid filtered
from the sulphide of lead yields aloeretto acid by evaporation. (Mulder.)

10 PRIMARY NUCLEUS C»H^ : NlTMMnrCLKUS CmX'Hs.

— t. Crude ^ajmmmie and » boiled witk ewbonmte of potash; the
liquid filtered from the ehrysamimte of potash is preeipitated bj ehlmdo
of htftriun; and the precipitate deeompoaed bj nitrk acid. (SohundL)

Pffiperiia, Brown amorphous maasL (Mnlder.) When boiled irith
nitrie add, it is eonrerted, first into aloetio, then into chrjaammie aeid.

— With potassh, doda, baryta and lime, it fimas brown, aoloble, nncrystal*
liaable salts; with the oxides of lead and silrer, it forms insolnble salts.
(Mulder.) The lea<i-oompoand prepared in the manner abore described
contained in one preparation 63*0 p. c. (o At) of lead-oxide; in another,
58*24 p. e. (3 At). The latter eomponnd was conTerted into the former
bj boiliag with water. The organic substance combined with the lead-
oxide, gave the following e(«iposition :

14 C 84 -.. 42-7 42-eO

N 14 ... M 7-40

H 3 .... 1-5 « Mr

12 O 96 ... 48-7 47-83

C"NH'0»- 197 .... 100-0 100-00

AloeticAcid. C"NWO". 1

B ScnuNCK. Ann, Pharm. 39, 24; ^5, 235.

o! J. MuLUEB. Scluik. 5, 173; J, pr Chem. 48, 39.

Formation. By the coutinued action of nitric acid upon aloes, chry-
Mainiiiic acid being formed at the same time.

J'rrp'iration, 1. Crude chrysamraic acid (p. 1), obtained by treat-
ing fi\nvH with nitric-ncid, is washed with water and boiled with
ftlrohol whirh diHHolvcs the aloetic acid and leaves the greater part of
f|,o rh/yMHiiiniic' acid. The chrysammic acid separates as the liquid
i'jfU «nd Hio filtnito when evaporated yields aloetic acid still slightly
^/'riNrr.inafid with chrysammic acid, which separates on cooling fcom
n^AuU'.u in l^oiliri- Mlc<,hol. The residual solution yields, bj CTaporatioa,
. L rryfKUi\\\u*^ nlopfir acid. (The mother-liquor reteiiis aloeretic acid.)
' 7 (tn'U^ rhryMaiiimic acid is boiled with carbonate of potash; the
U^J'a fiupfi-l from i\u^ chrysammate of potash, which senarates on cool.
.Vt rZ^'l will, rhiorido of barium; and the liquid filtered from the
' .: ' .... 'I J/,-fH;i^^ of baryta (alocretate and chrysatrato, a^rdiog to
iiJC, I- /"'^'^'i ^'^'* "'^""'^ ^^'^^^ "^^'""^ separates the aloetic acid.
lAh /

^0iijf0 Orantfe-yollow crystaUine powder. (MoMer.) YeUow
jTly-l^ (Hclieock.) Has a bitter taste and raddsoa litmos

AIiOBTIC

16 0 .,... n

2 N ^ 28

ACID.

l0S€kMn9i.
.... 41*82
.... 12-»9
.... 1-71
.... 44-78

40-781

:::::::: '{:?!

4 H 4

13 O 104

45-93

C«WH*0» .......... 232

Catculaiiim, aeeordtn^

14 C 84

2N 28

.... 10000

io Mulder.
.... 41-4
.... 13-8
.... 1-5
.... 43-3

i i

3 H 3

1-53

no 88

42-47

OWH'O" 203

Calculation.
14 C... 84 ....

.... 1000 10000

Mean of the analyses by
Schunck and Mulder.

39-6 : 41'18

2 N 28 ....

13-2

1303

4 11 4 ....

12 O 96 ....

1-8

45*4

....... 1-66

44-13

OWH^OW 212 ....

1000

100-00

41

lAorent {Compt Chim, 1850, 165) assigns to aloetic acid the formnk O^Xm^O*,
nhich requires 42-86 per cent, of carbon. — According to the formnk C^^N^H^Q^,
aloetic acid is isomeric with binitrobenzoic acid C^'*X^H^,0.

D^compoeUions, Aloetic acid treated with strong nitric acid, is com-
pletely converted into chrysaramic acid, with evolution of hyponilrio
acid^ bat without formation of oxalic or picric acid. (Schunck) :

CWN'H^O" + 2N0* = C"N2H20" + 2H0 + 2N0<.

Protochloride of tin converts it into hydroaloetio acid. (Mulder.) When
dry ammoniacal gas is passed over the acid, it takes lire even at 0%
giving off a large quantity of gas and forming a carbonaceous substance.
(Mulder.)

Combinations, Aloetic acid dissolves sparingly in cold, more abun-
dttitly in boiling water. (Mulder.)

The aloetsted are for the most part easily soluble in water.

Aloetate of Potash, — Small shining needles, which dissolve in yrtt^r
with blood-red colour, the solution when slowly evaporated depositing
long mby-coloured shining crystals. (Schunck.)

Aloetate of Baryta, — Obtained by heating aqueous aloetic acid with
acetate of baryta. Brown-red nearly insoluble powder. (Mulder.)

Mulder.

BaO 76-6 .... 27-39 27"30

14 C 84-0 .... 3004 30-77

2N 28-0 .... 10-01 9-84

3 H 3-0 .... 107 1-09

110 ..« 880 .... 31-49 31-00

C>*N»»BtO» .... 27^-6 .... 108*00 100-00

18 PAIMART NUCLEUS C^U^: MTR0-NUCLEU8 C>«X?H^

Alodate of Lead. — On mixing a solotion of aloetaie of baFyta in a
lam qoantitj of water with neutral acetate of lead, a dark red powder
if obtained inaoluble in water. (Mulder.)

CMNniH)"

2 PbO

... 2030 .
... 223-6 .

... 47-6
... 52-4 ..

Mulder.
54-5

PbO,C'*Nm»PbO"

... 426-6 .

... 1000

Aloetamide.
C"N»H«0'o = C"H>AdX«,0»,

Mulder. Sdieik. 5, 178; abstr. J. pr, Chem. 48^ 9.

Formation* By the action of dilute ammoniacal goa on aloetic acid.
— The acid diseolves in aqueous ammonia^ forming a solution of a
beautiful yiolet colour.

PreparaUon, Ammoniacal gas, largely diluted with air is parsed
oyer dry aloetic acid; the acid then loses water aud assumes a deep
violet colour.

Properties, Aloetamide is much darker in colour and much moro
kolnblo than chrysammide.

Mulder.

14 C 84 .... 39-81 39-16

3N 42 .... 19-90 20-58

6 H 5 .... 2-37 2-54

10 O 80 .... S7-92 37-72

C"NMPO'« 211 ... 10000 10000

DecomposUioHS, Nitric acid converts the compound immediately into
aloetic acid and nitrate of ammonia. Heated with hydrochloric acid, it
yields sal-ammoniac and aloetic acid. The aloetic acid thus obtained
has a green colour.

Chrysatric Acid.

SoBlTKCK. Aun, Phaf^. 55, 240.

MrLnsR. JSckeik. 5, 194; abstr. J. pr. Chem. 48, 16.

PnHlucetl by the action of alkalies, caustic baryta, or lime, on chry-
•ammic acid. Was regar^led by Schonck {Ahh. Pharat. 65, 234) as
alooretic acid.

Chrvnauiuiic acid heated with potash-lov is diissolved, forming a dark
brown ihiM from which aceite acid expels earbonio aiid formieaeid%

cniiYroDiN.

«f

13

I li^^ When strong po^li-#o1attoii is used,

! Itlitiou of an acid, hydrocyanic acid p]

riL^id ia boated with moderately strong

']=' is diissolved^ the addition of acetate of

rise to a brown precipitate of cbrysatrate of

Host TaTiTonrtm*ep,

447'2 .M. 5S-90 ........ 5871

114-0 .,.. 18-90 ........ 1908

420 ,... 5-53 , 6'5I

60 .... 0-/9 0-78

12fl0 ..., 15^82 .„ 15*92

75:) 2 .. , ICO'OO ........ 10000

" Ti 0 3 p. c. of lead oxi Je was obtumetl ; but the oi^aoic
. iimu composition. (Mulder.)

lelt, tlm solution of chrysammato of potash is
ije resulting brown precipitate he uaTnoa aloeretio
'El is precipitated by chloride of bariam, and the
I ted with B, small quantity of sulphuric acid, a
li contains baryta and wheo eYaporatod leaves a
inae containing;

?6e

72*0

23*0

4-0

720

00*27 30-&0

28*47 ». 28-03

11*22

VbS 132

lOO'OO

252*6

Cturyiodin.

heik 5, 200; abatr. J>pr. Chem, 48, ID.

mnic acid boiled with oH of vittlolj is converted, with very
^evolution of hyponitric acid, sulphurous acidj carbonic oxide,
Wiiio acidj into a dark violet substance wiiicli Mulder calls

56 C 55*1

3N 6-9

B H 1*3

2b O B6'7

Mulder.

65-50
G"35
1-90

36*26

C=«N>IPO» .

100-0 10000

din heated with strong nitric acid, yields a large quantity <
1 add yapoarSy and a red eolation, which does not cental

14

PKIMARY NUCr.EUS Om* : NITH0-NUCLEU3 C"XSH».

clirysfimiiuc nclJ* It tUssolroi in tlilute pf*t?isb-ley, forming a beautifui
viofet*coioiipeii limtld (mux wbjch it is aga»u sepanited as a violeL-c«loarcd
jelly by kydrocbloric ne\d,

ChryiofliD U but fHiiribDy eoluble in ainmonia -, the iindiasf>lTe4
pQftiQXi, after being wxabed with water, forma a blue jelly of chrymiumidet

Calcutaiion.

524

13^

Zll ,

at 120'.

5245

._..„...._, H'03

8 H

.„.....,. 2gl

13 O...

_ ...«. 3071

C»N»H'0^

... looa

10000

Tbe portion dissolved in ammonia yields by evaporation, mdigo-
Cdloured ekr^hdide if ammonium mnoiuhh in pure water, ■"

IS c

me^oHm.

49-d .....

10*3

29 ..,..
30*8 ......

Ai VZQ\

&oa

4 N .

16-4

10 11 ._._

3'2

13 0

,„......*«...

30^3

a^l^HVH}

w ^^^ ^,^^,^_

100-0 ...,

100-0

Tbia compound disholvei fea<1ily, witb oYolution of atnmonia, in"
Oftinic potaib, forming a violet solntmii wKicU is preeipltated by bydro*
cblorio acid, When beated witb bydroebloric acid» it yieldid aiuiuonta,
the colour of tbe wartii sjotutioii becomipg ligbter.

Hydiochryfiammide,

E. ScntJKCK, Ann.Phmm. 85, fi4L

Frodoeed by the action of reducing ng^nte on cbryiommje or aloello
aobL

1. Wbeii cbryiftTfimio acid is introduced into a boiling iolntTon of mil-
pbide of potassium coutaining ex€c^ of potasit, it dissolves wttb deep hhw
colour, and ibe fiolution^ on cooling, deposit* a large quantity of ncedlo-
•haptd erystals wbich are recry^il^llisod from boiling potaab-fcy, and tbeu
wi»iicd and dried.

2. Cbrv^nmniio acid ii boiled with an aqueous solution of proto-
cblorido of tin^ whereupon tbe h^ml immediately turns blue, and after
iho ejcceas of acid and of tin-salt hm bi-^n removed, and tbe re«idae
distolved in boiling jwtasbdey, ibe bydmchryuammide crystallia^a ou
emding, hot i^ difficult to frt'u from oxifle of iin.

Indi^fcj colon rod, nearly black needles, c<*piH;r'eoloure<l by refle-
l^bt^ and liaving a mot«lhe liutrvi, — Wlion Ldatod la a tubdi tbojf

HYDROCHRYSAMMIDE. 15

off violet vapours which deposit blue crystals on the cold parte of the
tabe; but the greater part of the substance is decomposed, \vith evolution
of ammonia.

Scbanck.

14 C 84 .... 50-60 50-64

2 N 28 .... 16-86 15-32

6 H 6 .... 3-61 3-52

6 O 48 .... 28-93 3052

C"N2H«0« 166 .... 10000 10000

[According to this, the substance is isomeric with nitrobeniamide » C*'*XAdH',0'|
bat as it decomposes without detonation when heated, it does not appear to contiia
bjponitric acid, and is perhaps CWAd2H20« (= C^AdSH-OSO^ ?). L.].

When heated on platinum foil, it decomposes without detonation. —
Boiled with nitric acid, it gives off a large quantity of red fumes, and
yields a dark brown liquid not containing chrysammic acid. — When
suspended in water through which chlorine gas is passed, it is gradually
decomposed and dissolved.

It is insoluble in water, but dissolves with brown colour in oil of
▼itriol, whence it is precipitated in small flakes by water. It dissolves in
caustic and in carbonated alkalies, forming indigo-coloured solutions,
whence it is precipitated in blue flakes by acids.

In boiling alcohol , it dissolves sparingly, with faint blue colour.

Haider (Sckeik, 5, 208), by heating chrysammic acid with amn^onia
and passing sulphuretted hydrogen into the warm liquid, obtained a b]ae
liqaid and a blue substance which remained undissolved: this latter he
designated as chrysindide of oxide of ammonium.

The blue liquid yielded by evaporation a blue residue, called by
Holder chrysindamide. Both these bodies contained sulphur mechanically
mixed, and were otherwise constituted as follows:

Chrysindide of Omde of AmmoHtum,

28 C ..

Calculation.

; 48-0 V

Mulder.
47-5

5 N ..

20-0

20-1

8 H .

2-3

2-5

13 O ...

29-7

29-9

1000

1000

28 C ..

5 N

ChryMindamide,
Calculation.

43-0

Mulder.
43-4

17-9

17-5

9 H..
18 O ..

2-4

2-7

36-7

36-4

100-0

100-0

Bv boiling chrysammic or aloetic acid with excess of protochloride of
Mulder (SeheiL 5, 181; J. pr, Chem. 48, 12) obtained a black-vio
irdar can««tiDg of hydroaloetaie of $lannic oxide.

16 DENZTLSKB : PRIMARY NUCLBUS 0*R^.

Mulder.
S SnO« 52*4 520

14 C 19-5 19-3

2 N 6-6 6-4

4 H 0-9 M

11 O 20-6 21-2

1000 100-0

This compound, when immersed in potash-lej, gives off ammonia, and
assumes a lino blue colour; heated with nitric acid, it deposits binoxide of
tin; and forms a red solution with evolution of nitrous fumes. In ibis
reaction, aloetic acid is first formed and afterwards cbrysamniic acid.
(Mulder.)

BENZYLENE SERIES.

A. Primary Series.
Primary Nucleus C"H*.

^. A reilnoQS body having this composition is produced by tlH action of IliiorUt
of boron on benzylic alcohol. It gare by analysis 92*86 p. c. carboh and 6'82 p.e.
hydrogen, the formula requiring 93*33 C and 6*67 H ; but the physical prBpertiei of
the Ix^y show that it is rather polymeric with benzylene, probably rtilbene C^'H*'. ▲
resinons substance having the same properties and probably also the same competition
it obtained by the action of oil of vitriol, chloride of zinc, anhydrous phosphoric acM or
anhydrous bnracic ccid on benzylic alcohol or benxylic ether. (Cannizzaro^ .^flii.
Fharm. 92, 113.)

IT. Benzylic Ether.
C'*H'0 = C"H«,HO.

Cannizzaro. Ann, Pkarm. 92, 115.

Formation and Preparation. By the action of anhydrons boracio
acid on bcnzylic alcohol. Fused and pulverised boraoic acid is mixed up
to a paste with benzylic alcohol; the mixture heated for some honrs to
between 120" and 125*^ in a closed flask placed in an oil-bath; and the
resulting hard brown mass, treated with boiling water and solution of an
alkaline carbonate to remove the boracic acid. A greenish brown oil
then rises to the surface; and on subjecting this oil to distillation,
unaltered benzylic alcohol passes over below 300^, and benzylic ether
between 300'' and 31.5*'. In the retort there remains a quantity of the resinoos
hydrocurhon above mentioned (C^U® or C^U*^) saturated with benzylic ether, which
cannot be b<-paratrd from the resin by distillation, because it decomposes at the tem-
perature required to effect the 8?paration.

Propertifs. Colourless, oily liqaid, exhibiting when viewed in certain
directions, a slight indigo tint. This colour likewise shows itself on the edsct of

OTHYL0BEN2YLIC EtHER. 17

the rennont hydrocarbon when it is saturated with the ether. Boils between 300*
and 31 5^

Cannizzaro (mean).

14 C 84 .... 84-83 84-51

7 H 7 .... 7-07 7-28

O 8 .... 8-08 8-21

Cim^O 99 .... 100-00 10000

May aUo be regarded as C»H"0« = c^H?}^^-

DecomposUwnB, 1. The ether heated in a sealed tube, a few degrees
above 315°, assumes an amber colour and is decomposed, yielding a very
small quantity of the resinous hydrocarbon, bitter almond oil (which
may be extracted by means of bisulphite of soda), and a light oil which
has the odour of toluol, C"H*, and, like that body, does not solidify in a
freezing mixtura Probably, a portion of the ether is resolved into water
and the resinous hydrocarbon :

C^&*Cfi = 2HO + C»Hi2;

and the rest into bitter almond oil and toluol:

C»H»02 = Ci^sos + C"H^

No gaseous product is evolved. — 2. The ether heated with oil of vitriol
or anhydrous phosphoric acid is converted into a resinous substance, which
appears to be identical with that which is obtained by the same means
from benzy]ic alcohol. (Cannizzaro.)

IT. Ethylo-benzylic Ether.

Cannizzaro. 11 nuovo Cimenio, 3, 397; Liebig & Kopp's Jahresherichty
1856, 581.

Vinobenzylie ether, Benzylovinic ether, Benzylate of ethyl, Ethylate of benzyl.

Obtained by the action of chloride of benzyl on ethylate of potassium:
C"H7C1 + C^H^KCP = KCl + C«Hi202.

Chloride of benzyl is boiled with an alcoholic solution of potatih in an
apparatus in which the condensed vapours can continually flow back; and
the resulting liquid is decanted from the chloride of potassium, and mixed
with water, whereupon it separates into two layers, the lower of which
is a concentrated solution of potash, and the upper, ethylo-benzylic ether.
The latter is distilled, and the portion which passes over at 185°, is dried
by contact with chloride of calcium and rectified.

Colourless, mobile liauid, specifically lighter than water, and having
an agreeable odour. Boils at 185°. Insoluble in water. ^.

VOL. xn. c

333ZTL23Z

CAjy-TTifci. 'I*.53 . ^»a. =itf?TL ?■•. :2!>: J*.i>2: »i^ll3; M^^lf.
— X;« fiZj: '/: **,w :^afcn£ij. I. *4: i 211: 3^ aXT.

f:m rsJ Frrp^xnc^: «. — I. Wjjol & «]£jisaw«f 1 tqL ftAt^

Kxc4 visa adCG&utie pca&& aad beujlk uc&nl:

SC-^HWs - ECHO = C>gqE*> • C«B^Ob.

Tks \mifA£/t f.f pcca^k L9 dJsclTcd cat W ko€ vmfter: tke aleoM dii-
t3I«i o#; vACtf xd'iai :•> tW reniie dH &W ii^sid bcni to Amm tt^
Mi^: fiiie UqixSi iLea sba^es sp «i:k ech-^r, viuek dnsSTes tke bcsij^k
mle4b#>i; tiie eifcer erpellcfi frvm th« r>I:iu*xi kj tke Wml of tke wmter-
Wk ; tl» krowtt oilj rcadse dimikd; aa-i ike^dwn'Thf rectified^ mfkr
kttraf beta delijdrucd bj fiucd fottik. — 2. Wkcn acetate «f Wnjl
<»kcaaM«l by boinn^ cbloride of bcurl or cUomoiaol vitk cMCffBtfaHJ
akr^^Ik pr.taah, is boLi«*l for a' couiiesable tiflM vitk a straw
a|i»{MiK Miotzoa of potash. &nd tbe greaser part of tbe Tiaic akoM
4utili«fl off", the pwidaal liqaii «»rpant€^ into two lajeny tke avperaioil
fl^ wbidi efwtainj bcnzjLc alcohol. Bj recti^rlnj; thu liquid and coUeei-
P? apart the f<>rtioa which gr>« orer at 204VbeiizTlx€aIeobol la obtaiaed
ia tbe pars itate.

Pr'/p^nrtUM. Coloarieas, etronzir refractbg oily liquid, baring a fiual
a^«»*ble odoar. Sp. gr. 1089 fCanniuaro) ; 1-0507 at 144^ or
1-WM at ^ (H. K<^, Jun. PAarm. 94, 313): boiliBg poiat »4*
(UaQjaaro;; 206 5' at 7514 mm. (Kopp.) Yapoar-deui^ between
3'94 and 3'85. (Canniaaro.)

Celeulci i9m,

14 C 84 77-77

«H 8 741

t O 16 14-82

o*mp ^ 106 _ 100^

VoL Dcnsi^.

C-fapov _, 14 d-8240

"-!•• - 8 0-4874

Q-f** 1 ..- 11093

AlegboUtapow.^.^ 8 7-4287

1 3-7101

BtTTER ALMOND OIL.

19

K«'

Wf'

Dmrnp^siHom. 1. The irapour pnased Uiraugh % rcd-liot tube filled
with epOTigy platinum, yields an oil which floats on water, nad is a
Iriure ofUn^ol (C^'H"), a volatile eolid body, and otber compountJa
•ai yet examined. — 2. A solution of beuiylic alcohol in bisuJphido of
carbon forma with iodide of phoephorua, a liquid which attacks the eyas
Btrongly, and appears to he hytlriodato of bcnzyleno, or iodide of ben 3^1,
C^*iri; with larger quantities of iodide of phoflphorus, a ciystallino
compound, C**H''0* is obtaineil* Cannuiuro found 72*36 p. c. C aod 6^3 H,
while the formula refiuire* 72-41 C ^nd 6'89 H. — 3* When hydrochloric acid gna
m passed into benzylic alcohol ^ the liquid becomes heated, and hydrocblorato
of ben^ylene or chloride of benzyl C"H^C1 m formed, — 4. When ben-
zyl ic alcohol 18 heated with 2 or 3 vol, of strong nitric ucid, a violent
action takes place^ continaing after the mixture has been removed from
the fire J bitter almond oil is produced and rises to the surface of tb©
liquid. ^ — 5. Aqueous cArom tc acic^ converts ben Eylic alcohol into benzoic
acid, — 6, Oil of vitriol produces a resin in soluble in water, alcohol and
ether, sparingly soluble jn NordhauKen sulphuric acid, and becoming
somewhat soft when immersed in warm water. — 7. The alcohol heated
with anhydrous phosphorw acid or with chhiide of zinc, yields a resin
^-iilar to that which is produced by the action of oil of vitriol, —
Fused boracte acid between 100'^ and 120' converts benjyitc alcohol
into beniylic ether C^*H^O [or C^*H^*0']; but at higher temperatures this
ether is converted into benzylene C^*H* [or etilbeue C**H**] (p. 16),
'ho same products are probably formed by the action of oil of vitriol,
^ ahydrous phosphoric acid, and chloride of zinc. — B, Fluoride of boron
nctd energetically and with evolution of heat, upon ben zy lie akohol,
forming boracic acid, hydrofluate of boracic acid, and benzylene C**H*
"* r fitilbene]. Fiuoride of silicinm has no action wpon benzylic alcohoL

10, When I vol. bcnuyiio alcohol is distilled with 4 or 5 vol. of a
tnrated alcoholic solution of potash in an apparatus in which ibo less
latile products can flow back, there paai^es over, after the mixture hm
become solid, a very mobile liquid, which is lighter than water,
resembles benzol, and consists of a mixture of unaltered benzylie
mlcohol, and a fluid hydrocarbon which boils at 114^ and ha« the odour
mnd composition of toIuoK Caiiniiaaro reoiarka that tbii oil is feinted lo tlie
benzylene series in the same manner h» marsh gas to the methylene aerica^ Should Ihis
Mppo*ed iJcntitf with toluol be efitabliahed, the btter roust take its pt*£e in the
hcnijlene sc^riee.

Cofiibinaiions* Benzylie alcohol mixes in all proportionfl with bi$ulphidi

of carbon, alcohotj it ha* and acdic acid.

Bitter Almond Oil,

MarteJ^* /, Pharm, 5, 289.

A. VoGEL. S^kw. 20, 06; 32, 119.

SciiRADBR, SerL Jakrk 1826; 2, 43.

BoniatTET, Ann. Chim. Phyi. 15, 29. — /, /*A^m. 8, 2D5; also iiin*

Ohim. Ph^i. 21, 250,
Staivob. Reperi. 11^ Z%^ and 361 ; 1% 80.

for

I

Vol

10 BESZTLENE SERIES : FfitUAlT SUCLEUS C»*H«*

BoBiQimr mud Boitfros CHAftLiBH. AmM^ CltM, Phsf$. 44, B52; ilsu i

WoHtEB A LtBBia Jnn. /^A<ir«. 22, 1; also Po^^^ 26, 3^8,
Wi>XKLi:ii, BepfH. 53. 2&0; 92, 328. ^Jakrh. pr. Fharm. 2% m
Lahrekt. Ann. Ckim. Ph^s, B% 23; 65, 102; 60, 181; 69, 30L— 1

#. ^*«i. CA»»>. /*%f. 1, 292; 36, 342. — /n«(. 1840, 362.—

^ev* icifTit IS, 200,
ZnfDf. Ann. Pharm. 34, 188,
EocHLEDES. ^tt»i. Pkarm. 37, 346.
VoLCKEL, Po^. 62, 444.
Lepage. J. C/nm, mctL 24, 365; abetr* X J. Pharm. 15» 4(k— |

JV, J^. PA^m. 15, 2T4.
GaEGOHY. Ann, Pluirm, 54, 372*
Quadrat^ Ann, Ph<xrm, 71, 13,
Bert AGXi»i, Ann, Pharm. 7d, 259; 85, 183,

Bt»t^Sde, LaurH mi, Kirttkieiri^frr&L Pe^ck^lt^/ oil, Pjltd^Ul^ifHlk]
IVam^^UtirieAfn^ Hydride 9/ B^znyi^ Otidt iff FitFemyi^ EMimet #«

Martr^s (lStJ3), Vogel atid Scltrader fonnd tbat almonds tiiajf htl
niade to yield, in addition to fixed oil and prus^k acid, a pecolmr volaAilr^
oil ; Staoge eliowcd tbat the crj^ tallied acid prodticid from bitttf
almond oil is benzoic acid; Robiqnct, Wobler k Liebig demonstrated ih
mode of formation of bitter almond oil ; and Wobler tt Liebig, in 183S
determined its composition and described its properties.

The amygdaliferous parts of Pomcie, Amygdale^T, and &linil*lj

eiiwt ready formed in ibe dry tiesnes of tbe plants; for tbc oil oxjjfi
from dry bitter almonds bae neither &mell nof tai^te (Martre^, Bobii
and no volatile oil j8 cictmjcted by alcohol or etUer from brni^od \
ikhnanih (Hobif|net & Boutrou Cbarlard), from dry laurel leftfi
(Wiiickler, Lepage\ or from the bark of Prunus ptidus. (WtnckltrJ
Lanret leavett treated with boll in j^ water and distille<l yield Utt]
or no bitter almond oil. (Wiucklcr, Lepage.) — Fresh laurel lemti
contain a small quantity — proportional to tlieir amount of water-
of bitter almond oil and hydroeyanic acid, which may bo ertmcted *
tther (Winekler, Lepa^); also the leavea of Prunm padm bjiA An
Mu* pfTika, (Winckler*)

Formation^ L By beating ben j^y lie alcohol with strong nitric weH,
(C&nni£juiro, Ann, Ph^rm. 88» 180.) — 2. By the action of hydride of
copj«?r on chloride of benKoyl (Chiozea, Compt rmd^ 3tj, 631,) ^3* By
thodry diatillation of sugur. (Y'6hkd,Ann. Pharm. 85, 68,) — Furfural
oUfiiGed hj tlie dry distillation of eugar, appears by it^ odoar to eonl»in
Imeiiof bitt4*r nlniiind f >iL (VtdckeL) — 4, By the action of isiotiii
bvdrt^n^ evolved by til e action of zinc or hydrochloric acid, uponcywildt
or Imsoyl (q. V.) hydrocyanic arid being formed at the aaine tiin«. Tilt
■amn tmnnfunimtion is eflectcd, thongb less quickly, by bcAtin^ Ik*
evanide of t»cnioyl with mi^rciity and bydrochJorie acid, (Kolb^^ ^iiil
rhartti, 9ft, 344.) ^-5. By the action of nitric acid upon oil of dn-
munou* (Mtildor, J, |>r, CAm, 18, 885,) By heating cinnatnio "^

21

(C'^li«0',0)CaO
benzuutc of Jiuiei

+ C*H03,CaO = Ci^ll*{>%H + Z(C«0,CO^).

form late of
lime*

bluer almond

^ith nitpJc acid or peroxide of lead, (Dumas <fc Peligot, Mulder,
Mitscherlieb*) — 6. By boiling styracin or styrono with sulpburic acid
and poroxiclo of maugaueso (Joelj Ann, Fharm, TO, 5), or styracin with
aqueous chromic acid* {Laurent.) — ^ 7* By heating stiLbene with aqueous
chromic acid. (Lanieut.) — 8. By boilings proteiu-subatances with
aqueous cliromio acid or with eulphuric acid and peroxide of manganese.
(GQckeIl>erg:er, Ann. Phmm, 64, 39 1 Keller, Ann. Pk^rm. 72, 26),—
0. By the decoinpoaition of maudelic acid. — TO, By the decompositioa
of ataygdalin. — II. By Bubjecting a mixture of benzoate and formiate

I lime, in euccossiv© small portions, to rapid dry distillation;
brown oily liquid then passes over, from which tho bitter almond oil
may be separated by combjnaiion with bisulphite of soda, (Piriai

(imcnfOf 3, 12(j; Ann, Pfutrm. t\ 104 ; Beo also Limpricht, An7i. Pharm,
Preparation^ Bitter almonds freed from fixed oil by cold prefiaingt
»/e stirred up to a thin paste with water, the mixture left to stand for
between 12 and 24 hours at the ordinary temperature (between 30"^ and
according to Bolle, iV^* Br, Aix/ij 37i 30) and then dia tilled with
tor.

If the distillation h performed over the open fire, the majis is very apt

froth over, especially, at the beginning of tho ebullition^ when tlie

ulsiou coagulates, aud forms capsular envelopes round the vapour-

►tibbles. It is necessary therefore to nse a capacious vessel, and to keep

le heat moderate at tho hegiuniug, or else to break the bubbles by

"rring, Haenle, after tnaceratin^ the almond-paste to a pulp, throws

into the still when the water is already boiling, (Iiq)ert. IS, 3B3.) —

nt t!»e surest way of preventing the mass from boiling over, as well as

>m burning) Is to distil it by a steam-heat, either by placing the almond-

ste (mixed with chopped atraw, according to Henssler, JahrLpr. Pharm.

', 367), on a cloth resting on the flat sieve-formed bottom of the etill,

d pa.*fS!ng stoam through it, or by covering the bottom of an ordinary

'ill with a layer of coarse sand several inches thick, and saturated with

ater (VelJng), or again by covering the bottora of the still with a

oderately thick layer of straw, pouring water upon this, then covering

with a coarse cloth, and pouring the almond paste upon the cloth.

iMobr,) Another method is to strain through a cloth the liquid obtained

ly macerating the almonds for 24 hourSj press the residue^ ugaiu stir it

p with water, and strain, and lastly subject to distillation the liquid

lus freed from tho greater portion of the solid matter. (Wohler, Hand-

^rterbuckf 1, 747.)

The heavy oil whicli passes over contains prussic acid and various
iroducts of decomposition {according to Henry & Plisson, J. Phan/t, 14,
■51, it consists of 74^40 p. c. C, 5-84 H, 5'9 N and 11 79 0), and there-
>re requires purification. This is effected: (a). By repeated agitation
ith potasb-le^r (I pt. hydrate of potash to 1 pt. water), (A. Vo^ol,
-hrader,) or with ferrous or ferrc^so-forric hydrate {obtained by mixmg
' aqueous solution of green vitriol or protochloride of iron with pottish
hydrate of lime (Schrader, Wtihler & Liebig, Winckler), or with

BBHZTLINE HEIES : PRIMAAT NUCLEUS

wmter mnrl m sm&ll qnatilttf of meieanc oxide (r* Iltiier)^ sud diittlltng J
-^ (^). Or bj agitating ttia oil iritb tbree or four timt^ ita ralume of &ft|
mqoeooa eolation of bi^nlpltite of soda, of 27^ B,; coUectini^ on a 5ttef 1
the cr/staHine tuaas which fonns aller aome hourg; leaYJng it to dr? oa j
r B porout tile; washing wiih cold alcohol; iheo dissol^io^ m the STiia)les||
t ^aanttty of cold vat^r; and decompoaing the solntiao with ^rhooate oil
poda> The oil whkh rises to the top of the Hc^uid is them de^niii^ tulj
dbtilled with ehlorlde of calcinm. (BertagniDl)

A qiuntitj of bitter almond oil whtch h«d mcqnired » jcflow colour frOtn tibi lnira«
^ of tke p»su, bcetBO ia the eour«e of fiT« moathi^ bla<:k-bmwii uid opftq«e> Cotton ^
t%m mttked in the oil md Hia liqaid dbtillcd i ft colourless oil then p&s^<t orer, tlic
leolonrlQf uatter iimiiBing attached to the cotton, (Schlp^nfer, Jt^eri, 12, 145.) —
I ntapectinf the preparation and puriSratioti of bitter almond ml, toe ihw G. Wblppk^ i
I PMmrm, J, IVow. 13, 597 ; and Gtotct, tfrirf. 59^,] |

^ 2. F/OOT Cyanide of Benzoyl. — Hydrochloric ncid is poured apoQ

ermnlde of benzoyl in a tnbnlated retort; heat applied suffieient to meUi

tne errstaUised cyanide; and grannlated line introduced. The OTolutloilJ

of hydro^n caused by the action of the ^nc on the hydrochloric acid,!

e^isett BB soon as the ve^el is shaken eo as to bring the cyanide of J

benzoyl well in contact with the xine, the hydrogen, as it is evolved, then |

. eofubining, partly with the cyanogen and partly with the benzoyl to forntj

bitter almond oil C"H*0\H; after a whilc^ the Uc|iiid cyanide in oontael]

with the fine acquires a yellow colour, the odour of hydrocyanic acid J

beeomes apparent, and afterwards that of bitter almond oiL A eoniW

^ domble qimntity of ^jdc is required to render the transforniattoti completi^)

( Towards the end of the opHeration, the zinc heconiei covered with a dirty |

* Vtllow unctDOQs mass, which when lieated with excess of potash-ley, if

i ooootnpoved, with formation of yellowish red oily drops; and on sdh^ic-'

^neolly distlUtDg the llqaid, bitter- aim and oil passes over in couMderahlti j

Suantity [and may he further purified by tneaas of bisulphite of aoda ji
le manner above described], (Kolbe.) — At a Uter period of the disti

I Chi ditltUate becofnea tmlkj and contains brnzotn* a bodf polfioeric «i|h bitter i
#11, To prcrvent this confervioo of the bitter almond oil into hen>oIfi» a fffrtion

I fvtkw tuictaoot inaai was diitilled with milk of lime, after addition of pmlonilp
fif iron J ttn? *lii»MI1fit^ boivever contaitifd only tracea of bitter almamt oil i hmc^ Kolbtl
aondndei i !. ■ ■ ; : >w *n*M cont&iua bitter almond oil, not merely m m rtnte of irnvtur^ f
%n| ehnnic ud « itb tome oth*r tub.^tnnde (perhaps with bjdrocTanic add M ]

p fexTih^d bjr ^ uii^'i, Foffff, G2^ 4ii), fonninjf a compound which ia druompcofd hf J

I feol ptmtk*lff, bill not bj li^rdrate t^f lime, f '

Pr^rtitM, Colourleis, mobile, itrongly refracting liquid. 6p.gr, liHI l
(WAIer A Liebig); 1*075 (Chardin Hadaucourt ; 10409 at HIT* or I
; %m$$m% 0* (H. Kopp^^jtn. Fhartn. 04, 314); boils at 180''; (according to [
) Xopp, lis bollttig point is 179*1^, when the barometer stands at 751 3 tam.) {
I *- It bat ft peouliif odour and burning aromatic taste, VVhen perfectly '
J fri# from hydroeyauie acldf it exerts merely a gtimulating not a poiaoaoni i
laolion. (Eobiqnet, Oriudley, E^peti, 37, 222; Wuhler & Frerichs, ijtii, ,
fham. 66, m$.)

tiC
30

Wlfthler Se
licbts.

II .... tPU .,^ 73*520

I ». fi'ift ft 7i6

IS ... IfiU ... U-73S .„_ UOA

.... Iff'll ....... fM

6*S0 ^...... 5-f

ni

C»H«CF.,- W

100*00 .... lOOOOO ...... 100 00

lOlhO

BlTTBIt ilLMONB OIL,

S3

W The radical ttjeory assiiin^ tUe eiUtence of ft radical, Bmmfl ^ Bi j ftnd if, as J

kmmfid bj Wdhler ^ Liebig, tbU radical = C^^'H-^O^, tbeti bitter almond oil u thg I

^^dride of beoioyl = Bill, stid bypothetical Dnhydroua benzoic acrid is B«0, or if, I

Boei^diiif io the hypQtb^&ia of BcrzeJius, Bz = C^^H^, tbea hitter almoiid oilia B^Q^HO, I
Hnd hypothetical anhydrous benzoic acid b ^zOK Laurent fi5suinei the existence oral

widical t^WtA, picramift, Pcrr = C*^H^ the oitide of which is bitter almond oil == PcrO^, I

J^ Aa bitter idmond oil treated with alcoholic potash jields benxjLic lilcohol and benzoic 1
kid, Liil U Limpricht {Ann, Phurm. 9Qj 190) suppose that it is analogous In compo-
Htion Co the compound ethersi and to be regarded as C^^B^O.C'^H'^CR ; bnt vince

pDannizzaro has actually formed the benxoate of benar^^lf and ^hown thst it possesaea J

hotaliy different properties^ it h best for the present j to regard bitter almond oil as thA 1
pdchjde of the benfjtene «eriei,

I Deeompodtiom. 1 . The vapour is not deoompoaetl hy merely passing i
Mironfli a red-hot tube (Wohler and Liebig), but when slowly passed I
Blirough ti red-hot tubo filled with fragments of pumice-stone, It b resolved
mto benzol and carbonic oxiJe gas. (Barreswil and Boudalt* If. J,
Vhatm, 6, 265}: J

I am«02 = C«H« + 2C0. 1

p. Bitter almond oil, in contact with oxy^ea gas either dry or moist, or

nrlth the air, absorbs oxygen, and is converted into heuKoio acid (A. Vogel, j

Btange^ Robiquet, Stenlioiise, Ann. Pharm, 89, 253), without tho^simnl- |

paneous formation of any other products. (Wobler and Liebig.) The I

bctioD is accelerated by beat (Stange) or by aunshiue. (Wohler St I
Ejiebig.) It burns with a Inmiuoas and very sooty flame, (A* Vogel,
RVohler (fe Lie big.)

I 4, By dry chlorine , it is eouverted into chloride of benzoyl and hydro- J

Mbh>no acid; by bromine into bromide of ben^ojl and hydrohromic acid^ |

BWuWer&Licbig): 1

I C^m O^ + 2Cl = CWR^CIO' + HCK '

pVhen chlorine gae is passed for i^3veral days into bitter almond oil^ and
■the liquid ultiniatcly warmed, there is obtained a cry^tallinQ mixture of
Kien^Eoic acid, chloride of benzoyl, and stilbcsoua acid. (Laurent*) In
moi{»t chlorine gas, hitter almond oil immediately becomes white and J
fcrystalline (A. Vogel); when saturated with tnoigt chlorine gafi, it yields i
ftenzoato of hitter almond oil, and hydrochloric acid* (Robiqiiet &
Bl. Cbarlard, Liehig, Laurent,) — 5 In cold strong nitric aeidf hitter-
mlmond oil dissolves without decomposition (Liehjg & Wdhler)i by fum-
itlig nitric acid or by a mi:iture of nitric acid and oil of vitriol, it is con- j
perted into hydride of nitroben^oyh (Bertagnini.) — By continued boiling j
prith aqueous iodic acid, hitter-almond oil is converted into benzoic aoi<L I
IWithout any formation of carbonic acid* (Mullerj Compt. rend, 19, 27L) I
|h- 7, It dissolves in cold oil of vitriol without decompoaitloni the solution I
bhen heated^ becomes purple-red, and then black, with evolution of oar- I
pionic acid, — When 1 pt, of fuming sulphuric acid is poured upon 3 pts. I
Elf bitter-almond oil^ the liquid becomes heated, ttirns brown and thick, I
bud on cooling forms a solid mixture of nnalterod bitter almond oil and I
bilbylous acid- (Laurent.) With anhydrous sulphuric acid, bitter '
^Upnd oil forms salphomandelio acid. (Mitschcrlich^ Zehrh. Aufl, 4,

W~ 8, Bitter* almond oil heated with penla^kioride of pkosphoruSf forms J
bbloride of benzylene and oxychloride of phosphorua (Cahours, CompL \
bend. 2$, 125):

I C»H«0-* + PCI* = C"H«C1* + FC1^0>.

Is. With cMorid^ ofgxdphur^ bitter-almond oil becomes aome^wWi %Vt^\^^^

*2.\ UKNZVLENE SERIES: PRIMARY lOJCLECS C^B*.

lio:il(fil, and llic liquid on cooling jields cirstmli of stilbjkNis irid.
(LauriMit.)

10. Hitlor aliiioiiil water containin;? bydrocjanic mcid, erapontcJ
wilii hjiih'iu'hhn'ic ncid at a temperature beloir 100% jields bjdroeTunte
tif liiitiT aliiiniid uii. (\i}**\Ay Poa*j. G2, 444.) On boiling tbeliqiid,
iiiaiidclic aciil is produced. (Wincklcr, Licbig, Ann. Pkarm, 18^ 310.)

1 1. Hitter alniuHil oil in contact with aqueou9 pfniatkj is conTeited in
a few wci'ks into henzoin. (llobiquct, Wohler & Liebig, LAUcnt)
'riiis traii>roriuatioii is very much accelerated by the presence of cjtnide
III' |Htt:i.'Niiiiii. — Hitter almond oil which has not been rectified, nA
iliiTelntv ruiitalns ]inissic acid, when shaken up with dilute potash ud
II I roll (il, i.s ron verted in the course of 24 boors into bensoin. The oil
livi|(ieiiily rem:iin!!i liquid after 48 hours, but if then agitated, it aoUdifici
ill 11 le\v*nuuutei». (Laurent. Amu C'lAim. /'^y^. 66, 193.)— When bittir
(iliiiiMitl (til enutainini; pi-U8oio acid, is dissolved in hot aloobolio potash, it
Mtliditie.N alter a few minutes, into a yellow crystalline mass Gonmstingof
lieii^iiin Nli^htlv eoiiiaminatod with resin. fZinin, Ann, Fkarm, 34, 186.)

N\ lieu «>i[lieV ]Mire or oomniercial bitter almond oil is mixed with \ of
it't \olunie of ueailv anliydrou:: prussic acid, and the mixtore shaken ^
with aleoliolie pit:i^Ii. there is formcii, after a while, a floocnlent predpi-
l.»le ei»uM>nu:: of C*lP\\v=0*. Pure bitter almond oil is oonTertel
into ^eusoin \x ith nearly equal fneility by contact with a weak alcoholic
mOuiiou of ev.»nide of" p.*>ta*>ium. ^/iniu. Ann, Fhamu 34, 188.) Gregoiy
ol>i.nueJ I lie >.p.ne Kmv 1\v leaviuc otMumorcial bitter almond oil for ten
\»»i \\\ i\r.;.jeT \^.\\\ >:rinij: |vta*hley. (-4h«. Pharm, 54, 371.)—
N\ \w\\ V^\w\ ,4 ir»«v..i o.: i^ he-'itisi with solid kytfrate of potash, hydro^
I V- t- e\oNed ,;ita l\v:A^:e of iv:Ash formed. (Wohler A Liebig.) — In
.»!•»•!»»: 0 v.", ;-V. owv. ..;: ot ooniao; with the air, bitter almond oil
t....M l/'\.M;e a V. .,-/., ^».;^v: tvol:.t:eu of hydrogen. (Liebig &
\\ .!,;,> ^ *;\ ,:.' .;.. ..: xi ;C.,\\k<w jvtiih upon bitter almond oil,
|.. . J', ..,••.: ' vr. :,.,,: 0;v.:vrnirv\ Jun. Pkarm, 88, 129.)
\\ : . .. J. ...•. .•.,".,.'. > '..oAT.v, w::b aUvholic potash, bensoate of
... ,,\ [■■ si ' s- ^.- ^^ :> *v. ei'v liquid which appears to be
{.; * ,. ,\' .: I ^ A I r.::. -t : :':.r-n. 90, 1J>0.>

I • \\ ; '. :. r:< a ciystalline mass con-

, », ,, x.'.U . ..-. O-N*::". — Rectified bitteralmond

\, ,; .. .-vs .^. V. '>■ •*# .vkiTvi w::h aqueous ammonia,

. .'...'. ..i. :^ : • > ^o? ^*T ^' *"* ^^^ "'■* *^

. , _;' r«rhrpuw hvdroben-

i — :^!::er almond oil set

VN . • \. : -i:>l xyzf^.-z* azmonia, is eon-

' T-oc: rjil: Ic iFowncs. Ann.

. : '.>->^'*: ' j.^:mcgs amBonia and

. :• .^ :- .^i. : i* — 4'* h^''^tr? ac oidinaiy

'MO- *-• :>.' ":*.'i.i3^ roini of the

j^ i.a.^^ .* £ whicb onsisis of

. » >•• » * *a ^r«!»a viscid resin

\ . ... .... ■ \'t^i. «l. ^A) —

} y ,...i X \yl » 1 :'!''T»iirfcf xjva, then

.. ^.•.. ^ . is!<<:*.' Ji cixataicc with

, ,, , ^ .».-: -i i:*:c a whLIe. and

'« ».« ■ .itiu '.V 'w wiiuL&ed The

. x>.,.»» .• .:>w>i .i'^ ii w-i.w crTstalline

-*% ,, ..i4:«.«i.. V Ani CttM. n^s*

BITTER ALMOND OIL.

3tf

u

Befmvwur of crmh eommtt*cial hitUr almond oU CQntmnin^ pr^tsnc
{icid and altered iy variom Infiitaices. with ammonia. — In contact with
aqueous ammoDia, tlie oil slowly beconies tiijcker, and ultimately quit© J
sol ill and friable after drying in tliD air. {Ivarls, l^off*j. 10, fi09,) When I
aminoniacal g^ is passed lkroii|j4i bitter almond ojIj the oil beconieg j
pastyj but not solid. (Laurent, Ann. Chim, Fhi/s. 62, 24.) — Commf^rdal '
bitter almond oil covered with an equal volume of strong ammonia was
conrerted in fonr weeks into a yellow resinous masa consisting of;
1. H^jdmhmmmitU, C^^^HV';^^: Bm:^^h/Hhamtdf, C^N'H^^O^; — a A
body [azobenzoilidel] sparingly soluble in ether, very sparingly in alcohol; ,
~4. Jtobejiiof/l, C*-N'H^*;-^o. B^ntoyhioiiih, C^'N^H^^ (Laurent,!
Ann, ChinuPhtfs, G6', 18; Laurent & Gerhardt, Compt. Ckim. 1850, 113,)— j
Bitter almond oil obtained from almond paste by vapour- distillation from |
above downwards, which had a yellow robur but turned brow^n after a j
wbilei was left in contact with ammonia for four wc^eke: it then betame brown 1
aud viscid, did not yield either hydrobouxamido or ben^hydramide whea
treated with boiling cther^ hut after being treated with ether and boiling
alcohol, left a residue of amorphons azohenzoid-^j C^^i*H^. (Laurent, Ann^ A
Chim. Fhys. C*% 790.) — Crude bitter almond oil wag distdled by itself, ■
and the first two- thirds of the distillate set aside with ammonia for 14
daysj and repeatedly shaken. The whole then solidified into a mnsa
consiat i ng : J . 0 f A zob c n z oy I ^ — 2 , jH eedles d i ssol v i n g with tolerabJo ■
facility in alcohol; — 3, An oily substance- Another portion of thai
same oil, spread over the flat bottom of a vessel and covered with ammo*
nia, solidified after eight days] cold ether extracted from the solid mass an
oily gubstauco, a body crystallising in needles, and azohenzoyl. The
white powder which remained undiifsolved was decomposed by hot ether
into insoluble bonioylazotide and a^obenzoidin C^N^H^, which crystal-
lised in six-aideil prisms. (Laurent, iV. Ann. Chim. Ph^/s. 1, 302*)

13. By the action of hydroi^olphate of ammonia on bitter alraoud
oil, sulphide of benzyleoe (=iC^H"S*) is prodnecd^ together with varioua
products containing sulphur and nitrogen, and differiug according to the
purity of the oil, and also according to the quantity of the hydrosulphate j
of ammonia and the nature of the liquid in which it is dissolveih — * I
Bitter almond oil freed from pruseic acid by potash and chloride of iron, '
and dissolved in S to 10 tlmea its volume of alcohol, yields sulphide of
benzylene on being mixed wiili hydro.'^ulphate of ammonia. (Laurent,
A^ Ann. Ckim. Fhjs. 1, 292.) — Oil purified iu the same manner was
distilled; the distillate received iu three separate portions; and eacb -
portion placed in contact with hydrosulphate of ammonia. The firsi j
portion became thick in four weeks, without solidifying, and when treated j
with ether left a white powder. The second portion, in the course of"
four weeks, was for the moat part, converted into sulphide of ben xylene;
the third portion still remained liquid after four weeks, but on mixing
the oil J liquid with an equal volume of hydrosulphate of ammonia, ili

Iwaa partially converted into sulphide of benzvlenc. From the productij
of the second and third portion. s, ether extrticted an oily body, which I
became solid when mixed with alcohol and hydrosulphate of ammonia, i
aud a mixture of hydride of eulphozobenxoyl with a substance which
crystallised in needles. (Laurent.) — If the distillation of bitter almond
oil purified by potash and cliloride of iron be interrupted after f hm
passt'd over, the residue deea not yield any sulphide of ben^ylene wlien
treated with alcohol and hydrosulphate of ammonia. (Laurent, Iff* Ann*
Chini, JPAi/s. 1,292.) — When a boiling mixture of B to 10 vohimce of

¥

I

^

mmi^

SKRISS: PBlMARf NUCLBUS €^mK

r f^«L kjdfoeiilphate of ummoQitt is mixed iritb m fev diop
rinH«l€i,«thiek oily precipitate Is formed, but no eulpiiid
"**■« ol I ¥oU crude bitter almond oil, 1 voL hjdjti-l
1 1 ToL annnonia wag left to stand lor a year; ao4
mm waa boiled witb ether, hjdrosulpbate of umJ
left imdisioked in the form of a white povderA
__^^_ Fi^ 1, 300»)— When 1 vol erode bitter iilmotsd
$ ar 10 tulames of alcohol and 1 vol, hydrosulphate of
5f «Ui4^ft iepamtion of sulphide of benzylofie almost
■rafwalMilea Small qoantities of bydrQ^iilpbate of
It m htSmg tkc^olic solution of bitter altnond oii
i— m Bif iiii pggmpitate of sulphide of bon^ylene. If
W Wti^ tfca %iiia Bometimes yields on cooling, loog
«f a mJk^lmmm fi«t jet ftirther examined, whick dij«
i; tlie solution when evaporated depoehi
mmmik (Uarent, A^, Ann. Ckym. PA^t, I, 2B2.}
<t<i*i>H<*" ■hiiiii oil in 5 vol ether, mixed irith 1 tqI
^ wmmmk^ iiMiiiiii in the courae of 3 or 4 i^eeks Into ^
rstalliaed from ether* yields pnn>
(lytknidin) C^BW^K (Unrent, InM.

^ np* 3it 342.) — Crude foar-year old peaeb-

^mA ftl^l^de of ammoninm (Splr, Bepitni),

I

»• ^^J^^k, ^A . ^ „__ , ^ ,_, ^-,-

^.11 kass a mMiib yellow masi of waxy eonsl^tene^^

^ti vttli eUitr, left a residue having the properljM of

«i k^ciim^^'^^^ ^^^ ^^' dissolved in pcntasislfihidd of

«bI the tdttfi^^ ehftkt?Q up with atjueous ammonia, yieldtd

Tibi kmm ■ Wllowiih oil whicjh solidified after d days. Ttit oO,

1 ia pftper, yicldod a crysTtalUne, yellowish body, which

l^Ug alcohol, and formed a red liqnid with oil of vlirioL

Ann. F^rm, 37, 34G.) — When the mixture of difftsroot

«r<Mlueed by treating hitter almond oil with sulphide ol

la distilled, water, ammonia, sulphareited hydrogen ud

mk 91151 over first, and then an mly JkuU^m mmMng of

rtilbJff^ thJonessal and lophirid. {Laaiwit, A«^ tckniif.

piafyl *tilbe»^ tUJones:*** «*.» -^i^" . ^^ -o™ «Tcn.*/,

i!^'vVh..fl bitter almond oil is mixed widi ammmi<i aad hwOphide pf

^" tIXer.1^^ proJ«icecl, the npper ol witi^h p»dnally tami «J

•^iL «tl iulpljui^tted hydrogen when tmtiMl with add, it the Miai

■^^S * todr BolMe in P«ta^h aepaiates out ; in iJie lower iiqiil,

"*^ T* *«#rilf jr'*o^l»''*^^^^^^ ^^ sulphocyanoheniylene, C"NB^p

fit liS'a- «.t «ii--;«, ^^-J

I
I

1

IL ia»t4iJ cmdiiiiHj
'*^ a dark ma^-
oil heated

^ iak>

with tfrto jWds

frooi Utiftr alBK»d oil;
a ttma iia« Mag eoa*

i aniflne, benfoyIaiiilM<J-

BITRR ALMOND OIL.

27

Combinatmm. ff, WUli mUen Bitter almond oil diesolTef in 30
paria of €ald water

6. TTt^^ BUulphUe of Ammonia^ — Sulphiie qf Ikniomim and AimmniUm.

' With a saturated salution of bisulpliitc of ammonia, bitter almond oil

nixes iu all propt>rtloD3. Tlie resulting compound cannot liowever bo

pLtained in the solid state. It appears to bo capable of dijisolving an

teem of bitter almond oil, iiiasmnch as, on adding water to a sol lit ioa of

large quantity of bitter almond oil in bisnlphite of ammonia, part of

be oil separates out, — Ammonia renders the aolulion turbid, and after

while ihrowa down a bodj baring the properties of bjdrobenzantide.

l(Bertagnim.)

e. WUh BmilpMte of Poiaih, — Wben bitter almond oil is sLaken
,p wjtb an aqueous Eolution of bisulpbite of potaeb of 20-^30'' Bm.^ a
rjstallino magma is almost immediatelj^ formed, with spontaneous rise
if temperature. The cryataUiue mass is left to drain on a filter, then
Iried on a porous tile, wasbed witb cold ulcobol, and dissolved as quickly
a^ possible in boiling alcohol; as the liquid cools, the compound separates
in crystalline lam in to.

When crystallised from i^ dilute solution, it forms beautiful crystal-
Hqo lamtnie. It dissolves very easily iu pure water, very sparingly in
water containing alkaline sulphites, and is nearly insoluble in concen-
trated Boluttons of tbose salts. In cold alcohol it dissolves sparingly, in
boi 1 i n g alee b ol readily.

The crystals do not change by exposure to the air. The aqueous or
coholic solution is decomposed by boiliug. Dilute acitJs do not act
ipon the compound at ordinary teraperaturea, but on beating tLo liquidj
utter almond oil separates. Alkalies decompose the compound^ with
formation of an alkaline eulpkito and separation of bitter almond oil,
(Bertagnini.)

a With BmlphiU of Soda. — Bitter almond oil sbaken up with 3 or
times its volume of a concentrated solution of Insulpbito of soda,
inickly forma a crystallino magma containing all tbe bitter almond oik
This crysla.1 lino mass is dried and repeatedly crysfaUliaed from hot alcobol
T 50 per cent. — The compound forms small wbite aggregated prisms
ivlng a faint odour and taste of bitter almond oil and sulphurous acid,
;issotves readily iu water, is insoluble iu cold alcohol, sparingly soluble
hot alcohol and dissolves pretty readily id hydrat^ alcohol.
(Bertagnini.)

H C

S H

ft B .....
8 O

OmH>^ + NatO,2S03 + 2Aq ..,. 219

Berta^^Qini.

31 ,.

.. 1414 .

..... 14-15

81 ..

,.. 38-36 ..

38 16

8 .

.. 3'B5 .

3-70

32 .

„ 14*61 ..

.. . 14 72

64 .

„ 29-24 -,

20-27

219 .

... leo^oo »

100*00

[Mi|- be regarideil as enlpluteor benaoinm and BOdiTam ^^ |2S0^ + 3Aq. (GerLardt.)]

The aqueous solution is decomposed by boilings the oil separating and
Ipburons acid gas escaping; the addition of free acids accelerates the

BENZYLINR SiMES; PEIMAKT HUCUUS C»H«.

ftbobol uid 1 tff 2 vol hjdroji alp hate of ammoniji \m mbeed frith afeir ^ropii
of ertid« bitter 0.1 m on (i oil, a thick oily precipitate h formefi^but oo sulphide
of HeDXjktie,— A mixture of 1 ro). crude bitter slmond oil, 1 voL hjdro-
«ulpbato of ummoum and 1 roL ammonia waaleft to stand for a year; and,
when the iiiarly aoU4 mwm was boiled with ether, hydrosulphate of bmho-
b«hso^l C**NH**S*, was left nndissolred in the form of a white powder,
( Lull rout, ^* Ann. Chim. PAyi. 1, 300*) — When 1 voL crude bitter at mend
eii tn di«*olyed in 8 or 10 volomea of alcohol and 1 voL hydrosulphat© of
aaninania gimdtiaify iKl<lod, a sepaiatlon of salphide of benzylene almosi
tlwajfi oeenxi sfter a hw minutes. Small qnantities of hydrogulphate of
iinisioiiift add«d to a hoi ling akoholio solution of bitter almond oil
immediately produce a copious precipitate of sulphide of beniylene. If
eherry-Mione otl be used, the lif|uid eometimet yielda on cooling, long
rudiated ticedlea of a «ubitanco not yet further examined, wbtch dis-
iolves readily in boiling aleoliol; the eolution when evafiorated deposits
in oil an<l cry«tallino aoalcf. (Laurent, N, Ann^ C/iym. Phpi, 1, 292.)
^ A iolutioii of crude bitter altnond oil in 5 voL eiher, mixed with 1 toI,
hydro^iulphale of annnouiuj jjolidides in the course of 3 or 4 weeks into a
crystal litjH uitiaM, which wbeu recryatalliaed from ether, yields pure
hydridti of tjulpbobonxuyl (tbiobonaaldiri) C"NH^*S*, (Laurent^ InML
1840, 30^; iV. Ann. U/nnh Phy.^. 3(1, 342.) — Crude four- year old jieach^
leaf oil **bakon up with polyaulphide of ammonium (Spir* Begnini),
depoailcd itfter 8 — U hourjs a rcddi^fb yellow ma^s of waxy consistence^
which » when washed with ether, left a residue having the properties of
■ulphido of bensylene. — The aamo oil diiwsoked in pcnta^ulphide of
pota>4^itim, nud the aolutiou ishnkcu up with ar^ueoua amiuonia, yielded i
after a fow \\m\m, a ycllowi.^i oil wbith eoHdifioi after 8 days. Thi« oil, |
when pm^iiml in pfipor, yicided a crystal line, yelbwish body, whicl^ I
diftj-oivrd in bciiliug^ alcohol, aud foimed a red liquid with oil of vitriol*
(IWhlrdLT, Ann. l-hat-m, 3?^ 340,) — When the mixture of different
tubitaneo!! produced by treating bitter almond oil with sulphide of
amitioniiiiil Is dittilleil^ watery amntouia, sulphuretted hydrogen aufl
•eveml oils |m«a over ttint, and then an oily distillate consisting of
piorri* stilbone, thioaes^il and lopbitio. (Laurent^ i7«v, menii£

14. When bitter almond oil is miied with ammonia and bmdpkidt of
mr^m, twu layers are produeedi %ko upper of which gmdually tnms red
md givo« o^ »ulphu retted hjnlltifei when Ireated with acid, at the aame
tlaio thai a body soluble in potaah sepamtee out ; in the lower liquid,
mlMnkm^ generally granular crystals of sulphooyanobentylene, C"NH^^
«re formed, but j{<eneratly disappeiar again if Mi for some time In ih«
tiquHK (Quadrat, Anm. Pkarm. TU 13.)

15. Piitu»lim does not iliniiiiile hydrogen from bitter almond otl |
but th« intlftl ftadaally diiaMetfe» Ibe nil ml the auue time beiiif oom.
varied ills m 4aA wmm. (Lowig« l^krim^ f, 630.) — le and 17.
Bttt«r ^mmA ml h«iled with Mi-ta jieldi m mAH wmm el beuey^

and with anilUie^ beeeeylaaUUe:

(LattffeiiiaQfdiA7ih» €^mpt. OUb, ll$t, IIT.)

BITTIR ALMOND OIL. 27

(hmhinatiom* a. Witli wUer. Bitter almond oil diasolres in 80
pvtt of eold w»t€r.

h. With Buulpkiie of Ammonia, — Sulphite qf Benzo*um and Ammonium,
— With a tetnrated solution of bisulphite of ammonia^ bitter almond oil
mixM in all proportions. The resulting compound cannot however be
obtained in tne solid state.^ It appears to be capable of dissolving an
esceis of bitter almond oil, inasmuch as, on adding water to a solution of
a bnm quantity of bitter almond oil in bisulphite of ammonia, part of
tiie ou separates out. — Ammonia renders the solution turbid, and after
a while throws down a body havbg the properties of hjdrobenzamide.
(Bertafnini.)

e. With Bisulphite of Potash. — When bitter almond oil is shaken
up with an aqueous solution of bisulphite of potash of 20 — 30"" Bm., a
onrstalline magma is almost immediately formed, with spontaneous rise
of temperature. The crystalline mass is left to drain on a filter, then
dried on a porous tile, washed with cold alcohol, and dissolved as quickly
as possiUe m boiling alcohol; as the liquid cools, the compound separates
in o^itiUline lamioas.

When crystallised from a dilute solution, it forms beautiful crystal-
line lamins. It dissolves very easily in pure water, very sparingly in
water oontaining alkaline sulphites, and is nearly insoluble in conoen-
iiated solutions of those salts. In cold alcohol it dissolves sparingly, in
boiling alcohol readily.

The crystals do not change by exposure to the air. The aqueous or
alcohoUo solution is decomposed by boiling. Dilute acids do not act
upon the compound at ordinary temperatures, but on heatin/^ the liquid,
bitter almond oil separates. Alkalies decompose the compound, with
formation of an alkaline sulphite and separation of bitter almond oil.
(Bertagnini.)

€. With Bisulphite qf Soda, — Bitter almond oil shaken up with 3 or
4 times its volume of a concentrated solution of bisulphite of soda,
quickly forms a crystalline magma containing all the bitter almond oil.
This cr3rstalline mass is dried and repeatedly crystallised from hot alcohol
of 50 per cent. — The compound forms small white aggregated prisms
havinff a foint odour and taste of bitter almond oil and sulphurous acid.
Dissolves readily in water, is insoluble in cold alcohol, sparingly soluble
in hot alcohol and dissolves pretty readily in hydrat^ alcohol.
(Bertagnini.)

NaO..

14 C

8 H

2 8

8 O

BerUgnini.

31 ..

.. 14-14 ...

1415

84 ..

,.. 38-36 ..

3816

8 .,

... 3-65 ..

3-70

32 .

... 14-61 ..

14-72

64 .

.. 29-24 ..

29-27

119 .

... 100-00 ..

100-00

C»«HH)« + NaO,2SO» + 2Aq .... 819
[May be r^;arded as tnlphite of benzoram and sodium ^^ |2S0S + 3Aq. (Gerhardt.)]

The aqueous solution is decomposed by boilinj?, the oil separating and
snlphurona acid gas escaping; the addition of tree acids accelerates the

2B

BENZITLKNE SERIES: PRIMARY NUCLEUS C^m*.

deeotnpesittoti. Dilute acida do not act upon the compound nt ordinary
teTupcmtures. Caustic alkulies and their carbonates produce turbidity,
aad fieparate the oiL — Iodine and broniiue diseoh^a witliout colour in tho
ac^ueous solution, aulphato of eoda being formed and the oil eeparatcd.

Tlio coinpound may be preserved without alteration in cJosed ve»$eJ3|
and changes but very blowly in contact witb the air. When heated in
the air, it is decomposed without charring, bitter almond oil volatilbin^,
aud the eulpbite beings oxidised. In a strejim of hydrogen, It gives off
water and bitter almond oil, even below 100°* Nitric acid converts the
Bulpbite into sulphate and separatee the oil.

The aqueous solution forms with chloride of lariitm a copious pre-
cipitate soluble in hydrochloric acid, and containing a portion of tbe oil,
Lead and iiiver-Bnlts ate precipitated in like manner,

«, With Bkhhiith of Tin, bitter almond oil yields a compouuil which
forms fine cryetaU, but is diftlcult to purify and decomposes when dried
in the air or in vacuo. (Lowig. Compt. rend, 21, 371 ; abatr, •/. pr. Chem*
37, 480)

/' Wt(Ji 71^ J f oceanic acid. — When bitter almond water mixed with
bydrochloric acid is evr a p orated at a temperature short of lOO"", this
compound separates, when only a amall quantity of liquid is left, in the
form of a yellowish oil, which may be freed from adhering hydrochloric
acid by repeated aj^itattoa with water, and dried in vacuo over oil of
TjtrioL

yellowiah oil, nearly inodorous and having a bitter taste. Boils at
170°. Sp. gr.= I'12i. Dissolves sparingly in water, (Volckel.)

16 C _„,

,„ 9S ... 72* IS ...
.., U ... 10 53 ...
... f «« 526 .-
.,. U .... 12CKI ...

VfalckcL

N

7 H ..„„..

2 0 .......^.....

.., 5-34
..... 11*67

C^*H«0«,C«NH „ ,

.„ 133 .

100 00 .„

... 10000

It is partially deeompoged even at 1 00"", and when boiled ii resolved
into hydrochloric acid and bitter almond oil. FoU^^h innnediately forms
cyanide of potasMi urn and liberates the bitter almond oil. — When tbd
compouod is evaporated w»lK hydrochloric aeid* water is taken up, and
jiabanimoninc and mandelic acid produced. (VolckeL)

it disiolves readily iq alcohol and ether, (V'olckel.)

g. Wiih Cj^nic acM. — WLea cyanic acid vapours are pasted into
bitter almond oil, great beat is evolved, and a white heavy bo<^ separates
wliJcU incteues on addition of ether — WbUe po^-der soluble in aleohol
«nd cryitallising tberefrom. (Llebig, Jnn. Fharm, 23, 140.)

h. Bitter almond oil dissolves in all proportions in alct^hol ftnd eihtr.

BITTER ALMOND OIL. 29

Appendix to Bitter Almond Oil

Laurd-oU, — From the fresh leaves of Prunus Lauroceratus. Light
yelloWy hearier than water, having a strong balsamic taste and smell.
(Spandaw de Celli^.) — In contact with the air, it is converted into
benzoio acid, and likewise yields this compound in contact with moist
dilorine gas. (Stanee^ Eepert. 14, 829.) — When treated with lime-
water and afterwards with chloride of iron, it forms prussian bine.
(Roloff, A. Oehl. 1, 662.)

Peach'Uaf oil contains, in addition to bitter almond oil, an oil having
the odour of the fresh leaves and fruit of the peach, quite different from
that of bitter almond oil. (Winckler, Bepert, 67, 159.) Produces ben-
zoio acid. (Bragnatelli, Ann, Chim, 96, 96.)

OU of tlie Portugdl Laurel, — May be obtained from the bark, leaves,
flowers and seeds. — Transparent, colourless oil, heavier than water.
Contains hydrocyanic acid and produces benzoic acid. (Giese.) Con-
tains a peculiar volatile oil, which has a pungent disagreeable odour and
does not form benzoic acid when exposed to the air. (Winckler, JRepert
67, 1, 56.)

Bitter almond waler; Laurel-water; Cherry-water; Aqua amygda-
larum amararum; Aqua laurocerad; Aqua cerasorum'^sxe essentially
aqueous solutions of bitter almond oil containing prussic acid, as they
are generally obtained, together with bitter almond oil, in the distilla-
tions of parts of plants containing amygdalin and emuLsin. (According
to WiudleT^ JRepert. 52, 289, they contain cyanide of benzoyl.) — For
the preparation of these liquids the following directions have been
given :

a Bitter almond water, — 1. The residue of 2 pounds of bitter almonds
completely freed from fixed oil by pressure between hot iron plates, is
stirred up to a thin paste with cold water in a distillatory apparatus
which admits of being closed, and distilled after 24 hours digestion; the
distillation is best performed by means of steam (compare p. 21) or in a
chloride of calcium bath. Two pounds of the distillate are collected.
(Geiger.) — 2 pounds of bitter almonds freed from fixed oil by cold press-
ing, are stirred up with 10 lbs. of water, 4 oz. of highly rectified alcohol
added, and the mixture distilled till 2 lbs. of liquid have passed over.
(Pharmacopbor,) The addition of alcohol before the distillation is said
by some to diminish the amount of prussic acid in the distillate; others
on the contrary maintain that a stronger water is thereby obtained.
To these prescriptions, are annexed Tarious appendices, which for the most part directly
contradict each other. Compare Gassier (N, Br. Arch, 10, 50), Mohr, Commenta zurpr,
Pkarmaeopoe, §. 210), Pauls (N, Br. Arch, 48, 154.) According to the Parisian pharma-
oopoeia, a double qoantity, and according to the Saxon, a treble quantity of water should
be distilled oflT.)

* Notwithstanding every precaution, bitter almond water is often
obtained of different composition and strength by the same mode of
preparation. In general, it is a more or less milky liquid smelling and
tasting strongly of bitter almond oil containing prussic acid. The addition
of ammonia produces a strong milky turbidity, the more quickly as the
liquid is stronger. (Veltmann, Ann, Pha^^m, 34, 235); Lepage, J. Chim.
mid. 24, 371.) — (According to Weber, it is not altered by ammonia
jT. Br, Arch, 85, 32.) — Its therapeutic action depends on its amount of
prussic aoid as well as of bitter almond oil. According to Duflos {Pharm.

28 DBNZYLKNE SERIES : PHIMARY NUCLEUS OniK

decomposition. Dilute acids do not act upon tbe compound at ordinsiy
tonjporaturaa. Caustic alkalies and tlieir carbonates produces turbidhjfj
and separate the oil. — Iodine aud bromiuo diesolye witliout colour in the
aqneou$ solution, sulpbate of soda bciug formed and tlie oil eepamted.

The conipouod may be preserved without alteration in closed vesseki
and cliatigea but very slowly rn contact with Iho air. When be sited ta
the air, it is decomposed without cliarriog, bitter almond oil volatilising,
and the sulphite heing oxidised. In a stream of bydrogenj it gives ofT
water and bitter almond oil, even below 100^* Nitric acid converts the
eulphite into sulphate and separates the oil*

The aqueous solution forms with ehlorido of barium a copious pre-
cipitate eoiuble in hydrocbloric acid, and containing a portion of Ihe ml^
Lead and «{7vifr-salt« are precipitated in like manner*

e. WitA Bkhloridt of Tin^ bitter almond oil yields a compound which
forms finQ crystals, hut is ditlicuH to purify and decomposes wbca dried
in the air or in vacuo* (Lowi^, CompL rend. 21, 371; abstr. J. pr* CkefiL
37, 480.)

/ With StfdrtH^yanic acuL — When hitter almond water mixed with
hydrochloric acid la evaporated at a temperature short of 100^, tliis
compound separates, when only a small quantity of liquid is left, in the
form of a yellowish oil, which may be fn/ed from adhering hydrochloric
acid by repeated agitation with water, and dried in vacuo over oil of
vitriol.

Yellowish oil, nearly inodorous and baling a bitter ttate. Boils at
1 Ttl''* ^\K gr^= 1*1 24, Dissolves sparingly in water. ( Vokkel.)

16 C ...,».„.... 9G

N .^.......„ U

7 H ,«-...., 7

2Q .„.., U

C»*H"0»,r^H 133

Viplckd*

7218 _ .. 71 99

Wh% 11 '01

5'2fi .....,- 5-34

1203 ..,..„ n$?
\mm „ .. ,, loo-oo

It is partially deoomposoil even at 100^ and when boiled h resolved
into hydrocbloric acid and bitter almond oih Potash immediately forms

cyanide of potasj'ium and liheniies the hitter almond oil — When I ho
compound is evaporated with hydrochloric acid, water is taken up, and
sal-ammoniac and mandelie acid produced. (Volckel.)

It dissolves rea^lily ju alcohol and ether. (Volckel.) I

g^ Wilh C^amc acid. — When cyanic acid vapours are passed ioio
bitter almond oil, great heat is cvt>ivod, and a white heavy l>ody aepftni.t««
wbicb Increaaes on addition of ether. — White powder eolublo in aleob«l
and cryvtallining therefrom. (Liebig, Jnn. Pharm. 23, 140*) —

A. Bitter abnond oil disaolves in all proportions in ahoh^ and ifker.

BITTER ALMOND OIL.

S0

Appends to Bitter Altmnd OU.

Laur

Light

urA'oll — From the freali leaves of Prt
yellowi heavier tban water, having a strong halsaniic taste and ameli*.
(Spaudaw Ue Celiie.) — lu contact with the air, it is converted into
benzoic ackl, and likewiae yield a thia componnd in contact witk moist
chlorine gas. (Staiige, Iiepert. 14, 329,) — When treated with lime-
water and aftcrwardis witli chloride of iron, it forms prussian blue.
o\oH\ A. G€kL\,6Q2,)

Fmch-kc^ oil contains, in addition to bitter almond oilj an oil having
tLe odour of the fresh leaves and fruit of the peach, quite different from
that of bitter almond oil* {Winckler^ J^eperL 67 j 15fl.) Produces ben-
lic acid, (Bra^matelli, Ann. Chim. 96, 96.)
Oil of the Portu^fd Laurel. — May be obtained fri)m the bark, leaves,
flowers and seeds, — Transparent, colourless oil, heavier than water,
n tain 8 hydrocyanic acid and produces benzoie acid, (Giese.) Con-
ins a peculiar volatile oil, which has a pungent disagreeable odour and
■es not form benzoic acid when exposed lo the air* {Winckler, Mtpert,
1, 06.)

Bitter uimmd wafj^r; Laitrel-waier ; Cherr^-ivaifr; Aqua mn^^da-
m amm'urum; Aqua fnitroceran; Aqtia cerasorum — are essentially
ueoiis soltitions of bittet- almond oil containing pnissic acid, as they
B generally obtained, together with bitter almond oil, in the distilla-
tions of parts of plants containing amygdalin and emnlain. (According
to Wiuckler, I^eperL 52 ^ 2^S9, they contain cyanide of benzoyl.) — Per
the preparation of the^e liquids the folio iring directlona have been
iven :

a Bitter almond water. — 1 . The residue of 2 pounds of bitter almonds
impletely freed from fixed oil by pressure between hot iron plates, is
jrred up to a thin pa.^te with cold water in a distillatory apparatus
hich admits of being closed, and distilled after 24 hours digestion; the
istillation i« best performed by means of steam (compare p, 21) or in a
hloridc of calcium bath. Two pounds of the distillate are collected,
'Geiger.) — 2 poundss of bitter almonds freed from fixed oil by cold press-
g, arc stirred np with 1(1 lbs. of water, 4 ok. of highly rectified alcohol
Med, and the mixture diatiiled till 2 lbs* of liquid have passed over.
^iiamiacophor.) The addition of alcohol before the diatillation is eatd
some to diminisb the amount of prnssic acid in the distillate; others
the contrary maintain that a stronger water is thereby obtained*

*o these preaeriptiotiSi lire annexed ^arioufi ftppendlces, which for tbe most part directly
iBtrAdtct each other. Com pare Ge^aler (A''. Br. Areh^ 10, SO), Mobr, Cmnmenta zftr pr,
^karmacopGe, §.210), PAub {N. Br, Arch. 48, 154.) Aecording to the Pamian pbflrma-
poeift, a doable quantity^ and according to the Saxon, a treble quantity of water should
dUtilledoC)
Notwitkstanding every precantion, bitter almond water is often
ibtained of different coniposiLion and strength by the same mode of
ireparation. In general, it is a more or lees milky liquid sinellin^^ and
ftating strongly of bitter almond oil containing prnssic acid. The addition
if ammonia produces a strong railky turbidity, the more quickly as the
iqnid i** ^tront^er. fVeltmaun, Ann. Phamu 34, 23.i); Lepage, J, Chim,
^id, 24, 371.)^ — (According to Weber, it ia not altered by ammonia
^ Mr. Arch, 35, 32.) — Its therapeutic action depends on its amount of
mxmic acid as well aa of bitter almond oil. According to Duflos {Pl^irm,

BENZTLENE SERIES I PBIMABY WUCLEUS C?*H**

BO

{kntralhhU^ 1837, 560), it contains on i\\% arem^ r2 per coot, of litter
almond oil containing prnssic acid or 0* J 73 p. c- of tbo acid* The Fmiraii
pharniacopmia requires that it shall contain 0-14 percent, of pniBsic
aeid.

h. Laurel tpaler. — 2 pta. of the fresh leaves of tbe common Itnrel
(Prunm hurocframs or Cef'^Bm laur&cemsm} are distilled with water
and 3 pts, of tlie diatiUate collected. (Geiger.) — Eachibitg the pto^
perties of hitter almond water — Mixed with ammonia, it becomw
turbid after some time only and in a leas degree tban bitter almond
water* (Veltmann, Atm. Fkar-m, 34, 235; Oswald,^. Br. ArtL
38, 100,) Weber found exactly the contrary. — According to Lepagv,
laurel- water behaves with ammonia in the same manner as bitter almoml
water (J. Chim. mid. 24, 365.) — Leaves gathered in different yeari(
BeasoTss yield various amounts of prnsdc acid. (Bischoff, Phftrtn, Ceni
1841j 889.)

I?, Chtrr^^waUr. Aqua cerasorum nigrorum. — 20 lbs. of wild
dierriea are bruiaeil, together with their kernels, water ponred npon the
mass, and 20 or 30 lbs, of the liquid distilled off after 24 hours. — The
diatillate exhibita the properties of very weak bitter almond water
Winckler {liep^t B5, vA distilled 45 lbs, of ripe black wild eh erries^
containing about 1 2 lb. of kernels with 80 lb.g, of water, till 30 lbs. of
lif|uid had passed over, and the last portiones of the distillate wer© nearly
inodorous; tbe dif^tilbte gave 30 grains of bitter almond oil containjag
pruisie acid equivalent to 6*1 p. c. cyanogen.

Valuation r*f Bitter <tImond tmlerj Laurel water ^ ^-e. — Since it if

asaiitned that the elHcaey of bitter almond water is proportional to its

amount of hydrocyanic ivcidj the valuation is limited to t lie estimation ©f

the latter. This is best effected by Liebi^s nietbod. {Ann. Ph&rm. 77»

|102,) The water to be estimated is mixed irith a quantity of caustic

Dtash snffieient to produce a strong alkaline reaction, then diluted with

pure water till the turbidity arising from sut*peuded oil-drops dissappeaiti

and a dilute solution of nitrate of silver (contatninfi^ ^ grm. of silver in

llOO cub. cent, of the liquid) adde<l frttm a burette till a permanent preci-

rpitate of cyanide of silver k produced* 1 At. silver thus precipitated

li equivalent to 2 At, hydrocyanic acid in the liquid. Or 62 grains tj{

fqAea nitrate of silver are dissolved in 503T grains of water; a anflicieat

quantity of ibis solution — 300 graina of which contain 1 gratn «f

I ftu hydrous pruK&ie acid — counterpoised in a balance; and tbSs aolutiofl

fftddcd by drops to tbe liquid under examination, previously mixed with

' eautftio potash and a few drops of solution of common salt, liU a turbi^'*^

la produced which docs not disappear on stirring. The amount of r^

I acid is then calculated from the loss of weight of tbe tilrer^tol

[(CompftreTiU ilO?,)

D«compmtim4, In wall closed bottles eomplelelj illcd, VUter I
ilmotid and kiiml water remain nnaltered, exhibiting, amt Uie lape« nf
i yetkr, tii9 w»m% amount of hj^drocyanio acid as at tret, mA hmratf
ipeiltcd only a slight yellowish sediment (Paton, J. Chim. mM
||0, 203; Lreptige, J. Chim* imd, 24, 377.) lu well closed bottles cont»ili*>

fha air. and moro quickly (in foar w^eks) in bottles covered only wilh
[l^ibulous mfKjr, bitter almond water loses the whole of \U bydrocyanie
yiQid and bitter almond oil The water then contains amnioniacal mIu^

I

tb\y bamoftt* wd formiftto of snimouia. Laurel wM«r kittft

J

BEK20IG ACn>«

31

^^1

cop

longer, (Lepage.) In the yellowisK sediment of concentrated bitter
almond water, Y eViug {I^, Bf\ Arch, 43, 297) found benzoate of timniomft.
According to Wincklerj ether extracts from thia sediment a- »u balance
smelling stronglj of bitte? almoTids, and leaves another body which
agrees in composition with the compound C*^H**'Cy'0*, obtained by Zinio
from bitter a.lniond oil and potaeh* {Jieptti. 92, 321^,)

1 . Tincture of lodhie adclcd in sufficient qnantity to bitter almond
ter or laurel water {15 — ^20 drops to 30 grammes of water) forma a
limpid mixture which reddens litmus strongly, and doca not produce a
blue colour with starch . When the mixture is evaporated to one-fourtL,
oily drops sepamte, which, if the iodine ia not iu excess, are colour-
Jess, pungent, taste and smell like bitter [almond oil, dissolve in
ether and aicoLol, and yield iodine when treated with nitric acid
(they are probably a mixture of iodide and cyanide of benzoyli the
liquid contains hydriodic acid.) (Lepage.) — 2, Two or three drops of
hrotnine impart to bitter almond or laurel-water a dlgbt colour and
imell; the mixture exhibits reactions similar to that which is formed with
iiie, (Lepage-) — 3, A eolution of fiw//j/((a^ ^j/" ajjf>^er strongly euper-
turated willi ammonia and added by drops to the water, immediately
■roducea a milky turbidity, which in an hour or two, changea to &
copious Hocculent prectpitate : after the litjuid haa been shaken, a yellowish
iinous matter collects on the surface and in tho course of 24 or
hours settles to the bottom and may bo separated by filtration; it is
illy fusible, soluble iu alcohol and ether, and doea not contain copper
(probably a mixture of hydroben^amide, bonzbydramide, azobenzoilide,
:.). — The filtrate is colourless, and, if the copper has not been added in
ceas, does not coat iron with copper even after the ammonia has been
expelled by boiling, although it contains the whole of the copper that has
been added. (Lepage,) — *5. When 1 pt. of iodide of pofassium is dis-
Ived in at least 600 pts. of bitter almond or laurel-water and a solution
' eorrotim ^limcde added by drops^ a white precipitate soluble in iodide
I potai^aium is immediately producGd; with a larger quantity of iodide
potassium, the precipitate is scarlet. (Lepiige,) — 6, Calomel is
ilackened by the water, especially if warm, and yields metallic mercury,
Drrosive sublimate, cyanide <d mercury, eal-ammoniac; and on evapora-
ion, maudelie acid, (Winckler, IkperL 37, ^88 ^ Prend le Loup, J^. J,
7wrm* 6» 47.) According to Prend lo Loup, an oily compound of bitter
mondoil and sal-ammoniac is formed at the same time* — 7* A solution
terchloride of gold ja not reduced by bitter almond water or laurel
a ter, as by other distilled waters. If the mixture be immediately
iled down to ^, it becomes decolorised and yields a slight yellow deposit,
be strongly acid liquid is not altered by protocbtoride of tin (cyanide of
Id and hydro cldoric acid appear to have been formed.) (Lepage,)
Di^thictitm hdw^en JJiUcr alirwnd imtei* and Lnurd waia\ — 30 dropa
a solution of chloride of gold, in 100 pts. of water do not exhibit
ly immediate reaetjon with either of those waters; hut after eight hours
e bitter almond water no longer exhibits any yellowish colour, while
e lanrel water retains its colour for 24 hours. (Lepage*) — The state-
lent of AsohofT, that 0-05 grm* sulphate of quinine mixed with 10 drops
" laurel water quickly forms a solid mass, whereas bitter almond water
loes not exhibit such a reaction, is not confirmed by the observations of
lepage; neither is Riglinis statement confirmed, to the effect that a
dution of sulphate of quinine in tartaric acid immediately produces a
hito tarbidity with laurel water, but not with bittor almond water.

BENZYLENE SESIES; PRIMAHY I4UCLEUS C"H**

Benzoic Acid, cm*,0*,

_ JEELE. Opuxc. 2, 22} also CtelL H. Entdeck, 3, 98.
LiciHTExsTEiN. Crdt aY. EnidKh 4, 9 ; also VrtlL Auu. «/, n,

1, 319; further 1, 335*
GoTTtiNQ. Aim. 1780,70.
Hermbstadt. CrelL Amu 1785, 2, 303,
Trommsdorpf. CrdL Ann, 1790, % Zm,~A. Tr. 1, 1, 162.— J^, Tf\

2, 134.
GiE8E. Scha: J. 8, 170 and 25 U.
BircHOLZ. ^V. Gehl 9, 340. — 2fWc/ir/iZ^. 1810, 50*
Hr^iNGER, Ab/uindlurtf/efh 3, 152; also Sch^^t^ Ann. 2^ 37,
Berzeltus. ^\ GehL 2, 217,^ Ami, Chim, 94, 315. — Po^^. 2G,

also Ann. Fharm. 3^ 282*
Lecanu & Serrat* /* Fhnrnu f>, 89; alio iV", f'^^ T, 2, 98.
Btoltze* i*'t'r/* Jahrk 25, ], 75.
Stange, Iteperi. 14, 329.

WiiHtER & LiEDiG, Ami. Pharm* 3, 249; also Pogf^. 20, 32S.
VoaET, N, B}\ ArcL 3, 29 L
Erdmann & Marciiand* tL p}\ Chf.m. 13, 422«
F, tj'ARCET. Ann. ChittK Pkt/t. C6, 99; also J. pr. Cl^m. 13, 477.
Korni* AniK Phann* 29, 177.
Plantamour. Ann. P/iarm. .10, 349.
EuLEii Sl HERm%iiGER. t/cfAr&, pr. Pkartn, 2, 308,
Wodr^ER. Ann. Phn/m. 49, 245.
Bahreswil & BoDDAULT* ^V. »/. Pharm. 5, tlft5.
Dbssaig^cbs. jinn. C^em* Phys, 17, 50,

Klowera t>f Wnzoin wero noticed as e:irlj as IG63 by Blaiso
VigeutT^^ ScUeelo and others pointed out more advantageous modei i
prepariDg tliem; Woliler and LicUig determined theif truo compoaUUiu*

Smtrcn. In gum beuKoin, dragon*e Ulootl, etorax, Peru balsam {C\
Chrnk J. I, 58; Meiberger, Repert 05, 219); iu Tolu balsam (E, KopphJ
Compi. rmt-L 24. 714); and OpobaUamurn iiccttm^ in resin of Botany Baj
(Langier^ Bollaort); in oil of marjoram {Oiittliijf^, I'aschfnb, 1800, 59)jj
ID oil of borgamot (C J. Fiscbcr, Bt\ Arch. 14* 175); in ointi&iiioii-ci«ii
and oil of cinn:ifiLon (Dumcnii, ScAw. 21, 224; Henkel^ Hrpfrt, 4, 3d0
Buchner, RepfH. G, 1; 8, 184; Ballaert, Qu4^i< J, of 8c. 18, 340
[Schwciniiberg, Ma^, Pharm. 26, 386); in the ripe frnit of the clore-1
LfBoLlaert, QmrL J* of Sc. 16, 378; also JSckw. 42, 122); in the seed
rj^wMyfiitti EuropGcut (SchweiKcr, J* pi\ Chem. 53, 437); in v^nille an<l|
i^mus root, ii» tbo root of PiiapiaHla mxifmifn (Bley), and of IhuIm
\ kdm mm ( R- \ t*eber, ^r-f ^r^ . 30 » 1 G 9 ) ; in t r cfo i 1 , HoIchm a * hf*a 1 1«» A nil
[nn^ifin 0dm-afum (Vop^l, ffi//;^. *H, HjI; k'ustn. Jrch. 5, 413), A^permh
|«tflorato (Vogci, iifm-rt, 66, 248); in sternani^, in myrrb (Brtuidca), aa4
lappartaily, aeodrding to Braconnot* tn tSuhla sciarm. — ^ Iti Cmioren^^
mm^^i$kwm (Laugier^ Baika, Bmudcs (N. Jh\ Aixfu 1, 197) iia4J

iJBNiOlC ACtO.

33

i

\mi tanm^etue. (Riegel, Jah'h. pr. Phanrt. 6, 34; Wohhr, Ann*
Pharm. G7, 360). — lu tha anne (vid. Hippurin aekl)

Occurs as a copula in hippuric acid (Dessaignea), and m populin.
Pirb.)

^€»rwifiiiofi, 1, From bensylic alcohol when healed with aoueoua
chromic acid. (Canniszaro.) — 2. Prom bitter almond oil heated with
solid hydrate of potaah or treated with alcobolic potash {Licbig &
Wohler); by absorptiou of oxygeiij or by oxidation with nitric, iodtCj or
chromic acidj henco also in the oxidation of cinnamic acid (Dumas,
Peli/^ot, Siraon), aud of protcin-coni pounds, (Proyst^ iV* GekL % 241;
Guckelberger, Amu Phai^ni, 64, 30.) — 3. Tu the decomposition of
brouiide or chloride of benzoyl by water, (Wohler k Liebig.) — ^4, By the
continued action of dilute nitric acid upon cumoK (Abel, PhlL Mag. J.
Z% i^.) — 5. By heating' cinnamrc acid witfi hydrate of potash, (Chiozza,
OmipL rm*L 36; 70L) — 8. By the dry dtstillation of kiuin acid.
(WcVhler, Amu Phtum. 51, 145,)

^B Frepnralwn, 1 , From Gum benzoin, — a. By aublimatiou . — The
^■est mode of conducting the proceea is to \\\j the coarsely pounded resin
^Bm the bottom of a round shallow iron pot, 8 Inches in diameter, 2 inches
^^Kgh in the side, and having a piece of coarse bibulous paper .-stretched
^Bk^r its mouth, and closely cemented at the sides; a cone of thick paper
is then tied over it and the vessel gently heated on a sand-bath. — The
^vapours are purified in passing through tho bibulous paper anil condense
the inner aurface of tho cone in beautiful crystals having a faiut odour
benzoin. — Or the iron vea^el is rurinountcd with an exactly fitting
liallow funnel of tin ydate^ and on its ncck^ which is tolenxbly wide and
nly an inch high, is placed a capacious boic of wood or pasteboard . The
aoro slowly the sublimation takes place, the more abundant is the
iroduct; the treatment of 1 pound of gum benzoin takes throe or four
kours. The quantity of acid obtained amounts to 4 per cent* If the fused
e«in, after being heated, be broken npandaijaiu sublimed, a total product
obtained amounting to 124 per cent, (Mohr,) — Eulcr hi Herbcrger
|/oAr&. ^>r, Pharm. 2, 305) heated gum benzoin in a retort with a
aiver ti!l no more vapours were evolved, dissolved the contents of
be receiver in hot water aud obtained in this manner 13 or 14 per cent.
bf tolerably pure benzoic acid, — According to Hatchet^ benzoic acid is
bbtained in beautiful crystals by heating the resin with oil of vitriol
Veltmann {B}\ Arch. 7, 100) obtained by suUimation from the resin^
|4'4 per cent, of acid, and by the use of oil of ritnol^ 1<] per cent. — '
!, When 1 pt, of finely powdered gum benzoin is boiled for two houra
rith 16pt8. of water, the coagulated resiu pulverised and again boiled
rith 8 pts. of water, and this treatment twice more repeated, the quantity
bf pure acid obtained from the aqueous solution amounts to 6 per cent.
jfEuler & Herberger.) — c. I pt. of gum benzoin is dissolved in 4 pis. of
fclcobol; the filtered solution mixed with 12 ptf?. of water; tho alcohol
listiUed offj and the remaining liquid^ after separation from the resin,
ftvaporated; the benzoic acid then crystallises out. (Bnchdz, N. GthL
340*) The product thus obtained amounts to 13*S per cent. (Stoke.)
1 pt. of gum beu^oin is dissolved in 3 pts, of alcohol of 75 per cent.;
be liqnid exactly neutralized with a solution of earbonute of soda in a
reble quantity of alcohol and an eight-fohl quantity of water; '2 pts,

TOL, Jtit* U

BEMYLENE SEEllS : PRlMAai NUCLEUS C«-H**

move of water tlien added; tlie atcobol distilled oflj tlie watery B%u
decanted frim tlie reeini the fc«iE wa^lietl; and the benzoic acid ptecip
ta ted from the aqneous iolatioxi hy tulpliuric acid. Thti product hlB [4
cent* of benzoic acitJ, (Stolze.) — -d. Pulverised gtitii benzoin is liiafeolve
with the aid of heatj in an equal volume of alcuTiol of 9U or 93 per cenl
the liquid while atill hot ifradoaHy mixed with funitng liydrochlorLc aci
UU the resm begins to bo preeipitated, and the mixture diatillcd as loij
na the eon^i^teuce of the residue permits. The cooled residue h a^ij
distil Jed with water as long as drops of benzoic ether pass over; tJ
diatUlate oontaining hydrochloric acid, aJeohob and benzoic etber dii^eat^
with potaih-lcy, till the whole of the benzoic ether is deconi posed; iOl
the benzoic acid precipitated from the liquid by b?drocbloric ac'''
(Wobier) — e. A mlxturo of 4 pts, palveris#il gum oenioin and 1
crystallised carbonate of fioda is stirred up wiib water to & tbiu ;
and beated for three hours with constant stirring, and so gently
resin cIo<m not cake together (to between 40'' and eo*)^ the nuu
boiled up with a larger quiintky of water j the liquid decanted; and ll
coagulated mass of resin washed with water. The liquid coiitittnifli
carbonate of aoda, benzomte of soda and the cumijound of the reain wilj
iod& IS neutmtized at ibe boiling heat with sulphuric acid; the rcsij
©wcip Stated by a slight excess of that acid; the liquid filtered; a.nd tl
nJtfate treated with sulpburic acid to sepaiule the benjcoic acid^ wbiil
thcR crystallises on cooling. (Bucbolz.)—/ Four pts, of pulv«fiii
gum benzoin are mixed with 2 pts. of hydrate of lime; the mixta
digested for some hours with 40 pts. of water; the liquid liuallj
bailed for half an liour, and the solutiou containing the heuioato of liti
6l£cred from the insoluble compound of lime and resiu. The ^Ylm
together with the wash-water^ is strongly concentrated by evnpor
tion, decomposed by exceas of hydrochloric acid, and the tenzoic sciJ
which crystallises out on cooling is washed with a small quantity q(
water and recrystalliged from boiling water. (Scheelc) Equal |»arti i
finely pounded gam benzoin and hydrate of lime arc mixed us intimakj
aa poa^ihle in a mortar; the mixture boiled for some hours with 40 pta. <
water, and filtered; and the liltrate evaporated to oDQ'third ft&d mi"
with liydrocUloric acid. If a enmller quautity of lime Is iisedt
mixture cakes logetber^ and the extraction of the beuzoje acid i» in
feet. (Gciger, Bandif, d. Fh, 5 Aufl. 668,) Lg. — S py, of pulverli
gum benzoin and 2 pts. of hydrate of lime, stirred up to a thin p*
with 16 parts of water, are digested for ii hour^^ with frequent a^taiim
aod renewal of the eFaporutod water, tbeu mixed with 100 pts* inor« (
W«t«r; the liquid !>oi1ed, with constant stirring till about 30 pta, of waii
arc oraporated, and filtered hot; the residue boded with 50 pU, of ^
m4 the liquid Itttercd aud evaporaledf together with the firat ^Itrut^
only 02 pts. of liquid remain. To this roiiidual litjuid hvdroch!oria|
ii adcted, with con^^tant stirring, aa long as any white turbidity is U^
9fodlused< Thu lieiixoie acid ^hich tfepnrate^ on cooling la rocrVit
irom 20 timc!* its weight of boding water. The reain thus troatcd yieM
irttm 1%'S to iH'j per ccut. of acid. (W^ittfitoiu.) Tbia moibod
Imble to thr
pnwluct. (li

• 47, ^0; Blcy ii. Diesel, /V, Arc/i. 4^, 17 )
cattnMted from gum beiiioin bir means of benzol. (Do la Hue & i

I*

, inasmuch as it yields a purer and more abuaq

:iw]er k Herherger, Friekhinger, Wittstein, M^

hc^eb /V. At'c/i* idf IT ) Benzoic acid is Ig

BEMOIC ACID.

M

I 2. From ike hauim &f Asperula odo^mta, — The powder of the dried

Ksulm gathered in the flowerlog aeastm, ia macerated with 4 pU, of cold

Imlcohol of 85" Tmiles, and completdy exhausted bj pressure and repeated

Mrenching. The liaoid^ which has a dark green colopr, with red-brown

mideacea^e, h distilled to |; and tlie re-siduo, which has an acid reaction,

Ptod an agreeable odour of melilotj h holhd with water, to separate

volatile oil and soft rosin ^ and filtered while hot. The filtrate yields bj

evaporation, crystallised benzoic acid (from 12 to 15 gr. from J 6 oiincea

of the haulm.} (Voget, iW Br. Arek 3, 291.)

3. Prom IJippuric acid. — Thie acid is boiled for half an hour with
airoDg hydrochloric acid, and the benzoic acid thereby separated is washed
with cold water, (Dessaignes.)

The acid prepared by sublimation, according to Mohr'a directions, and
that which is obtained by the process 1, f^, is pure, with the exception of
traces of a Tolatilo oil, which imparts to it an odour like that of vanille,
and is considered of importance in its pharmaceutical applications. The
acid obtained by the other methods is sometimes eolonred. Tt may he
purified from odorous or colouring matters by the following processes:
a. By sublimation. This process however does not '^uite remove the
dour, — b. By digesting its eoliition in water (or in alcohol according to
)erfurt) with charcoal. (Stoke, Lowit^.) — c. By recrystal ligation
^ Dm dilute sulphuric acid, which retains the oil. (Righini, Winckler,
Suler L Herberger.) — (L By solution in alcohol and precipitation with
rater. (Giese.) — e. 1 pt. of the crude acid in suspended in 6 pts. of
F&ter, and ammonia added till it djssolvesj the sol ution digested with
nimal charcoal whicb has been purified by hydrachlario acid; th^
olutiou filtered and deocm posed by hydrochloric acid; and tho acid
hereby separated, after being washed with cold water and pressed,
% dissolved in alcohol and precipitated therefrom by water. (Jans-
ens, J, Chim, med. 18, 2tj3.) — / When the crude acid is combined
rith lime) and carbonic acid gas passed throu^^h the solution, carbonate
p{ lime is precipitated together with resin; and on evaporating the filtrate
D dryness, dissolving the residue in water, and decomposing the solution
rith hydrochloric acid, pure benzoic acid Is obtainod. (Bouillon
^range^ *A Fharm^ 7, 204.)

Propertiei. L Prom a solution of neutral beuKoato of ammonfaj

ensoic acid crystallises by spontaneous evaporation of the ammeuia, in

eautiful right i bom bio prisms, (Waijkenroder, J. pr, Chem. 23, 204.)

VV« not thb the nod sok.^ L.] Sublimed benzoic acid f or nis white opaquo

needles and laminai, having a pearly lustre; nccording to Laurent, sijc-

lided prism.% derived from rhombs of 40° and liO\ {liev. icimt. 0^33.)

protQ solution In oil of cinnamoti, the rtdd cq'statliscs in tnmspireut iii-sid*d jirismst

linvinf two of tlieTr lateriil fjicei broader than the rest. (Buchnor.) Vfhfn the mlA

s-y*^tlilfe3 by coolii^gfrotn a hotaqueoHia solution, it forms nPCilkn, but by ffponlnncou«

Tdporatiou, it »cparatea \n laminie, Bcridhti, LeArbuth^ 4, 3] 2.) — Vapour-dcnsity

H*27. (Mitscherlich.) — Melts at 120 5^ like fat, and crystallises in

ifadiated masses on cooling; at 154^ it begins to evaporate quickly, and

[ftt Saf*" It boils. —Melts at \2\^^; sp. gr. of the liquid ncid 10835 at

It I '4* ooinpare<l with that of water at 0"" as unity. Boiling point 249-2'

it 740 mm. (H. Kopp. Ann, Phftrm. 94, 302 ). — The vajiours excite

Itears and congbtn^. The acid reddens litmus, but not violet juice. In the

fpure elate it is inodorous. Its taste \^ iaint, but persistently sour and

[irarm.

of

36 DENZYLENE SERIES: PRIMARY NUCLEUS C»H«.

Bcrxelius. Wd^ler & ErdmMm Domas -^^

Liebig. &Marchmnd. ttStu. "**"»■

U C 84 .... 68-85 6885 .... 6902 .... 6883 .... 6896 fio-fl

« " 6 -. 4-92 4-99 .... 5-03 .... 497 .... 4-95 "" H

< O 32 .... 26 23 26-16 .... 25-95 .... 26-20 .... 26-09 Z 25-6

CMl-O*.... 122 .... 10000 100 00 .... 10000 .... 100-00 .... 100-00 .... 100-1

Vol. Density.

C-vapour 14 5-8240

H-gttS 6 0-.S658

t)-g« 2 2-2186

Benzoic arid ▼aponr. . 2 8-4084

1 4-2042

Erdmann & Marchand onalyeed the acid from borse-vrine ; DeriUe that froa

IVltt-bAlMUil. '

'llie radical theory assames a hypothetical anhydrous bensoic add *» Ci*H*0>aRs.
— .\iHvrding to Mits^-herlich, benzoic acid is a cor.juntcd componnd of hemal mai
mb^uii acid: 0*HK>* = C»-H* + 2CO--.-Con$ideml asaderi^n of thTwatlw!
tTpi» H*0-. bcntoicacid is a hydrate of benzoyl = ^"^*^|o5.

i^\^mf.*^mtio§u. When benzoic acid is heated in a retort with coanelj
iHUiiuiisi punuce-«ione. and the ^-apours passed throngh a red-hot tube
fln«sl with fmcntont^ of pamico-stone, it is completely resolTed bj slov
disviuwvticiou. into oarb«^nic acid gas and benzol. If too atron^rabcat
ia appiitsL thore are likovrise fonne«i empvreoniatic prodocts, naphthaliBi
(Nil Collie oxide cs^ and charcoal. (Bamrswil <& Boodaolt, A^ «/. Pkarm.
\ iJ^t.^.> Houillon Lacrange {J. Pharm. T. 200; .V. Tr. C, 2, 343)
hoiitisi (»onioio acid in a n^tort with ignited alomiDa ; at fint needlei
"lublimed; thon \vllow granules, with cvolation of carbnrctted hydmea
and \'arlvuio aciJ. and an odoar of prnssic acid. In one distillation, an
«mI |^«^ over having the odoar of bitter almond oil [benzol 1]. — When
bi^nsoio acid va|H>nr? are passed thn^ugh a red-bot tube filled with iron, a
yellow empyr uniatic oil is prvvli:ce<l. which smells of almomla. and wbei
diiitiiUsi at the heat of tLe wator-Vath. yitlds a residue of tar and a
di^tillato of benz'^I. At a gentle heat, carbonic acid is also prod ncfd;
nt a stronger heat, carbonic' oxide. tF. d'Arcet, Ann. Ckim, PAw.
tUI. l«7.)

2. Benzoic acid fa^t/yJ in contact with the air, bams awiy
without roMilue. and with a bright fuliginoo? flame. — With % spiral of

idatinum wire, vapoor of benzoic add exhibits slow comDastioa.
II. Miller, J w/i. PAarjii. 12,21.)

«1. Pry chlonti'' gn$ acts but very slowly upon dry bonioie acid in
tho nliiido: but in sunshine there is gradually formed a moist, tough,

Jfiininiy. rotidish mas^, from which carbonate of potash extracu chloio-
HMiioio arid, leavini: a brown red substance, which becomes resinous on
i«hpi»Niin* to the :iir. h.ij: a peculiar o< I our distantly resembling that of
ImiKiiin. and contains chlorine. (Herzng, 3'. ^r. JrdL 22, 15.) — Is
IM'UMtiini of water, benzoic atid is not perceptibly decumposed by chlorioe.
Iii|{ ) WhiMi cliloriiie ira^ is pas-^od into a hot aqneoas ndation of
\\\ iioitl. \arious aciiis are pro«Iuct^d. in which 1, 2 or 3 At faTdr^*
iri* litpljMvd liv chlorine. (Steuhouse, Ann, Pharm 55, 10.) <—
I n auliiliiMi of Wnzoic acid in excess of potash it saturated witk
119 ipi"« rhioronicoic acid C^HriHK)' (xi, 176) is produeed. (St.

BENZOIC ACID.

Eyre, N^ Ann. Chim. Phtfs^ 25, 48C,) — 4. Liquid h-mime placed t<>ge-
tlicr with ben znic acid in a dnsed vessel and exposed tcv tbe mm' a my 9^

k

acta more quickly tban chlorine gas, produi^in^^ a friable yclbw jnass,
from winch cnrbonate ttf putaab extracts i>fomobenzoic acid^ :md separates
a greoDLsb oil c^njiahiitig broniiue^ wbtch becotnes eoHd and reemoua on
cipuaure to the uir. (Herzog.)

5, Benzoic acid sbiiken ap witb cold strong nUric add difisolvea
but sparingly; it rigea to the surf&ce of tbc liquid and does not form
any deposit fof nitro ben zoic acid), (E, Kopp, Ann, Chim. FhgSn
1849, 1 49*) — When benzoic acid is heated witb nitric acid, nitr^^enzoic
acid aud water are formed:

C*^H«0^ + NO* ^ C*^(NO*)H*0* + HO.

(Mulder^ J. pr. Cktm. 19, 3B2.) The action takei plaee immedtHtely: if
nitrous vapoura are at tbe eanio time given off, ihey arts© from the action
of the nitric ucid on the nitrobenzoic acid* (MitBcbetlich, J. pr\ Ckem^
22j 106) — Wbeu benzole acid is diijlillt?d with nitric acitl, a small quan*
titv of nitrous gas is ^iren off before the lir^iiid begins to boil; but tbia
evolution of ^as soon ceaaes, and tbe benj5oic acid dii^solves with yellow
c^dour; towards tbe end of the action nitrous gaa is n^^ain given off iu
large quantity* The ditilillate consists for the most part of nitric acid
laving an odour of prussiic acid, wbich hi^wevcr cannot be detected in it
jby reagents; the residue contains benzoic acid InitrobenKolc acid; L.]

ud traces of oxalic acid* (Bouillon Lagrange, J. Phann. 7, 200,)
0* Benzoic acid boiled with aqueoia chloride of lime yields three d if-
fcrent acids in which 1, '2 or 3 At, hydrogen arc replaced by chlorine;
":f»ClH*G*, C'*CPH*0*and C'*CPH*0', Tbe san»e reaction 18 produced

rhen benzoic acid is boiled with chlorate of potaeh and hydrochloric acid.
'^Stenhotiso, sijtn. Pharm. 55, 10.)^ — Field {Ann. Phartn, 65, 55) by
boiling benzoic acid with chlorate of potash and hydrochloric acid,
Bblained cblorobenzoic acid, C'*C1H^0*,

7. PentacMof ak of phosphor tis does not act upon benzoic aeid in the

oldj but virdently at a gentle heat; hydrochloric acid escapes, and a

aixture of orychloride of phoaphorns and chloride of benzoyl is pro-
'du^d (Cahours) :

FCi* + c^^H'^0* - PCHO^ + c^m^ciov

8* With anhydrous sulphuric acid, benzoic acid forms sulphobenzoio
acid^ In oil of vitriol it dissolves without decom position*

Aqu^'oui frKiomir add ia rn>t redurert by benzoic iK^id*

9. Poiftmum and sodium decompose benzoic acid at temperatures
Dnsiderably below their melting points, charcoal being separated and the
Detals oxidised: tbe action is not attended with emission of light.

10* In tbe amm'fl or^mmm^ benzoic acid is converted into hippurio
cid, (Wdhler^ Ore, Kellerj Garrod, Schwarz^ Marchand.)

Cumhinatwm. Benzoic acid dissolves sparingly In cold water (in

aO pts J according to Bucholz; in 480 pts., according to Li ch ten stein;

500 pts,, according to Bergmann); it dissolves in 24 pts, of boiling

tier. (Bergmann, Lichtenstein, Dirfurt); in 124*5 pts. (Bucholz); in

pts* (Tromnjsdorff ) It dissol via readily in Avater to which 1^ pts.

bhosphate or 4 pts* s alp hate of soda haTe been added* (Urc, P^po-t, 75,

S8

^B BERnisi PBriiAFr nucleus C"H<,

oi^^

64 ) Benzme ncid dissolves readily io oil of Titriolj and Ib precipitalt

unchanged fruin tUo coburbse eolutiou by water,

BensmUn. --Beji^ow aeid decomposes carbonates. From an aleobolli
BolutioD of benzoate of potasb, bowevcr^ carbonie acid ^s tbrows dow^
cavbo na te of potas !i * ( L i i ii j » rk !i t <t List.) — Most acids separa to be u «o l€
acids from its mlts. — Most of the benzoaies are crystal li sable. They
ccmtab I At. base to eitlior 1 or 2 hi. acid. Most of llie normal
(monobasic) beoJEoates yield by dry distillation, beneol, benfopbenine,
ndphthalin (or compouoda polymeric witb it), undccom posed benxoio
aeld, and a nictaljic carbonate — When they are heateil witb pbospborio
at- id, beozoie acid sublimes uadecom posed. — Nearly all benzoaica are
soluble i« water, and most of them dissolve readily. Many are likewise
soluble in nleobol. As the beneoates are for the most part more solabli
io water than the free aeid^ the acid is separated from their solutions
the addition of strong acid.s, a milky turbidity being lirfit produced, and
the benioie acid afterwards orystaliiaing oat* — The moro Bparin<^ly soluble
benzoates dissolve readily, according to Lecanu St Scrbat {J, J^hutm.
Oi 811) in aqaeoDs acetate of potash or soda, and in nitrato of soda, bal
not in nitrate of potash^ or in sulphate or bydrocblorate of soda. ^M

Bm:o<tU of Ammonia.^ a* A^orr/ia^ ~ Benioio acid la disaolred

nearly to saturation^ in warm eon cent rated aqueouip ammonia, and lb6
solution left to eool.^or a more dilute solution of bentoicacid in ammonia
is left to evaporate and ammonia added tn it from time to time. Tho
salt crystal Hsos with dilKeultj in threaildiko cryijtals; it has & Ajwp
tnfite. At cording to TronimadorflT, it may bo sublimed j but aeeordl^^^H
Ber^isliusp it is converted into the aeid salt, eveu during tbe evapof^^^B
of it^ salutioUi When heated in a retort^ it U converted into tm
trite and water:

pise

iblM

an^l
ib^

tnt^m*

J

jiob--

When beated, it tnelta, gives off vapours of benzoic acid, and doet
leave any residue* (Ure, I^t^peri, 75, 64,) — VVhen passed over \m\
at a dull red heat, H yields beittonitrtle and a erystaUine body. (Lanrei
& Cbnncel; CompL chlm, 1^49, 117/) — It deliquetices in tbe air (Lioli-
tenstein), diiKolves readily in water and alcohol (Tremm8dorff)i but Im0
read i ly i n at eobol tk i n t be potash ^ i&l is , (Be tm\ ins. )

Ik AciiL — Produced during the spontaneous evaporation of a soltitton
of tbe normal salt; it then separates in lar^ irreg^ular crystals, a portion
howerer efflorescing on the ed^s. When the stdution of a is boUed,
ttBimonia e^capesp and the acid snlt separates m needles uniied in feathery
lirfU or in gmnulei* aceordnigly as the solution is more or less onickly
oooledp It dissolves Sfiaringly in water and is less soluble tu aosolate
alcohol than the normal »alt. (fierzoliusj _

Bmsmfe of Pota^. — a, A^'ormal — Cryatalligea from a hot-^atnmted
alcolmlic «olution, in needles United In tufts; or, if It separates from tll*|
solution while still bot» it fonns lamlnK? ht»vingr a prarly luwiro F
the ni|urou3 solution, it crystnllitte!i with difficulty m u^edlr^ nnite^
f€*7thf*rj iufu. 'Ihe solutions elEoresce when abandoned to s|H>ntailfKifl

BENZOIC ACID. 89

evaporation. — Potash exactly saturated with benzoic acid jrields a salt
which separates in delicate pointed crystals, and deliquesces in moist air
[because it contains free potash: L.j; if a somewhat larger quantity of
acid be added, the same crystals are obtained, but they remain dry when
exposed to the aid. (Trommsdorff, A. Tr, 1, 1G2.) — Benzoateof potash
is difiBcult to crystallise from watei, but crystallises from absolute alcohol
in unctuous masses. (Lichtenstein, Berzelius, N, Gehl. 2, 277.) — The salt
luM a sharp, somewhat burning taste. (Berzelius.) — At the heat of the
water-bath, it gives off 1 At. water. (Berzelius.) — Dissolves very easily
in water. — Distilled with arsenious acid, it yields benzol. (P. d'Arcet.)

b. Acid. — Produced in presence of excess of acid. (Berzelius.) It
is contained in the residue of the preparation of anhydrous acetic acid
from chloride of benzoyl and acetate of potash, and after washing with
water, crystallises from solution in boiling alcohol, in beautiful laminss
having a pearly lustre. (Gregory.) — Contains 13'4 p. c. potassium, the
formula requiring 13*8 p. c. (Gregory.) — Leaves the normal salt when
heated. (Berzelius.) — Dissolves in 10 pts. of water (Berzelius), and in
a large quantity of boiling alcohol. (Gregory.)

Benzoate of Soda. — Somewhat efflorescent pointed crystals, soluble in
water and sparingly soluble in boiling alcohol. (Lichtenstein, Tromms-
dorff, Berzelius.) — The anhydrous salt treated with protochloride of
sulphur yields chloride of benzoyl, together with chloride of sodium,
sulphate of soda, and sulphur:

2C"H'*NaO* + 3SC1 = 2C"H*0=C1 + NaCl + NaO,SO» + 2S:

and the chloride of benzoyl, if heated to 150° with excess of the benzoato
of soda^ forms anhydrous benzoic acid. (Ueintz, Fogg. 98, 458.)

Bemoate of LUhia. — White, opaque^ amorphous mass, which dissolvee
nadily in water and does not deliquesce on exposure to the air.
(C. 6. Gmelin.) — It is easily soluble and dries up to white saline maai
which becomes moist when exposed to the air. (Berzelius.)

Benzoate of Baryta. — Slender needles^ permanent in the air, sparingly
•olable in cold, readily in hot water. (Trommsdorff.) — Large taUei
which become opaque at 100°, aud contain 47 '07 per cent, of baryta.
(Piantamour.) — Gives off 2 At. water at 110°. (Limpricht, prlTata
oonBOuication.)

Limpriclit.
BaO 76-6 .... 36-90 36-60

omny 1130 .... 5443 54-43

2 HO 18-0 .... 8-67 8*97

C"BaU*0* + 2Aq.... 207-6 .... 100*00 100-00

Benzoate of Slrontia. — Resembles the baryta-salt. The crystals^
when exposea to the air, lose their lustre but do not effloresce: they
dissolve sparingly in cold, readily in hot water. (Berzelius.)

Benzoate of Lime. — Sometimes forms needles having a silky lustre,
and united in bundles or feathery tufts, sometimes granules. (Berzelius.)
Long thick needles^ having a strong lustre. (Plantamonr.)

^.

D£NZYL£N£ SIS RIB S : PRIMABY NUCLEUS C^W.

CaO *.i.-i».-

. 28^ ..
.. B40 ..
.. 7*0 .
,. iO'O ,

,.. 17*66 ,
,.. 52-80 .
,.. 4"40 ,
„ 25-14 .

irm

H C ..,...,.„*•

7 H

5 0

51-85

4^05

,. 26*42

C^H^CaO* + 2 Aq

. 159-1 .

... lOO'OO .

100-00

IttOOQi]

aeidl

Has a sharp atid svveeliBh taste. Becomes liqutd when heated, and

yielda by dry distillation, benzol, Uen^one (benzophenoue Eccordiog to
Chancel) » iiaphthaihi, henr.oatc of liuiOj and carbanate of lime. (FelJgoL)
— Disnolveei in 29 ptt. uf cold water. (Buchoh^ Lichtonfiiein .)

BtnzoaU ^f M(ttjne$ia. — Short feathciy crystale having a somewhat ^
bitter pang en t taste, slightly effloresce ut^ easily solable in wilgM
(Lichtensteln, Troraniadorff.)

Cevam Btmoaif, — Benzoato of potash or ammonia added in exc
the solution of a cerous salt forms a permanent curdy preoipili
(BerzelinsJ When hydrated cerotis oxide is boiled with an a<jni
, solution of impure benzole acid, a compound of ccrous oxide, benzoic i
|»nd tmvn remains undissolved, and the Bolntion when evaporated, first]
yields crystals of benzoic acid, and then pure ceroue beiizoatc in whit
crystalline grannies^. (BerzoUus & Hisingor )

ErtiZoaU of YUna, — Benzoate of ammonia forms with hydrochloratd
of yttria a thick precipitate sparingly soluble in water (Hisinger)! h
according to Bcrzeliu% it u insoluble. — Concentrated solution* oryitri»-H
salts do not form an immediate precipitate with n1 kali no benzoatea, hot
wlien the mixture is left for some time in a warm place, ben toatc of
yttria separates in the form of a white powder. Dilute solutions yieldJ
the esait after evaporation in small crystalline granules, whichj wlie
examined by the microscope, appear to csoufiist of four-sided priscmt i ^~
lu J:pherical groups, Tiro mU doe€ not appear to contain wai
dissolves in SO pt^. nf cold water^ more readily in warm water* (i

Hfjizfiatf of (riitcina. — a, Biba^ic, — Precipitated by double de
poiiition of bibaiiic glucina-salts with alkaline ben^oates; the precipiii
IS not immediate, but» after a few (iecond;*, a gelatinoui precipitate i
jratc^, which is not di .solved on a*ldition of water or on boiling.

6. Moftfihmk^ — Neutral ^diicina-salts are not precipitated by alkaline
benioates; but the mixture abandoned to spontaneous evaporation first
yields crystals ref*embling bonzfjic acid and containing but little glucina,
and the niasa aftcrwurds solidities into a jelly which appears to coti«kt of
normal benzoate of glucina*

Benzoato o/ i4/«mi«a, *^ Obtained as a curdy eryetalliim pn^dnitate on
tnixlog a somewhat concentrated solution of nn alumina salt with licnioftti
of potash. Ha§ a rou^h taste. Reddens litmus, {lachtenstein, Trommt*
dorf.) It disflolveM prettjr readily in water. (Hisinger.) The h^^m
eatn rated solution solidifies m a crystalline masa on cooling. (Berzeliiii.^|

Bmzo€Ue of ZirconiiJ. — Benzoato of pota&h added to sirconia aalta
throws down a blutsh grey powder, sparingly soluble in water. (Hialnger.l

41

Ckmmom ^mtoai^t^-Protochlonde of chromium forme with benj^mtB

of potash a light greyish precipitatej which becomes bluish green on

exposure to the air. — In vimuo over oil of vitriol^ or in & stream of

faydrogeu at 100^, it ^v^u off water and aisumes an neh-grey colour,

r (Moberg^ J. pr, Chmn. 44, 330.)

Dried.

CrO 3G

U C fil

5 H ..._ 5

a O 24

C^CrH*0^ HO

Moberg.
24^6 ........ 23^47

56-37 56-03

S3S 3-42

1611 17-08

lOO'OO .... 100-00

Vrank Benzoaie. — Obtained W double decompositiun. Pale yellow,
iTerj slightlj soluble in water (Rich tor.)

Matiganou^ Bentaate. — ^Transparent, colourless needles, which are
tpernmnent m the air, taete at fir^it sweet and rou|rh, afterwards Htter,
ldias4dve in 20 pta. of eold sva.ter, aud iire much more soluble in hot water,
[(John.) Sparingly soluble in alcohoU (Trommsdor IT.)

MnO.

.,.. 35*6 ,

,. 22-59 ...
. 7170
5-71

John
2"4

C"H*C^ ....
HO

... 113-0 ,

CHMiiH*0*

+ Ah .

157-6 .

.. lOO-OO

Ar$miou$ ^teid dissolves reailily in hot aqueous benzoic acid; the
solution yields efflorescent feathery crystals, which have a souii' and
r lather pungent taste, sublime ai a moderate heat, are decomposed at a
Lttronger heat, and dissolve readily in hot water. — Tej^oride of antimony
[obtained by calcination diasolves readily in aqueous henscoic acid, and
[yields a white laminar masij pcmmneot in the air^ and easily soluble in
[water and alcohol. {Tromms<lorff.) — * With Teiiunc mUsf benzoate of
ammonia fonns a white nearly insoluble precipitate. (Hisinger,)

Benmaie of Bismuth. — Benzoate of ammonia forms with nitrate of
j fcismuth a white precipitate partially soluble in water. (Hieinger.) —
lit tliaeolves when heated with excess of benzoic acid and with water, and
[iepaffttes on cooling in needles which die/rolve in water and alcohol, with
[■ep&mtion of oxide of bismuth [basic salt?]* (Trommsdor^)

Be^uottte af Zbic. — Pendritic, efflorescent crystals which have a
rough sweetish taste, and dissolve readily in water and alcohol. (Tromms*
tioi-ff) Ben 10 ate of ammoiiia doea not precipitate sulphate of jtiac.

' (Hisinger,)

Benmakof Cadmium. — Aqueous benzoic aciil dissolves a rety small
ijuautity of hydrated oxide of cadmium; and the solution when evapo* '
rated, yields crystals of boQjsoic acid together with a yellowish powder.

4f

BENZYLEKI SERIES J PaiMART NUCLEUS C**H^

Staniima and Stannic Benzoai^. — Obtaineil by double 4eeartti|
ttllon. White precipitates soluble in wat«r especiaU^ if hotj infi&lublel
ycoIioL (Tromiufidorfl'j Htsiiiger> fiet-selitiB.)

Bmzoate of Lead, — a* Tribasic, — Produced by precipitating
acetate of lead with benzoate of amtnonis, or by treatin^^ b witb i
White powder; anhydrous* (Berzeliue,)

3 PbD .«....«», 3S6 .... 74-Sa

CMH*0> ,...„... 113 ».. 25-17

2PbO,a^PbHW..... „.. 44^ .,„ lOQ-00

100

>. Mm<}hmus or Nm^moL — Protoxide of lead dietolves in &qt
benKolc acid; and the solution yields white, ebiuing, cryftUilline lanilnV
soluble in water and alcohoL (Tromm^dorft') By precipitating nenin
Imd*«a1t« with norma! benEoate of potash ^ a light crystalline powder
obtained whioh At a tcniperattire eoniewhat above 100^ mette and ^iri
off 3'78 per cent (I At.) of water. It diesolvea when boiled wifi'
dikto acetic acid, and separate*} on eooliug in shining crysti^lline i
reaeniblbg the free acid, (Beraeltus.)

^O «*....«.... 112

C>*H«0»„...„ 113

HO .„_„..,.. »

C^^Pba*0^ + Aq ... 234

B«rieliuj,

iVm 4649

48^28 4y (S6

3*8fi ...... 3*8&

100 00 ,...,., 100 00

JUti^^ntmtg fif Lead. — Wlien benioate of lead is diM|«l
m ftcetate ut letui, the loose pulverulent precipitate gradually 1
lifiAvy and eryst^line, and acetio acid may he detected in iu {Ym
Ifafpj Ann. ^kartt^ 35, 7 a)

8 Pb ,, .,„,._ , _ fi94'4

22 C , _.,.., 132-0

UH ..,.^.«„.^..«„^_.^..„^.„.., no

9 Q .....■■. 72-0

2PbO.C»H«0* + 2(3PbO,C*H*P*) . 1109 4

Y^r«ntt«pp,
80-01 ........ 81 '01

1194 ,......, 12^09

l^-tf » 1*01

tm i^et

lOODO 100*^

F€rTou& SmtoaU crygt&IUses in needles, whieb effloresce and tnn
yetlotr when eJtpooed to tbe air. They diuiiol ve in water and al^olio
BensQiite «! ftmmoma doea not precipitate ferroue salta, (Berieliua }

thrie Benw&aU, — <i, Il^pfrhasic^ — a, Tf a eolution of seflquichlor^d

^ Iron be mixed with so much amntonia that iti? eulour becomes dcei

red, and after a f*-w hours a small ijoontiiy of fiew<piiv\uJc retiming undjf

*fd at ibe ixittoin, and if a neutral Wnsoutc of an jilktili Iw tbtm addcJ

ry bulky fldnliHsidourod precipitate In formed insolubk in wmb

"I by oold wator (Borteltus.)

BINIOIC AC1D« 4g

Hifinger. Tbomioii.

2FeH)* ^.... 160 .... 26-24 24 .... 25

3 C"H»0» 339 .... 63-47

15 HO 185 .... 21-29

2FeH)",3CWH»0» + 15Aq 634 .... 100-00

[BcrwHai loppofef Um Mlt to contaiB only 12 At. wattr, bat tecorduig to kiMt
fappofltiaii it thoiUd eonuin 26*34 p. c. ferrio oiide. L.]

B. Remains nndiaaolved when 6 is treated with cold water. (Ber-
seUtif.)

h. Baaie, — When a solution of ferric oxide is mixed with a quantity
of alkali sufficient to turn it yellow, and a normal alkaline benzoate
then added, a reddish white mass is thrown down, which is insoluble in
the saline liquid; when washed on a filter with water, it becomes darker^
and a llauid containing an acid salt runs through^ while a more baste
compound remains on tne filter. (Berzelius.)

e* Ter-aeid or Normal, — A solution of ferric oxide in aoueous beneoic
acid yields jrellow crprstalline needles which are dissolvea by water or
alcohol, a basic salt being left behind. (Trommsdorff, Berzelius.)

d. Acid. — Prodaced on mixing 6 with wateri while a, /9 remains
uadissolTed. (Berselius.)

B$ntoaU of Cobalt and Benzoate of Nickel are soluble in water and
may be obtained in the crystalline state. The cobalt-salt is red, the
nickel-salt green, and both dissolve in alcohol. When the solution of
either of these salts is mixed with the oxide or carbonate of the same
metal, basic salts are formed. (Berzelius.)

Cuprtc Benzoate. — On mixing an alkaline benzoate with a cupric
salt, a bluish precipitate is formed, which acquires a fine ^reen colour
when dry, and is somewhat soluble in water. (Berzelius.) Insoluble in
alcohol. rTromtnsdorff.) When precipitated from a hot solution of
sulphate of copper, it forms a loose aggregate of bluish green needles.
^Ettling.) It does not contain water. (Mitscherlich.) It dissolves in
dilnte acetic acid when heated, and crystallises therefrom in small needles.
By dry distillation it yields benzol, carbolic acid, benzoic acid, benzoate
of phenyl, and an oil which boils at 260° and when heated with oil of
yitriol, is resolved into carbolic acid and a crystallisable hydrocarbon,
C^H*. (Bttling, List & Limpricht) At a bw temperaturci cuprous
MlieyUte remains in the residue. (Ettling.)

Jiereuroui Benzoate. — Formed by precipitating mercnrons salts with
aqueous benzoic acid or alkaline benzoates. White, very bulky, crystalline
precipitate, consisting of slender needles. (Hifinger, Harff.) Acquires
a lignt yellow colour by exposure to light. When heated, it acquires
a dark yellow colour, swells up strongly, then turns grey, and ultimately
becomes white again. — When it if qnickly heated, a sudden glowing of the maat
takes place, and a poront charcoal retnaint behind. At the bejiinning of the deeom-
petition, beRMlc add tubnuei nnaltered. so that a baiic Mlt remaint befabd s afterwards
eBBpyreamstie mponra and nercnrial vaponn are given off. (Bnrckbardt, N, Br. A^^k^
11* 250.) The salt sublimes partly undecomposed in white feathery
erystals [nnleti these oonaiit of benzole acid. Gm.] and moreoyer yields mei^
cttty-fapoun and charcoal. (Harff.)

BENZYLENE SERIES : PKlMARy NUCLEUS C^H\

Harff-

H«S0

... 208 „

.. 64*75 „.,

„, 6401

C»H^oa

,.. 113

.. 35-25

c^-HrH^o*.... 3ai .... loo'uo

iDiolable in cold water, in ilIcqIioI and in ether. Dlssolres in at^neou
b^DEoio acid (Harff); is insotable m aqneoas benKoic acid and m bent<ia|r'
of ammonia or putash* (Biirckhardt.) Dissolves in concentraled lotil
ti*jns of alktilluo acetates aod common emit, la ile.ompsiaed by buUin
water (Harff), and alcohol (BurckhardtJ^ witli separation of meu "
mercury.

Mercuric BenzoaU, — a. Bmk^ — u. When benzoic acid is boiled witi

water and excess of mercuric oxide* a lii^bt white crystal linia puwder
formed, wUich 19 eaaily separated from the me re uric ojtidc by Jerigatiod
It is iuaoloble ia water and alcohol. According to TronimsdorS*, [
Eublinies in feathery cry^tiib. — ji. Tbc neutral salt contiauon&ly boil«
with a concentrated solution of carbonate yf potash, carbonate of ncida, n
phosphate of fioda^ i? converted into a yellow basic ealL Insoluble ti
water. Aqueous benj?oif acid converts it into 6. { Burckbardt.)

h. NorjfpiL — Obtained by precipitating a solution of corroaaive fub-^^
IJlUMte by an alkaline benzuiite, or mercuric acetate by aqneuue betiioi^H
acid. (Burckbardt.) Whiti merc^uric act;tatc is dtfcumpoied b)- alknHiie bcnt\>iitc<|^l
pttfE of tlie nacrduric: btnaoate remnini dissolved iu the ulkulint; acetate* White balky
p rec i pi tate gracl ual 1 y bee oni 3 1\^ crystal line ( H ar ^ , m ado up 0 f al efi d«t.
needles. (Burckhardt.) Poes not blacken when exposed to llgbl
(Burckhardt, N. ArcL 11, 277.) ,

HO , .

108

113

9

46-95
3 91

Unrff.
4S'33

3-3

Bnrckbtrit

. 46 00

Ci^HgHW.. 230 ... 100 00

SuVimes in a glass tube partly nndeconipoaed in featbcrf erystab

fbentcoic acidi Qni], yielding at the tame time mercury and chaftiotls
HarflT.) Ueaolved by beat into benzoic acid^ carbonic acid, carbouic oxidi
tnerciiryj and cbarc-oaL (Burckbardt.)

The aalt ia ins^duble in cold water, but dissolves pretty freely in bo
water, and eceptiiateft out unaltered on coolin;^ (BuFckhardt); boirm|
water converts it into an insoluble basic salt which doee not dissolveg^
(Harff.) — Alcohol dissolves a portion of the salt, and sepamtcs a ba^i^l
«alt which is converted Into oxide by continued boiling. Jt ia in^labUj
jn eiber. (Burckbardt.) It diejjolvea in 370 pts. of alcohol, and i#
resolved by ether into a basic and an acid salt; which dissolves in 2 pts.^
^ iif ether. (Harff.) ^

Ammvmm-mireiii^m Smioate, — Obtained by treating luareotQa
benioftte with ammonia; the resulting black powder, after bciu^ wmali«
land dried contains 80 90 per cent, of mercnrons oxide. (Harff.)

mitj^^ ortfaeuLi igrera Ihrrefi^re with the fomiuk 3llgHM:^^HM)3 1^ NH^ tWllI
_ lim 80*11 p, c, mer^'Uftiut oxitjr* H*rff (AV Br, Arth 5, 2U5J adapts I he fonovt* j
'Hg*0,C**H*0*+KH*, which reqaire« 5;'46 p. C tiieirurgos ^iide, h.} The mil

AMORPHOUS BENZOIC ACID.

ih

whBtL heat^l gives ofT oxygen gas [? Gm,], ammonia, benzoic acid and
nerciii-y. Heated with pfitaah, it gives off ammonia. Insoluble in
rater or alcohol, but dissolves in acetic acidj globules of metallic mercurjr
Bparating at the same time. (Harff.)

Ammonio-m^rmric Btnzmte, — By treating mercuric o^ide with
'ammoiiia, a white powder i& produced which, after waslibg and drying,
contaios 69' 92 per cent, of mercuric oxide, (HarflT, jV. Br. jirch.5, 287,)
[llic formula 3HgO»C'<H^na ^Nbt^ mjuir*;s 07-78 p. c. of mercurv. Hurff adopti
the formuk Hg;n,C**H''*CF+ NH^ which roqiiire* 4l'22 p. c, of mer^urjua oiide.]
When the salt is heated, mercuric Uenzo ate sublimes [IGm.], ond oxygen
gas [1 Gui,] escapes together with ammonia. Polaeh turns it yellow and
^■elirainatos aiiimonia. It is insoluble in water. DiBsolvea in 1500 pts.
^Kr atcohol and 2000 pts. of etlier. (HarC)

^B Btnto&te of SUtm\ — By mixing the solutions of nitrate of eilver and

^Kd alkaline benxoato, this tmlt In obtained m the form of a white spongy

^■precipitate; it h al&o produced by treating oxide of silver with atjueous

benzoic acid. (Trommsdorfl'.) The thick white precipitate becomes

^^omewhat crystalline when heated with wuter, dissolves completely in a

^Hlrger quantity of bolHiig water, and then crystallises iu long shining

^^byatalline lanimiD, wh^ch do not h^se their lustre or diminish in weight

^B^ drying in vacoo* When healed it melts and swells up, and after the

^■tfiarotial has burnt away, leaves white crystalline silver. (Wohler &

Liebig) [The shinin* silver which remains when bcnzoate of stiver Is

ig^nited contain? rather a large quantity of carbon. (Liebig & Redten-

bacber, Ann. Phrrrm. 38, 130: E, Kopp, Comply Chint. 1849, 158.)]

Kg ^ -

14 C.

G H »....».
iO..

84

6

32

4M6

30^68
218

47-04 ,.. 4683

C'^Hgtl^O* .... 229

10000

Dissolves in 100 pts, of absolute alcohol at 20^ (Mitschorlich,
^pr, Chm, 22, 194.)

B^mmti^of GohL — Obtained by dissolving toroxide of gold precipi-
ated by potash in hot aqueous benzoic aeid. Forms small Irregular
tystals, permanent in the air, sparingly soluble in water, insoluble iu
alcohoL (Tromm.'sdorff,) — Hydroclilorate of auric oxide is not preci-
pitated by bcnzoato of potash. (Berzelius.)

Benmale of Plitmum, — Obtained by dissolving platinic oxide iu

Ibe acid. Yoilow, velvety crystals which leave a yellow powder when
jnited [I Gm.] ; they dissolve sparingly in water and are iuiSoluble in
Ic^ih^iL (Tronimsdorff,) — Beozoate of ammonia does not precipitate

;>latinuni-5alt8. (Hiainger.)

The compounds of benzoic acid with auric and platinic oxides

Obtained by TroramsdorfT, are probably double salts. {BerzeliuSp Ltkv

Inch 4, ;n9.)

•, In pdiadous mhs. benzoate of ammonia produces a white precipitat€,
ol ttble i n water, ( H i si nger . )

k.

49

BENZTLBNB SERIES j PIUMARY NUCLEUS Om*^

Benzoic Bcid dmolvm in 2 pts. of cold and 1 pt of boiling absaluti
i^<iIiol; m 2."i (>te. of etJt^r, wbeth*?r cold ot UoL (Bucbola.) It disaolvti
readily in mis botU>^«sti and miaiiie.

1. Amorphous Benzole Acid.

1, Kopp, Cmnpt chtm. 1849^ 154*

Parabtnzak stid.

Formaiitm and Pnparation, Wh^n 1 pt. of gum benioin or Toln
lMsIii U beated wjtli 6 or 8 pta. of nitric acidT not strong enough to form
^sitrobenzoto aeid^ a Tiolent cvolation of nitrio oxide and carbonie aeid
ioon takes pkce, and tlie re^in swelb up to an ortto^e yellow masi. Ai
toon B^ tbe action ia Hnisbcd, tbo nta^s is introdocod Into a CTapaciotu
fetort and distilled, tbo liquid wbleh pasees over bemg poured litidl
from lime to time, Tbe viscid liquid ultimately left in tbe retort b
miifed With 3 or 4 pts, of boiling water, which separates a yellow resin; mud
tbe liquid decanted therefrom deposits on cooling, a yellow powder,
picric and nitric acids remafn d I evolved. Tbe yellow powder is poi
from adhering colouring matter by repeatedly dissolving it in hot
and leaving the eolution to cool; or it is mi^Lea with milk of lime^ whtrt^
upon tbe resinous colouriug matter remains undissolved, together wi
lime, and the filtrate ia precipitated by hydrochloric acid.

Prrfpertiei, When perfectly purified, it forma a white amorphoni

powdt?r; but it m commonly mixed with a small qnimtity of a yellor

roahi wbich posses with it into all ita compounds. It then forms light-

r yellow cnists and warty crys-talline gran u lea (e); baa a slightly eow

" * ' ' ' y hitter taste; melts at 11 3"^ to a yellowish hrown

; becomes covered ^hen cv posed to the snn orgenilr ^

^4icftleri, with white crystals of benioio acid; and when dittilled, yiclik ^

i ben2oic acid, with a small residue of charcoal. The

(f) obtained by

into crystallised

rhite powder
. hf 4]0ltllation
kreiidne

repeated ijurification^ is converted
benzoic acid, without leaving any

|4C._

4 0..,,.

68*85

72-95

70^50
4'iQ

697S

4'm

69 10

6900

I

100*00

When distilled with Lime, it yields henxol,

V^mhin^^n*. Tbe acid of cotnposition r, forme with
' which are leas soluble than those of pure benzoic acid.

Thi» mimamimmh \» yelloir. The Umi^mU eryilalLisei in yellov
^nodulex by ipontaotoiti evaponition. The kud^^ii, f^hi^Xm^ by pneifd*

^^T" H

CARBOBENZOIC ACID.

At

ig tbo lifiie-flalt witb neulral acetfite of loa4» or the eoda-salt with
Tiiirate of kad is a. jeUow, nou-cryatailines msoluble precipitate consist-
iDg of 2PbO, C**H*0^ -J- rei<in. The copper-aaU obtained I by precipittitiDg
the lime-Sill t with acetate of copper, ia of a beautiful green colour, ainor-
pboas^ and yielJa l>y dry flistillation, benzoic acid and benzol, leaving
metallic copper and charcoal. The silmr-mU obtained from nitrate of
silver and the annnonia-i'alt^ h dark brown and k reeolvod bj boilrng
with water iuto an tnsokble brown amorphous body, and a soluble portion
which cryfitalliees in dendrites.

The acid dissolves readily in aie<}hol and ether.

The compound ether obtained by treating this acid with aleobo! and
Iiydrocbloric acid is a reddish oil* heavier than water, having an aromatic
odonrand bitter taste; when distiUed after dryings it yields pnro benioate

^■^ Preparation. Cinnamein is mixed with concentrated alcoholic potash;

^Hie soapy mass diluted with water, and repeatedly distifled with fresh
portions of water till all the cinnamio ether and peruvin have passed
over; the residue dissolved in water; the eolntum decomposed by hydro-
chloric acid; and the cintiamic and carbobcnzoic acida thus separated are
washed with cold water and dissolved in hot water, whence the cinna-
111 ic acid crystallises on cooling. The motbcr-li(|uor yields after evapora^
tion, first a mixture of laminar ciuuamic acid and cauUflowerdike carbo-
benxoic aeid; the last mother- liquor yields only carbobenzoic acid. —
2* From the mixture of cinnamic and carboben zoic acids precipitated by
hydrochloric acid, pure carbobcnzoic acid sublimes between 120^
and 150^

Pr^^riieA. CrystalHno grains grouped in masses like cauliflower-
beads. Melt? at 150"; boils at 250 ; sublimes a little below its melting
poiDt in granules united in caiiliflower-lieads and destltuto of lustre.

2. Carbobenzoic Acid. C^*H*0^

LAKTAMonn. Ann. Fharm, aO| 341.

[Beoioiq acidi with n small nuanlity of cinniimie acid ? Gra,]

15 C „

6 H

4 O

.. 90 .
... 6 ,

.. 32 .

., 4 G2

. 24G7

Plantaroour*
70*37

a*iB

24M&

C^HH}*

,„ 128 .

.. 100^00

........ 100-00

CombiTiatimf. More ?=olub1o in water than benzoic acid.
The earbobcnioates crystallise in caulidowerdike m^sae^, which cake
together when heated.

Ca$*hohmzoaU of Baryta^ — Obtained by disiolving the ctystflllisod
Ecid in hot baryta-water, Anhydroua,

li

BENZVLKNE SERIES; PRIMAET NUCLEUS C»H*,

B«0

15 C

h H ...
3 O .

7M *... a8*4l .^ 40*07

fiO-0 .„, 46-49 , 4^20

y^ . ^5J ,«»» 2-96

24H> -„ ia"57 ,„ lOTl

C'*B*HH>*.. 195*6

100 ati

100 -Od

Carbobmmai€f>fLiwu, — Vte\*^Teii like tlie barjrta-s^lt.

CO

15 C ....
ft H ...
5 0 .

£B*I
9li-0

24-0

57-98
20-2$

... 18 87

,« 57*96

... 3fll

... 19SS

C"CnH*0*...,

147*1

100*00 ....^. lOO'OO

CufhAmnoate q/'Xcocf, — Becomes waxy nt 100°,

PbO .»»««.. 112

15 C ....».,. _,.,-. !KJ

5 H .., .„» 5

3 O . ,..„ 24

C*PbH*0* ...... 231

Pltntimonr.
48*03 ........ 49' 2»

39-48 _...„ 39-31

214 ,. 2*2f

10'3S . . 10-11

100*00 ...„.., 10000

CarhchemoaU of Siha\ — By precipitating tlie ammonm-salt with
nitraio ol silver* Flocculeat precipitate* Decomposed by ersfN»mtio&,

Pbnt4iiiiour.

Af... »....,„ 4S'S4 , 4: "12

15 C .„.„. ..„. 38*4^ 37-1*9

6 II ..,.«..» 8-M ...„. . 2-52

4 0 1411 .............. 14'17

C**AfHW ....,„ 10000 10000

Carbobenioto acid dissolves readily in €tU^l and e*4^*.

3. HsTpobenzoylous Acid.

LoWtO & WEl0»\Nlf. P(^. 50, 105.

F^^mati&n and Freparation, The tnixture ol^tained by
beotoato of ethyl with soiliiim (p, 01 ), is washed with sDhydrotie eUMf*
which leaves undia^^olred & saline ma»« conaUiing of ctiiylar© and htnwmJtM
of aijfiiura. The dark brown litjnid hnvjng been freed from rthcr li|
dislilktion* there romains a brown oil (impure hyiKibenzoyUte of cthylf
which is ititfflable in water, dissolves re^driy In aU-obol and ether, Is W
■lightly dcconipgtod by afjueoas potash, but readily by tleaholic

SULPIUDE OF DENZTLBNE.

«•

with formation of email quantities nf beniaute and hypobenzajlite of
potash. If the alkaline aulatlan be diluted with water and the alcohol
ee|)arated from the clear lioijid \tj distiSlation, hydrochloric aeid then
throws down from this Hquid a lEixture of hen^^oic and bypoben^ojloae
acids. This miitnre is boiled with water, in which the hjpohenzojlona
acid is insoiuMe.

Frcptrtiea. Yellowish brown; resinous; In the cold it baa the con-
'iietence of thick turpentine, but melts very easily at the heat of the
water-bath, into a transyiErent yellow liqmd. The alcoholic solution
reddena litmus allghtly. The acid is nut Tolatile,

14 C
2|0

Lowig $L Wddmann*

84 .... 7e-37 , 76^67

6 „„ 5^45 5^60

20 ... 18*18 73

IIQ

100*00 100*00

At a higher tern perat are, it decern poaee like the resina* — It appears

i be oxidise<l by nitric acid.

It is insoluble in water, but dissolves very readily in alcoholic potasfa,

'fonning a yellow solution whence it Is precipitated hy acids in its

on^inal state. The solution neutralised with acetic acid tdl it begins to

be turbid; then filtered, and precipitated with acetate of lead, yields a

yellowish white precipitate which, after drying at 100^, contains:

FbO_. ._ 112

U C ,,._ 84

b H 5

UO ,. 12

£25g 5290

3944 39*13

2Zh ...... 2-n

&*G3 5-04

213 «... 100-00

100^00

The solution of the acid in potash neutralised with nitric acid, forms
with baryta or lime salts a yellowish precipitate; with ferric salts, a
yellowish hrown; with niercune nitrate or chloridej a white; and with
ihrate of eilverj a yelbw precipitate becoming brown when heated.

Sulphide of BenEylene.

Paiioiths. (1848.) N. Ann. €Mm. Php^. 23, aaS; /. pn Vhenu 45, 133.

Formation. Produced by treating chloride of beniyleni with an
obolic sol at ton of iulphide of hydrogen and potasaiunir

yoi. XII-

C"H«CP i^ KS,HS m Om'S? + KCl + HU.

m

BENZYLENE SERIES: PRIMARY NUCLEUS C"H*.

White crystalline scales having a pearly lustre. Insolable in
Melt0 at ^4'^ and solidifiefi id the crystalline state oa cooling.

u c »_. u

6 H ,..........,.„. 6

2S .. ..„. 32

0*H»83 __...„.. 122

_ mm ........ 68-76

_ 4 92 4*97

.. . 2619 , 2600

.... 100 00 ........ t9*73

The compotind when strongly hedted turns l>rown and volatiliM
being at the same time partially decomjKJsed. — It Is violently attacka
by nitric acid even when dilate, with format ion of eulphurie acid and i
suhstance which dissolves in alkalies and crystal! ise© in yellow scalea.

It dissolves sparingly In cold, readily m hoiling alcohol, whence it
crystallises in ©hining scales on coaling.

Hydriodate of Benzylene.
C"H'l = C"H^HL

CAnntzzAMQ. (1854.) Epistolary communication.

When a solution of beni^lic alcohol (p. 19), in bistulpHid« of i
ii mixed with a saturated solution of phosphorns in bisulphide of carbon^
iodiije gradually added, and the sulpliide of carbon distilled off after the
action is terminated^ there remains, besides iodide of phoephoroa, a li<}aid
which irritates the eyoe strongly and probably consists of hydriodate
bentyleDc.

Hydrochlorate of Benzylene.

CAKKlJEZARn, (IBSa) Ann. PAam.
45, 408; Autu Pharm. 06,240.

88, IZ^, — N.Ann. Ckm-

FrrparatMm. 1. When hydroebloric acid giaa j« pa^ed thro»f!i
hen sync alcohol, the liquid becomes heated, aiJfiumei a brown colour, and
divides jnm two layer^j. The apf»er layer is aqueous hydrochlerio odd;
the lower, winch consists of impure hydrochlorate of hentyleon^ m
itsaiovi»d| distilled in a current of dry hydrochloric acid gas, wai^hed will
^arhonatu of poUiaL, drieil by chloride of calcium, and rectified.—
% Toluene, C**il\ie repeatedly distilled in a current of dry chlorine |ii|
and the product le waihed with water and solution of potash^ um

CHLORIDE OF BEN^YLlNfi.

fil

(lehydrnteil by clilonde of calcium, and repeatedly rectified* The liquid
thus obtainedT hitherto caJled cliltjrotolueao ur cblofotoluol, is identical
with the precediug.

PrGpertiei* CoIiJurless, strongly refracting oil, heavier than water-
and haring a very pungent odour* Sp. gr. of (1) from 1'1136 to !^1 179*
of (2) = 1-117. Boila between 175" and 176'' (180* wid 185" iccording tl
C«ntiixzaro'9 earlier itAtement).

Healed with alcoholic ammonia over the water-bath, it yielda sal-
am tuoniac and a ^.Tystallbcd ulkaluiti which nielta at n, hi^'her temperature
then toluidine. — Heated with alcoholic potash, it yields chloride of
potassium and benzyl ic alcohol* — Heated with an alcoholic solution of
aedtat« of potaish, it yields chloride of potaasium and acetate of benzyl;
And with alcoholic cyanide of potassium^ it yields ebloride of potassiutn
and cyan ide of be n zy K

Insoluble in water ; dissolves readily iu alcohol and eiher.

Chloride of Benzylene.

jAUOvns. (1848.) if. Ann. Chlm, Phff*. 23, 320 ; J. pn Ckem.
40, 130^ abstr. Ann. Fhai-m. 70, 329.

Cht&robem&L

Formation and Preparation, Bitter almond oil aitd pentachloride

of phosphorus act upon one another with great evolution of beat; and if

the action is assiijted by gentle heating, a mixture of two liquids passes

ver. One fourth of the distillate boils between 108"' and 112", and

insists of oxychloride uf pho^spborus; and when this is distilled ofi^, and

the reaidae mixed with water, cliluride of beuzylene separati;s in the

form of an oil, which may bo wa.^hed with dilute potash- ley and after-

arda with pure water, then dried over chloride of calcium and distilled*

Colourless liquid^ the odour of which is faint in the cold^ but strongly

penetrating at higher tem|)erafures* Sp. gr. 1'245 at 16^ Boils between

SOa" and 208"". Vapour-density 5 595.

14 C ...».*„.

6 H

2 CI ., ,,

... 84-0 .,.
. 70-8

. 52-26

3-72

. 4402

C&hoan.

........ 52^33

....... 3*72

13-80

0m«CR....

^A C*Tsuour ..

.. 160 8 ...
Vol

.,, u

. 100-00

99'91

Derwitj.
5-8240

■ H-gM ".:;

6

0-4158

r ci-gM

.»»*..* 2

4^9086

4 *

Vapour

2

11 1484
5*5742

52 BEXZTLE!TB SERIES: PUIUKT 9CCLKI7S

It is Bo4 deeomposad bj yotusk^ ern vhb tke aid if knL
With u ak«^Uc solatioo of salphide of kjdiopm mmd poteanna,
jields chloride of potasFiom and sulphide of beurleneL

It 18 inaolable in vmter. bat diasolres readOj in olooftol and dker.

^. Cyanide of Ben^L

Cajexizzabo. ir. Jiiji. CAtni. Pk^ 45, 468.

Obtained by boiliofr chloride of benzrl witii a coaccaiyated aleoboGe
■olation of cjanide of potassinm, tOl no nore dikfide of potaariiB
aeparaies from the li^nid, and distilling the filtrate to renoTe tbe Tiaie
aleohol. The residaal liqaid then separates into two layers, tiie apper
containing cyanide of benxojl, which maj be obtained from it hj
rectification.

Colouries lianid which by boiling in strong caostie poCadi, ii
coaTerted into tolaic add, C**HH)*:

C^^W + 4HO - C»H»0* + NH». ^.

Acetate of Benzyl.

C^H^W = C"H'0,C*HK>».
CAKKi22Aao. (1853). Ann, Pkarm. SS, 130.

Prrparaiion, 1. When a solntion of benijlie aleobol in f toL aesHe
aeid is mixed with a solution of 1 toI. oil of vitriol in 4 or 5 toI. aestie
acid, the mixtare becomes tarbid after a short time, and an oily layer of
acetate of benzyl forms on the surface of the lianid. This oil is removed,
washed with a warm mixtare of acetic acid and oil of ritriol, and a^e^
wards with carbonate of potash, then dried orer chloride of ealciom, and
rectified. — ^. 2. Chloride of benzyl (prepared from tolnol, p. 50) ii
boiled for two or three hours with a strong alcoholic solntion of acetate
of potash in an apparatus which allows the condensed Taponra to flow
back again; the precipitated chloride of potassiium separated by filtration,
and the greater part of the rinic alcohol remored from the filtrate by
distillaticm. The remaining liquid then separates into two layers, the
npper of which, when rectified yields acetate of benzyl. T

Colouries oil, heavier than water, and baring a very agreeaUe odovr
like that of pears. It boils at 210*».

Boiled with strong potash-ley, it yields acetate of potash and bensylie
alcohol.

8ULPH0BKNZ0IC ACID. 53

Benzoaie of Benzyl.
C»H"0* = C"H'0,C»*HW.

Camnizzaro. (1854.) Eputolarj commanicatioD.

Betaylie Benzoaie^ Beneoe'benzesier, Biker bemo-benmique.

When chloride of benzoyl and bensylic alcohol are distilled together
in equal numbers of atoms, hydrochloric acid /zas is evolved, and benzoate
of benzyl distils over in the form of a yellowish oil. At the beginning
of the distillation^ small quantities of benzoic acid and hydrochlorate of
benzylene likewise pass over^ but at a later period, the benzoate of benzyl
is obtained in a state of purity. The yellowish oil crystallises on cooling;
the mass thus obtained is pressed between paper, and distilled over
benzoic anhydride; aud the distillate is washed with carbonate of potash
and rectified. On cooling, crystals of benzoate of benzyl separate in the
midst of the yellow liquid.

Colourless crystalline laminsB melting below 20^ into a colourless oil,
which remains liquid long after it has been cooled below its melting point,
and often requires the aid of a freezing mixture to crystallbe it again.
Boils a little below 345^

CanDisaaro.

28 C 168 .... 79-25 7917

12 H 12 .... 5-67 5-84

4 O 32 .... 15-08 14-99

C»H"0< 212 .... 10000 10000

The yellowish oil from which the benzoate of benzyl has crystallised,
has the same composition as the crystals. The mixture boils between
340'' and 345% and consists of, 79*13 p. e. Q 5*94 H, and 14-93 0;

Sulphobenzoic Acid.

C"H«S*0»« = C"H«0*,2S0».

MiTscHEBLiCH. (1834.) Fo^ff. 31, 287; further, iV. Ann. Clum. Phy$.

7,5.
FzuLiNQ. Ann. Pharm. 27, 222.

BenzoesehwtfeUdMre, Benzoe-uniersehwrfeUdure.

Formation and Preparation, — 1. When vapour of anhydrous sul-
phuric acid is passed over dry benzoic acid, or when solid anhydrous
sulphuric acid is gradually mixed with dry benzoic acid, heat is evolved,
antf a viscid transparent mass is formed. If 2 pts. of benzoic acid are
mixed with 1 pt. of anhydrous sulphuric acid, an additional portion of
oenzoic acid must be added after cooling, and the solid mass treated with
water, which dissolves snlphobenzoic and excess of sulphuric acid, while
benzoic acid separates out. The aqueous solution is saturated with car-

M IXSTTLXn S33S:

iufBK if VBTTSL, fJss^L ^-TainssffL »£ xoii «Ue f«m hoi with
kjcrvaL-.p-!*! fc;i*£ ft=t£ FuiLiQ^cnasr if %vn dien arpumtos in
crjRu fc£ ue 1*7XL'£ :< •!•':& r^rirsit -rT^Cftjs sn^ fczifiei br rKXTsUllia-
t5:i!L. laii Ld»:i.-r<*£ jx -v'i::'£r. -3!<- mzTn fcmeitucd \j mn exMtlf
e.x:Tfc>rL: :i:Li-L-j :z ?LTd.ir-jr *=!•!: ^a* sum:* «f liujtm sefwrtted
^•T il:rLTJf:c . uii li*^ i^irud wa»!iains-^£ ;lZI h b* Inagfr boils mt 15(f.
TY* icii i? :J:*?L :.:CLi»!-i iz iii» j<:3£ ficn ^a cooaBf. — 2. Bj tin
ac%>:4i :-: fl'T'IiSt aiei'i fir TexsTiiiirije. *B«ekiom i: Hofaaaii, xi,
I^<u — ^ 3t iif» bT^ia :c -w-iZi^ m <ajini!B];pb9beame acid. (Lim-
fnekt it T. f sJar. ^ t. i i^i-nt 1 1:*. i5i .

Pnf^.'iia, S:V.i cttr^LEk ass viSek anj W kaled to 159*
wixbovt decoKpic«K:>:«: h -Sec-iTEpfixiK end^aJlT m Moirt air, bvtreeofCB
hf eolid fcrna is % drj &£i:p3if^^«re.

Iknmp>»'t\^:m»^ — I. Br beaifix sxIrbolwBmr acid or aiij of Hi
silu wTxh exces of kj-irase cl p:-T&?c rll cocaplece decoMpoaitioB eoflMii
•olpliite and silpSiaze of pota^k are prodacied. (Fckfiag.) — S. The add
gentlr heated vith pectachlc-nde cf phccfkorvs fenns chloroffidplio-
benaoic acid, together with wmter acd chl^rophospboiic add. (Limpiidt
& T. Ufilar):

C*H*SH)" • PC? = C^H^CTSW - 2HO ^ PCPOe.

SHlphrJbfnsaniet. — Sn!phobeiia*>ic acid forms both DC«trd and add odti
(C"H*MH>,2SCH aod C-*H»MO», 2SO>^i. — It deconpoflce aitiate and hjdio-
chloTate of baryta, prodacinz an acid barrta-calt. ; it also decompoMS
hjdrochlorate of ferric oxide. ( Mit^cheriich.) — Accnrdinir to Mitadierlich,
the fonnola of the acid $o!phobenzaate$ is M0.C*'*HH)',U0;BO'. and of Un
neutral salu : MO,C ♦H^CP^SCH - M'XSCH. Fehling has shown thatUie
perfectly dried neotral salts conuin 1 At water l«s than this formala
requires, and regards the acid as a conjugated hyposulphorie add
= C'«HH3>,SH>* + 2H0. As it is difficult to expbin on this hypothedip
why hjrposolphuric acid, which is monobasic, should saturate 2 atoms of
base, Berzelius supposes the acid to contain the copula C^HK)* united
with 2S0*. (ZeAr6. 5 Aofl. 4, 324.) — The bibasic nature of the add
finds a ready explanation in Gerhardt's law (rii. 222). Accordini^ to this
riew, the fonnola of the acid is C"HH)*,2S0*, and of the 6 atoms of
hydrogen 2 At. are replaceable by metals.

Sulphobenzoate of Potash. — a. Xevtral. — Obtained by double de-
composition from neutral sulphobenzoate of baryta and neutral sulphate
of potarih. — Beautiful crystals which deliquesce in moist air. — 6. Acid.
— By (lecomposin:;^ aciil sulphobenzoate of baryta with neutral sulphate
of i>otash. — Beautiful efflorescent cry^tals. (Mitschcrlich.)

iSulpkr;bnizoatf of Baryta, — a, XtutraL — The solution of the acid
salt IkjiIchI with carbonate of baryta and evaporated, yields indistinct
cryHtals, or generally mere crystalline crusts. The salt is rery soluble
in watff. ( Mitschcrlich, Fehling.) It bears a very Mrong heat without
deconipoHition, remaining unaltered even at the temperature of boiling
**!!. Deflagrates when suddenly heated with nitre or nitrio add!

hiing.;

ACID*

SB

Felilmg,

Mit.cheaich. ^^ZZ:^^

2 B»0 ..,..„ 153-2

14 C 840

4 H ,... ^ ., 40

2 O . .,. ISO

2 SO*.., ,.„, 80*0

CMH*B««0<,2SO» . ,. 337 2

45*18 ..

.... 44-88

25-26 .,.

... 2526

M8 ,,.

„.. I 46

4'?4 ..

.... 4-89

23-84 ...

.„. 23*51

100 00 ...

.... 100*00

..^„ 43*68

45 31

h. Acid. — Prtparaimn p. 53j also xi, 157. — CrystaUiaea easily la
oblique rhombic prisms belongiDg to the oblique prismatic system.
^t : K = 82'' 21'; inclinfttion of base to lateral eJge = 9^^ ^\ The
Siblique lateral edge is generally tmacated; mostly also the acute summit
&f this laiemL edge; uiore rarely octobetlral facea occur. The crystals
arc generally inacled. (Fehlbg.) — Permaueut ia the air. Soluble in

10 pts. of water at 20°. Thesolutiou Kas au acid reaction ♦ The crystals
ive off 0^3 p. c. (3 At.) water at 200°. (M itched ich.)

BaO ............... 76 6

14 C „, ..,..„. 84*0

5 fl 5 0

3 0 ... 24 0

2 SO» 80-0

MiticherUch,

28-27 ....... 28-36 ...

31-22 _.... 31*40

l»a5 1-86

8-92 8'66

2974 29' 73

Btioktnn Limpricht
At Hofin^iift. &T. UftLtiT.
.. 28-34 282

C"H*BiiO*,2S0a. . 269*6 .... 100^00 „. 100-00

The salt ia not decomposed by fuming nitric acid. (MitacberHch.)
The acid solphobenzoates of maimettia^ zinc' oxide, fen^m oa^ide^ cobali^u*
ttd^y and cupric o^^ yield fine cryitals. (Mitscherlich*)

r

^H Neutral SuipIi*)bai^onte of Lead. ^ Ohtmned by boiling' the aqueous
^Rusld with excess of carbonate of lead, — Sleucfer ueedlea united in
radiated groups; the solution in hot water Bolidifiee almost completely on
.cooling. — The salt gives off 7 '93 p. c, (4 At.) water at 220^ (Fehhng,)

Dry,

2 PbO 224

14 C 84

4 H 4

2 O 16

2 S09 80

Fabling,

54*8<» 54*52

20-58 ....... 2085

0*98 101

301 .... ... 4-03

1964 ........ 10*69

C^<H*Pb50S2SO* .,,. 408 ..., 100-00 ...,.,.. 100 00

Neutral S^dphohentoat^r of Sitifer. — Crystallises in vacuo in small
jellowish crystals which in drying give off 4 195 p. c. (2 At,) water.
(FebUng.)

2 A«0. 232 .

14 G 84 .

4H,.^. 4 .

2 0...... «........, 16 .

2 SO* 80 .

.. 55*77 ...
.. 20-19 ...
.. 0*96 „,
.. 3-85 ...
.. 19-23 ...

FebUrtg. ^^M
3*69 ^^B

C»H'Ag=0\2S0a ... 416 .

„ 100*00 ...

. .., 100-00 r^M

0ENZYLENK SEUIES: PRIMAET NUCLEUS

BeBEoate of Methyl

DtMAA A Pblioot* (1835.) Ann. Chim. Ph^s. 58, 50.

3mM&^ifrme*ifr, fc«tro«t^*WYf Meik^h^d^ Bm^oaie de MH Anient.

Frtpm*ai%mi. L A luUture of ] pL womUspirlt, f pU, beazoic Srei4
and 2 t>ts. aiL of vitriol h &ubj«H!te4 to tlistilliition; tlia i^due ag&iD
dia tilled two or three litiiea wiib fftfgh wocKl-^pirit; and the tiuited dU-
tillatoa mixed with wntor. The impure beozomte of niethjl wUick Uun
«iuki to the bottom is wadhi^d two ur three timest with water, a^tated
with ehlorkie of ealctaiii, decauted^ auil distilled orer dry oxide ^ kid.
■^f* Neutral sulphate of methyl m distilled with heD^oate of [^msl or
terj dry beuxoate of aoda. — 3, Wood-spirit is di^tiUod witli ail of vjtiiol
and hippuimte of lime,

Pfopertitg. Coloiirleai liqaid of ip, gr. MO at 17% lOSTG at 153*
or ri02ti at 6% (H. Kopp.) — BoiU at iBH5'' when the bammdAT
atands at 761 mm. (Dutnaa k Pel i got) ^ li)9*2% bar. at 7-ia 4 niiu.
(U. Kopm^an. Pkarm. 9^ 3070 V'^poor-d^iaity 4 717, HaM m

i

«gf«tftUa

bak&mio odour.

16 C ,

e ii.

4 0.

9$

i

SI

T05I
1353

*.*, II 4

thimMM h Pit] a got.

71M

GP«iro*. — lit ~ 100 00

lom

«« 100*0

Drrisitjr,
f'fi560
05544
22196

Y^MWOf

of M«Ckj|

1 _,,.
1

9*4f90
4*7145

/ks-tympot^iemi. 1. Tk« TapfMir faneJ ikRiagk a Tetlhot tube fiiy
with linm uc'ldt beaaciL Piolnlilj th« (Ma^tait & Hofmaao, Aum.
i%trnu H,\\)i

c»MW - c«»H* ♦ cnp ♦ lew

t, Ilrtiitrnto of aic'thT) abiorbt chiotm g«i «nik(mt rkibl« aJl^rmthi;
ir tiiiwKi^i'r tbo taiunitisl l^aid bi hmkmk Marly to tbo boiliw polat, i
liiiir«» i|M>ititily of hydroehloho noid ia jpvM o". tnj^tber witb a tittle
rhhifidii i<r methvh tl^ t«Mdwl tiflif pnerirti f«t the BIO0I pari d
_jtdi(rid(* T I 1 ' - '« I T1in»fcirtfci «f lUf li^aid lUitib oror al 194* or
III tkwfij of tfckfMt af baaaioyl; Am portmi vbkk

mj>eratare hm m eoaataat boiUw painty yieU«

ml lotniic adds vb

>4ltiJ!iiyi ui iiiio'

af MadiyL TW

ltfta(t«rslic

MANDBLIC ACID.

5t

dbtitlate at 195^ baa piLssed over, 1^ thick, black, and contains bettzob
acjtl, benzoute of methyl, and perbapa cbbroboaJGoat© of oiQtbyL
(Malagutij Ann. Chim, Fh^fi. 70, 387)

Mandelic Acid.

^fcriJfCKLEB. (1835.) Ann. I'harm. 18, 310; Fo^j^. 41, 375; IleperL

Br 57,314.

^T-lEBio. Jnn. Pharm, 18, 319; Fo^ff. 41, 384*

Laubkkt. Ann. Ohim. Fht/s. G5j 202,
^^ouLER. Anjt. Fharm. C6, 238,

F^rmtibeHzoic acid. FormabeuzoeMditrt, Adde formabemoidquet MandeU'dur^,
BHi ennartdiiio la m i*henA U are*

^Ebn

Farmfition, 1. By beating blttar almoad water witb bjdrocblorio
;id. (Wiuckler.) Tho bydrocyanic acid is then resolved into aiiiiuouift
,tid formic a€jd, wbicb, at the niometJt of Its foruiatiao, uuitea witb iUq
ijtt^r ttlmoud oil (Liebig:); — 2, By the actioa of fuming aulpbuHc acid

n bitter almond oil. (Laurent.) — -3. By beating amygdalia witb

fEtinbg hydrocblorio acid. (Wobler, ^n». Fhanrt. 66, 238 J

PreparatwiL Bitter almond water — obtained by distilling 80 oz. of
bitter almond paste witb 90 lbs. of water till IGO oz. bave passed over,
then taking 80 oe. of tbis liquid, and sbaking up tbe distillate witb the
bitter almond oil — it njixed witb 4 oz, of bydrocbloric acid of s[j. gr,
1'12, and evaporated to dryness over tbe water- bath, till all the bydro-
cbloric acid is expelled, Tbe yellowish crystallino residue amelliug
filightly of bitter almonis, leaves pure sal-ammoniac when treated witb
cold ether; and tbe ethereal sulution yiebl8 by spontaneous evaporation,
a eiigbtly yellow crystal I lae maisa, which, when treated with water,
leaves a reainous flooculent body having tbe odour of bitter almonds.
The aqueous solution la transpaicnt and colonrlessj, und contitina pure
mandelic acid which cryatalli^e.s on evaporation. ( Winckler.) — 2. When
bitter almond oil is treated witb J of its volume of fuming snljihuric acid,
heat is evolved^ the liquid becomes brown and thick, and tiolidifios In a
eomiKtct maas on cooling. The mass when treatal witb water yiehta jiu
^^apper ^end-solid layer containing undeconipased bitter almond oil and
H^itilbylous acid, and a lower layer containing mandelic acid and OKcess of
^Bsulpnnric acid: tbe mandelic acid cry stal lilies from the latter on cooling*
" f Laurent.) -^[3. A solution of amygdalin in bydrocblonc acid is evapo-
rated over tbe water-batb and tbe syrupy mags treated witb ether, which
^^lisiolves tbe mandelic neid. On evaporating tbe solution, the mandelic
^Bioid cr y d tal Uses , ( W i;}h 1 e r, Lg ) ]

FtoptrlUi. Scaly cry sLil line mass, (Winckler,) Crystallises some-
times in rbombic needles, sometimes in rhomhoidal plates, frequently bav-
in;^ their acute anglea truncated (Laureut); in plate* bel >nging to tbe
^^rhomhlc system. (J, lleusser, Fuijf^, 94, 637.) — Has a very faint odour
^Hfrf sweet almonds^ and a j^trong acid taste with a somewhat i^typtie after*
taste, MelU easily, witb lo^s ol water, into a yellow oil, which^ on

58

BENZVLENE SERIES: PRIMARY NUCLEUS C'W,

cooling, iolidifiea to a translucent giuih {Witickler.) — Wlien a eoTutici
of umndeiic aeid iti strong hydrochlonc acid la eya|>onitped nt a trmpen
tiire above 100", it becomes amorphous, and afterwanlfl frtmia a salutbi
with a sniali (juantity of water, but is precipitated by a larger quantity ii
tbe form af a heavy yellowish oil (Wobler, Ann, Pkarm. 6Bf 240,)

IISC .
SB
60

36

S

€8

5-26
31-59

Llebig*

63 10

5-52

31-38

C'«H«0«..„ 152

lOO-OO 100-00

DecompositionM, The acid heated above its oi el ting point, difluaes an
agrce^ible odour recalling those of white- thorn bJosaoms^ hyacintb and
gum benzoin. — Heated in a distillatory app^iratus to a teroperatnre abort
of carbon iBarion, it is cooTerted into a dark brown, resinous, bulsamio
mass, which dissolves sparingly in water^ bat readily in alkalies and In
alcohol. A large quauiity of bitter almond oil passes over at the same
time, — The acid burns with a red einoky flame, leaving a bulky, easily
combustible cburcoaL (Winckler*)-^ When it is boiled with nilrie <md
as lon^ as nitj*ous /tunes coniluue to escape^ the formic acid is decomposed,
and the bitter almond oil is converted into benzoic acid^ which crystalliaes
on addition of water, (Liebig,) — When chioripe gm is passed throogh
an aqueons solution of mandelic acid, an oil smelling like ehh>nde of
benzoyl separates at first; and if potash be then a«lded and the paasage
of the chlorine continued till this oil has completely disappeared, the
iolution, when subsequently treated with acid, gives off carbon ic'acid and
de}K)sita benzoic acid in the form of a crystalline magma. (Liebig.) —
The acid dissolves in oil of viirhf, and the solution when gently heated,
gives off carbonic oxide. (Liebig*) — The aqueous solution boiled with
pffo^ith of fimn^antm yields carbonic acid and bitter almond oif
(LiebigO

ComhbialimB. The acid is very aokble in water.

1

Mandehtet — The acid neutrnlises l>ases completely and expels car-
bonic acid from its oonipounda* (Winckler.)

Mandrtittr qf Ammonm, — The aqueous acid is slightly supereatunit
with animonia and left to evaporate* — The salt ia very difHcuU to en
talliae, and generally forma a yeMowish white mass. It has a very mil
taste. When heated, it decomposes in the same manner as the free acid*
— U dissolves in the smallest quantity of water and rc^iiy in aloohoL
(Wiiickler.)

Mamii'laf^ €if Pfitmh, — Obtained by nearly neutral ising carbon ate
potash with the aqueous acid, so that the liquid retain ej a slight alkalin
reaction, isvaporatinir to dryness, exhausting the dry mass with alcohol,
•mnd teairitig the aJcoholic Bolution to evaporate. White, soft, essi^y
friable, soapy mass, having a very mild, scarcely saline taste, faintly
retiembling that of sweet almonds. Oecompoi^a like the free acid when
heated, takes tire easily ami burns away completely, leaving pure
ejtrhomU* of potash. — Dissolves Yery readily iu water and aJaihol.

&te«

^id^^

»1.

J

^1 ^

A

MANDELIC ACID. 59

I of Baryta. — Obtained bj decomposing carbonate of baryta

lie acid. — 20 pts. of the acid decompose 1338 pts. of carbonate

(1 A i acid : 1 At. BaO,CO'.) — The salt crystallises readily

1 ^ nibly hard needles. W hen heated, it behaves like the potash-

iiiuch less soluble in water than the potash-salt. (Winckler.)

uiaif of Magnesia. — Crystallises readily. (Winckler )

**'n(e of Lead. — Precipitated as a white, finely crystalline powder
_- tnandelate of potash to neutral acetate of lead. When care-
€t<id in close vessels, it yields an oil which appears to be nearly
itr almond oil. Scarcely soluble in water. (Winckler.)

^ddateof Copper, — A solution of sulphate of copper is precipi-
Tiiandelate of potash. — Fine light blue powder. Behaves like
:ilt when subjected to dry distillation. — Nearly insoluble in
alcohoL (Winckler.)

Liebig. Winckler.

CaO 40 .... 21-86 215 •

16 C 96 .... 52-46 5241

7 H 7 .... 3-82 3-96

5 O 40 .... 21-86

C»H'CaO« 183 .... 10000

^ff'Tctiri^ Mandelate, — Obtained by precipitating mercuric nitrate
a mufifliate of potash. — Its reactions closely resemble those of the
i|ier«di (Winckler.)

Manddate of Silver, — Obtained by precipitating nitrate of silver
iih amitral mandelate of mercury. White, heavy, crystalline powder,
ksr to wash. Grystallbes from its aqueous solution saturated at the
iiuag hmi in rather hard crystals having a slight yellowish colour.

Ago

16 C

7 H

5 0

.. 116 .
.. 96 .
.. 7 ..
. 40 .

,.. 44-82

... 37-04 ....

... 2-70

... 15-44

Liebig.

.... 37-15
.... 2-87

Winckler.
44-5

C"«H»AgO« ..

.. 259 .

..^ 100-00

Bfelts at a somewhat high temperature into a dark mass, and yields
tbe same products of decomposition as the acid, leaving metallic silver.
(Wioekler.)

Handelic acid dissolves in the smallest quantities of alcohol and
Ma-. (Winckler.)

60

B£XZ1LENE SERIES : pRJMAKf HUCLEUS C>«a«.

Benzoate of EthjL

SCUEELB* OptiK. % Uh

J. DcitAs tt Put- BoULLAir. iX Fharm. 14, 1 13.

WoHLER <fc LtcBiG. Ann, Fharm. 3, 274; aldo P<^J* 2%, 4Tf .

DETJL1.E- X An$u Chim, Fh^s. 3, 188^ J, pr. Chtm^ 25, 353.

^ormaiwH. 1. When alcobol h added hy drops to bensoMM
h^ftied to it5 evaporating j>oint^ a large quauCily of beo^oie eihm m
proUueed. (GauUier de Claubrj, Compf, rmd^ H^ 501.) ^ U^Uea btnsotte
acid and etber are boated togetUer in n clu^ vesael for tbree boon to
360"*, on«-foorth of the ether is oooirerted into benzoate of etbyU fmsL
alcohol and benzoic acid» I be impound etber u formed at 1 00°. (Beh
thelot, Compt, rend. 37, 856,) — ilcobol an J beujoie «i?id iiiiit be di«utJed i
rrpcatedJ^, wttboat furiuiitg wiy com pound ether- (Scbetrlc, ThSuurd*) A i
solution of bciuoic add mixed with hoe ii]e<r>hot iniy be kept for weckji in m vr&Ma ^
^Ithoiit ronuiiig benxoic etber. (Lkbi«[, Attn. Pharm. 65* 3dJ ), — 2. Cblofido
benzoyl forms wilb alcohol, benzoic ether and bjdrocbloric acid. (W^
4 Liebig.)

3. Wlien to u saturated alcoholic m>ltition of benKoie acid, lliaft ilf
aibled a few dropif of fuming bydrochlonc acid, or better^ of mlcolioi
Kitn rated with bydrocblorio acid gas, lite mixture, if kept st ag^iitb
beat^ Is for the mo^^l part converted, ia the course of eight ur fourt««a
daya, into benzoic ether. — Aa a very small 4uuntJty of bydrocblorle adil
in sufficient to e0ect tbe couverniun, it in probabie lliat dilorido of Wtimyf
i§ formed in tbc fir^it instance, and immediately converted into bcnzcH
of etbyl aud hydroddoric acid, from wbich a fre^sl* (quantity of chloril
of benzoyl ia produoetl, and in this manner ihe prucess is cuutiuni^l -
4* When tolu- balsam la subjected lo dry distillation a mijcture of toln
and benzoic etber passes over towards the end of tho process. ( Devilh
i\r. Ann. O/tim, /*Ay«. 3j 1S8.) According to ScharLug, boweverj _
eotijp{>nDd etber obtained by tbc dry die<tilJaiion of tolu*bal«aiii ii iot
benzoHto of ethyl, but beusoaie of met by 1 (p* 55)* — 5. CaboutSi by
Bul^jectiii^ glim benzoin to dry Ji^ttUation, obtained an oil wbicb wi*
probably impure benzoic ether. {JiulL de ta 90C. phihmaL)

Prtparatton. 1. A mixture of 3 parti alcobot, 1 pt beuiuie aeiil
1} pt. hydrochloric acid, ia diatllled, the receiver bein^ changed a«
iA the benzoic ether begins to poiis over: the ether partly floata on
watpr and partly ainks. (Scbeele.) — 2. When 4 pl^. of alcohol
(listtlleil with 'i pta^ of heiiioic acid mid 1 pt^ of funilng hydrocblutic i
till only one-third remain*, alcohol pa^^es over together with a &mall t|uaa^
ttty of benzoic etber, while the greater purt of tbiit ether r^uiaina m ^^
retort, covorcti with a mixture uf ulcohol, hydrocblonc acid, and
MCi4; tho beamlc crtbor ia wa^bed willi \ioi ^^^Kmx %tv4 ^ ^leekalV v^OAiitatj

BENZOATE OF ETHYL,

SI

potasl). (Thenard.) Dumas S^ Bonllny poar thedi^tinnte liar k- intf* tlie retort
nasoou as half of tlie liqiiid haspasaetl overj and repeiit tbb treatment once
more; jiredpitate tlio l)enKOTc ether wit^i water; wn^lj it with water; digest
with oxide of lead till all the acid h removed, and diBtiK — H* Kopp pasfies
liydrocliWic gns into an atcbulio isolntion of beo Kioto acid; ^epamtes the
Len^oic ether with water; wawhes with a solution of carbonate of eoda;
dehydrates with chloride r^f calciiiTn, decanta, and rectifies. {Ann. Fhtirm.
04, 300.) — 3. Chloride of heozoyl ja dissolved in alcohol, the aolation
being attended with rise of tcmperatnre and evolution of hydrocldoric
acid. As soon as the action is tinished, the hcnzoie ether is precipitated
by water, repeatedly washed with water, dehydrated by ag^itation with
fragments of chloride of calcium, then decanted and distilled. If thelit[iiid
ht dwtiilecl in contact witli tb? chloridt of c»himn, the hl?ii tpniji<?rature required muses
« j^nsiderable qumitify of water lo pnss OTCt. (Wuhler& Lieblg ) — -4. From
Tolit-haiiam. The mixture of toluol and benzoic ether obtained hy the
iry distillation of toln babani m slowly heated to 200"^; at which tempe-
rature the whole of the tolnol distils over. The residue is repeatedly
distilled, the first portion only of the distillate bein^ collected [^free
lienzoic acid remainti In the retort), then digested with oxide of lead, and
distilled, (Deville)

ta«te. Sp. gr

Colourless oil, having a faint aromatic odour nnd pungent
= 1*053D at lO-d"* (Dumas & Boullay); lOS at 18"

J8C ..«,.

...... 108 t,,. 72*S7 .....

Tkmn
& Boalhif ,
... 73-32 .

... 7^87 .
... ie-8l .

WUhler

St Licbig.

... 7253 ...

... 11^69 .,.
.. 2078 ...

Dmllr
71 '9ft

10 n

.,.„. 10 .,.. 6-56 ,„..

nm

4 o

..... 32 .... 2i^o; .....

2112

c'*H»or.

... 150 ..,. 100^00

Vol.

. 18 .....,.„

,.. lUO^OO ...
Dondt}r»

.. r'4e@o

.. 0-69.iO
., 22186

100^00

■i

ll-ga*. ,*„.,....*.«*.

0-g«i.....

» 10

.. 2 .........

Vapour of Betiioic Ether

* 2

1 .,„..,..

DetmnpoBiliom, 1 , Ben?.oic ether barns in the air with a bright sooty
,nie. (Scbeele.) — 2. Chiorinr begins to act upon it at temperaturea
iween G0° and 70"^, producing at first hydrochloric acid and chloride of
Wbyl; but after the action ia complete, a ctvmponnd of chloride of
lien^oyl and bichlorovinic ether, C^"H*C1'0", distil« over at 100*'; then at
195^ chloride of benzoyl; and the black residue, which boils at 200^ is
a mixture of benzoic acid, benzoate of ethyl^ a black fluid mass, and a
email quantity of chloride of benzoyl. (Malaga ti, Ann. Chim, Phyn.
70, 374.) — 3. Benzoate of ethyl treated with &ttowg nUrk ac\d
'E. Kopp), or wUh n cold mixture of nitric acid and ov\ ci! V\it\ci\ ^\tcs.-

WE.]

RflZTLtJIg suits r PftiyAlT Ni

iiociaB potttih liPWiei thitk M sea

Wten fliivie acid

Willi «trDDc «^i09aB V^^*^ liPWiei thitk M memAf mVfd; if vaier b
tkm added, a^porti^ii difw»]f««, vbilo tk« tiat siiiIm Io iIi« boUaa iid
dimppemn j^n^lDill?. (Drrille) — Thm Mm tkak^m ttp ler iMBttUM
witb pateiih, dUip|i«Ar9, tlie liqatd lliefl esoolaratiig micolivl md bfaaotto

«f Ljdislt of potub mad i|aick-lune^ lnrdnig«o w en»K^ mod ^ifrrt^
and acetate ol pota^ an prodoeed. (bmmM k Stfti» .'luff. Ckam, Fkfk

73| 15f,) --€* Sodium doe« not acl mpon beoiotc «llier in tW eotd: tk
wcMktm be^Df at ^"^ or t^, mad is raCii«r lively ml 1 W. Tli« li^iU
Ism btt^va, and yieida, with«>ut eTolutioo of ga% ft iaijd iitUlafe«f
livp<A«]i<aj]it« af elliyt, afid a amall qaaaUty of ttadtciomfKMed hevam
m vibjlt tQg«ttier wtlli beoioalt of toda and olbjl«i« of tofii
(LAwi^ a Weldm^tm, /"osj^. SO, 105) — Bosiaie Hbrr b mm aoackid I

E ipaiiad^^l

Cbn^'iicili^wj. I . Bensoie «tber b iu^latile in cold^ afid \ ^
aolable in hiA wmier. — 2* It ab^riis immomii^atd ^m^ t^amm^^
mmm^ whicb is rc^oWed bj water tcito uad«eom|M«ed b«ii«yie ttlwrtil
ammoDia: acid^ aeoekrmla thb deoonspoiitioa. (Drvltlf*,)— » Wbto Wt
fa contact for vome lime witli a^iieo4i« amnoQia, il furtnt bcnaavidfi — -
3. With bichloride 0/ iiM it fomtt a orYitaUtAlib eo«B|io<i«d« wlikA [
difileuH to purifjr aDtl rerjr apt to dMompoae. (Ukw^« Cbaipl.
2t,mi.} — i^ It diauWea rtadtljr la uMkd mad <<l(r.

i- Sulphobenzoate of EthyL

LturRicnr Jt t, UtLAli. ^lu Pharm. 102, «5*2.

AbaoIat« alcotiol b«eome« itronglj 1)<^at«d tn comtaet with dJ<k
•ilpboliraaoic i«id C**H*CI^'0*; byilnicHlorio acid mmd cbloridt of odij^
mm given olT; and on erapomtiiig tLe liauid uver llio wmter-tNith^ 1 ' "
bwioattf of etbyl rcmuini in the furtn of m syrupy rwidn^ bariaf 1
atlHirral odour. --^ 1 1 tli^iolvaf in water in aJI pmpoHioaii and 1
iboidbrB bo pnriSeii, like tnoitt oompoaad olberv, by wa«liiof witb
Om beating tbe mi|tieot)e ioliitioii« Ibo other i« rosolviHl into alcotiol 1
itdpboliettiote acid. Tbo ctli«f Cftaaet bo diittlle^l without doeompoidlaoii*
wben boatful in a rc*tort« it loareo a hr^ qu^ntitjr of diarcoa^l, fwoQi ap
OtiniiiJvrKUy, ami ylMt a »iimU t^unntity of dtstillAto bavitig m diaa^fi**
able odour. Treated wftb ^aaooui or a<|0OQtu ammonia, tl yietik «lb^
lo4ntpl]oWnioate of amuintiia*

BTflTLOSULPHOBENZOIC ACID. 63

IT. EihyloBulphobenzoic Acid.
C»H»<«H)»o = C*H*0,HO,C»*H*S»0«.
LiMPBicHT & V. UsLAR. Ann. Pharm. 102, 255.
Smipko^eniotfmie acid.

Produced in the form of an ammonia -salt by dissolving cblorosul-
phobenzoic acid in alcoholic ammonia, or by dissolving salphobenzoio
ether in alcohol and passing ammonia through the solution. On eva-
porating the liquid, the ammonia-salt is obtained in crystals; and by
diasolring these in water^ precipitating the ammonia with bichloride of
platinum, removing the excess of platinum by sulphuretted hydrogen,
and evaporating the filtrate at the heat of the water-bath, ethyfosulpho-
benioic acid is obtained! in the form of a yellowish syrup, which does not
show any signs of crystallisation, even after standing for several days.
The acid appears however to be crystallisable, but difficult to obtain in
the crystalline form on account of its proneness to decomposition; for on
decomposing the baryta-salt with an equivalent quantity of sulphuric
acid, and evaporating the filtrate over the water-bath, a syrup was
obtained which solidified in a crystalline mass on cooling, but on being
saturated with carbonate of baryta, yielded a mixture of sulphobenzoate
and ethylosulphobenzoate of baryta.

The Ethylo9ulp1i6ben2oat€9 are all very soluble : they are most
readily prepared ^m the ammoniasalt by precipitating the ammonia
with oichloride of platinum, removing the excess of platinum by sul-
phuretted hydrogen, and neutralizing the filtrate with the required
base.

EihylosulphohenzoaU of ammonia, — {Preparation, vid, tup,). The solu-
tion when evaporated yields crystals to the last drop. The crystals are
four-sided tables, very large and well-defined, especially when separated
at a winter temperature, and have a very distinct cleavage parallel to the
shorter side of the base. They melt at about 183°, into a transparent
visdd mass, which does not solidify till cooled below 150°; if the heat be
raised to 250° or above, the salt froths up strongly without blackening,
and the residue left after the frothing has ceased, solidifies in a crystalline
mass, which dissolves readily in water or alcohol, and crystallises there-
from in small nodular crystals, which give ofi* ammonia when treated
with potash, even in the cold; but if the heat is raised above 300°,
complete decomposition takes place, water, benzonitrile, benzoic acid and
salphurous acid being given ofi^ and a strongly tumefied charcoal remain-
ing behind. The salt is decomposed by potashrley even in the cold, with
evolution of ammonia. Heated with aqueous potash to 100° for a few
hours in a sealed tube, it is decomposed into sulphobenzoic acid, alcohol
and ammonia.

18 C

13 H

108 ..

13 ..

.. 43-7

5-2

5-6

.. 130

.. 32-5

Limpiicht &
T. Usiar {mean).

43-8

5 6

N

2 S

10 O

14 ..

32 ..

80 ..

5-8

13-7

311

C"H»(NH*)S20>«. 247 .... 1000 1000

M

BENZYLENE SERIES: PRIMAHT NUCLEUS C:»*IR

The salt disaolres readilj in water atitl alcohol, but U insoloblo *^^^^
etlier. Tbe solutione are neutral u* test paper. H

Eth^lomtlphohmmate of Soda. — Prepared as above, or hj mixiisg
aqueous solution of the ammonia-suit with carbonate of soda, eTapoial
\t\g over oil of Fitriol at a vqtj gentle heat, boiling the dry resliltt
with absolute alcohol and leaving the alcohol to evaporate. Milk-wtiiti
needles united in nodules easily soluble in water and akoboK

IB C

f H „.

K» _ «_..

2 8

...«. 108

9

31

32

tiiiiiprieht it t, tltlat*

„„ 42-9 4:>^y

..,. 3-5 .„ 37

... 9-1 Q*5 i

.... 12-7 ■

10 0

80

.... 31'9

C^»H*NftS20'» ....

...... 260

... 100-0

The Rait appears to contain 2 At. water of crjitalllsation^ part i
which is piven off in drying over oil of vitriol. Two crops of cryet*'
which bad stood for several days over oil of vitriol, gave otT 5*3 1
5 7 p.c. water at im\ (2 At = G a per cent.)

Eth^hmlphobtntoatt of Bar%ftQ, cryBtallteea after iome tini© from t

hiffbly concentrated aqueous solution, in small, well defined, rh«
tablea, which wlien left over oil of vitrtoli give off their water of i
tnlliaation and fall to pieces.

Ci*H S'^O'* ......

... 227*0

. .. 77*2

...- 22-3 .

Limprlelit

Uft ..,..

6s*e

...... 22-7

C'll'BmS^OW ......

295^5

»« 100 0

Eth^lomdphiimttmfn of Sltvrr. — By decompostnjs tbehjiryta^saft '
sntphnte of silver and concentrating tbe filtrate at a gcnile beal.
ffilver-«ilt IB obtained in ^nmll transparent needles arranged in conoentriif
gronpi (Limpricbt 4 T. Uslar.) ^j

BenzoglycoUc Acid.

Al>. StllEarmR, (1«47.) Aim. Pharm, 68, 54.

N. Soo^LiiPF $c Ad 8trk€KRIi, Ann. Pharm. 1% 3<50; 80, 18,

Oi'iiSMANN. Ann, Phann, 00, 18 1

fhrmt^ion ami Ptepfsrathn. U Dry bJpporic acid ia r^ibl^d «p to i
(bin pftitt with coiTiTDercial nitric mldf and a curront of nitrie oiide gt

BfiNZOGUCOLIC ACID.

fiS

fi

into the uiixfciire, wliidi is kept cold and frequently siiired;

\n gas !3 then evolved and the bippuric acid dissolves, Wlien the
ljquic[ €xl lints a green colour {which it does after five or six hours), part
of the beniogljTctjlic acid is already separated in the crystalline state.
The portion which still remains dissolved is for the most part precipitated
by treating the liquid when cold with a large quantity of water. The
?'ellowisb crystalline mass obtained by filtering and washing out the acid
iquid is sasjHinded in water and neutralized with milk of lime, the jmste,
which is thin at first^ then fiQlidifylng into a hard mass; the liquid
obtained by heating is filtered while etill hot; and, as the liltrate coola,
the lime-salt cry^talliscii in slender needles, which may he rendered
colourless by washing w^ith a smali quantity of cold water, and prca-
fiure between paper. ^ The somewhat yellowish mother- liquor may be
decolorised by animal charcoal, but generally contains a small quantity
of benzoate of lime, — The acid liquid which has run off from the crude
!>enKogly colic acid still retains in solution a small quantity of that acid,
whieh may be separated from it by neutralising it exactly with carbonate
of potash, eryatallifiing out the nitrate by repeated evaporation, and mixing
the last mother-liquor with strong nitric acid. The benzo^lycolic acid
thus separated is generally contaminated with a large quantity of benzoic
acid, which however may be removed by exactly neutralising one half of
the mixture with linie, mixing it with the other hdf, evaporating to
dryne^, and extracting the benzoic acid from the residue by means of
elher (being the stronger acid of the two, it remains in tha free state);
bonzoglycolate of lime is then left undissolved.^ By dissolving the lime-
salt in water, and decomposing it with hydrochloric acid, pure benxogly-
Oollc acid is obtained as a white crystalline powder; larger crystals are
obtained by dissolving the lime-salt in alcohol^ decomposing it with
eulphuric aeid^ filtering from the gypsum^ and leaving the filtrate to
evaporate, (Socoloff & Strecker.)

2, Hippuricacid is diaaolved in excess of moderately dilute potash-ley,
and chlorine gas passed slowly through the liquid^ whichj as soon apS the
evolution of nitrogen gas is terminated, is carefully neutralised with
hydrochloric acid^ then concentrated by the application of a gentle heat,
and mixed with a slight excess of hydrochloric acid; the solution then
solidifies in a crystalline mass. If the liquid be kept warm, the benzo-
jlyeolic acid separates in yellow oily drops which solidify in the crystal-
ine form on cooling. For purification, the acid is dissolved in ether,
and the ether carefully distilled off from the watery layer below
it; the acid then separates as in oil, in the mid&t of the water.
(Gossmann.)

^

Propn-tm. Prisms of sr 40' and lia"* W\ frequently taking the
form of thin plates.— Melts when heated and solidifies in the cr^'stalline
form.

K

18 c ,.,.,..,„ loa

8 H 8

8 O , 64

.C^H'W... 180

Soeoloff Be Strecker,

fiO'OO CO^OU

4-44 4'6S

35-515 ,.,..., '6b 2b

lOO'OO ..* 100-00

L

TOL, XU.

<te BENZYLENE SEHIES : PRIMARY NUCLEUS C^H*-

Dtcompodtmu, Tlie acid wlien boiled for some time with water, il 1

gradually resolretl into glycoiic and benzoic acids:

A more irapid ilecompoaition is effected by boiling the acid with watorl
cotitainio^ a little sulpbtiric acid. {k\^. Gl^coUc nt^iJ,) — 2, Beiiin^dy-1
colic acid boated above its nieltitig point givei off vapouiis coataiQi^fl
l)cn7,oio acid^ wbich excite coughing, and leaver a am&ll quantity of ^sily
cotnbuetible cbarcoal.

C^m^iWitiotii. a. Th^ oeid dbaolvea rcry Bpariugly in cold, wf^
reidily in hot water. When boiled with a quantity of water not '
dent to dissolve lU it melt.>^ into oily drops.

b, BamyglycohteA. — The acid neutral iaea baaes completely,
salts ha«'6 a faint but peculiar taste. They are for tbe most part \
in water, many also in aJcoboJ. From the greater number of 1
the benzogly colic acitl ia iepn rated in tbe crystalline form on tbe i
of stronger acida. They may be boiled with water for a long
without perceptible deeonipoaitioiii

BemoglymlmU of Ammonuf* — Obtained by eatumting the acid witi
ammonia, or by decomposing the lime-salt witn carbonate of ammonia. —
Giires off ammonia when evaporated,

Bm^oglymlatt of Potnsh — Prepared like the ammonia-salt, -^V«
easily soluble in water and atcohob Byspontaneoue evaporation it f
cauliflower-like maiSses, From a hot-sat nratt^d solution it
in broad, very thin plates^ on eooHng*

Benfoglymlait of So^a, — Crjrstnllises more readily than the
^nH ; from a hot saturated lolutionp it separatee on cooliniif in'
large rhombic tables. At 100"^ it givefl off 21138 p, C (6 At,)
and becomes opaque, but retains ite lustre.

Ai \m\ Socoloff h Strieker.

KftO 31 2 .... 15-43 ,.^.... ni2

C»«H?0? 171-0 .... 84S7

C»*fl?NAO"_ 202-ij ..» 100-00

£fmoglu<^ht€ (f Baryta, — Delicate silky needles^ whidi glT« of
€-61) p. «. (2 At) water at 100'.

Soooloflr h Strecker.
BiO 76-6 ... 30-94 ... 30-92

c^H^ty. ^ m-o .... 60 06

C»«il?B«<)* . 247-6 .,., 10000

BmiOffty&iiai^ af Lime, — Obtaiueil by saturating the acid witli tniUl
of lime (p. §5)* — Dtdicato silky ueedlea^ united iu <^acentrie gTt»iip#.

BSNZOGLTCOLIC ACID.

if

Ig c

28 .,

,. 108 ,.

.. 13'4G
„ filt2
.. 3*85

. 30^77

13*33

5203

8 H. ...,..„

_,„.. 8 ..

..» 4-16

SO

., 64 .

,...,... aa-4*i

C«H?CiiO*

+ Aq., 208 -

. 100 00

100 oo

The ciTstalliml ealt givee off 4^24 p. c. (I At) wat^r at 120^. — It
dissolves in 43'32 pis, of water at 11'' and in 7*54 pt«. at 100^ Tho
Bolution aatumted at the boiling; boat often deposita but a small qimntity
of salt on cooling, but if it be tbcn stnuned, it becomes turbid, and la a
few seconds ©olidifies to a ibick jelly; if the liquid be thea filteredj tbe
moiber-liquor geacrally eolidifiee a secoad time,

Benso^li/colate of Afa^nfdar — Prepared by mixing tU© boiling solu-
tions of sulpbat© of magne.«ia and benssoglycolate of lime, and exhausting
witb alcobol the solid mass wbicb form3 on cooling. Long, very slender
needles.

Bmiof^I^mhit nf Elnc, — A eotution of the lime*^lt saturated at the
boiling beat, and 'mixed wUb cbloride of zinc, yields on cooling, long
biu needles, wbieb completely fill tbe vessel j tbey are separated bv
itration, wasbed with water, pressed between paper and recrystalligea.
The crystals give ofT 14 71 p. c. (4 At.) water at 100^

At 100*

ZnO 406 .„. 19*19

C'^H'O^ 171-0 .. SO'&l

19-42

C^WZnO^.., 211-6

100*00

Benznt^lfffolfttt fff Lf^d. — a, Sesthasic. — When the cold sol^iJtion of
be lime-sult is precipitated by basic acetate of lead, tbe preciprtate
"itially washed, then immersed in cold water, and tbe liqnid filtered,
(jBltrate yields after a while, short slender needles united in stellate
i; tbey may be freed from adhering carbonate of lead by elutriation*
— The ciyslals give off 2-63 p. c. (2 At.) water at 100"*.

I

Ai \m\

C»HW m

Si>«otoff & Streck«r«
79*72 ,„,_ 79-71
20-28

Ci81FPbO«,5PbO _ 843

100 00

The precipitate obtained by mbin^ a bollmg solution of the time salt whh neutral
acetate of lead, ia a mixture of aeverid basic salts contaiQing 75*6 per cent. o( oiide of
k*d.

^F &. Stiquihcmc, — Tbe eold aqaeous solution of the lime-salt formi
with solution of neutral aeetate of lead, an abundant^ curdy, (locculent
precipitate which dissolves sparingly in cold water, and when boiled with
water, 6rat melts and then dissolves in it completely; tbe liquid, yields

I<on cooling, firat an aniorpbouB deposit and afterwards crystals. When
Uie original precipitate is covered with a quantity of coM water snSieient
io dissolve It completely, and tbe solution filtered, tbe sesquibasic salt
|»parateff at first in hemispherical groups of crystals ^hk\i m^\t aX XQ*^",
^rtngoff 3'83/>, c. (6 At) w^Ut,

PiBIART NUCLEUS C"B*,

-. 49-56 ^ 49 29

„.. 50^14

lOO'OU

aiatiier'liqiior of 6, after standing far mme ^m^
- erystala which resemble those of the »U a,
fKkfiitiou &t 100°.

Ai l<m\
112 „
. 1X1 ..

3958
6042

3927

283

100-00

— The solution of the Hme-Balt jields wili

, m le#h-coloured precipitate insoluble in water, whii^

lA tli» tnrface when dried. After drying in th^ iir« U
|k «. {2$ At) winter at 100"^. M

At 100^

513

28 32

7^m

...M. 23-27

tl^lO'.SC^m^O' ^".- 669 -« 10000

<g^ Oj^J'Pfr. — A hojHng saturated soltition of the'liin«-

wilk litjmia of copper, yields on cooling an abandmni crop

ip^Me taUee, which may be washed with cold water and foeip-

w tW«7i^ become green aad opaque at 100% but retain their

^^ Smirt »|mrin^lY iu cold, aomewhat more readily in umi

^^« they are hcatea with a quantity of water not aofllcteiil to

l^igi^ ihiC mfidissoUed portion forma a green powder^ piohihlf

^ SUt^r^ — The neutral amnion ia-^alt is precipiti
'^Ith^fi »a*i the precipiti^te waahed with very cold water i
,^1 fr\^ UkIUu^ water.

ml^^oicopie crystals which quickly blacken in the tight vhti
^klt ^Hvolt* ip«wigly ia ^M, readily in boiling water.

I

Socoloff & Streckc

11^ ... 3r-6S 37-76

7 ^.. «-44 2*7

TOH .,, 3763 _.. 37-64
64 .., 22-3a ........ 2203

FAfO*.-

1S7

tO0iH»

.trei readily m a/^roAo/ and fM^r«

iiicglTColic acid gives off a peetiliar l^
ui«. ^m alkc^WlW ^lution of beiixogl|

FUPPURIC ACU>. ^^^^^" 69

late of Jitoe, in whicli an additional quantity of lime-iaU ii snepended,
yieldsj when bydrocUloric acid gaa is passed into it, not benzoglj<5olio
but beniow ether. ,

I

Hippuric Acid.
C"NH*0" ^ C"AdH^O'.

ForacROY & VAuauELTW. (1700 ) ^. fV. 6j 197, 87, 199,—Scher. J.

2, 432. ^Farih^T Ann, Chim. 69.
LiEBin, (1830.) Po^t;. 17, 389; abo Br, Arch. 34, 207;— ^ fin. Fharm,

12, 20,
BuMAfi & Peligot. Ann, Chim. Fhyt. 57, 327; Ann. Pharm. 14, 69,
MlTS€H£RLlGn. Fof/ff, 33, 335.

Pelouze. Jnn. Phami. 26, 60; alao J", pr. Chem, 13^ 420.
Feb LING* Ann. Fharm. 2«, 48-

Ure. /. Pharm. 27, 646,— J, CA^fWt. M4d. 17^ 648,— iJfperi. 75, 61.
BcawARz. ^nn, P}mrm, 54, 29; 75, 195,
DsesAtCiNEB. Compi, rm*/. 21, 1224; N. Ann. Chim, Phi/s, 17, 15^

J. pr. Chem. 37, 244.

ffippurtdurf, flrimduref P/erdekamsUure, A^de hippuriqne. — Dieeoyered in
iior§e-uriii«, by Fqurcroy & VauqueUiij but ttilBtakeii fur uric add ; recogujaed u a
divtiuct itibataiice by Licbig.

^^ S&urt^^ In tbe urine i a. Of maUf — in am all quantity onlj, under
normal eonditions (Lbbig, An7i. Pkarm, 37, 82); abundantly iu diabetet
(lOO pts, of urine yielded 0*025 of crytlalJised bjppurir acid: Lchmann, I
*r. pr. Chan. 8, 552; Hiingeld, J. pr. Chem. 8, 552j; tbe urine of a girl |
ibirteeii years old^ wboee food consisted of apples with a little bread and
water, con tamed as nmcb hippuric acid as tbat of berbivorous animals. I
(Pettenkofer, A nn. Fharm. 53, 86.) — ResptH-ting the occurrence of hippuric
add in hwmati unne* spe aUo Duchek (Schmidt's Jukrh. d, ges. Med, 84, B), — I
h. Of JionUf es^pecjally when worked but not overworked, (Liebig,
Thierelumie^ 3Aufl. s. 86.) Riding-borses yield abundaace of hippuric
acid; agricultural horses yield beuioic acid (Erdmann k March and,
J. pr, Vhem. 26^ 4i?2) ; the utine of riding-borses which had before
contained only bippuHc acid, yielded benzoic acid, when they were put I
to Larder work (Hulsteinj ^V. Br. Anh. 66, 274); hippuric acid is |

• presont in tbe urine of liorsea when they are fed on oats and hay, not
■when they are fed ou barley and efcraw . (Landerer-^ N.J. Fharm. 20,
288,) — c. Of oxcuy — only when tbey are fed on distillery refuse (Sch warz,
Ann. Pharm. 54, 31); — d. Of camd^, — in large quantity (Schwarz); —
e* Of eiephuntt.^ In ^uano {E. Marcband, .A^. J. Fharm. 7, 134); in tho
excrements of the caterpillars of butterflree and bawk-moths, and also |
in those of tbe insects tbeniselrej? (J . Davy, A^, Ed. Fhxl. J . 45, 17); !
ill ox-blood (Verdeil & Dolfus, Ann, Fhattn. 74,215); in tbe scales j
formed in icbtbyosia (Schlosaberger, Ann. Fhartn, 90, 378).

ForTnatioju I. The compound of glycocol witK oxide of xinc ijila^ed
together wiib chloridtj of benzoyl in a close vessel | jve\4a Vv^Y'^tVc wi\^

L

HtpMzieacii

cetilnled jieUi

hipnum add. (W^^bte,
voided tiro " ^

IS^^AlM^.^ Iks

I

m Ikit &itiiii&I <
•i^ m tiio
off Wttjoie mod, ««f« pr
2.0bi. 4 AkI. Bd. it, 376.)

ii wiA Of HT bjdMhlOTtil My

ne «oi wlOck wkea misdt vitt

doee oat cootmlii nrie aei>4 ^^ wbe« i

sod eTaponted, jicid« d^slBlB of . .

dilute Dkrie aiid aad fBcrated to '^rfmam, jmAaam m §mm mA fiaipll

eokuT vrkti mttwumni. (AL I^ M^mri, Ti, «1 ; fuit^ ^f. M«rm. xT,

(r460 KdWr, befuf^ fo^f to ili^s toA S pMnet of l»esMM teil|

the Brine voided la tke »iffgl>g EmI ■■ ■aeoaiaeBlj i

iitd yieliiiHl cfjitala of blpporic actd wbea mixed witk h^rMshiork \

lU'tcr coaceutntioti, Kiid inoieeTtr ooBtauied «r» mad mm meid id :

proportina^ {Anm, Pkarm, 43» lSt| eMifaic H. Se^vmfx, Anm. Pkmrm.
32.) A. B. Gmrrod foQad lup^nie Md^ li» nw mfter takiiig bitvM

ork aeiifl
Urm5l|B

p,rt witli sUfto i««d mad aniMiim ikm ifMlkn oliierrcd ^/Ml
le ecmtoiaed m toauh uie md mi wfcen mm Wnme mdd wm4 I^H

SO mud 30 grains oi beamqw m«U. The eijstmlm of liippmiie Md ^
inixtHl with gmn^lei of one mcid, w^ich Mnmimed mudunlTed wBea ti^etttj

I did not ^

I the ttrine <

t </*A»^ J/^rf^. J. to, 501; J.pr, Ckem. fl, 3S6,)— Mmnlimiid, after i

I 90 If rain 8 of benioic meid, ft>ai>d S^i gimiM of kipforic mcid in hm \

Tho b<?tiiot<- meid mmA kmve tmken up cmiWi, mi otlimrwiio il 90ttld i

hnvc yicHed 04 39 gmm of kippim add. If C*XIPO^ were addn.

tUo Wtixote mdd, 90 gnim «f »e Inter wonU jield 44 01 grmiai

hippuric ncid. (J. |»r. OUm* SS, 9091)

Ffiparatim* A, f rwn l«rW <»r ^lonn* mWW. — Horse- oriiio ^per-l
•atumted with hjilroclilorie acid Tieldj, after m whUe, a jellowi^h bt^naj
jirtoipitftlQ of itiipiire hlppurk a«ad. (Lidb^ I^, 17, B$B.) — Hof3o4
l«riii« aij»ed with hjrdrochVric aeid* •eUboi mM§ bippuric acid nitlionll
aruparnfioti^ heuM it cbotdd be eraponUed to ^ or |, tUen mixM withi
^ liyilrc^cUlonc *cid and ibe cryataUi^eii hipparic s^id puriEed. (Schvr^x^ j
Ann, Pkarm. 54, 2& ; see mho DMaigii<«. S, J. Plmrm, 32, 45.)^
loo pti. of cows* urifio mixed wicli 3 or 3 pt». of erode hjdrochlone ad^ [
dep4i»^it hippuHc acui, (Rilcv^ CTam. iSbr- ^. /. 5, 97; A\ */. /*Artrw. '
^ Si2^ 3AI ) — 12* TUff fn^li urbe uf hoisee or euws b im media tcljr uilied
ezooii of milk of lime; boiled for a lew mitiatee; wauied; the
evapomtod to | or ,V ate^rd'^Qg U» t^e degree of omcmotmiioBt
irr^iturakMl with h_vari>clilor»c add. (GregofT.} Fwah oowi' j
laixod with hjdrat^'oC little; boiled op oBoe, doeanled Irom ibej
td ovupomted to J, i1iim% eapenalttmted with hTdroelilorto add
JJ, mad tho hippuric acU eM^t^iA ai\« \1 ikftntm. If llw

nippuRic Acro.

71

boilings witii milk of If me be longer continued, a brown j rasinoua hody is
produced which greatly iuterferes with the punficatiou of the liifi|)urio
acid, (Stadeler, Ann, Pharm. 77, 18.)^ 3, Fresh horse-yriue ia uiixed
with eaecess of sulphate of zhic; the liquid together with the resulting
precipitate evaporated to J or | uf the oHgiiml hulk, filtered (|uickly, the
rflildtie washed with a small qiiautity of hot water, and the hippurate of
xinc in the filtrate decomposed hj moaDs of dilute hydrochloric or sul-
phuric acid, Hippuric add thou separatos iu the form of a white initgDiai
which may be wa^bed with cold water, pres^^ed between filtenog paper,
and recryetalli&ed. {J. Lowe, J. pr. Cfiem, Qb^ 372.)

Hippuric acid 8ep«irated by hydrochloric acid ha^ a brown i.sh colour
and disagreeable urinary odijur, and therefore requires furtjicr piiriHca-
tion: a. The solution le boiled with quick Jlme; t!*e filtrate mixed at
the boiliDfj beat with chloride of lime till the urinary odour is deairoyedj
animal charcoal then added till tbe liquid becomei colourtesa; and the
iltrmte is mixed with hydrrN:hloric acid and left to cool. {Liebig, /^o^f/,
I7j 389.) — Tbe urine evaporated to a Sjrap is mixed with ao equil volume of cntde
faydrochlohe acid, chlorate of potai-ii added till tbe liquid hecamej^ colourleai:, and the
soiation left to cool. TLe chlorati! of polaab iirieri^lj' decoccipO!f!es the* re^ia aiid euitrac-
tite mutters. (Rieekher, JoAri. pr. Phann, 10, 244.) — The nietliod of |iurifi*:atioa
with cliloride of lime (or hydrocJiloric acid and chlorate of potush) most he rejw'ted,
becftuae a portion of tht hippnrif^ acid ia tJiereby conrerted into benzoic add. (Duinu
& Peligot, Scbwarz.)^^^. The crude hippuric acid it^ once reerystallised,
dissolved in caustic soda, and the solution while boiling hot mixed with
succesaive 8 mall portions of man^^natc of pota^h^ ilLl a filtered sample
dropped into excess of hydrochh^ric acid prod aces a pure white preci-

' pitate; the liquid ifi then fiU^^red and the pure hippuric acid precipitated
by addition of hydrochloric acid* (Go&smann, Ann. Fhami. Bd^ 373.)

1 [Js not tlii^ metliod open to ibc iwitije objection a^ tbe preceding? W.] c The

cmde acid is pressed, mixed with 10 pts, of boilioi^ water and excess of
milk of limej the strained and expressed liquid mixed with solution of
alum till the alkaline reaction disappears, aud left to cool to 4 0""; car-
bonate of soda added as long aa a precipitate is formed; and the solution
latrainedj pressed, and precipitated by hydrochloric acid. The precipitated
[lippuric acid is washed with water, prei^jsedj aiid dissolved in boiling
^ater; blood-chiircoal added (1 ok. to a pound of hippuric acid); and the
olullon filtered through paper while still at the boiling heat. (Bensch,
inn. Fharm, 58, 267.) — d, The crude acid is boiled with railk of lime,
the ^ffeater part of the fibriu tbcn goiuL' down wdth the precipitate; the
IBUrate precipitated with oxces-^ of carbonate of soda^ boiled, filtered
[again, and precipitated with chloride of calcium, the carbonate of lime as
fit falls down carrying the colouring matter with it, — then filtered a
L third time, and precipitated with hydrochloric acid. (Schwara, Jnn^
^^Pkarm. 54, 29.) — e. The crude acid is suspended in an equal quantity
t of water, mixed with -J of nitrie acid of sp- gr. I "3, filtered after 24
[iours and washed with cold water, {llutgtein, iV. Br, Ar^. 60^274. —
The crude acid dissolved in a large quantity of water is boiled for some
Htime witb finely divided zinc; a small quantity of recently ignited animal
charcoal added to the boiling liquid as soon as the action upon the zinc
^becomes weak ; and the llquiil filtered into dilute hydrochloric or sul-
t phurio acid. For purifying considerable quantities of hippuric acid, the
'erude acid diss^dved in the smallest possible quantity of water, is
aoutralised with carbonate of soda, a slight excess of sulphate of zinc
hdded; tbe liquid boiled for a short time with animal cU^ti^viiuV^ tLYv4W\Q\v

I

7t

B£?(ZTLEKE S£BCE3: PRIMARY NUCLEUS C^mp.

Altered id to dilnto ffnlphiirie ftdd. (Lowe.) — [From nfimixed beanie
acid, crystallised hippuni: acid is purified bj [touring a little water en i]i«
mixture^ adding ether and agitalaog, whereby tlic bea^oia acid U eoo^
pletely dissolved* (Liebig.)]

B, From human urine. — The froab urine is eTaporaled to a ejfw
over the water bathj mixed with a small (jaantity of bydroohJorie acitt wi
ihaken up with an equal volame of etUer^ wbiob di&solves the hippanc
aeid. ir the eibercal solution does not aepArate in the C'ovirge of an houu
a qnantUy ^f alcohol =yV ^^ ^^'^ ^^^^ ^^ ^^^ miitiiie should be a(i«M
the liquid then immediately dividei into two layers. The upper liqai*
in addition to the hippurio acid, contains a email ijuHtitity i»f utm\
dissolved by the alcohol; it is therefore shaken up with a little wmKf,
which takes up the alcoljul and the urea, while the hippuric acid reuiaio$
dissoWed in the ether. The hippuric ac:d which crystallines as tb« etbfr
evaporates^ h colorire^J yellowish or brown by a resiuoua subetaneep ithiclk
however is easily removed by a little blood chafooal. (Liebig^ AnsL
limrTn. 50, 1700

I

Propertm, Long, transparent, eolourlesfl or milk- whit© priem*,
bclonijing to the right prismatic system. Cleavage jiarallel to
IJ-faces, u\ V, jf and t; u z u' — 80' 8'; u' lu^ n"" 52; i : u— 2lA'
(I)aul>er, Jjin. Pharm. 74, 202); u : w'= 80^ 1'; n': w = m^ 59'; i
fifi :W I yip^ 88 30' ; i \u—\ ir 49 ; g.u^ 123'' 15'. (Schabi
Wim. Akad,Bei\ 1850, 2, 21 L) The rutio of the axes is 1 : 0 »7€a
1*1605 (Dauber) i = 1 : 0 97442 : i2mQ. (SchaUs.) — Reinech, _
spoutaneoue evaporation of the solution, obtained crystal re«embliaf
(ictohedrons* (Jahrh. pr. Pharm, 20, 217,) — The crystals faaTe ai
Ittictnous diamond lustre. Sp. gr. 1-308. (Schabus.) 1" rrepsring hip|isne
Mm from hi|rpu He acid and alcoUol, Ltpbii^ obs^rv^d hippuric acid in cauUdctirrr41&
Wisnii Sehwiin (Ann, Fhurm, T5» 101) in prepiinni^ hippuHc ether ob»rT«d iJht
Minff kffld of mufipe to form in the mother-liciuorj they Aeisflratird niwUpred from tWr
IkiI B(|Ufoui lotutioii, but on dissolving them iti ammonm »titl addiEi|r hydrochlonf mU,
thn hk|i|itiri(^ ndd ttns predpitatcd in the crysUlline farm. — The acid ineU« wbcS

hctttCMl, and solidiBes in the erygtaJline form. It reddens litmus eli^^htlj,
Itat 4xm not taate sour.

1

i

tOfl .M M'74
14 ... 7'»2

4i >», 2a 4§

60 69 .
Se HO .

Pdigot.

. SO 5 _

. 7*7 ....

. 50 ,..,

. 26 8 ....

Seivtn,

6063

in

2649

59 17
515

53i
2641

IVHUH)^ iff ,.100*00 .. 100*00 .100-0 ... 100 00 imm

Ptl0iti« ruffardi* hippnrie acid as a oompotind of bitter ilQumd eil#
hyirmffmlis icld and formic acid :

wImh iubjopled to dry distillation or boiled with |>oroxid0 uf
Ipit iod iiijl|i]iiirir ncid, it yiebis c^arbonie acid, benzoic aeid mnd
I Oft ihii iilhtr hand, 8<jcoloff & Strecker rtsmark, thai otWr

y 4HHtU^mug forutie aoid in eonjuuction with an aldidei jiald

HIPPURfC

W

tlie altlide itself under these circumstances: e. g, mandelie acid (p. 58).

— As hipparic aciil wLeu boiled with water nnd |>en»xide of lead, is
resolved into beu^TuuiJe and carbonic acid, Fehiing regards it as benza^
mide conjugiited wiLji funj&ric acid :

^ith regard to wliich view, Socoloff and Streeker observe that funiaric
acfd boiled with peroxide of lead doea uot yield carbonic acid. — From
the decorniiasitron of hippuric acid into benzoic acid and gljcocol,
Deaaaignes conclndes that it is a compound of anhydrous benzoic acid
with anbvilrons g!vcocol (jtnalogouB to eolphosaccharic acid, ix, 251):
(C"NH''0«-C*NH*O^C"H*0"), a view which appears also to be sup-
ported by the formation of hippuric acid from t^hloride of benzoyl and
ihe compound of glyeocol with oxida of line; but then, as Berielius
remarks, the decompovsition by peroxide of lead cannot be explained,

— H. Schwarz [Ann. Fharm, ?5* 210} sappoiaa that hippuric acid
eontaiits benxil and glyeocol:

P 2CJ>NH*(y^ - 0SH»O* 4- 2C<NH*0^. I

According to Socoloff & Strecker^ hippuric acid m the amide of benaogly-
colic acid, iince, wheu treated with nitroiis acid it behaves like other
Pinides, yielding benzoglycoljc acid. It ia distinguished from most
'^midogen-acids by the fact that it ia the amide of a monobasic acid^ just
as, for example, anthrantlic acid h the amide of monobasic salicylic acid.
{Ann. Fharm. 80, 17; compare Heinti, Zooekemie S. 283.)

Decompmitions. L The acid blackens when beated^ yields a crystal-
litie sublimate of benzoic acid and bensroate of ammonia smelling etrongly
of bentoin, emits at the eame time a powerful odour of hydrocyanic acid,
and leaves a large f[uautity of porous charcoal, (Liebig'.) — Heated ia
a retort, it yields at 210*^ a depoiJt of benzoic acid, and boils at 240"^,
giving off red-coloured benzoic acid, at the same time that hydrocyauio
acid is evolved and benzonitrile distils over. In the retort there remains
a resinous body, which is brittle in the cold, becomes soft when heated,
is ^pariDgly soluble in water, but dissolves readily in alcohol and ether.
(Iitmpriclit k V. Ualar, Ann. Pkarm. 88, 133.)^ — ^Dry hippuric acid
heated in a retort with quartz-sand and dried chlf>riLie of zinc yields
benzonitrile, carbonic acid and charcoal ( Gosmann, Ann. Fharni,
100,60.)

L [0«NH'0= - 4H0 = a*NH* + CO« + 3C]

% Put© hippuric acid may be boiled for several days with water

without undergoing any altemtion. (Stiideler.) — When horse- urine fa

t^ery quickly evaporated, an odour of atnnionia ia evolved, and the uritie

pi found to contain benzoic acid. {Fchling.) — When the urine is boiled

lly itself, the hippuric acid is readily converted into benzoic acid,

{Duma a & Feligi>t, Gregory.} Cowa' unne rapidly boiled does not yield

enzoic acid. (Stadoler.) — 3. Hippuric acid boiled for half an hour

excess of poifish or eoiht yields glyeocol and a benzoate of the alkali

a. i goes.) It ia not decomposed by boiling with milk of lime,

egory, Schwa rtss.) — 4. From hot concentrated hydmckhrk acidf

lippuric acid crj^stalliaes without alteration (Liebig)j but by coTxtxux^a^

T4 BENZyLBNE series I miMARY NUCLEUS C"H«<

bmlin^ it Is oomplelely reaotved into benswjic acid and glyeocol; the mmk^
decomposition is induced bj oil of vitriol diluted witbSpts, of water; '
20 tuitiuteti' boiling witb ttitric acid^ benzoic acid ?itid nitTo-mei^harie i
are produced: oxalic ((cid boiled for two hours with a very strong solutJ<
of hippuric ncidj converts tbis acid into benzoic acid, tJie motherdiqa(
containing oxalo-saccbaric acid. (Dessaignes,) This transformation tt^
not attended with evolution of gas; 100 pte. of hippuric ««cid boOed with
bydi'ucbloric acid, yield G7"49 pta. of benzoic and 59 08 of hydrocblofth
Baccbafic acid. (Culcubtion re(|«ire« 68- 15 be-oi^icatid 52' 09 hydrtMrliloiti'HfriaiEti
iw-id.) When I pt of lisppurio acid ia boiled with a eolatioD of i pit.
^blonde of liuc iu an 04 vial weigbt of water, benxoic acid aubli
and glyeocol remains behind, mixed however with a small qaaiitij
beu^oate of zinc, rosulting from the deconi posit ion of the cbtori
boiling. ^ — 5^ A solution of hippuric acid in cold nitric acid, la oan'
by nittvuM acid into benzoglycolic acid, nitrogen gas and water;

C««NH»0* + NO* = C>«H«0* + 2N + HO*

Hippuric acid ia not decomposed hy boiling with nitrit© of potiAi
because it does not set free the nitroua acid. — Hippuric acid in the at«td U
Cfdd aqueous eolntioa ia not decomposed by nitrons acid; bat OH '^
application of beat, nitrogen and hjqiouitric acid are evolved; a&d
bitter producer further decomposition. The e^ilntion of bippnric au^id j
oil of vitriol 18 n<^t decomposed by nitrous acid, (SocoIoJT JL Stftt^kei
— 6. In aeold miatiure of oil of vitriol and fujning nitric acid, bipptiti
acid U converted into nitrohippuric acid. (Bert:ifnini.) — 7* Whi
the solution of hippuric acid in oil of vtiriol ia heated abov^ 120", j
blaekenS; beniioic iicid eublimeaj and aulphuroui acid is evolved. If tb
beat be discontinued when the £;ulphnrou3 acid begins to go off and ti
black mnm be then ponred into waterj no beuzoic acid will b« found
t ho liquid. (Liebig.) — 8. The aqueous solution m not Jccotnpofled
chftirine tjoi, but when it is boiled with a large exee^ of cki&ndfii
deconipositiou t*ikes pbxce^ {Liebig.} — When chlorine gm k fmam
an aqueous eolntion of hippuric actd^ nitrogen is evolfed and ben
coiic acid produced. (Goisanmnn):

C>»NI1X3« + 3K0 + 3Ci = 0*BXir' + N + HO + 3KC1,

0. When hippuric acid is boi ed with peroxide of mmf^nese anl

dilute sulphuric acid^ a largo quantity of carbonio acid it ^m

benzoic acid eeparaiea on coolings and the lic|uid contiiins sulphate
ammonia. (Pclouae.) — 10. Hippuric acid boiled with peroj^idt ^ Ui
and water yields benzainide, carbonic acid and wat4.*r (Fehling):

C'«Kli'0< + fiO - C"NH*0^ + 4C0= + 2H0.

When hippurto ncid is heated with peroxide of lead, and exeew of
or sulphuric acid, the product formed are carbonic acid and bifif
(Sehwarz, Ami, Pfmrm.lh, l^j.) — When hippuric acid ia Wile
water and jwroxide of lead, and eulphuric acid is added from

irritates the eye* and lungs; and the water which distils over at the t
time n^ldcns htmiii slightly^ reducea nitrate of silver when tiiixoil

"mpptjftid ACID.

75

amTnonia^ but tloes nut loie its peculiar odour on the adiiitloTi of potash:
it caonot tberofore be formic itcid* (Scbwurz.) — 10* Ilippuric acid
g©tiUy heated with exoe^e of lime, does not give o IT a triice of ammonia,
but yieJJd a liquid which smella of benzoT, aud when treated with
hydrochloric acid^ is converted into white cryatalJiue ecaleaj after reo-
tificsticm however it yields pure benzol [bemuTiitrile ? L.J (Gerhardi)
I^Hrftt. By the action of afn-tnent in presence of an alkali, hi ppuric acid
miJMlved into bensoic acid and glycocol (Duchnerj Ami* F/mrm.
78, £03.)

Conibhaihni. Hippnnc acid dissolves in 600 pts* of water at 0°,
more readily id hot water. (Liebi^.)

It decomposes the alkaline carbonates* The ffrppiirates are generally
C*'KH*A10^ and most of tbem are fiolnble in water*

From tlieir aqueoua solutions, the hippuric acid if« immediately pre-
cipitated by stronger acids ia the form of a white crystidline powder,
urithout pro V bus turbidity as m tbe caae of the heuzoatea. (Schwara.)

Hippurate of Ammordcu — a* Normal. Crjetalliaoa with difficulty;
the Bolmiou ijives off ammonia when ev^aporated (Liebig.)

I, Acid. — Cryetullises by evaporation from a solution of hippuric
acid In ammonia, even when the ammonia ia in excess. Microsct^pio
e<|aare prisoitj, acumiiiatcd with four faces resting on tbe edjijcs. The
crjttmis ol thii lower tttj-iiium nre miich be Uer timn thoAe of lUe upper^ wiiicli in f^ui
consUt* of mdifitnict crjstnlline cmsts. — The salt, after drying over oil of
YJtriolj gives off 4) 15 p* c (2 At) of water at lUO^ (rfchwaii*)

m as c _

■ 3 N

■ 23 H

At 100^

_.^*. 216 „
.„^. 42 .,
........ 21 ..

.. 51 05 .

„ 10-69

. 2S'50

Schwa ra .
.„« 54 51

....^* 6-05

14 O ...

112

C'NH»(NH*)0* + C^»NHWHr JAq .„ 3^3 .., lOO'OO

Between ISO'' and 200", it gives off a large quantity of ammonia and
leaves a red residue, which, when dissolved in water, yields rose-coloored
crystaU of hippuric ac«d. {Liebig, Schwarz,) — Disdolvee very readily
in water and alcohol, spurijigly in ether* (Schwarz,)

Hippurftfe ttf Potash. ^ — a. Narmal. — Hippude acid ia dissolved in
carbonate of potash; tbe exccaa of tbe alkali carefully neutralised with
aqneou'a hippuric aeiti; and the resulting cryatals pun tied by rccrystal
ligation from alcohol^ waahing with etherj and finally by several crystal-
lisations from hot water, if too much acid ha^^ been added, the acid
hippurate of potash crystalltaea out first. If the cryatals are immediately
dried after being washed with ether, they deli*iuesco into a gummy mass.
(Schwars.)

KO

18 C .....*

At JOO'-

47*2

io«*o

.... 21 "73 .„.
.... 49-72 ....
..« 1^44
.... 308 _
.... I8M3

.... 21-74

N

8H .,.

5 O ,

14-0

8*0

-.. 400

.... 5-87

217^2

.... 100*00

76 BENZTLEXS SERIBS : PRIUART HUCLBOS O^OK

KO 47-2 .... 20-06 19^1

18 C - 108-0 _ 45-92 45-78

N 14-0 _ 5-95

10 H 10-0 .... 4-25 4-30

7 O 56-0 _ 23-82

C»NKa»0« + 2Aq .... 2352 .- 100-00

The salt when charred f^res off an agreeable odour, like that of
Salurtja hortauii, and quite different from that which is emitted bj fne
hipparic acid. It disaoires readilj in water, bat is oot preci]Mtited
therefrom bj alcohol or ether; it dissolres in absolute alcohol or ether,
sparinslj when cold, more readilj when warm, and aystalUses theiefoiB
on cooling. (Schwarz.)

h. Acid. — Obtained bj disaolring an exeen of bippnrie acid ia
carbonate of potash. — CrvfiUllises, eren bj slight eonoentration, ia
broad satiny laminap, which nnder the microsoope appear like sqiuif
prisms with tnincat^d terminal edges. Gires off 4-77 P- e. (2 At) water
at 100". (Schwan.)

Ai 100^. Schvn.

KO -.- 47-2 .... 11-18 H-28

36 C — -. 216-0 ..- 51-SS 52-01

2 N -. - 28-0 .... 6-63

19 H 19-0 -.. 4-50 4-72

14 O -1120 .- 26-43

C»*XirKO* ^ C*XUV ^ 2Aq ... 422-2 _ 100-00

IVi>b«bW nochin; bat hipparic acid mued with the Bonoal ak. Schwws'sanalyai
WM made with too unadl a qoantitT. ^GcHurdt^ .V. /. Pkmnm, 21» 314)

Hipp^irnte (f S(kia. — Obtained bj carefnllj nentralising hippuie
ncid with carbonate of sods. CTaponting to dryness, and dissolving ii
aliHthoK Crystalline mass haying a slight yellowish colour. A fter drjing
over oil of vitriol, it does not give off anr water at 100\ (Schwan.)

SckwsR.

2 NjiO 62 . 15 or 15-01

5*i 0 216 .... 52-55 52-57

•J N 2> . . 6-Sl

i: H ir ... 414 4-29

\\0 . >S . . 21-13

//i/7»wiM// «:'*/»''^»''»* — *> Hwf?. — Wh« the aqoeoottolstioaortheaeMii
IimIImI mm It «i«i(HMMti« «^f IvArttA, «ml rUcrr^^ tbc alkaline liqaid feUtinises on evopoi^
lI'M.i )(..|,U !»• \x *^**»'*' ^^**«' |s*t\>fU:r.»l.if 0TT>caU:aDd afterwards toUdiiea eoa-
fl< i> I) riu* mii««. A(^«r «t(>ti'jL «'^ vaca>\ B'<c!t» vnhout kxa when hcatcd» and fonati

I. ,y,,, ^,,/ \\ hni \hc ^U 4 :» ii^MCtvU ia water and aectie add added till •
)\ iiH.OiMi t« vi\Htu«>rJ. the nx^r«Ml talt crystal lite* ia truspamt lanias.

|ll|t|miu' soil! i:^ di:M^lyed in excess of banta-wmter, and tbe
Imiyln |ii^HMpit4toxl by cjubonic acid: or carbontte of baryta t»
^|||i'ii^.oM« of a(|M<K^ttji hipi^ric acid, the carboBata of faaijts

n

solution, when evaporated, yielda crjitalline
^erusts consisting of microscopic square prisms. After drying over oil of
Mrltriol, it givas off 3^74 p. c. (I At.) water at 1 00^ (Schwarx.)

^^^^ BaO.... 76*e .... 31 OG Um

^^^^ 18 C ^,^... ^» ... lOS-O .... 4379 4S^^9

^^^K N ....„ ................. 14*0 .... 5*Sa

^^^l B H .... do .... 3 24 ........ 3^ie

^^V &0 .. 40 0 .... lfl-23

^m C^NllsBaOS ..._.„..„, 24a*G .... lOO'OO

^^^K BaO ?6-6 ... 29 97

^^^K 18 C 103*0 .... 42*25 41-79

^^^m N „.».....^. .,.. 14*0 ,.., 5-48

^^^B 9 H 90 ..., .3 52 . .„„ 3-73

^^^H 6 0 ....... 4B-0 .... 18-78

^^^P C^^irBaO* + Aq .... 255*6 .... 100^00

^^ Hippuro-benzoaU of Ear^tft. — A mixture of Lenioic and hippurio
I acids — whether in equivalent proportion or not — saturated with baryta-
water, treated with carbonic acid, boiled, filtered, and evaporated, deposita
&t first* silvery laming of benzoic acid, then by further evaporation,
"waxy^ rhombic tables of hippurale of baryta, and at last, the syrnpy
luoiherdiquor yields dull cryiitalline nodules of the double salt, whieli
may be pickea out from the admixed crystals of hippurate of baryta,
and recrystallised from water. The salt gives off T'iO p. c. (4 At,)
rater &t 100°. (Schwara, Ann, I-'hinm. 75, 192.)

At 100*.

2 BaO 153-2

32 C ^ ...» * 1920

N .„...« 1 4 0

14 H 14-0

g O 72*0

Sehwan.

34*42 34*24

43*13 43*42

3-14 3*61

3*14 ........ 3-59

16-n I.VU

C"H*BttO* ^ CWH^BflO* + Aq 445-2 ..„ 100-00 10000

Hippurate of Strontia^ — Carbonate of strontia is diasolvmi in aqueous
hippnric acid, and the crystals several times recrystallised from cold
alcohoL — From its hot solution in water or alcohol, the salt crystallises
in broad laminmj which fill the entire liquid, and under the microscope
appear aa square prsi^ms with perpeudicular terminal faces. — It dissolves
Bomewhat sparingly in cold water and alcohol, readily in hot. Gives off
3-74 p« c. (5 At) water at 100° {SchwanO

Ai 100*, 8chwar«,

SrO ................ 51-8 .... 23-35 23*42 *J

IfrC 108*0 .... 48*69 48-83

N 14 0 .... 0-31

8 H 8-0 .... 3*61 ........ 4*01

5 O 40>0 .... 18*04

Ct^iNUsSiO* ........ 221*3 .,.. 100-00

ft BENZYLINE SEEIES : PRIMARY KUCLEITS C"11V

Cfy§UiUi*4d. Schwm.

SrO 51-9 ..^ 19-41 -* 19*40

C*«NH^,.«„... , 170 0 .... 63-72

5 HO ■■„..„.. ..„,... 45 0 „„ 16 87 »..». U 2^

Ci*NH«SrO«+ SAq... 2fl6-S .... 100 OQ

I/lppura(e of Lime, — Hlppuric acid la dissolved In milk of Iiifie, t!i«
BolutioD filtered, carbonic gas waa passed through tb© fi Itratej the \h\\i\A
arraJn filtered, and the clear solution left to crystal Use. (Sehwan )
The aqueous solution of the acid heated with carboDate of lime, yieldft.
rhombic tables on coolings and shining lamime hy eTapnratioTt. (Liebi^.Jf
Oblique rhombic tables. (Sehwar^,) Four-sided prisma belongiog
to the right prismatic syatein. Faces «, u\ a, a\ n and t ; « : t/sJ
83^ 44'; a : a'= lU^ 18'; a : a' « 134' 18'. Ratio of the nxeM ^j
1 : 1 9244 : 03897* (Schabua) Sp. gr, 1*318. (Scbabus, Wim. Ak
1850, 2,214.) Gives off UBl p. c. (3 At.) water at 100^,

At XOO^ Sdiffjitt-

CiiO..... _. 28 .... UU „ li.1l

ISC ,. 108 _. 54-5 1 54-40

n. 14 .... 7-07

8 H 8 .,.. 4 04 ^ 4 01

5 O 40 ,.. 20-21

C»li*C«0*. ..,.....- 198 .... 100*00

C»0 28 ,.., 1214 ,^..,.. IZSa

C»«NH«0* 170 ,... 65-57

3 HQ ...... 27 .■■■ 11-90 12-CO

C'*'irc»0« + 3Aq,... 225 ,„. lOO'OO

H^puTdU of Magntda. — Obtained by dls^lytng c^bonmto
tD«^efia in the aqueous acid. Crystallises from a tolerably concentre
solution in crystalline nodules, which must be washeil with the imalletl'
possible quantity of water. After drying over oil of vitriol, il ^reioi
15 35 p, c. (4 At.) water at 100^ ^~

MgO..

18 G

N ..«..
9 H ......

« O .....

At 100*.

20

...*..,. 108
...™ 14
........ 9

.„ 19

„.* 10-07

^. 54 »7

«. 7'Oa

.«. 4-52

... 24*11

Scbwjifs,
..«..- &374
« 503

The salt
(Liebig.)

C"N11»M|0* + Aq 199 .,.. 1O0-O&

dissolvet in 18 pts« of cold and 9 pta of boiling wi|«fJ

Uippurateof Zinc,^Z\fifi dissolree with erolntion of hydrogwT
aqueoui hippuric acid at the boiling heat, and the li^iiiid after botting for

iouie tim©^ solidifies on cooling' into a white crystalline marina, Ttt

same salt »eparates in the oryatalUue farm on mijiini^ coiiotnttmt«d mh*

HIPPURIC ACID.

n

k

tlona of a iaU of hippurie acid, antl sulphate or chloride of zino, —
CrystalHaea from the aqueous solulien on cooUug, in laminas united in
©tGllate groapg, Tim crystals give off (5 At.) water at lOO"" ■ I pt.
of tb© anhjrarous salt diflsolvei in 53' 2 pts. of water at 17*5°; in about
4 ptfi. at 100°; in 60*5 pis. of alcohol (sp. gr, 0'^2), at 17*5°; in ether
it is nearly insoluble, (J, Lowe, /, pr. them. 65, BQd^)

ffippurafe of Leitd. — a. Ba»ie, — Wben oxfde of lead Is boiled with

ippttfic ackl and water, a portion dissolves, while the rest forms a vi»cid
niaas which soon turns hbek even under water. When the solution U
evaporated, a crystalline film forms on the surface, and at a greater degree
of concentration the whole solidifies in a white mass* (Liebig.)

b* Normal. — ^The hot solution of a hippnrato mixed with neutral
Aoetate of lead yields on cooling pearly lam*na?, which effloresce in hot
air* (Liebig.) Cold hippurate of potash forma with neutral acetate of
lead a white curdy precipitate which dissolves sparingly in cold water.
The solution diluted and filtered at the boiling heat through a hot funnel,
deposits tufts of delicate silky needles, which often, especially in concen-
trated solutions, suddenly take up 1 At. water, and change completely
into broad ahmlng laminuj easily recognised as four-sided tables. The
solntlon of the salt yields either the needle-shaped or the laminar crystals

^cording to its degree of dilution and the time that it is left to stand.

!oth kinds of crystals give off their water of crystallisation at IQO',

' ihwar«0

Jf 100\

PbO _...,. 1U"8

18 C .„,.„.«. 108 0

N * 14-0

8H » «. e^o

h O 40 0

Schwarz.

39*67 39-3f>

33-33 3fl*50

49?

2^84 3-02

U 19

^B C^^NH^PbO^ ...281-8 ,.

.. 100-00

^^^V m^dttM,

Scbwara.

^M PbO .. 111^8

.... 3?^2S

........

3692

^r C«NU«0« .... 170-0

.... 66*72

F 2 HO.., 180

... 6*00

^H a«NB^PbO* + 2Aq,.. 23y-8

.... ICO 00

^^^ Lamina.

Liebig.

Schwan.

^^ PbO 111^8 ....

36-20 ....

3&'04

...- 36-08

► C^NH'W ..„ 170 0 .».

65-05

3 HO ^. a;'0 ...,

8-75

D"NH»PbO« + 3Aq.,.. 308S -,.. 100*00

JVn-rc Hippuraie. — Soluhle hippuratea form a rust-brown precipitate

ith ferric salts. (Liebig.) — Neutral eesqui chloride of iron forms with

dd hippurate of potash, a ligUt cream-cotonred bulky precipitate, which,

,/ben immersed in hot water or dried at 30% gives up water, and deli-

inescee to a brown mass having the consistence of temperature. — The

m is insoluble in water, dissolves readiiy in alcohol SB^maVl^ ^\xt5i'a. 1

80

BENZTLBNB SERIES: PRIMARY NUCLEUS C^H*.

hot, and tejparatee as the solution oools, partly in tho amorphoiis state,
partly in tufts of red oblique rhombic prisms.

Ilippuratf qf Cobait, — Carbonate of cobalt forms with aqaeon
hippurio acid a red solution, from which the hippurata of cobalt ii
precipitated by alcohol; it may then bo washed with alcohol and reem*
tallised from water. Rose-coloured nodules consisting of concentricailj
gronped microscopic four-sided prisms which, after drying over oil of
ritriol give off 17*53 per cent. (5 At.) water at 10U% ud amuat a
violet colour. (Schwan.)

CoO

18 C

Ai 100*.

S7-6

108-0

.... 1811 ....

.... 52 oa ....

.... 6-71
.... 3-84 ....
.... 19-28

Scbwara,
.... 17-90
.... &1-9?

N

8 H

140

8-0

.... 4*06

5 0

40*0

CWNU'*CoO«

207-6

«.. 100-00

Hippuratf of yicM, — Obtained by treating carbonate of nickel ii
excess with aqueous hippurio acid. Tho solution, after evaporation over
oil of vitriol, yields indistinct crystalline crusts of an apple-creen coloir.
The salt dissolves very sparingly in cold water^ better in hot water or
alcohol, but is insoluble in ether. (Schwars.)

At 100*.

NiO 37-6

18 C 1080

N 14-0

8H 8-0

bO 40-0

Scbwart.

1811 18-02

52-02 ftl-62

6-74

5-8& 4-lS

19-28

C»NU»NlO« 207-6 ....

NiO 37-6

18 C lOHO

100-00

.... 14-86
.... 42-76 ...
.... 5-55
.... 515
.... 51-68

Scbwmnk
42-75

N

\:\ H

no

130

5-85

10 o

80-0

C»»NirMO« -h 5Aq .... 2526 .... 100-00

Ilippurate of Copper. — Separates, on evaporating a solution of
sulphate of copper mixe<i with a soluble hippu rate, in green crystals whidi
may be rocrystallisod from hot alcohol. Microscopic oblique rhombie
prisms sparingly soluble in cold water, reailily in hot alcohol After
being drieil over oil of vitriol, tho salt gives off ld'3d per cent. (3 At.)
of water at 100''.

Ai 100*.

CuO 39-8

18 C lOS-0

N 14-0

8 II 80

5 O 400

Schwars.

.... 18-97 18-77

.... 51-48 51-39

.... 6-68

.... 3-81 4-04

..» 1906

C»NII"CaO* 209*8

100 00

HIPPUtATi or BTHYU 61

CbO .«««... I

ont^im

. 89«8
. 1080
. 140
. 110
. 64*0

... 16-81
.... 46-61 ...
... 601
.... 4'64 ...
.... 27-08

SwWMTSt

18 C

48*82

K

11 U

4-01

8 0

CMNH"CttO*

^ SAq...

. 386-8

.... 100-00

Jfereur&tu HippuraU. — Bo\tM§ hippnimioo form m wbiU onrdy
procfpiUto with meroarotui nitimio.

l/ippnraU of SUwr, — Hippuimto of potaih forms with nitrtto of
oilror % wbiU ourrly prt*oipiUto; Atid when this procipitftto is diMolvod
in boiling wator snd the •olutioo flltoroil hot, silky needles sepftrate on
eooltng. — The 8»lt| after drying over oi< of vitriol, gives oiT d'43 p. o.
(1 At.) of water at 100^ (Schwars.)

^1100*. D«aMM ii Pelifot Sobwan.

18 C

... 108 .... hVH
... 14 ... 4 80

... 108 .... 87-76

... 8 .... 2'80

... 48 .... 10'70

.... ^vn ..

87-67

N

Af

8 H

.. 87-21
8-86

6 0

C»NM«A80* ..

.. 286 .... 10000

lie. 108 .... 86-61 86-44

N 14 .... 4-75

Af 108 .... 86-61 86-40 .... 86'.12

OH 0 .... 8-08 8-10

7 0 66 .... 18-98

C»n^H«A80* + Aq... 296 '. 100-00
Hippurio aoid dissolves readily in alcohol, sparingly in Hh$r.

Hipporate of EthyL

STBftnovsn. Ann, Pharm» 31, 149.
LtMio. Ann. Pharm, 95, 361.

Formatum nml PriparatUm,^ I. When an aloobolio eolation of
bippurio acid saturated while hot is left to stand for some months In a
warm placoi hipporic aoid separates at flrst in oauliflower-like masses

S. 7*2), and ultimately, crystals are formrd which exhibit the characters
bippttrie ether. (Liebig.) — 9. A solution of hipporic aoid in alcohol
of ep. (|r. 0'816 hi distillM for several boars, while nydrochlorie aoid gae
is ooalmoally passed tbrougb it, the alcohol which disUk ovai VmM
tepealedly ponfed baek« A§ 9oou m Ibe liquid ban \MMOttia IVVaV muI

Sfl

BINZYLENE SERIES : PRIMARY NUCLEUS 0*HK

oily, tbe liippurio ether may be precipitated by water, in the form oft
tLick oifj which sol id i Res in the cryatnlHue ^orm after being freed from.
tbe alcobot and the acid. (Steubuaie*)

ProptHien. Cryatallises from a ef>mewbat dilute alcoholic solutfoti iu
wblte eitky needles ufictuuns to tbe touch. Inodorous. IWte^ like tnr-
pentine, Sp. gr 1 043. Melts at 44"^, and solidifiea in the ciy^uUioe
form at 32^ (Stenhotiee,)

22 C

132 .
14

n .

48 .

.. €377 ...,
. 676
.. 6-2B

, 2:i-19

. 63-72

StenUoiiJie.

' N

13H.„.,

6 0

5^6

6-4t

2&ia

C«NH'K>»..

. 207

100^00

lOO-tMl

Decomprnkianx. K The ether is |>artiallj decompoeed by cfufifltfDMlV
tbe odour of bitter almonds then becoming perceptible. When heitii
in contact with the air, it gives off benzoic aeid and after wards tftkei
fire. — 2. When heated with nitric iteidf it girea otf nitric oxide g»a, and
yields bippuric acid at a gentle heat, benzoic acid on boiling. — 3. Hgdro-
chloric a^id decompoijes bippuric ether into hippnric acid and aleqhoL —
4, When the etbor is heated with oil of tntnnl, it blaekena and yielJi
benzoic acid. — 5, Dry ckhrine gas if absorbed by fuaed bippuric ether,
with evolution of bfdroehloric acid. After tbo excess of chforiTie hu
been driven otT, a white substance n obtained, which sjtiells like chlorida
of benzoyl, doe^ not yield benzoic aeid when treated ^vith watfr, dissolrM
sparingly in water, readily in alcohol and ether, and depurates from Ibi
solution in tnftetl crystals, heavier than water and perfect !y ueatnl.
When heated with potash -ley» they yield chloride of puLassiuni, anii tb»
liquid when acidulated, deposits cryutnls which do not reseiuble mAm
bippuric or benzoic acid. — 6. Hippuric ether heated with pedasth-i^J'
resolved into alcohol ami bippuric acid. Solutioti t^/ ammonm ai
tbe jsaine moaner; dry ammoDiacal gaa does not act upon bippuric «
(Stenbonse.)

Appendix h Eippurk Acid.

Hipparaffin*
C**NirO»(^ C"CyH* + 2H0 f Gm.),

IL ScEWABZ. Ann. Fharm. 75, 201*

Foi-maii/in and PrYpftraii&n, By beating bipparic acid, water, and
i»efoxide of lead with a quantity of sulpbnnc, phosphoric, or nitrie aeid,
larger than i» required to neutratifte tbe resulting protuxide of lead. —
Hippufw add U gently beaied with water and a large exe«« of p«i»s*dt

mPPARAFFIN.

B3

of lead and salpbarlo acid; the paaty mass tbroTfn upon a 0!t@r wUila
«tiU hot; and the acid completely was^hed out with water. — (Tho liquid
deposits a ernall additioual quantity of kipparaffin on cooling, and the
Bolation filtered therefrom yields a still lurgcr quantity, aft4^r being a at n-
rated with ammonia and evaporated; a small quantity of beujEamid© ia
also formedj and a portion of the hippuric acjd remains unaltered, if tho
heating has not been long enough continued.) — The residue on the 5lter
18 dried, pulverised, boiled with tolerably strong alcohol, filtered hot, and
tlie residue washed with boiling alcolioU The alcoholic solutionj cooled
and e%*aporatedj yields need lea of hipparaffin down to the last drop.
These cryatals are dried over oil of vitriol — if heated^ they might deli-
quesce ID consequence of alcohol adhering to them — then boiled and
washed with water containing a little ammonia.

Properties. Crystallises from hot alcohol in extremely fine soft
needles having a iilky lustre and ammired in thickly interlaced bundles.
Inodorous and tasteless. Melts a I 20 Q°, solidifying in the crystaHine
form a^ it cools; at a stronger heatj part of it distils without alteration,
the refiddue turning black.

16 C

N

8 H

20

9C
U

n-61

10-45
5 97

Schwarx.
7VU

6-09
IV9\

C"NH*0* ........ 134

100*00

1 0000

i^ecQinpo^Uions^ 1. Bums with a bri^jht eooty Home, leaving a Bmall
quantity of easily combustible charcoaL — 2, In nitric acid, even when
concentrated, it dissolves without decomposition at ordinary temperatures,
and h separated again by water without alteration ; the soiution^ when
heated, gives off a small quantity of gaSj and after a while no lon^'er
yields hipparattin on the addition of water Hipparaffin dissolves in cold
red fomiog nitric acid, and melts into an oil; but if tho liquid has not
been heated to the boiling point, it is eepnrnted without alteration on
mixing the li<|U id with water, — 3. Hipparaftin is not decomposed by
solution uf iodine^ by chlomte of polabh and hydrochloric acid, or hy
sq neons chromic acid, — 4. When fused with caustic potash it is hat
partially decomposed, with evolution of ammonia; the undecomposed
portion eeparutei again on addition of water, — When hipparaflin is
Ignited with potash lime^ benzol U produced, and the whole of the
nitrogen goes off in the form of ammonia.

Hipparaffin dissolves sparingly in hot water^ hut is quite insoluble in
cold water, which does not even wet it] the solubility is not increased
hy addition of sulphuric acid, hydrochloric acid, ammonia or potash.
Hipparaffin dissolves readily and without colour in oU of vitrioi^ and
18 precipitated by water without much alteration. It dissolves readily
rjo boiling akokoi, and very readily in ether.

G a

44 ftBNZTMNE SERIES ; PRIMARY NUCLEUS C»*H«,

% Benzoata of Allyl,
C»H^*^0* = C*H*0,C»*E*0*.

ZiMiK. PeUrsh. AJcad. BtdL 10, 360 j X pr, Chem. «5, 269; Ann, Fk

dS, 362.

Cahours & HoFMANN. FML Ti^ni, 1857, t", 9; Ann, Pharm, lOS, W^
BfiUTHELOT & De Luc a, jV. Ann* CAiw»» i'A^*. 4S, 286,

B€m^9ait qf Fropsftinifl, Btjumi* qfActyh

Formation aiid Frepur^thn. By the action of iodide uf allyl on
foate of BiLver (Einm, C^liouri <t Hofinaun, Bethelot ^ De LucaX or «f
chloride of beuigyl on allylic alcoUoL (^Caboura k Ht^fmaim.}

[C**H*0*,a + ^^*} 0* - ^^^) O* + HCQ.

J

ZlniD recttSea the product obtained hj the first methcKl orer 1>eDiott« of
fiiU^eft wasbea the distillate with carbonate of soda, dries it over elikhdt
of ealciuruj then rectifies it over oxide of lead, and lastly pet $e*

Fr^pertm- Yellow, oily, neutral licjuid^ heavier than water^ a»<^
haTing an odoor like that of benjEoate of etliyl. Boils at 242' (Zialn), tl
22a' (Caboars & Hofmann}, at SSO'' (Bertbelot Jt De Luca).

», j Cibo^r*

Ot Hofttiiiiii.

aaC*.M. 120 ..- 74 07 ........ ?i'29 . . 73'iO

10 H «„,.,. 10 .,» §17 . .,. fi*44 „.. 624
4 0 %t .. 1976 .„■„. 19-37 2066

C^Hi^}* .... 162 ,. 100*00 ,,„,.. 100*00 „ 100 00

Bt boiling with pf^ta^h-ley, it ia couverted into benzoate nt
and all^^lio alcohnl. (Ca^houra ^ Flofm&nu; Berthelot 4 De Lucm.}
It IS inaolnble in water, but diaeolvea in wood-mirU. uicok^ md

Benzoata of AmjL

BitCRHeE. Jakrt, pr. Fharm. 1^ 15] abstr. Ann. Pharm, f|^
N.J, Fharm.Xi.Zm.

Ohtained by dJatilliag a mixtnre of 1 pt fuiicI*oil and 2 pt«. ail rf
vitriol with exeeoa of an atk&line bpn^oate (iliecklier); — or by wituratiif
a iolution of bvuiiiic acid lo amy lie nlcohnl with hydrochlorio acid fldfl
wmthin^ the proiluct with a<{ueouB carbonate of aodft^ (Item (mnoe U i

BENZOKE,

ratea but elotFlj frotn water on account of its nearlj equal density), with
Boluti^in of chloride of calcium, and rectifjing. (H. Kopp^ Ann, Pharm*

Liquid baring a foint yellowish oolcinr, and a peculiar, not unpleasant
odonr. (Rieckher.) Sp, gr 0 9925 at 14 4^ or 1 '0039 at 0°. (Kopp,)

Boils between 2 52"* and i25 4" '^' '* ^ --

745*6 mm. (Kopp.)

(llieckher)j at 2G0 T"" with the barometer at

Zi C
4 0

144
16
32

75-21
16^59

Hieckh^r^
7543

16-06

C»*H»0* - 192

100*00 .„.,_ lOO'OO

It 18 easily decomposed by alcobolie potash.

Benzone.

MfTSCHEllLlC H. P€^g^ 29, 231 .

Feligot. Ann. Chim. Pky^. 5€. 59; also Ann. Pharm, 12, 39 j Poff^.
I 3tJ, 69.

LiKBiG. Ann^ Pliat^in. 12, 50-

Chancel. Compi. rend. 28, 83; Compt chxm. 1849, 87* — Further,
C&mpt. c/iim. 1851, 85; also J. pK Chtm, 53,252; aWtrp jlnn,
Plharm. 80, 285.

Fermttiitm and Prq^^arMion. I, Dry henxoate of lime mixed with
3'^ of tjuick lirne is distilled from an iron mercury-bottle. When tb©i
crude di&tilkte is several timea redistilled, a large quantity of henzolr
pasaes over at lirst, the boilin"^ point then riising- rapidly; and above 315*^
or 325'^, nearly pure ben ion e distils overj, solidifying iuto a straw-coloured ^
mus&; it may be obtained pure by crystallisation from a mixture of ether
and alcohol. The quantity of bensone obtained is eqnal to } the weight
of the lime-aalt, (Chancel) — 2. The crude distillate is diJiSolved in oil
of vitriol and after a few days, sufficient water is added to render th
li^juid turbid; there b then formed on the surface a very abundant ctjb^J
talline layer, which is to be taken off, washed with water, and crystallised '
from a mixture of ether and alcohol. (Ghancel.) — 3. Strong nitric acid
acts very violently on the crude distillate; if the action has not been
carried too far, a brown viscid mass is obtajned insoluble in water but
easily soluble in alcohol and ether > If the sol 11 1 ion in ether-alcohol ta
mixed with hydrosulphate of ammonia^ the henzone separates in beauti-
ful yellow crystals. (ChanceL) — Peligot hcnted cryitBllia«a bemoatc of lime to
•bout S00° »rid ilistilied the liquid wbich p&ssed over with water. A Isr^e quantity of
bemol Chen }Ki5fied oier and the residue distilled over the open fbfo, jiddeil, Itr^C water,
and then in oti which boiled >it 250% Tr^m which nRphChaiin (^) Bf|}ar4leti Kt — 2U°. Th«
i lightly etnpyreiimutic otl« fioAting on wiiter and boiling at 25 0^ which was decanted
from this substanc^ep contained BT'Zb C and S'OS 11« and was called henzone bf l*eU%f^",
but according; to ChoDcel, it ii a mixture of tke true benzoue (QiajLCfiTt W.^^Q^\ueiLQ^^
witb hf droearbooj, bitter almond oii Se^

BfiTCZYLEKB SERlES-i TOTMABY NUCLSUS CWH«.

Frapertiet. Thick, transparetit, pale yellow rbombto prisms, af \
with hexagonal summits. Melt3 at 4G^ to a thick ml, which aoHdii
only on agitation. Has a pleasant slightly ethereal odour eomewl*
like that of benzoate of ethyl. Boib at 315°, and volatitUes und
poaed, (Chancel)

2n c

156 ,.

.. 85-?l ....
,., 5-50 ..

Cliaoc*K

10 H ...,_..
2 O .......

... 10

C*H»W ..

182 .

. 100-00 ..

1(1000

The ketone of the beoijlene-fteri^a. — According tq Mit»cherllch^ it li
conjagmted witli carbowic oiide i C»H'"0^ » 2(Ci2i|«^cO). fl

DteomposUiffiu* 1, The vapour is easily set on fir© and bums with a
hrlght ftame.

2. Ben zone' boiled with fumin;,' nitric acid forms a thick oil ref
Boluble in ether* which retains its fluidity for a lt>ng lime iu tlte cold, bi
aeraratea almost instantly from ita ethereal stiluiion in the form of ap'
jellowish powder; this oil is i/iniin/baiiQm (i^aopltinon^ ^mU

26 C ......*..,. 156 .

2 N .,......, 28 .

10 o,,. m .

C«(N0^fH*02. ... 272 ,

Lhmtketh

h7t^ 57 18

10*30 10*55

2 94 .... 3 OS
2341 2&2i

100 00

100 00

Bfnitrohenaon© treated with hydrosulphate of ammonia yields flariDC
(Chanct4,)

3* With poki^'lhue nt about 260°^ ben zone yields benzoic acid tad
pure benjioJi withotitevolutionofhy drogcn , (C b ancel ) :

Combtnniions. Benxone is not soluble in waten It dissolroA aboiH
Btly in oii of viin^l and in miric amd^ and is eejiarated from t!ie tolii'
by water in its original ^tato* It dissolrea with tolerable facility ifl
aicohoiy and very readily in rtAw.

I

Banzoaie of Phenyl.

Ettuwo. (1845.) Ann. r^rm. 53, 87; aUtr, J. fn\ Ckem. 20, t$f.'

PhU. Mag, J. [3] 27, 3.
SrofnousR. Ann. Fharm. 53, 91; 55, 10.

L^UEKKT fit GRitUAm>r CompL chim, 1849* 429, jinn* PAarm. 75,73^
GBRaARDT* Ann. Pharm, 87, 161.
li»T & laM^MiCBT, Ann. Pharm. ^0, 1^0,

BENZOATE OF PHENYL. ^^^^^ §7

''Ben£^»&ur€ CsrAo/irffwre* Bettzoeo^yd, Btuzftyhx^dj Phdntdm^ Bfrnioji^dnid,

Bettzoj^lr bfnMWtsurM PJtmyhjT^d.—EniUtf^ utiJ JstuiiUiiiife regwrdifd the eabi^tance
foriued. hj the (iry diAtillaCion at benzoate of roppf^r at an oiide C'Hl^CFf standing
beiow benzoic aciit ; Gerhirdt prepBi^d tlie tamt subittunce from anhjilmus benzouiU-
cylic Acid, mtifJ rej^&fded it «» tlie radical bji-iizojfL (p, 23}; List Ss. Ltmprkht bttye shown
that thr iybstan^e obuined b]r either of tlieie proociiM ia idetiticat wtth Laurent &
^Gtrhardt'ft benzoplif^nidet

Fortnaium L By heating chlorfJ© of benzoyl with carbolic acid

J^ I^r^nratifm. 1. Carholic add ii heated with ehlonde of benxoj^l^
^le a*)dition of tKe latter Wing cmj tin tied as Jong aa hydroclilonc acid
eoniiDQes to et$cape, and tlie c*Mjled cry«tain»e nias.»*is dissolved in a mix-
ture of etber and alcobcil; on leaving t!ie mihition to evaporate, the
compound crysLiHises in needles. A small tjuantity of henaoic etbor
separates at the same time, being formed by the action of the eatceeji of
ebloride of benzoJ on the alcohol (Laurent & tics rhardt.) ^ — *i, D17
benzwiite of copper is ilistilled at a temperature not exceediug 220"; the
eabkimate which forms in iheneck of the retori, freed from admixed benzoic
aeid by means of dilute pota^fli; and the residue repeatedly crystal IJecd
from alcohol (Ettliti^.) Sienhouse treats tb© crystalline maas witb
carbonate of goda after pressing it between paper, and crystallises the
washed residue several times from alcohol or ether. — Dry beoKoato %^f
eopper is dis^tilled over the open 5 re as long as vapours continue to
escape; tbe buttery distiUute covered with water, then eu pertain rated
with carbonate of soda, and distilled as long as oily drops of benzol con-
tinue to pass over with the watery vapours. The roflidue is separated
from the lj<|nid containing carbonate of eoda, washed with water and
dieisolved in hot alcohol The crystals which separate on cooling, and
■re contaminated WJib an oily body, are heated with a small ..quantity of
alcohol wbicb chiefly dissolves the oil a-t*d repeatedly crystallised from
Eot alcohol (List & Limpriebt.) — 3. Anhydrous ben 10 -sal icy lie acid
ti heated, and the product boiled with potash ley; the oil which floats on
the litjuid eolidifies in tbe cryHtaUiae form on cooling, and yields needles
when crystallised from alcohol (Gerhardt.)

PropeiiUis, Colourless^ transparent, hard, shining, rhombic prisms
often half an inch long. Fig. 81 ; « : w = 100^ 48' 24"; u:i- 81^ 2/ 19".
Ratio of the axes ^ 1 : 1-2089 : 0']962, (Danl*er.) Has a faint
Agreea b1 e od ou r of ge ran i u ms and 1 em ons^ espec i ally w h e n h eated. M e I ts
at 5D^ (Ettling); at 70"^ (Stenhonae); at 66' (Gerhardt; List and Lim-
prlcht)- Solidifies at 49^ in a radiated crystalline mass. -— At a higher
temperature (abiive 100^ according to Ltet Jt Limpricht), it appears to
volatilise without decomposition.

Ettllng. Will. Steobo«*e.^-^^f;GerWdt.j^^^^^^^^^

26 C ».. 156..,. 7a 7&... 78-6S 7876 .... 79^81 .., 7B'4 ^ 79-53 .. 78 21

10 H .-» 10 .. 505,,. 5 03 .... 5 0fi .... 5 11 ..,. 50 _ 505 ,„. 6 04
40 _ 32.... 16*ie ... 16 30 .... 16-16 .... 1508 ..,. 16*fi .... 15*42 .... lfi'75

88

BEN2YLENE SEEIE3 : PRIMART NUCLEUS C"H*,

Dec^mpoiitians, 1 . Tbe compaond barDs in the air with m red,
mi6ky flame* — 2. Exposed to the action of chhrins pas far & daj li i
warm temperature, it is converted into a soft yellow maas consistitigj of i
liquid ana a solid c1dorine*coni pound. (Steotioiise.) — ^3. With liqujl
hromine it gives off liydrobromioamd gas, and ii converted intobeDZOste i
hromoplienyL (Laurent & GeHiardt, List k Limpricbt.) — 4, BuUitt^
nitric acid con'^rerts it into a yellow fused masg^ witli evolution of hrown-
red vapours (Lanrent k Gerhardt); cold niirQ-sxdfhuric acid ©otiv^rt* it
in to n i trohen zoate of hi n i tro ph en jl . (List k L i m p ri ch t . ) — 5 . Oili^J
mtrioi diisolves it, with altgkt evolution of heat] and on adding wat«r io
the solution J ben&oic acid is precipitated and sulphocarbolic acid remaiiii
in fiolution. (Laurent k Gerhardt.) — 6. It is not altered by |>cnt»-
chloride of phoBphorua* (List ik LimprichL) — 7* It ia not decomposed
by boiling with aqueous potash ^ and remains unaltered when heated witli
potash-ley to 120" in a seated tube; if the heat be kept for eome time it
150°, henzoate and carbonate of potash are produced, (List k Linrprichi)
^^ The eumpjund boiled witU aqiieauB polish ttikrt up oxf|^?[) and is ciortTcited ideo
twnRojc ftcid. (Steiihouse.) When fussed with caustic potash^ it forms C3U
bolate and Uenzoate of potash (Laurent & Gt^rhardt, Gerhardt); (an
gives off hydrogen. Stenhouee. [? L,]), Also when treated wilj
alcoholic potash (Stenhouse), even m the cold* {List A: Limpricht)-
B. Heated in ammoniacal gas or hniled with an ammoniacal soluiioii
ammonia^ it yields carbolic aeid and benzamide. (List k LimprichL)

It la iui^oluble in water, hut dis^tolves with tolerable facility m
ulc^ol and filier, readily in the same lit^uids at higher tetoperature««

Benzoate of BromophenyL

C»H*BrO* = C"H'BfO,C^*H»0'; and C»H»BrH)* = C"H*Br'0,C*HW
L»T k Ltvpriciit. Ann, Pkarm, 90, 196.

J^ormotion and Preparation, Bromine is ponred upon dry heuL.^
of phenyl in a retort, till no more hydrobromio acid gas ia evolved^ evi
on neating the liouid; the excess of bromine is then^distilled off^ and '
muBfl which solidifies on cooling is washed with water and roj
cryatallised from hot alcohoL

Propcriirs. Largo colonrleaa needlea arranged in arborescent groupt;
they melt below lOO"" and appear to sublime without decompositioa

1$C,, 15* .._,

4 0 -« — M ,^.,.

. 6631

. 2i-&8
11*66

Otleuiatim f .

26 C . IH ....,.» 43*82

«H ...^.». i ...... 2-23

2 Br ..., , tm ,. iiU

4 0 ..,,..,„. . 3t ,.»„„ ft M

mM»g

<?iH«Bf*0* .... 5M „...„. lMh«t

B1N20ATE OF CHLOROPHEKYL,

^

sec

156 ,...._

.......* 35*S6

B

7 H

3 Br ,„..

7 ..._,

240

»....„ 1*G1
55' 17

^^

4 0

32 __

....... 7-36

F

Anmlyw
a.

- 435 „_ 100 00

» by Lwt aod Ltmpdclit.
*. c.

54-79

., 3*19

32 4«

50'] 1

1 H.::::.::::

, 3*88 .

293

34 ej

12-31

C_.

Br „„.

0

. 46"55

. 2-46

.. 43-15
., 2'59

3^e9

A.
... 42-82 .

J 00-00

t\
4274

2-04
... 45'42

9-80

10000

Hie miiljae^ abow th^t: the fiubAtaoce ib a mixture of two, or probably^ &s indicated
aiwlysu t, oi three iubstitution-procfactftf «bi€h catvnol be separated from oae
itlier by crystal lisatioti. No nDaltered benxoate of phenyl coqM be present, because
L ntOMt of broiiime wai uied in the preparation^ and benKoate of pbenyl diiiohei.
pretty easily in cold alcohol.

The inothet4iqt»or which remain i after the finti recr^EUUisation retatna in Boltitioa
an oUy substance which separates when the liquid is rery much concentr&ted ; its solu-
tion in ether yields hy etrapt»ration small colourless crystals, perhaps coosiitJnf of the
npound C=^H'Br»6\

i

Dtcmtptmtkns. L Cold nitromlphurit add converts the eompoand
into nitrobenzoate of bromopbenyL — 2, It dissolves ia oil of vkn'ol,
forming a greenish eolutitm from which water throws down benzoic acid;
and the aqueous gohition eatarated with carbonate of baryta yiehla a
luWe baryta-salt — 3. Benzoate of bromophenyl diFSolves readily in
Id alcoholic potash; the solution does not become turbid on addition
water^ hut when treatod with sulphuric actd^ it deposits benzoic and
Toniocarbolio acids*

This compound ts insoluble in water^ very spannL'ly eolnble in cold
alcohol and ether, but diesolves readily in those lifiuids at higher tempe-
ratures.

Benzoate of ChlorophenyL

' SxENitousE. Ann, Pharm. 53, 95.
List k Limphicht, Ann, Pharm^ 90, 199<

Ben^QtwaufT Ckhr^artQUdHrtt benzQt^auTn Fhert^hxyd.

When chlorine gas is passed for several days over benzoata of ^b«\i^V,
dark yellow mixiuie 'mptodaeed^ consisting of eb oWy and ^ %^3\\^\icA^,

m

BENZYLKNE SERIES: PK I MAKY NUCLEUS C»H*,

whhh has a very diaagreeable pungent odour, aad strongly e^eites teS^
Tbia product is pressed between Uibuloufi paper at a gentle beat, and ll
flolid residue repeatedly recrystalltsed from ether. (Stenbouee.)

PropeHki. Large flat crysLib wbicb melt at 84% and £DUIiine ml
four-sided prisms at a. bigber temperature. Has a faiiili not unple***"*^
cMlotir, resembling tbat of iesquiehbride of carbon. (SteuUoase.)

Stenhouse.
26 C , 1560 ..» e7'10 ..« Or 97

9 H , . 9(1 .... 317 3-99

CI ..,.. 35*4 ... 13'77 16 21

4 D ......... 32 0 ... 15-26 _ 13 83

C^H'CIO* .. 232 4 .,. 100 00 lOOOO

It U therefrtre benzoate of chlorophrnjl mi ted with benxoaCc of hi- or tri-i
phenyl. (Liit & Lim|inf4u )

Heated with dcoholic potash, it yields chloride of potallium, bensoftto^
of potash, and a email quantity of benzoate of ethyl Hydrochloric acid
added iu eitceii to the alkaline liquid, throwe down beuzolc ilcM and a
dark-coloured resinous bmly, emelling of creosote^ (Stenhonse, )

The liquid cblorme-compound produced by the action of chlonne i
l>enzoate of phenyl {vid, *«/?.) may he dissolved out from the bibulij
paper by ether, but it is diflicuU to separate from ibe solid compouEd.

SteuhjOUU;.

20 C ,.....«... 156*0 ..,. 51*79 ...... 53*43

7 H 7*0 ... 2*32 .„. . 323

3 CI 106 2 ..„ 35 26 ...._ 29 6tf

4 O 32 0 «.. 10*63 ....,, 13 75

C»H^CTO^ 301-2 ... IWOOO lOO 00

[It is therefort benzuafce of tricKloro phenyl mUcd wUh bfnsOftte of ehfor«:»phflij1 m
hicthbri>pheti5U Tbe Lmc in i\A pure 8tfit« rcqiiiret 58' 43 p.i?, C, 2-09 U. Moi
26*52 Gl. L.I

Treated with alcoholic pofasb, it yields cbtoride of potaesiitm, ben-
jEoate of potash f and a quantity of the resinous mass larger than " *
wblcb h yielded by the solid compound. (Stenbonse.)

Beiizaate of BinitrophanyL

LAUti£}tT k Obaharpt. Co]iip£> Ckim. 1840, 429; nbstr. Ann. M
75, 77,

Crystals of binitrocarboUc m\d moistened with chloride of boupoyl
are gently heated, aa long as they give off bydrocbloric acid (longer b<ftl-
ji^ wanld alter tbe product); aa4 any bimuo^arbolie acid that may hare

BIHZOATf O? TRmiTROPHEI^Tt,

rremained onchanged, la dnsolred out by dilute amniouia, washetl with
|eold alcohol, &ud crystallised from boiling alcoUoL
Yellow rhombic kmine.

LaoreDt ^ Gerlmrdt

26 C ...,_ 1&6 ..,. 54-17 54" I

2N 28 .... ^72

8K ...» » § ..,. 2*7« 2 7

12 O - m .. 33-33

C»WH*0» 2S8 .. 100*00

It diss^dw-ea partially in boiling potaijh, forminj^ a yellow sola t ion.
It ia inaoluble in water, and nearly insoluble in boiling ulmhol^
Disaolvee rather freely in warm etiier.

Benzoate of Trinitropheayl.

liAURisT & Geahabdt. CompL Chim. 1849^ 429; abstr, Ann. Pharm,
75, 77.

Bfmottaurt Trimtrocarboit^urg, Hntowmur^ lYiniirophwnylo^d, TnnUf^*

keTii&pAdnid.

PlcriG acid is treated with chloride of benzoyl^ ae In the preparation of J
beoKoate of binitrophenyl, and tbe product ie washed with cold alcohol till [
that liquid ia no longer culonred by it, and cryBtallised from hot alcohol.

Gtilden yellow rhombic lamina>, having a strong lustre. Mctts when
beated^ aJid fiulidiHes in the crystalline form on cooling.

Liiureiit $t Gerhardt.

26 0 ,.156 ..., 46-85 ..,. 46 G

3 N _...._.„ 42 .... 12'fi4

7 H 7 ... 2' ID ..... 2*1

la O 12B .... 38*13

C»K^H?0»* 333 , „ lOU-00

When strongly heated^ it asenmes a darker colour and explodea.
It dissolves in boiling potash with deep yellowish red colour and
■eparation of crystalline rlakes. — When boiled witU ammonia, it remaiui
for the moist part undlssnlved.

It i» inaolnble in water, and less soluble in cold aieohol than benzoate
of binitrophenyL It dissolves sparingly in cold, somewhat more abun-
dantly in warm ether ^

92

rLENB SERIES : PRIMARY NUCLEUS C^H^

BeEzolactic Acid-

CWR^O^'^ - C"H^^0*'',2(C»H»O')»

SocaLOPP & Stheckkr. Ann. Phafm. 80, 42.
Stbecicer. Ann. Phami. 91, 359*

Formation and Prtparation. BeDaoic and ketic acids mre tieated
together to IHO'^ aa Wif as itqaeous vapoar contmuea to escape; Uie
solidified refiinoiia maes is djesoWed in water cotiLnining potash; dilute
Bulphuric acid added to tbe warm «olotian till benzoic acid do Icmffr
scpamtci on cooling, but crystals of aaatber forQi make tbeir appeamDrej
the preci|iitHted benzoic acid tben aoparated by filtmtion; and ibe filiralf
treated with sulphuric acid, A copiuus precipitate is thereby produced,
which when boiled with water, Bret melts and then ditieoWea lo a larfor
(quantity of water. As the lit|ind cool 9, the ben zo lac tic acid is deposited
either io drops or in crystals, and may Ijg obtained in the crystalliDe state

by solution in ethen (Socoloff & Strecker.) T Or betters Id pis. of

syrupy lactic add are heated with 14 pts. of benzoic acid in a retcrt to
150 ; water then passes over, a aurall quantity of benzoic acid t^ublimet,
and, after the mixture has been bcatci for several hours to 200 ', there
remains a fused brownish mass* which on cooling gradually eolidifies in a
network of crystals conaiating of benzoic sind beuzolactic acids. On
boiUng this residue witli a quantity of aqueoiia carbonate of t^oda not
sufficient to dissolve the whole, the tienzobcttc acid is di.^solved iu gretlci
proportion than the benzoic acid; and the resulting solution » from wl^^^J
the snmll quantity of benzoic acid may easily be removed by agitafll^P
with ether^ yields, on additi<>n of hydrochloric ncid, colourless crystals of
benz<»lactic licid, which may be purified, by rocrystallizatiou frona water, ^—
Of from a mixture of ether and alechol. ~ H

Properties. Colourless tabular or spear-shaped crystals, unctuous to
the touch: In the dry state they m fit at 112"; the fused acid rematns
liquid for a long time after cofding', and then solidifies in a crystallixie
moss. The acid docs not sublime between IQO^ and 120"^^ but when
strongly heated, it boils and appears to sublime unaltered. After drying
in the air, it does not give off any water when heated to its melting poiol«
(Streeker.)

Air-dfitd* itreeker.

fOC 120 ..,, ei-fi ...,„.. 61-e

10 H ,,..„ IQ ,,„ 6't *. 52

8 O ..„„..^. <4 ,„. 53-0 *.>,— S3-2

C»H*"0« .,„,,.... 194 .,.. 1000 ....... 100 0

The «.id ^.r U r^^rded « C"H*(C^H^)0»j ^, ,,^^ ., ,^ ^^ ^. ^^^^-

hi which 1 At. H within the ndi^l Cbftniojrl) l» T«pJftced bj Uctyl C*a*0*. Iti ,
fomiAtioa it rcpreicated by the equation t

ANHTOaOUS BENZOIC ACID.

98

b moAt of fornaaCli^ri m{||ht lend in the concluiion that the add b bibAMc and iboald

Iht represented by the forma la C*^H^O^* j but at the honioU>goua com pound betiiogly-

colic add (p. (i6) h motwbasic* and lu rormula could nut be doubled without doubUnf

also the furmtila of hlppnric acid, and therefure aUo lUiit of gtjcocol, it. ii best oa tba

whole to regard betisolactie acid as monobasic (Streckcr.)

" Decompo^ithn , The acid boiled witK water, is very slowly rosolred
into benzoic and lactic acida; the decomposition ia somewhat accelerated
by addition of dilute sulpLtim acid.

» CGmbmaiions. The acid dissolves in 400 pta. of cold waierj aad in ai

amaller quantity at tlie boilini^ heat.
^ The Btmzolaclai'g, C"H'MO', are for the moat part eoTtible in water.
^hTheir neutral solutiona are not precipitated by neutral acetate of lead^
^kii character which distinguishes benzolactic from benzoic acid.
^^ BenmlaUoXe of Soda cryatallisea in colourlei^s needles.

^K Bemolaetate of Bary(a. — CryKtallises from ita aq neons solution ill
abininE, thin siir-sided lamince. The atr-drled «alt girea ofiT IT'S p. o,
(6 At.) water at 100^

BaO

At 100'.

...... 7fi3

185*0

29-3
707

Stre^^ker.

(PHoBaO^ 2%Vb .... 100*0

BmtohdaU of Silver. — An ammoniacal eolution of beniolactic acid
Qixed with nitrate of sillier forms a floeculent precipitate, which di^soWei
lin boiling water and crystallieea in slender colonrlesa needles on cooling.

3trecker.

C20H*C^,.,.. 193 .... Gi'S

Ag 108 .... 35'&

3C1

C»H«AgO" 301

lOO'O

off A Strecker faond 37 per cent, of siWer In the tiltj the excet« uitiof ^

Tob«*Wf horn admiiture of benioic acid with the benituUctic.

The acid dissolves readily in alcohol and €ther^ {Strecker.) ^,

Secondary I^uclei of Bmuyhne.

Ojttfgtfi-nuclem C"H*0.
Anhydroua Benzoic Acid.

I'Oebhardt. if. A\m. Chim. PAps, 37, 290; Ann. Fhat^. 82, 187;

87, 163; J. pr. Chetn, m, 280.
t Wir*N»Eii. J, pr, Chem. 61, 498.

BenZQh Aahydridt^ Beriwatw pf BfniQi/t, Benzoic Bmizoaie^ Benz^eMUur^'Anhy*
dridt ^aMterfreie BtTtzoraUure^ benfutejaurt Benzfindure, Benvrate b^nzaiqu^^

Fotmation L By the action of chloride of benzoyl: {a) on o-tialv^
IftGid, or (6), on alkaline benioates (Gerhardt), and tbetftfaT^i t^aQ ^c^^ N^^

M

BENEYLKNE S OXVGEfJ-NlICLEUS C**H*0.

•,4he action of pentaclilcjnde of pbospliorus on alknline benzoates, the fitit j

[«tAg«} of this action bring the f<jrrii:ttion of chloritie of benzoyl (\Vund©r)j|
Un like manner (d), by tlie action of protochloride of aul|jliar on alk4lii~
^leuzoiites (Heintz):

a. C^K^O-* + 2C'*lPClO^ = 2KCI + 2C'^H*0> ^ 2C0 + aCO^j

e. 6C"H*NaO^ + PCI* - 3C"H*N«0^ + 3C"H*CK>s + NaO^PO* ^ fNaCi.
rf. 2C«^H*NaO^ ^ 3CIS = 2CWH*CiO^ + NmCI + NftO.SO* ^ iS.

2. By distillation of acetic benzoate or caminic benzoate. (Gerbardt.)

Prepamlwn. — L Perfectly dry oxalate of potajjh is heated vit^ "^
I equal weight of cbloride of ben soy 1^ keeping tbe vessel in contlnint^^
r Tnovement, till tie odour of chloride of benzoyl is no longer peroeptibl«p^^l
The cooled inasa is suespendcd in cold watt^r; tbe resulting c^liloride of
potassium washed with cold water, to which a little ammonia is added
for tbe purpose of removing any benzoic acid that may have been coii-
iuined in the cbloride of benzoyl; ami the residue is crystallised frtmi
alcoboL (Gerhard t) — 2. When equal parts of dry benzoate of «oda
and chloride of benzoyl arc heated in a eandbatb to 1 30 , a clear liquid ii
produced, and at a temperature somewhat above 130"', chloride of poU^
eiuin scpanites out; the cooled mass washed with cold wuter and solutloa
of carbonate of soda, leaves unbydrous benzoic acid in ;he fonn of a white
L mma. (Oerhardt.) — 3. Oxydiloride of phosphorus* h gradually addrd
^ to an esicesa of findy ponnded benzoate of goila (about five times the
r weight of the OKy chloride), best iu a Ha^k, which k kept in consti
^ tnoiion^ ao that tbe reaction which takes place as soon as tbe fiabstj
come in contact, may extend itself throughout tbe wbole i
mixture is heated to 150'' in an oil-bath or air-bath till it no longer #meU[
of chloride of benzoyl; and the cooled niuss ia auepended in cold waU
to which a small quuntitv of anininnia or carbonate of «oda ia addcij, .
remove any cbSoride of \)f*nzoyl that muy remain, aiid then washed wit
water. In this react ion, cbluride of benzoyl h first formed and afterward
I acts upon the benzoate of i^oda, (Gerhardt.) — 4. When pentachlnrid
' of phosphorus is mixed with dry benzoate of soda, a strong evolution <
heat Utkcs placC; and tbe mass is converted into a syrupy liquid Th
i^ heated for i^onie time to 130% the mass which solidiBes on ooolii
treated with cold watcr^ and tbe residue crystallised from boiling ate
(Wunder) In preparing con^iderahle quantities of anhydrous hei^mi^
A«id» tbe purification is bej;t efleeted by distillation. Well developed
I crystals are obtained by leaving tbe fused substance to cool slfiwty» and
P decanting tbe still liquid portion from tbe eolid matter, (Gerhardt —
^. 5. Tbirty^seven ^rdrnmea or rather more of perfectly dry and fineljr
pounded bcnEoate oiF soda, are intimately mixed in a flask with 10
L gmnimea of protochloride of sulphur; tbe fla.-^k well clo«e*l and left al
P rest for 24 hours; and the contents, which then smell of chlonde of ben-
zoyl» arc beat**d ahove 130', whereupon the nia^ss li((uefieft and tbe odoar
of chluride of benzoyl di&apfiears. The contents of the flask » when ooM«
are thrown into cold wat4% triturated therein with addition of ft lillli

* Ao^rdin^ to Gerhtrdt^ ojtychUiHiJe at pbDi|ihorLi8 h moil kd^anliiffQ^
pnrp«rfd by cltitilhug |>CfitiichU>riiie nf pW'KplHinis^ wiih pcrftctjj drj ojtalic i "
L liquid dUtilkte Itmi abtaijiptl cuntbti mhoUy of tbe oiycli bride :

^^ PCI* 4 C*ll*y* - P€^Cl» ^ IHCV % CO + CCP.

ANHYDROUS BENZO-ACmC ACID.

onate of ioda and afterward a washed witU water; tlie r^sidae pressed
aod melted in the Wiiter-bath- the fu«ed masa trc;*ted with alcohol of
about 50' till it \s completely dissolved, with the exceptioa of suipbur;
a-ud the filtrate left iij a cc*ol plaice till the auhydrou?} betiMic acid
crystallises out If the liquid separated from tliese crystals be mixed
with hot water till the turbidity thereby produced no lotager disappears,
and again left to eool, it will yield au additional quantity of anhydroua
betizoic acid in perfectly pure cryytala. The crystals which first separate
from the alcolioUc aolutioD still contain a little eulphur; but by melting
them in the water-bath, decautiug from the sulphur, dissolving the
decanted portion in the exact quantity required of alcohol of 50^, de-
col orisiDg the iolution with recently ignited and washed boue-charcoal,
and graJusdly couling the hot- filtered solution, anhydrous benzoic acid
IB obtained in pure colourless crystals. (Heinti, Po^^, M^ 458.) %

Properlm. Acute rhouiha or oblique rhombic prisms^ having f?onio-

les a alight odour of bitter almond oil. Melts at 42^^ and remains

Inid for a long time under water, even when agitated. Din lib without

decomposition :U about 310\ Its fresh solution iu alcohol or ether has

effect on litmus. (Gerhard t.)

GerhwdL W under,

lie... 84 ... 74 32 7410 .... 74 35

5 H... 5 ... 4'it ...... 4-51 ., 4-68

3Q. 84 ... ai'26 .» 2J-27 .... 20i>7

c"H*o^ ... 113 .,- imm loo-oo .... loo-oo

Dtcompositmns, 1. When boilcfl with water ^ it communicates an acid

■reaction to the liquid, and by continued boiling it is converted into ben^Eoio
IM^id. — 2, Poktjf/i-ln/ converts it into benzoic acid. When heated with a
vm^ill quantity of solid caustic potash^ it yields benzoate of potash and
benzoic acid. (Chio^za.)

t-0. ^mwoiiia appears not to act upon it in the cold, but on the appli-
Bfttion of heat, the anhydrous acid di^olves quickly, and the concentrated
lolutioQ deposits benmniide; nevertheless, a large quantity of bcuzoate
pf ammonia remaius iu sulutiou, Antlms diy&i not act upon the anhy*
drone acid in the cohl: but on applying a gentle beat, solution takes
placet water separates, and tlie uiu^i^j as it coots, solidifies into a group of
needles of benzamide. (Gerhardt.)

Circus benzoic acid is iDioluble m cold water, but dissolves readily
and ether,
Anhydrous Benzo-acetic Acid.

GeitBABPT. JV* Ajin. Chim. Phyi. 37, 308; Ann, Pkarm, 87, SI;
X pr. Ohm* 61, 288,

BenMO^it^iic AnkydHde, B^zoic Actidie w Aceiie Benzoitie,

Fomiatmn and Pirparalion, When chloride of acetyl Is brougJUi
contact with beuioate of soda, a very brisk acUoii ta^ea ^\«^ic^) ^^^^

96

BENZYLENE: OXYGKN-NUCLEUS C"H*0.

fsootinuea to tbe endl without external halting* The sympy prodttct if"
washed with water aud aqueous carbonate of eoiia, the residue shaken tip
with pure ether, sod tbe solution left to evaporate at a geatle he«t«

Properties, Heavy oil, smelling like Spanish wine. Does iiOt«
the colour of litmus

18 C „

6 O

lOS .... 65-85 .

.»» 8 .... 487 ...
. . 48 ... 2928 ...

G«rliftrdL
«S'94

..... 4-99
..... 29^07

C"BN>*.

,..„ 164 .

... 100-00 .

_. 100*00

Dteompodtions. I. The compound boila at 120^ and aDbjdroiii
aoetic acid passes over, the thermometer riainir rapidlVi and the reaidoe
acquiring a slight brown colour. If the diatilbtion U interrupted at
160\ the residue contains pure anhydrous benzoic acid, — 2. When boiled
with water, it is alowlycon^^erted into acetic and benzoic acida» — Caustio
alkalis and alkaline carbonates quickly eonrert it into a benzoate and an
acetate of the alkalL

Anhydrous Beaeo-valeric Acid,

t^niozzkn Ann. Pkarm. Sij 100; J* pr. Uhim. 61, 29B,

Btmvt^aieric Anhydride^ V^ahHc BentQait, or Stn^k V&l^^U,

Obtained by the action o! chloride of benzoyl on djy Talerate of
potaih.

Heavy oil having nearly the same odour as anhydrous valerianic acl4
Does not chungo the colour of litmun. Emits pungent fupours which
excite ti^ars. It is resolved hy distillation into anhydrous benzoic and
Yaleriantc acids, hut not sti readily as anhydrous bento-acotic acid With
alkalis it forms a benioate and a valerate.

Appendix to Anh^it^m Bemmc Acid.

Oreoaelone. C^*H«0',

SciUtSPEBHAKji & WiHCiciiEB* Ann. I'kai^m. 51, 320.

Prepm^iof^. A rapid stream of dry hydfoehloric acid is p«as«40?fir
finely pulverised athanmntin, the powder being continually stirrtd, to
that every part of it mny bo exposed to the nctiim of the acid (pu 103).
Whon the whole is liquefieil and begins to scdidify again, the heat uiniit«d
to tOO^; hydrochloric and vaterlanic adds then pass over, and oreoailoiit
{mixed with unaJtered athamaiitin) retuaina aa an amofphoua

H

OR£0S£LONE.

97

mass. Thifl prodact is reciystalliaed from boiting alcohal; and tbe
BO lilt ion, when cooled or evaporated, deposiU oreoselone in yellowi^
nodules, which, bj washing with cold alcoholj are rendered whiter, and
are freed from adhering aUmma.ntiii. — Sulphurc»ug aetd luaj also bo used
in the preparation instead of hydroehlorio acid,

Fropertiu, Loosely coherent, cauliflower-like masSi which, when
examined with a magnifying glass, appears to be composed of ^leader
flexible needlei arranged in spheric-al groups. It has a faint yellowish
colour (which however ariaes merely from impurity^ inaamucb as oreoae-
lone undergoes alteration when its eotution m evaporated). Tasteless and
inodorona. Melta at about IdO"^ into a clear yellow liquid.

14 C ..„..,. 84

5 H 5

3 O ,. 24

C»H»0> 113

Schaedertnaiin h WUi«kler>
74*32 _,.. 74*79

442 4'59

21-26 ., 20*62

lOO'OO 100^00

iiom. Fused oreoselone solidifies on cooling, into an amber-
eoloiired maaa, which again separates in the amorphous state from its
solutions; wheu melted, it emits a slight enipyreumatic odour, without
however diminishing in weight VVhen heatetf above its melting point,
it becomes charred. — 2. Oreoselone disaolves readily in oil of vitriol^
and the solutioo, on being mixed with water, yields a copious yellowish
white precipitate, which, after washing and cfrying, forms a yellowish
powder, soluble with yellow colour in potash and in alcohol; it does not
however cry b tall iiie from its alcoholic solution, and it contains less carbon
and more hydrogen than oreoeelone. — 3, Oreoselone turns yellow when
treated with dilute potash or ammouia, and dissolves to a small amount,
forming a solution of a bright yellow colour; ^ttxni^ potash- kif with the
aid of heat, dissolves it abundantly. The red- brown solution yields with
acids a yellowish white precipitate, which, after washing and drying,
forms a yellowish earthy mass, becoming brownish and glutinous when
dry (especially if it baa been prepared from atliamantin not quite
pure); it dissolves with some difficulty in water, and (if prefHLred from
oreoaelone) remains in the form of a crystalline mass when the alcoholic
Aolution is evaporated. By repeated sulutiou and evaporation, it becomea
darker in colour and more readily soluble in alcoboL It contains 72'21
p. a carbon and 4*72 hydrogenj and is therefore a hydrate of oreoselone
ooniainiDg however less than I At. water. [The amouot of bydrogeu and

oSfpoD, !■ bowerer greAter u coni pared wilh oreoaeluae, Dot in the rutio of I : B, but of
1 : 11 j the tabatAiire h therefore uotbitig but Dreoielane iomewbat dt-compoAeJ, L*]

Ct^mbmntiom, The precipitate recently thrown down by acids from
the solution of oreoselone in potash dissolves readily in amnion ta»
farming an alkaline limiid, from which neutral acebte of lead throws
down yellow flakes. This precipitate, even when every precaution is
adopted in it^ preparation, to avoid any admixture of carbonato or basic
acetate of lead, exhibits a composition varying^ in different preparationsj
but nevertheless approaching to the formula C^^H^0^,2PbD.

I

EEJlIflMnE : <3XTGIK-4nr€LroS €^BH},

Si-t ._ 25112
S4i> ... 7-11

1-71 ..„ t*€«
f'U .™ 7'4S

ft WllMiUv.

fli It .- sf-fi

Mi *- H«

0»BK0^imO^ 334$ 100 00 ...-. 100-00 ^.. 100*00 „„ 100*00 .., lOChOI

Dreoedooe dissolTet l^ut rpannglj in afcohoi^ even w^^ ^*^nii«
fotmliig m jellow ^otioii, sad U» ftbout tbe same extent in fiJker,

Bodif Maimidfrim B^imMtraU i^AAmMmUn. C'«H«0«.

The ctystftllised eotepouad oC mt^atnaiitiii and hydjochlone walk
nettSy vliai Iwaled witii wmter, into oilj dfi>}i9 irhicli dissolve &foir
tigiliiig for MNno t»e. Tbe li^taid on cooling dqiomts eletider n«QJli%

inglj in tM^ V*^^ rasdilj m boiling wmter, easily in alcobol or etW
IM iOpttratot in saoH nlj ojila&i fram llie alcoholic 6D]iiii0Q| m
■If iar oeodleB from tlae albeml mtttaoo. The same body is soroetuofli
also pnckdtieeii wm hmiS^m^ ^ ttmSm maat of athamantin which haa ben
treated with bydfochlotio Md; wam^amm however nothing aepiiatoi
omte llfcon <imM8taiieee, bat oi^oseloiie and a few amorphous fl^ii
vkldl |Mi oiV«r ia Jktlllatioii togetber vitb the ti<|nid. The compoisal
dUnalw wHb jT^kv «aloar ia aHMonia and more residily in dtlai*
jiolttil Inj, aad tt fttcyttitdl bj add firkin the dilate golutioo in dttd^
' odottltiM «i7ital& Tl« aola^
piw^ W» witb waMtm of toad.

in ammonia, forms a beautlfal jelUv

lie

40.

U ^ m^U ,^.^ 69 05

t _ 4*»l „— ^ »02

St .„ i«f4 tfi-SS

____ 111

100-00 ^..._ 10000

Tbe ooHlpttMd Vlibi wbaa bealod ta a gbis» tnbo; at a ftrongtr boi
Ika liqaid cr^tm «» tba mim of ibe tabe^ MmA hmos % hrownlnh <ul, wliki
ilooi nol ioltdilT til alte aoaa daya. At tbe mine time, a elight «iii|tT-
laantaltoaittriTif ewlted aiid a lanll qnaxitlty of cbar^ottl eapaimieA*

MM wJTffiitafif (aalpimr ireed) ii^
^ifcirfii Jkvl*^imm {mmi^lmwai\ K Wifier haa •beini iM

FKUCEDANIN.

h:

WaokeDroder'« Imperatorin la identioal with tlie peuoedanin duooTered hj

Sclilattert

h.

p}*f-partition. 1, WbeD ih^ root of Peucedanum afidnale iB exhausted
hy digestion with alcohol of 80 percent and thenlcohol afterwards diatilled
off, peucedaom eeparates from the faltj residue in crystals which may be
washed with cold^ and recrystaliised from botalcoboL (Schlatter.) Her-
berger and Erdmana recryatalLise the product from ethtjr. Bo the leaves
th© comminuted root in contact with alcohol for some hours and then
beats the liquid to the boiling point; the filtered liquid, when slightly
eraporatetl, yields crystals of peucedaniu, which may be freed from a brown
reein by treating them with cold and very dilute alcohol. The cryatal-
Usatione from eubseouent extracts contain much larger ijuautitiea of reeio
than that obtained irom the first; from the last quantities of resin, the
peucedantn may be obtained by diluting the hot alcoholic solntion with
water, till the turbidity thereby produced begins to be permanent; the
cry stab which separate after long stauding are recrystallised from cold
her. (Bothe.)

2, The coarsely pounded rout of masitf-ttmrt is exhausted in a preet
ith 2 or 3 pts. of ether, | of the liquid distiHed ofiT, and the residue
ipooed to the air, whereupon it deposits crystals, which must be sepa-
ted fmm a green oil and re crystallised from ether. To free them com-
from adhering oil, they are washed with cold alcohol of SO per
cent, and recrystallised front hot alcohol, or melted at a gentle heat and
recrystalliaed, or left for some hours in contact with cold dilute potash,
then washed first with water, afterwards with cold alcohol , and recrystal*
lised from hot alcohol. (Oaann, Wackenroder.) — - Wagner exhausts old
toots of master wort (the frei^h roots do not appear to yield any peuce-
danin) with alcohol of 75 per cent, at ordinary temperatures; concen-
trates the extract "at about 60^, tiU it separates on being left at rest into
two layers, the lower of which is light brown and watery^ the upper
brown and resinous; spreails the latter upon a porcelain dtsh and leaves
it to itself for some days; presses the resulting granular crystalline mass
between bibulous paper {to remove a fixed oil resembling linseed oil)j
boils it with milk of lime; decomposes the resulting lime-compound with
acetic acid (whereby the product is freed from a substance which gives it
a burning taste); and rec ry a tail ises the peucedanin thus separated from
cold alcohoU

Propertiei. Oolourlesf, shining rhombic tables destitute of taste and
smell (Schlatter, Bothe), with angles of about 60^ and 120^; thick,
oblique rhombic prisma with terminal faces resting obliquely on the
obtuse lateral edges (Wackeuroder); the alcoholic solution has a burning,
aromatic taste, and produces a persistent sensation iti scratching iu the
throat. Melts at 60^ (Schlatter), at IS'' (Bothe, Wackenroder), and when
ileft at rest for some time, solidifies in a radiated crystalline mass.

24 C

12 M

6 0

.,. 144 „
... 12 .

,. 43 ,

... b^m .

... 23'&i .

Erdmnniii
...... 69-09 .

....... 5*&8 ..

24-4:i .,

Bathe.

. 70-53 .
.. 6-02 .
.. 23-45 .

Wagner. ■

.. 70-13 I
... 6-33 1
... 2354

,.. 204 .

... lOO'OO ..

imm .

... \m-m

1

ATHAMAKTIN-

101

When peacedattm is dissolved in caM etber, oxypmeedamn remaiui .
tie form of a granular residnc^ wUich may be freed from adhering-^
' peucedanin by rqieated cryataliisution and treatment with ethcr>
(Erdmann^ Bo the.)

24 C -...,.„.

11 H

7 O ...,.

.... 144 .

U .

56 ,

„ 68^25 .„
.. 5-21 ..

.. 26-54 ...

.. 6r80
. 2693

C**H»W .

. . 3S1 .

., 10000 ..,

.... 100 00

Athamantiii.

SCBTIEDISRHANK & WiNCKLER,

33, 39.

Ann. Fharm, 51, 315 i X pn Ckem*

^H Frtparatitm. The dried and finely bruised roots and ripe seeds of
^^Mkamanta oreos^limtm are exhausted with three times their weight of
^Bsloobol of 80 per cent, at 50° or 00^; the Bolution eraporated to dnrness
^^ orer the water-hath; the residue treated with eight times the quantity of
ether; and the ethereal solution deeolorised with animal charcoal, filtered
I and left to evaporate: there then remains a thickish pale yellowish oil
I which gradually solidifies into a cijBtalline granular mass. This mass is
dissolved m four times its weight of 80 per cent, alcohol; 60 times the
weight of water pijured into the solution in a thin stream; and the mix-
tnre well shaken and left to stand in a cool place. The milky liquid
After a few days or perhaps weeks, deposits a curdy crystalline precipi-
tmte; the addition of acetic acid or sulphate of soda accelerates the preci-
pitation^ but retards the subsequent purification > The precipitate is
dbeolred in a quantity of warm alcoh^^l of 60 — 63 per cent,, sufficient
to keep the liquid nearly clear after cooling, then filtered warm and left
to stand in a cool pkc«. The athamantin then separates in long needled,
generally mixed with oily drops of impure aihamantin. From a solution
saturated while warm, athamantin separates on cooling in the form of a
{>mwii oih The crystalline mass freed as completely as poafiible from the
oil-drops, is pressed between bibufous paper, and recrystallised from
alcohol till the crystals appear perfectly white and are no longer mixed
with oiK

The very loosely coherent, daiiling white, satiny mans consisting of
interlaced capillary fiextble crystals, very like long- fibred asbestos,
which is thus obtained, is not yet pure athamantin, inaismnch as It melts
at a lower temperature (between 59"" and 60'') and contains more carbon
and hydrogen (6S 8 p. c, C and 7'5 p. c. H), Pure athamantin cannot
he obtained from it by recrystallisation ; it is sometimes aecidentally
ohtaincd in large crystals which separate at the same time as tlie fino
needles, or when the oily mass separated from the alcoholic solution is.
left for some time in contact with the suprnatant liquid at 20^

Fropertiei of parr Athamantin. — Colourless rectangular prisms,
>mctimefl an inch long, with truncated enmrnitSi two of \Si© ltiWi<Lii.^Aat^.-

102

BENZYLEHE: OXtGEN-WUCLEUS C**H*0.

faces lying oppe&ite to each ottier being much larger tlisti tbe otber i
eometimee octoliedrotis having four of their summits in the «inie j)h
traticated. Has a peculmr raiicid enapy odour, esp€cia!ly when hem
and a raficid^ gome what bitter taste, leavings a slight ecratching eenwtin
in the tliroat, Melu at aUjut 7D% and forma on cooling a white maw of
the coneistenco of turpentinOj which after a wbiJe soUdifies in radiate<1
; resembling wavellite. Cannot be distilled with oat decompofiition.

Schnedermiaii St Wiiicfclir.

24 C ...,. 144 .... 6698 _„,. 60 78

15 H 15 6*98 6*97

7 O ._.. .„. 5G .,.. 26-04 _.,.. 26'2ri

C?*H»*07 215 .... 100*00 10000

If we luppoi^^ vilh S£:htiedet-niHnii & Winelrkr, that stbamAAtiii
inhf drotis Talftiiivnic acid ajufldnted with the body C^*H*0\ thift body most be i
as denved from the nucleus C'^H^O^ (Orcosdone ?), and mhamantin mm tuial
ib« rampounJ pthtri : C»*H*0»/HO + Oms'O*; on thi* tiifiposjtioti «tl
trcfttftl with hydrochloric add, ihould yield a conipoimd of C^^H*a»,HCl *ritli C^H*
which wheu heated, would rPAoke itielf into oreoseloiir, hydrochloric Kcid and raltr
aeiii^ But in tbnt cai^ei athatii«udii, when treated with |Kitash, shoald yield m I
untilofous to alcohol, *i!!., C'^H*0^,2H0, whereas the product of this r«actiun U »
C'*HW.— If nthamanHn be n^^^arded »s « conjugated compound of oreoteloiie
voleHnnic at*id = C'*H*O*,C^*H^*0*t the decompoajtion by potash u at otuse ezplai]
litvce the body C"H*0* may he regarded aa the hydrate of oreoseJone ; agaitiat thia i
howerer, it mnat be alleged that the fommtiua of thii compound ii iiot attetukd^ i
■hoQid be {p. 221), with formatioE) of water*

Decontpodlioni* L A th am an tin subjected to dty disi^aiiomf ' ,_^
a lar^f^e quautitj of valerianic acid together with other prodn^,-
2, With nUric iicid of 1 25 in the cold, it yields a colourlese ml whidi
floats on the surface of the liciuld, and after a while becomea ttirbid and
smells of valerianic acid. Uu heotiitg the liquid, nitrous fumes urn
evolved, and the odour of valerianic acid becomes stronger, ^nd ftt the
time an insoluble substance sepurate&f having the odour of fat decom-
posed by nitric acid. — 3. With iodimy athaniantin assumes a yellowitli
brown colour and yields a dark brown gummy mass smelling of TaJenanic
acid, — 4, It dissolves in oii o/vtfn'o/j with rise of temperature, fozittiitf
a clear brownish liquid^ while a powerful odour of valerian La emitted;
if the heat be kept down by external cooling, the solution acquire* b^
Uitle colour. On mixing the solution with water» a precipitate is foj
consisting of oreoselone more or less altered by oil of vitrioL On 4
jng the liquid, aqueous valerianic acid passed over, rendered turbid
Aoceulent substance which floats in it, and appears to be idtmticaJ wil
body OWO*, — 5. Heated in sulphnrom or kudrockJork add

boiled with aqueous hydrochloric acid, it is reiolved iiitoaiiMML„

iralerianic acid, — When hydrocblonc acid gas is paMdd into Ike aboMiA
KC^lntion, valerianic ether and oreoselone are produced. — 6, Poitmk imomr
pOttM it into valerianic acid and oreoselone, whieh^ by the fnrtber itftioa
if fOlAibi is converted Into the body C'*H''0^ A similar decompoiitioii
ii pvoduoed, though mucb loss qtackjy, by hnr^ta-water and ^Uk ^Umt,

ComUnaiitms. L In a current of dry tuiphwotu actd ^as, athamaotiil
melts at ordinary temperatures, slowly hut completely. Into m dettfj
/^low-bivtwuiBh ollp which generally doeampos^ after a hw boiif%

i

A*FHAMANTIIf,

103

oreoselone being eeparated in small crystals, and a strong odour of snlplinr-
ous and valerianic acidsj betng given ofT. The oil often remains apparently
unaltered for several daye, apct then solidifiea into a crystalline masa
wbich melts when heated; hut if the body be cooled with ice during the
action of the sulphurous acid, and the fluid mass afterwards kept cool
with ice^ small crystalline atars *?epttrato, after a while, and ultimately
cover the entire mass with a solid crust, while a portion remains fluid for
come time longer. The cryitalllsed majss is waxy and dry, diminishea
gradually in weiglit in consequence of the escape of anlpliurous and
valerianic acids, and nielts below 100^/but is decomposed by heat, oreoae-
lone separating out^ while sulphurous and valerianic acids are given offl
It dissolves readily in alcohol, and appears to remain unaltered when the
alcohol is left to evaporate spontaneously; but if the evaporation be
jasfliated by heat, valerate of ethyl is produced and oreoselone remain a
^ebind, — Athamantin over whicb sulphurous acid gas is passed, takes
|p 14 '63 SO^ {1 At), — 2. H^di-ocMoriK; acid ga* in absorbed by atha-
landn without perceptible rise of temperature, producing a clear yellow-
Town oil, which soon begins to solidifyj with formation of white needlea
►iranged in radiated groups; a portion often solidifies before the liqne-
action of the whole is complete, and thereby hinders tbe complete trans*
formation. The solidified ma&a consists, partly of needles united in
Itellate groups, and is partly amorphous, grej, moiat^ aud smells
^^tstan^j of valerianic acid; it gives off that acid indeed^ even when pre-
served in close vessels. When shaken up with ether, it left a metallio
powder, which, after rinsing with a small (quantity of ether, waa found
to c^naist of pearly microscopic pktes, easily soluble in alcohol and ether^
and consisting of a compound of athamantin and hydrochloric acid.

CIH. „..

215a

36-4

C»H"0^,CIH.... S514

SdiDedenQiim Sl Winckter.
8552
14^48 13*70

lOO'OO

^B The componnd Ima but little stability and was only once obtained by
^PBcbiiedermann k Winckler in a satisfactory state of purity. The ethe-
^^eal solution left on evaporation neeille-siiaped crystals and a masa
having the appearance of oreoselone; when the solution was evaporated
by heat, the residue consisted entirely of oreoselone. It melted below
lOO"" into a liquid which gave off bubbles of hydrochloric acid and
"radnally changed into oreoselone. Wben boiled with water, it yielded
be body C^^H-O* (p. 98),

Athamantin i» insoluble in water, but diasolves readily in alcohol
ren dilute j and in ether; abnndantly alao in oil of turpeniine and in

KM

BEN2YLKNE: OXYGEN-NUCLEUS C»H*0«.

IF, Ox^jgen-nticlem C"H*0'.
Conjugated Compounds.

Monobenzo'icin.

Brrtuelot. iV, Ann. Chim, Phyg. 41, 200,

PrfpartJthn. By Ueaiing a mixture of boufok acid and glj«eri]i ii
a sealed tube for 4i hours, eitUer to between 1*20'' and 150^ witb the aci4

io excess, OP to 200^ with the glycerin in excess, — or to 275^ for 5 to
20 boure. — At irjO°, only a few drops u^rt obtameil mfter 140 hours. At ordinary
temperatures traces are formed in three monttu. The product IS pnnfied bj
washing with carbonate of potash. — ^The liquid ihisu leparate* into two Jaw*
(if m tlie preparation of acetin, tx, 49r)t ^Joth of which are iniolublf! in ether. TW
up]ier layer left tit evaporate in voinio for seTpriil days eibibjti traces of crjstAlBaalioci;
il formi an emulsion witb wattf i and when heated yiiildi a DouAiderable quandl^ 4rf
alkaline ash. These phetiometm appear to indicate the e^tttence of a benzogt jeente «(
potwb.

Properiifs. Colourleia, neutral, very viscid oil, having a bitter aid
aromatic taate, and a alight balsamic odour^ eHpecially when heated.
Sp, gr. r228 at 10 ■5". At — 40% it forma a transpai^nt, nearly «^)i4
rem no OS mass, capable of being drawn into Jong threads. Begin a to Wi)
at 320"", but decomposer at the same time*

B

e r t

h e 1 0

t.

a.

».

t.

d.

20 C ........

.. 120 .,

., 61*2 .„ &98 .

... fil'O

.... 61 0 «

^ 617

nu ....

,. 12 .

.. 6^1 ...

61 .

... 5-7

.... 6-2 .,

. «-y

2 0

.. 16 ..

... 32'? ...,

art .

-. 3M

... 31*9 ..

.. 31-*

C^flao* .

.. HB .

... 1000 .,

100*0 .

.. 1000

..,. lOO'O ..

.. 100-0

«, wu prepared «t l&O', with exoesi of acid ; A at 200* wtth excm of ^jtmmt

DKmnposkim$. I . MonobenzoTein oxidises hut very alightt? 1
exposed to the air. — 2. When boiled, tt is decomposed, giving off i
lein, and a considerable quantity of benzoic acid^ exhmUiig at thd
time an odour similar to that which is evolves! in the dUtillation of
oil. — 3. Heated with caustic potash ^ it yields Henxoate of palatli. ^
4. Ammonia converts it into henmmide. ^^ 5. Treated in lh# col4 will
aloobol and hydrochloric acid it yields glycerin and t^ensoata of Hkf
Tli0 aame tmnsfurmation h produced by heating an aJeobolie 9o]tttioD
noiifibenioiein to 100^ for 48 hours. Tfie same alcoholio »olutiaii a«
the odour of hencoic ether when merely exposed to the air; bat \n a i
TMwl it remains unaltered.

TlttBENZOIClN,

lod

Vornhmntiom. MoTiobenEoicin m insoluble in wftter^ an<! nearly or
t|i]ite insoluble in bisulphide of carbon, but dissolves with grt-at facilitj
in alcohol f eiher^and b^nioL

Derivative of Afonohensdi^'in.

Ben^ochlorliydrin.

C»ffraO^ = C^*IPC1,C*H»0»

'Bebth^ot, #. Ann. Chim. PkyM. 41, 302,

Obtained by eatumting witb hydrocbloric acid gaa h mixture of
gljrcerin and benzoic acid kept for several hours at 100*^, and removing
lie exceas of acid after some time by means of carbonate of soda.

C**H«0* + HCl + OWO* - C=«H^^CJO'^ + 4 HO.

Neutral oil, wbieh solidifies at —40*, but resumes the liquid form ai
Da as the temperature riaes.

20 C ..„,

11 H .,_..„_

..„ 1200
..„ IPO

.., 56-1 .,
„.. 5-1 ..

..„ 1€6 ..
.... 22-2 ..

B^rthelot

5-4

CI _......

6 O

... 35 4
.... 48-0

17 0

21-2

C»H»C1Q«

.... 214^4

.... lon-o ..

... ,„ lOO^O

Maj be regarded ai mDnobenioTcin in wbich HO^ in replartd bj C[. — or at a
conjugated compound of the chloH tie* nucleus C^*H*CI, derived from the primirf
nueleoi C'Ml^

Benzocblorbydrin treated witb potash yields chloride of pota^^aium
and benzoate of potaah. — With hydrochloric acid and alcohol, it forma
glycerin and benzoate of ethyh — Heated with oxide of ailver to )0(r, it doc»
cot jietd anj chlorhjdnn (iji, 4^8), even iifter ir considerable time. Wh^u it is heiitcd
with miirfrqric acid to 240^ tir four houra, the tatter »ppcan to enter idIo Che netiCral
oomppund.

TribenzoiciB.

BERTHSI.OT. N. Ann. Chim, Phyi. 41, %%d.

T^h€7tzmtt o/ Gifcerin, Terben%wiU of GljftyL

^P Obtained by heating monobenzoTcin, for four hoara to 250^ with 10
^M^ 15 tinias iu weight of benzoic acid. On removing the excess of acid
^rti>y carbonate of soda^ extracting with ether, and evaporating the ether
over the water-bath, a nearly solid reeinous mass is obtained, which when
redisaolved in ether and treated with animal charcoal, yields by evapo-
ration in vacuo, small crystals grouped in velvety tufts. These crystals
-«fe preyed and redi^olved m ethefp and the iolutlou it Ml %,^ ^^^^xh^a

^«fe

loe

BEN2TLENE: SULPHUR- NUCLEUS CmiK

in a bottle havings its monlli covered wkU a ebeet of paper. Tbe ot»iiip<*inJ
is thus obiaincci in large, white, beaotiful nee4k«, which aro oetitml*
UTMjtuous to the touchy and fuse pretty readily. Treated with hjilfo-
chlgric acid s^nd aJcahol, they yield glyceriiv and benxoate of ethyL

4g C „....„».

ao H

288 .

&0 .
.. 2S'7 .

l«rtbelot*

» 71-9

.„,... 5*4

12 o .........

...... 96 .

.„,... 22-r

C«H»0^» ....

....... 404 .,

.„ 100 0 .

100-0

According to the radical theory^ glycerin ii a tii^t&mic ikobolr iormed itom I
HHO^
molcutes of yfaUr^ H^D< or H HO^, bj the aubEtitatiou of the triatomk ndii^l CE* i
HHfP

H O^

H>, «o that its formula ma^r he wHtten H(C''H<)Ol Each of the tlir««

H 0«

•tomi of faydrogfn may be replaced hj other mdicAU jioeilWe or negatiTe. Mvm^*
I ^enzoidn, U formed by the lubstitution of tbe mdJcd besijojl (C**B*0^ = Bt) lor

I At. H ; it b therefore H(C^H'} O^. The replacement oTa lecond atom of hrdfofis
H tP

Be CF

in the Mme manner would give tibmzotein Bi(C*H*)CF or C**!!**©***, a cotDpotnid nol

M 03

jet obtwned ; and the tltnilar replacement of tbe thin] atom of hydrofco bj 1
givtt iribfnzcidn, Bi*(C*H*)0*, BenzochhrA^drinj aft already obBerred (p. lOS)^ i
Le derived from monobenzoictD by tbe subBlituiion of CI for HO^, mnkiDg itt
Bz O^

H(C*H«)CK. Simtkrlf for the ac«tini, ^aterbi, &e, Co., 49fi; x«92| sii, 75; M

a

alio Wurti. N, Ann. Ckim. Fhyi. 43» 492), TI,

5t«/pAi*f i«uc;*«« C"8H*>
Sulphide of BeiiEoyl.

WoBLEE & LiEBio. (1832.) Ann, Phmm. 3, 2e7; «lao Pc^. 20, 341

ScAiififelbenz&yt, Schm^tltenzeldidt Iknsotbiadmiljidt Ojey^ckit^fihtnwo^L

When cbloride of benzoyl m dittilkd with 6nely pulreriBed ealphidt
of h&dj a yellow oil poefies OTer, which aoJtdifiea into a soft yeUow
cryMtalline tuass baniig an nnpleasant odour of euJphun — It bujoa with
a bright sooty flmne^ giving off sulphurous acid, U does not appetr Ii
be dc^composed by boiling with water. Whea boiled with a^Hioiif
fKktaah, it very alowly yields benzoate of potash and fiolphid^ of pol
uiuu. It du«8 not decotupoM in contact with alcoboL

i

DROIIO BENZOIC ACID.

107

k

Iodt7te^u€letis C"IH'.

Iodide of Benzoyl.

WoflLER k LiEBtn. (1832 ) Ann. Fharm. B, 267; also Fo^^. 2Bj 432,

Fod&ettioyif /orfimrfWiW, BevzGf&iacuodid, O^iadhmzoyl.

When cliloride of benzoyl ie heated with iodide of potassium, a brown
liquid paifies over, which f^olidifies into a crystal line mas^ coloured brown
by free iodine, — In the pure state it m colourlcaa and lamiuo'Crystallinep,
and fuses readily, hut with incipient decomposition, /;ivin^ off vapours of,
iodine. In odour and combustibility, and in its reuctions with water and
alcohol^ it resembles bromide of benzoyh

Bromim-nuctevi C"BrH».

L

^^^^p Bromide of BenzoyL

^J^^ C»*BrH*0* ^ C"BrH",0\

^BVrdBLER *fe LiEBio. Ann. Fharm. 3, 266; also Fo^^. 2B, 041-
^H BrmnhtHZ^yi^ Bnwihenzaldid, Baniaeiiacih'omidj Qjeyifminb&iioyi.

^^ Frfparation. When pure hitter almond oil is mixed witb bromine,
the mixture becomes heated and gives off hydrobromic acid, which,
together with the excess of bromine, may be completely removed by
heating the liquid.

^P Fmptrii^s. Soft, broadly laminar cryfitalHne maas, having a brownish
colour, and, semifluid at ordinary temperatures; smelJa like chloride of
benzoyl, hut much fainter and somewhat more aromatic. — Fumes in the
air, filightly at ordinary temperatures, etrongly when heated. Melts
even at a very gentle heat, forming a brownish yellow liquid.

It burns with a bright sooty flume. Decont poses very slowly in
contact with water, and when heated under water, remains ai the bottom
for a long- time in the form of a brownish oil, being decomposed only
after long boiling into hydrobromic and benzoic acids.

It dissolves readily and without decomposition in alcohol and e/^er,
And remains in the cryatailine itate when the soli^tion is evaporated

L

Pklicot,
Heezqg.

BromobeBzoic Acid.

C"BrH^O* = C^*BrH*,OS

(1836.) Con^L rend. 32, 11; alio /, pr. Cfkon. 7, 330; 8,65.

N.Br, ArchrZZ, 16.
Cow/t. rmd. 30, 325.

t

Formatiem and Freparatimu J* Benzoic acid together with bromine
exposed to sunshine in a closed vessel. The aci\ot\ \% latt^u^^t ^ti^

108

U1N2TLEKK : CHLOIINE-NUCLEUS C»*aH»,

i3oines to ED end sooner than that of chlorine on benzole aciiL The fas
friable maas which remains after the excess of brorsrine ha« been drirg
offp dissolves in carbonate of potash, with Reparation of a greenish <
containing bromine, which hardens when expoj^^d to the air and sni#U^
like gum benzoin; the aolution ia decolorized hy animal charcoal ftls^
precipitated by nitric acid. (Herzog.) — ^2, Bromine vapour is madt to
get gradaalljr upon ben^oate of ailver, by introducing from 20 to 24
grammes of beiiEoate of silver and an open tube containinir Iji^nid bro-
mine into a stoppered glasa ve«B©l, and leaving the vestfcl closod for t4
bonrSt WLiea Hquiil bromine is |)piired apozi bemiojite of siUert m nulent actioii Ukt*
place. If the resulting mixture of hroniide of silver and bromobenjcoie
acid he shaken up with ether^ aicohol or wooJ-epirit, and tbc aolatioQ
left to evaporate, an oil is left which solidiBea in a crystalline mats on
cooling. (Peligot) — Mllller heats benzoate of silver with bromiot,
whereupon benEoie acid distils over.

Propertks, Colourless, hard, crystalline maaa, which tnelta %X JOO^
and flubliniea at 2^0''. It bums with a green-edged flame. — The acid
precipitated by water from the alcoholic solution has less lustre wblfi
dry than benioic acid. (Peligot) ^^H

Comhinaihns. With bases, the acid forms crystal lisable salts, moel
of which dissolve very readily in water; the lime^ baryta^ cupric
mercnroua salts are however less soluble. The Uad-mlt obtained
precipitating neutral acetate of lead with bromobenEoate of potash
yellow crystalline grains; its solution in warm water jpielde bj .^
taneoui erapomtion, yellow bnihy crystals apparently of spherical almp<?
— The silver-aalt is soluble in warm water

14 C ..

Br.

Af.
4H .
4 0 .

$4*0
80*0

loa 1

40
320

.*„ 35-07

,.« 130
„„ 10'38

PeUgoU
2711
Sft-fit

34*4i

1-44

11 '41

C»<BrH*AfO* , 3081 ,... lOO-OO .,.._ 100*00

Ac(?ordin(f to MUllcr* bromobenKoic acid = O<BriHl0*.
The acid dissolves sparingly in uvrirr^ readily in wo^^ipirU^ utmM
and eiJ^tr.

Chloride of Benzoyl.

Wo0t.Efi k Ltt:Bm. Ann. Fharm, 3, 2€2; also Po^j^, 90, 337*
CAUOvm. Compt. rmd, 22, a4e ; alio Ann, Fharm. «0, Mt-

C<mpL rmd 25, 724.
GsRitARjDT. #» Ann. Chim. Phyt, 37, 291; also Ann. Pharm. 07, 63*

09iif e(/ Chhr^hfnt^lm^, VhiarhmMt^lt Ckiortmtnldid^ BtnMf^ithkfid^ 0*r-

CHLoams OF aenzoyl.

100

Formaiym. I. 6j the action of cblorine on bitter almoDd oil.

(Wohler & Liebig,)

C"B»OJ + 2Cl« - C'*ClH*Os + HCl

By the action of cbloriue on benzoatc of metbyl Of honzoa,\s of ethyl
* *agiiti, Ann. Chim. Phys^ 70, 374 and 387), and on cinnamein.
fremy, Ann. Chim. Phifi, 70, ^80.) — 3, By heatiug pentachlorlde of
[ pb ospC om s w i th be n 3! 0 ic aci d , ( C a bou rs. )

C^'H*0* + PCl^ = C'^CIH^O^ + PCl^O^ + HCl.
— 4. By tbe action of oxycbloride (or pcntachlonde) of phosphor txa on
I beQxoates, (Gerhard t.) — 5. By tbe action of protoobloride of sulphur on
^^alkaltae bensoates. (Heint;s^ p. M.)

^H^ Preparation. L Dry chlorine gas passed through pure bitter almond
^H^ilf is absorbed, with gre.it rise of temperature and evolution of hydro- j
^VehlorJc acid. The liquid must be ultimately heated to the boiling pointy
' till tbe chlorine, on passing through, no longer generates hydrochloric
^. acid. An soon as the evolution of hydrochloric acid slackens, the liquid
^Bftequires a yellow colour from the presence of dissolved chlorine, which
^Blkowever is given off on boiling. (Wohler & Liebig.) — 2. When dry
^Hl>enioic acid is heated to 100"^ with pentacbloride of phosphorus, a violent
^Bftction takes place^ hydrochloric acid is evolved in large quantity, and a
^Hmiictiire of oxychloride of phoBphorua and chloride of benzoyl pasaea
^^ orer, from which between ij)8° and 2t}Q\ the chloride of benzoyl dietils
L off, and may be purified from admixed pentacbloride and oxychloride of
^■phosphorus by treatment with a sniall quantity of water. (Cahonra,)
^y — 3, Oxychloride of phosphorus acta very violently on benzoate of
■ soda at ordinary temperaturee; and if to 1 pt (I At*) of the oxychloride
there be taken not mora than 2-81 pts. (3 At) of benzoate of soda, the
only products obtained are phosphate of soda and chloride of benjeoyl:

3C'nFN»0* + PCIW = 5C»H*C10* + 3N:*0,PO*.

With A large proportion of benasoate of soda, anhydrous benzoic acid la
formed at the same time* (Gerhardt,)

Pwperiiei. Transparent, col on r1 ess liquid, having a peculiar and
extremely penetrating odour, attacking the eyes strongly, like horse-
radish. Sp.gr. ri96 (Wuhler ^ Liebig), 1-250 (Cahours). Boila at
195"* (Malai^uti), at 196^ (Cahours)* Vapour-density, 4*987 (Cahours),

u c ,

5 H

..**.._ 84 0 .... 59-82 . ,..
,..„ 50 .... 3-56

WBhUr
& Liebig*
. GO-58 .*
. 3^74 ,.
. 24-42 ..
. 11-26 ..

Main-

fUti*
„ 50-02 ..
.. *l-fi7 .
.. 24 73 .*
.. 1258 ..

Cftboian*

.. 5952
3-52

2 O

,_,..„ S&-4 .... 25*21

15-0 .... n'4l

.. 25^02
.. 11*94

140*4 .*.. 100*00

C'Vftpour H4 .*** r..*««. ■«.»

. 100-00 ..

Vol*

14

5

1

^1 ,„

. 100 00 ,.

. 5-B240
. 0-3465
. 2-4543
. 1-1093

.. 100-00

L

H.gll8..». .„...»...

Cl-fii.... —

O^lffts .. ,..«.......« „....

1

k

Vipour of Chloridfi of BcdsoyI

2

. 97341
*, 4-6^1^

\

€?^W,C=?S« - C*5B' ^ CO* 4- CS»,

4m. Mvi^Si^ us.) — With Mipb*-

I

«f b«n»ii famu liil|«r

oil

G%N«0« ^ C»K:IHW - Ci*HHJ< -i- N«Cl * 2CO,

tb mMm amdh of fbrmk acid ^ei free l»v ibe Mtioo of the heMm
mad. {Omkmxdt, A hji. Pkarm. ST, 1S7.) — tO. Wbeii chloride of beoioj)
!• bttled villi tlw Alk^ise alia ^f tli« idonobvisic Acids, metAllie chloriJci
an fofiBeil^ lofetlier witli c«mfxMiEi<ifl of tbe &iibj<ln>uii toooobaaie add
wiik asbf droM besioic aeid . (Geiii&rdt) : i

C»*cm*0* * C*H»KiO* ^ C*H»0»»C*H»0» 4 K.CL !

] 1 , Cklf>nilo of beDxoji k«»tcd witb oxmlsto of poU»li formtt siilijilroai
bMliCik fteitl, cbbntie of putfi^iam, carWntc oxido luid carbonic lesid
(0«rhtttdt, p. 04.)— 12. The milntson of cbloriae of beoxoyj in m}mM
fmw$mm Imiod in » few mbotes to tbe boirmg fxisnl, give« off bjdio
Mofic ftctd, and wbco mis^ witli w&ter, depo^t^ oilr droiJi of ben'toaU
ofctliyK ^1

^ 13, Wbea ISneljr puUeri^ed alilebyde-umtnotim ia added hj^^^

iiTiall fHirtioDi to rblorulc t4 bemoyi" till tb« masa becfimpa ^^^|

eblortd« of ftuimoDiEiLfi aod benzoic acid a?« fumi^dp tog«*tbtfr wHP^H

•ttbilMiCtf bftftitfi wbeti dried at I0t>% tbo comtkoaitlon C^N'fl^')*^

or poIyiiMiho witb bipp4raffin, p. $2) Tba aal^anuiioBiaff '

CHLORIDE OF BENZOYL*

111

m4j he extmcted by water, tte benEcio a«jd bj fiolQlSoU 6f c^trbotiate
of soda, and i( the resMiie be tben digested in hot alcohol, a solu-
^on is obtained whicb yields the compound C^X'H*"0* in slender
faeedlea arranged in concentric groups. This substance melts whoa
beat ed anil sublimes partly undeconiposed at a higher temperature* It
13 slowly decomposed by hot potaab4ey, with formation of benzoic acid
and separation of a brown resin; it is not altered by boiling with fieroxide
of lead and water; but on addition of sulphuric acid, aldehyde is ^iven
off and theli":jnid, if filtered hot, deposits crystals of benzamide; aldehyde
and beDzanildo are likewise formed when the compound is stirred up with
water and exposed to the actian of nitrous acid. Sulphuric acid dissolves
tbe com po mid when heated, forming a brown aolytion from which water
eeparates a brown resin, and the liquid yields crystals of benzoic aCid.
The oamponnd i^ insoluble in water; it di3iiol\re§ sparingly in cold alcohol
Aitd ether; easily in the same liquids when heated. (Limprichtj Ann,
P^arm. 99, 110.) IT.

CoTnhlnntmnin Chlorido of benzoyl, with tbe aid of best, diisolves
mdphur and phogphorns^ which separate from it in the crystalline form
on cajoling. It mixes with bUtdphide f^f carbon in all proportions and
apparently without decomposition. (Wohler k Liebig.) It dissolves
Moridc of aXtimmium with facility when heated, and the liquid solidiHas
in a cry s tallinemassoncooliug. (Casaelmann,)

With Bkklorodnk JSffAfr. — C^^Cl'HK)' = C*Cl^H'0,C"ClH*0^ —
ChIorine gas is passed at 60^ — 70" through benzoate of ethyl, where-
upon hydrochloric acid und chloride of ethyl escape, and the Hqnid ia
distilled, after the action Is completo, till the boiling point rises tci
130*'. The residue blackens even if the heat has not been raised
to the boiling point. The distillate is shaken up with quicklime,
redistilled at a temperature below its boiling point, as otherwise it
blackens and gives off hydrochloric acid* and the liquid which passes
over batween 178*^ and 180*^, is dried over *|uick.Kme In vacuo. (When
chlorine gas Is passed for a sufficient time through an alcoholic solution
of benzoic acid, and the resulting oily liquid mixed with water^ a
yellowish oil is precipitated having an aromatic taste and snielL
Bouillon- Lagrange, J. Fimrm, 7, *200,}

Colourless liquid, of sp.gr. \'BA% at 10*8. Fumes slightly in the air,
and has a aufff>catiug odour like that of chloride of benzoyl. In dry air
it does not redden litmus. Boils between 188'' and 1 30^ The boiliDg point
rises imcaedbtel^ in c;on sequence of deco en position.

^ itc

1080

ea

.. 4387 ...
.... 3*24 ...
.... 43]3 ...

Mal-Rtiti.
.... 43*34
3*44

■■ 3 CI „..,..,...»..

..... 1062

..... 42'50

3 O

240

10-72

c«cim«o',.....,

. ... 246-2

„„ 100*00 ...

100*0(1

In oaotaiOt with water, the compound is slowly resolved into benzoic,
acetic and hydrochloric acids. (Mulaguti^ Ann, Chim* Phyt^ 70, 374;
80 Ann. Pharos 32, 43; /. pn Chem. 18, 56*)

Wiih Bitter almond oil — C=-C1H"0* = C"H=0\C^'CiHW —
Formed in lurge quantity when crude bitter almoud oil ia uw^^ileff^vV^

112 BENZYLEKi: CHLOEl?i£-|iUCLKi;S C^OH*, ^^B

deeompoded by chlorine; oDiiietiiiiae ftlio wbeo bitter «]jfii»<id oil u dfiooa*
poaed Oj excess of cbloriiie. Coloarleaa, shimng knuan revambliag hm^
I QIC 8£id^ Melt£ very e^ilj &iid reoiMnit a laog time 0ciid when 14 Tt0L
IncMiorooa in the dry state.

Idoreiit & Gerhardt,

28 C ^««„., 168-0 ..„ eS'lB .„...„ 67-8

11 H .._ ^ ll'O ..^ -i-ie „.._ 4^

CI ...._.»« 35-4 .., 14-57 „ 14-0

4 0 32 0 ™. 12't& . . 13*6

C»H'*ClO* , 240 4 .... 100-00 1000

Heated above its meltings point, it gives off ohleride of beiudyl.
When moistened with water or alcohol^ it gives off vapours of hydm-
chloric acid and emits an odoar of bitter almond oiL Heated with
water, it yields beiuEoio add and bitter almond oU. Warm aloohol lik*^
wise deeomposes it.

In cold aloahol the eomponad is sparingly ^nble. (Laiu^mii ^
Gerbardt, Compt. ehim. 1S50, 123.)

Chlorobenzoic Acid.

Her2oo. (1840) A^ J?n Atxh. 23. 15,

SciiARLiNQ. Ann, Fkarm* 41, 49; 42, t^S.

SrsNyocsE. Ann. Pkarm. 55, 1; also -PM. Ma0. X 27, ITS;

J. pr. Chcm. 36, 24 g,
E, KoFP. Oompt, rtmL 24, 614; also N\ J. Pkarm, 11»4S6; ibt

J pn Chart. 41, 4f5.
FiKLii. Ann. Pharm. Q5, 55,
Cuioz^A. *V, Ann. Chim. PAjft. 36, 102; atstr. CompL rmd. SZ^W,

J. pr. Chem 5?, 2S,
LtUFEiciiT & T. UstAE* -Inn- i^Aam, \Q% 259.

C:A/bn&fiif<>#ijiiire, ^rirff kwrnmrnqm m&mckhri, CktoromichmyUAmrt,

J

i'orwuifMni. 1. By the action of chlorine on bonxoio aeid. (HerM-)

^!SJ***"* ^ ^**** t^' ^'"* '^^'™' ^^^' <^^ '**^V)^ '^ M-ciUtd chfofOQioik wM
(C*^IHHJ*) which Sl^^Erre obubea by the nction of cbbriae on a tolatioa oflMHl*
«oid in ei^^ i^r fhjU^hf fxi, 176), i* nothing but rhlorobefifoir acid ainumioattd vill
Unn^tmM. — .2. By henting salicylic acid with pen tat? h to ride of ph^
pborus. (ChioKxa ) — a. By tbe action of chlorine on a heutin! mixturvof
cinnanifnic aeiti and strong w><ia-lev (E, Kopp), or by hcattnisr citmantic
aeid with aqueous solution of chJori^le of lime, or with hydrochloric »a4
and chlorate nf potaah. (Stenhouse ) — 4, By the at^tion of water ue
chloride of ehlorobeo^oyl (p. 117), f Limpricht & v. Uslar)

Prepamimn. 1. When chlorine gas is passed over Aty benaDtc
#xpo(ie*l to the snn, the acid is converted, in 12— 4« hours, mt^ a "
vieeid, guniraf, nomovhat redtlbih mass, which dissolvee lo
potash, with the exception of a brown. r^ substance which b
©Ui on expoeme to the air. The Ijrown ml solutiou is boiled wilh uimI
camreoal; the filiate mixed with dilute nitric acid; and the

into a Mi^l

3

CKLOROBENZOIC ACID.

US

pfrecipitate washed with water till the waab- water no longer forma a
cloud with nitmte of silver* (HerEog.) — 3* A mricture of ealtcylic acid

and pen tac bio ride of phosphorus melts with evolution of heat; on dis-
tilling the fluid mixture, the boiling point ri^a very rapidly, while bydro-
cMoric acid is continually evolved, and a light depodt is formed in the
neck of the retort; at lengtb the mass blackens, swells up, and leavei a
very light charcoal* On rectifying tbe distillate, the liqnid which passes
oyer between 200^ and 25li°, is & beavy, strongly refracting oil, which baa
a HulTocating odour and is converted, gradually by cold and immediately by
boiling water, into hydroeblonc and chlaroben7.oic acids. The heavy oil
appears to be a compound of cblorobenzoic acid with hydrochloric acid,
p ro d uced slmul taneo us I y w itb o xy c h I ori de o f pb oapho rus, (C hi o ^^a, )

Ci*H^O< + PCI* « c»*H*cio\cia + POCl*.

3, Urine [^neentrated by evEipo ration ? Gm.] is mixed with nitnc acid; the
Hqaid filtered from nitrate of urea; and the filtrate distilled. An acid
liquid then passes over, together with a greenish yellow oil (nitrocbloro-
micbmyl), and a mass resembling benzoic acid is ultimately deposited in
the neek of tbe retort. A larger quantity of this subsmnco is obtained
by neutralising the liquid^ after the oil has been separated^ with carbonate
of Boda or caustic animouia, evaporating to dryness, and distilling the
F^idne with dilute sulphuric acid (2 or 3 pta, of water to 1 pt of oil of
Titriol)* The product is purified hy washing with cold water and recrys-
tallkation from hot water, (Scharling.) [The acid thoi prepared h called by
ScbAflmg, chi&romhhmj^Hc acidi but according to his own statemeiita, it doea not differ
In an? rc£|iect frQtn chiorobeaEoic icid. L.]

1 4. Chloride of chlorobenzoyl is boiled with potaali; tBe alkaline
flolntlon precipitated with bydrocbloric acidj and the precipitated cbloro-
benzoic acid dissolved in hot water; it then separates in small yellow
needles which cannot be decolorised by recrystalliaation and treatment
with animal cbarcoal, but may be obtained perfectly white by combina-
llon with an alkali and reprecipitation by an acid. (Limpricht <$£
I r, UslarO H*

^m PropeiiifM. Colourless^ inodorous, shining needles very much like
f AalieyUc acid. (Cbioz^.^ Crystallises from the alcoholic solution like
I beniEoic acid (Herzog); in small concentrically grouped prisms, wbicL

never reeenible the crystals of salicylic acid. (Limpricht & v. Uskr.)
' Melts at a temperature a few degrees above the melting point of

benzoic acid (ChioEza)j at 98^^ (Heragg); at about 140", but sublimes at

a lower temperature in small needleSi (Limpricht & v* Uslar.) May

be sublimed without decomposition.

^

14 C
SH

a

40

Field. Chio«ft (2). Schafyng (3). ^' u^^f^^^t

S4'a *... 5371 ..., &3'22 ..,, 64 10 . &3 20 ..... 536

6^0 „.. 3*20 .... 3-22 ,.„ 3^23 .... 3*36 3'2

55*4 .„. 22 63 .... .... 23-33 .... 22 53 22'9

32'0 .... 20M6 ..., .... 19-34 .... 20-91 20'4

C"H*aO* 156-4

100-00

100*00 ... 100-00

100-0

pcid into nitrochlorobenioic acid

kpcid into nil

Cblorobenzoic iicid ia conviTted by fuming nitric

C^^H^CIXO*, (Llmpncl

1

T. Udar.)

ill \ mm^i rf Ap^i|«fMci ly hwfii^ liesisoic mM will
■ " " " - ^ - ^ (Fidi) Til* ml^Um «f

k T. r Jv.)

hf »lrt»it4 la crjftal^ Ml imui

-s.'sa^

«mttr. TbeMi

tmledaoia:

Aft

MMliiltt^ AJker^fjiap

{UmpnAi 4 r/Uiimr,)

.') — Tbe alt ptmmni with Uie sad (4) focmt Md

1(4)1
It-f p. c (3 At) n4er il Ifi

fti «r4 _ 3*e

30-49

C*HlH*BiO'«. «4-fi _ !«•<»

they ^T^ <>ff 13 2 p. «. (3 At) wtOmU ICKf. (LtDtpridii A t. ^

„, lis

Ai i«r.
c«ciH<o* _««^ 1144 ^ ta?

C» _„ 2«*0 11*3

CMCIHC^O* .. _ 175-4

IQOHI

C^a/io^eitiodlf of Lead, — White precipitate^ which, aft#r dnri^g <
oU of vitrM, does not mffer anj forther toss of weight At 110% W ■
and tarns yellow. (Unipricbt'^^ r. UsIat.)

Chkrohmzoaii of Copper. — Green prcelpk&tt.

Ckhrcbmzf^Uo/Stltffr. — When a Koi I ]ii|f solution of tho »niiii»n
salt is tnlxecl with nitrate of sflVer, imall hoary cryetala are itpodtA
md, AH the lit(uia ecioli, larger crystals scp<^rate out* (Chiofa.)*-
WhJto precipitate consmtinj^ of micrt^iicopio needlet* (LjQjprieht ^
r Unlar.)

CHL0HOBEN20ATE OP ETHYLi

US

Dried ovtr ml ^fmirmL Chiovxt. ^'^^™* *

14 C ,.,...^ 8i-0 ..„ 31^89 3278

4 n. 4-0 .... 1*52 ,.. 1^54

At , lOS^O „„ 41*04 40' ti ... 41-2

a ,„„„,... as 4 _ 13-44

4 0—,. „..„. 32 0 .... 12 11

C^K:iH*Aga* _.„. 263 4 ... 10000

Chlornbenzoic acid dissolves readilj in aieohoi and €ih€i\ and tbo
alcoholic aolation effloresceg readily. (Herzog.) It dia^olres in alcohol
und ether and crjetalliees frora the alcoholic soluliun in small concentri-
cally grouped prisnis. (Linipricht k y, UBlar.)

According to Stvahovtse^ when cmnamic acid ia boiled with a flaturated solutJion of
ehloHdo of liroe ai long as arvy oil passes over witb.the traterf vapoarSf and the liqaid
filtered from the reaaltLng carbonate of hme AOtl oiiiipouEid of lime witb renin, h treated
wilh hjdrocbloric jicid to expel tbe free chlorine^ a crjstaUine acid ii obtained on cool-
ing, which, in different preparatbna, is sometiimes chlorobenzoic arid, &nmetimea a
miJilare of chin robe nzoic acid with benzoic^ bicblorobeoaoic and tercblorobenzoic acidSj
which cannot be separated bf crystallisation. The same products are obt&inedj accords
uig to StcnhouEe, when benzoic acid is boiled with chloride of lime or with a miiture of
I hydrochloric add and chlorate of potaah<

^^h f . Ghlorobansoate of Ethyi

^^^ C"H»C10* = C*H*0,C»*H*C10».

^Ll»tPEic?HT k r. UeLAR. Ann, Phamu 102, 262,

Obtained by heating chloride of chlorobenzoyl (p. H 6) with alcohol, or
chlorobenzoic acid with alcohol andenlphiiric acid^ mixing the liquid with
water, washing the precipitated ether with water, then drying it over
chloride of calcium and rectifying.

Liquid smelling tike benzoate of ethyL Boils at 245^

Limprrctit St t. Ufllar,

liC„,... IM'O ..,. 58-57

fH 9*0 ... 4-88

a... 35 4 ..., 19 20 194

4 O....... .......... 32*0 ... 17-34

C«H«C10* 184*4 .... lOO^OO

The ether dissolves in a mixture of 2 pti. of oil of vitriol and 1 pt.
faming nitric acid; and if the liquid^ after standing for 24 hours, be diluted
with water, an oil is separated, which after a while yields crystals doubt-
leas consisting of nitrothlorohtnioatt of €thyl; from an alcoholic solution
this compound separates in large colourleis crystals. (Limpricht k
T. miar.) %

X %

lU

t: CaiABCV^nPCLBUS c^<c?.

or-
is-

Rivolnd bj lit

K ife ■fbIii of tb« diodlkdoB of t^ i

llMt^^Ntt «f ^wfc(p.ltI^»i«^bipMiirf hf nm^ trirtiinMt utt ^M

CMoride of CMorob€ii2oyL
LiMFKirffT 4 r. IMAft. !««. PAitrm lOS, Sit.

Aiiwiitfts, L Bj Ik* ictm of peilMlloiMt of

t. Br Utt deoutnpMilMNi of ebloFoanl^kltobeiixoic a^id;

^^be&foie Mid (pt. 54) b he%ted iii a retort witJi f AU puli-
.Ahimlianift, u bog u vokUle iirodiiets of clkllllaiioa |
jlOidiiliobeiiioio meki b Ui^it faimed and wibteqiieotljr i

CHLOROSDLPHOBENZOIC AQD. H7

poied in tbe manner §bowii by the preceditig oquatioti. The distillate
18 rectified, and hy repeated dietillatiotj a jeTlowiah liquid is obtititied
wbicb boils at 285^ and consists mainly of chloride of chlorobcnioyi, but
18 contaminated witb otber products wbich cannot be remoyed bj
dJititfation,

Prop^ks. Tbe chloride obtained by (1) is a transparent, colonrleat,
«lrongly refracting liquid, boiJing at 225 *

limpricht & w. Ualir (1).

14 C ,„. B40 _ 4S'0

4 H 4*0 .„, 2^3

2 CI ..,. ...„.,. 70*fl .... 40*5 „.„, 40 4

2 0 .., 16-0 ..., 9*2

c^m*ao\£\, n4'8 ..„ loo o

The product obtained bj (2) mmtmnfd about SI'S p. c. chloride and t p. c iuiphur.

Xkcompoaidcms, L By boiling with water for geraral honrs^ the
eliioride m resolved into hydrocbJoric and chlorobenroic acids. — 2* It ii
but slowly decorapused by dilute potash or ammonia ; but strong
a^neoue ammonia converts it iminediately into chlorobenzamide and sal-
amiDoniac*

C'^H^QO^^Cl + 2KH* = a*H*ClCF,NIF + NH«a*

N

GMorosulphobenzoic Acid.
C*H*Cre>0« - C"H*C1*,2S0» [= C»*H\S"0*)0',CP].

LmPHicBT & V, UsLAR. AfiH. Fkarm, 102, 250*

SHtphate of BichtoTQhrf^^tenc, Chloride qf SvlphobenzoyL

n

Preparation. By the action of pentacbloride of phoaphorua on sulpbo-
l)enioio acid^ watar and cbloropbosp boric acid being formed at tbe earn©
time;

C»*H*CSsO^)0^Jq^ ^ PCl'.CP - C»H*(SK>*)0^,C1* + PCIW + 2HO.

1 pt, (I At,) of perfectly dry and jtulveriaed euipboben^oic acid is gently
heated in a turbnlated retort witb 2 pts, (rather more than 2 At.) of pen*
tacb bride of pbospborus; tbe mixture beated after the action has ceaeed,
first over the watcr-batb, and then to 170° to remove tb© cbbropbos-
phoricacid; and tbe residue rapeatedly washed with water, which removes
tbe la^ portions of cblorophospborio acid bnt exerts only a very slight
action on tbe cblorobenzoic acid. The adhering water is removed as
completely as possible by means of bibulons paper^ and the last portians
by standing over oil of vitrioL

c

Properttfs. Yellowish brown, viscid oil which cannot be distilled
Itbont decomposition. The colour i» due to imptiritj. It is heavier than
ater and has a faint but unpleasant odour*

ns

BENZYLEB^E: CYANOGEN-NUCLEUS C"CjH»,

14 C

2a,

2S .
BO .

limpricbl &y^ Uiltr.

B4*a ,,, 35-1 37-3

4'0 .... I'fi 2*4

roS ... 298 .„„.„ 28-2

32-0 .... 13-4 13-7

48*0 .... 20^1 18-4

CHH^Cl^'SW 238-8 .... im-Q ,. 100^0

The difFerrnce between the AtiaJyticd anii catcnl&ted reaulCn doubtl^at Afiaci fa
decona portion takjog pltice durinf ttie: prepar&tiua*

Linipricbt St v. Uikr regard the i^mpound as the chloride of the bistomic radical '
iulphobenzoyl Ci^H*(SSO^)OS formed from benioyl C*ni*0^ by tb« iubatitutiQii of

S-O*, for 1 At. hydrogen, lulphobeiisEoic acid being ^ 'Hj | O*, and chloro-

,u:pb.be,..oic.ddC"«'(S'0*g}-

DfcompQiilwns. I . The aeid ia decomposed hy diiiillati(m. At tetn-
peralnres above 300'' it boils violently, giving off enlphurtMis acid, jieMiog
a distillate of chloride of chlorobenzoyl (p. l\G)t and leaidng a residue gI
cUareoah — 2. It is slowly decomposed by vfoter at ordinary teniperaturei^
and when heated witb water to 100^ in a sealed tube, it disappears ia
few hours, being cod verted into Uydrocblopic and sulpbobenEoie adds:

Qnm0is30» + 4HO - 2HCI + Ci*H*S50".

3. Ihefjicd alkalh decompose it, forming an alkaline chloride and a
sulphobenzoate. — 4, Gaseous ajjiTnonia exerts scarcely any action upen
it, and dry carbonate of ammonia decomposes it but slightly; but coa-
c^outrated aqueous ammonia dissolves it readily^ fornuag sal-ammoniftQ

and Bulphobenzamide:

I

CWH*(SW)0*,CI« + 2NH« = C»^H*CS*0*)0»^H^ -^ NH^O.

Alcohol saturated with ammonia dissolves it, forming ethylosulphoben-
Eoate of ammonia. When nninioniacal gas is passed through a salution
of thecompoand in ether, sulphobenJEaniide is formed, tugetber witb varloafl
other products, — 5. Anilhie in contact with it becomes strongly heated,
yielding sal-ammoniac and sulphobenzanilide.

ChloroBulphohenisoio acid is insoluble in water. Alcohol dissolves it,
but with great rise of temperature and deconi posit ion j forming sulpbe-
benzuate of ethyl. In ti/ter it appears to dlBsolve without deoompost-
tioo, IT.

I

Cyanide of Benzoyl.

C»NH*0' = C»*CyH^O^

W^ELlB k LllBfo. jiftn. Pharm. 3, 267; also Po^. 26^ Bit.
KaLB& iiftn. Pharm. 90^ 62.

Formation ami Prepamtwn, When eldoride of benioyt is distiUed
with cyani'lo of mercury, a goldan yellow oil h obtAinedj wbieb may I
rendered cohatkm by reetificaltoti (Wbolei£( Liebig), and after a wbii

]

NITROBENZALDIDB* -"""^ "^ 119

eolidifiee In a cryataUine maas^ which must be waabed witb warm water,
tUl the wash-water ia no longer blaiiketied by sulpburL*Ued bydrogeiij
then pressed between bibalous paper, and dried over oil of vitriol,
(Kolbe.)

Froperti^t, CrystaJIisee by alow eoolmg in tables an inch long,
melt« at 31^ and often does not soliilify on omVmg till after it hits been
agitated. Bolla between 20d'* and 208'', (Kolbe,) Has a pungent odonr
and excites tears,

liC 9fi .... 73-28 »..-». 73 3 !

N .....,..»....., II ..,. 10*68

5H 5 .... 3-82 ,,,,.... 3^9

2Q 1$ ... 12*22

C«NHK1».. 131 .». 10000 "

Very inflammable; burna with a white very sooty flame. With dry
mmmoniaeal gas it forms hydrocyauate of ammonia and benzamide.
(Wohler *fc Liebig.J

Nitrobeozaldide.

BcBTAGMKt, ilT- J fin, Chim. Ph^s 33, 465; also Ajitu Phann. 7Q, 258;
abstr- Compt. rmd. 32, 68S. ^Further Ann. Pkarm. 86, 190.

Hydri^ qf Niirnbtnmyli Niirobenz^ytwat9er*t(jif, ^itrebitttrmmtdtlilL

^F JVrwaiiOfi <md Preparation. When bitter almond oil is gradually
I added to furuirt^ nitric acid kept cool by external refrigeration, or to
15 or 20 times its volume of a cold mirtnre of 1 vol, nitric acid of sp. gr^
132 and 2 lol, oil of vitriol, and the resulting solution, whose formiitiuu
U attended with rise of tetnperatnrc, is mixea with water after standing
for bulf an hour or an bour^ yellowish drops separate out, which crystal-
lise after a few days. At the same time, a yellow oily substance is
produced having a strougand somewhat ailiaceousi odour, ^ — If the lioaid
19 not sufficiently cooled during the preparation, nitrobenzoic acid is
Likewise formed. — The crystsiliine mass, after being washed in linen
with cold water, and pres^sed between two porous tiles till the residue is
no longer yellow, and no longer renders the paper greasy between which
it is pressed, is dissolved in a small quantity of boiling alcohol, which on
cooling deposits the compound, partly in crystals, partly rn the form of an
oil which cryataliiiseii after a while: both portions of the product are
recrystalliaea froni alcohol mixed with water (or fJFom hot water, which
however dissolves a small quantity).

Proptrim. White shining needle-shaped crystals. After fusion It
begins to crystallise at 4G', on at^itating the melted mass, the thermo-
meter immcdiiitcly rises to 49\ May be evaporated in small quantities
-without decomposition. Kmit^ a very faint odour B,t ot^uiB^f^ VewvY^tia.-

^ritl

1

120

BENZTLENE: NITRO-NCCLEUS P*Xll'.

turei; but a rery agreeable odour when heated Bomewbat abovf tti

meltiiig poiot; when ijvaporated in cuneiderahle quantities, it emiu rtry
pungent vapours. Has a pungent taste, somewhat reeenihlipg thai it

bitter almond oil.

lie . 84

N U

5 H ...„. b

6 0 , 49

C^NH*0» 151

B^rtaffiiiiL
5362 53-76

9-27 .-.-.... 9'42

3-31 ». 3-49

31-80 31-33

100 00 »,._ 100-00

1

D€€&nipodti<m9, L NitrobenEaltliOe remains unaltered in the air
even when warm. It burns with a suotj flame, — 2, Heated with ao
oily mixture of nitric mul and oil of vilnol, it yields nitrobentoic ictd.

— 8, Id concentrated chrmnic acid^ it dtssolves quickly, with riae d
temperature, and solidifies into a crystal Hue mass of nitrobenxoie acid. •
4, Chlorine doea not act upon nitrobenzaldide in ordinary daylight, hi
in sunshine it forma chloronltroben^oyK — if/^omiW ciiisaolvea r^wiily i
fused nitrobenmldide, hut does uot decompoie it till beated above lOQ^j

— 5* It dissolves readdy in aqueous poiash; the solution remains uaal*
tered at ordinary tern pern t urea; but on the application of beat, niuo-
benzoate of potash is quickly produoedj the solution in alcoholic poiJu<li
Bolidifica very quickly at ordinary temperatures into a transparent jell?
of nitrobeuzoate of potash, in which small nodular crvstaU of this salt
make their appearance, [After nitrobf^'uzaldide haa l^een heated with
alcoholic pfituah, the addition of water throws down a brown Ti^cid tvatm,
while nitrobenzoate of potash remains in solution. (List ^ Limpricht)]
— * 6. Aqueous or alcoholic ammonia converts nitrohenxaldide into tejut'
trohydrobeuKamide ( *^X'N*H^*, which may change into tertiitrOttaartDi
by simple metamorphosis. — The same transformation takes pbeo Ib
antmoniacal gas^ a largo quantity of water being given oW ai the
time:

3C^^XH*02 + 2Nll» « C^X^N'H'* t mO.

mm^

7» The akohoUc solution of nitrohenmldide yields, when suiphartUt^^
hpdroffm is pfwied through it, a precipitale of sulpbide of nitrobeniylii^H
C"XH*SV — 8, When suiphuttited hytlmgen is passed through t^^
solution of nitrobenzaldide in alcoholic ammonia and tlie liquid heated
from time to time, a acmifiutd eub^tanco is deposited mixe^l with n larnH

Quantity of sulphur. When this suhstance is extracted with ether, aff4|
ecanting the alcoholic liquid^ an ethereal solution is obtain i?d< whifl
leavei on evaporation a reddish, very viscid mass, insiduble in water of
hydrocbluric acid, but disstdving with tolerable facility in warm alee'
when heated, it swells up, pves off sulphuretted hydrogen, and h\
with a bright flame^ leaving a slowly comhustihlc chareoal. Nit
Raid i do boiled with nitric acid yielJa sulpburic acid and a yellow
— 0, Heated With tidjJiitt of ammonia^ it yields a body which is sotthk
111 water and apffrears to be an acid. ^ 10 Strong hjfdro^^anie mSA
dissolves nilrobeit^iMide with facility. If the solution is sTafMimM
immediaUdy, tlie ititrobenialdide separates unaltered; but after staadliif
for A few hours, the solution yields on evaporation a viscid liquid petvft-
ntni m the f^ff which when dissolved tn hot water^ lepamtes m drifi m

KltROBlNZALDIDS.

ISl

coolings and when boiled witli hydrochloric add, yields sal-am m on lac and
another bcidy doluhle in water. — CyaniJe of potassium quickly convene
nitrobenzaldiile into a pecuh'ar substance. — 1 L When urea is thrown
into luelttid nitrobenzaldide and the liquid gently heated, water escapes,
and the whole eoliditiea on cooling into an opaquu ma^sB, whicb di^^solTes
iparinglj in pnre alcohol, bat readily in alcohol mixed with hydrocbloric
acid; nrea and nitrobenzaldlde being tfien reproduced.

f iPOfl

Cotnhinationi. 1- Nitrobenzaldide dissolTea sparingly In ©old water,
twjtb tolerable facility in boiling ttJa^r; the solution saturated at the
ipoffiitg beat becomes milky on cooling, and afterwards filled with shining
needles. ^ — 2* It diBSolvea without decompoajtion in oil of vUrlolj hydro-
Mori^ aeid nnAnkncaeid; from the solution in oil of vitriol, it separates
in abining laminar as the liquid absorba water from the air

3, With Bimlpkue fl/ .^mrnon/^. — C'*XH*0' + NH*0,2SO» + 2Aq.
— Easily obtained by treating nitrobenialdide with an aqueous solntion
of bisulphite of ammonia of SD'' B. or by mixing it with aqueous ammonia
and passing sulphurous acid gas through the liquid. On applying a gentle
heat, the nitrobenzaMidc dissolves very abundantly in the biaulpbite of
ammonia; (at a higher temperature, the sulphurous acid exerts a deeom-
pefling action;) on cooling the compound orystsilliies out. — It crystal-
lisei from alcohol in email, colourless, transparent prisma, which grate

Ethe teeth, and have a bitter and sulphurous taste.
I
compound is not altered by exposure to the air, tbough the
sometimes assume a faint violet tinge. — The aqueous solution
,_ _,,_.i posed by boiling, nitrobenfaldide being set free* Acids do not
alter the solution at ordinary tcniperatnresj but on beating the liquid,
decomposition takes place, atf;en<led with evolution of sulphurous acid.
I The compound gives off ammonia when heated with alkalis. The
I aqneous solution forms with Imrium, lead, and silver salts, white pre*
cipitates consisting of the sulphites of those metals, and after a while
crystals of the nitro-compound tmike their appearance; with chloride of
platinum, chloroplatinate of ammonia is prodacciL

The compound dissolves readily in water , and crystallises with diffi-
culty from the j^olattou. N itro be nzaldide dissolves very easily in w^ter
» containing bisulphite of ammonia. — The compound dissolves with
belli ty in boiling akohoL
4. With BmdMtc of Soda. — C"XHW+^iiO,HO,2SO»+ lOAq. —
When nitrobenzaldido is dissolved at a gentle heat in aqueous bisulphite
of so^la of about 27° B., the liquid yields on cooling, shining yellow
laminsBj which are rendered colourless by recrystallisation froui hot
water, effloresce in the ain and give oft 26*08 p. c. (10 At) water

u c

,. »..„. 84 .

. 28 ..

„ u »

.. 32-43 ,
.. 10-81 .
.. 4 24 ,

,. 12'3&

,. 40*1 r

Bertagnini,
^ 32^/y

2 N ...„.
U H ....

1112

4-40

2S „,
13 O

^i„..*.,^nmt-..m*^^vt

...^ 104 ..

C^KHKJS + NH^.aSO- + 2Aq ... 259 .... lOO'OO

122

BENZYLENB : MTRO.NDCLEUS C^XW.

4

a 90".

BertafBlni.

u c .,....._.._,,„

...,.« B4 ..

.. 32-94 ..

3265

N ,

--...« ., 14 ..

.. S'49

ti H

6 ..

. 235 ..

2-53

2 S ._„.

, 32 ,.

» 12-54

NftO,...

31 ,,

.. 1215 „.
3453

12« ^

11 o

BS

C"NH*0< + NaO,HO,2S(^ 25S

ItiOOO

The compound dissolves sparindj in toM, ^silj in boiling iraier;
tlie solution deeouj poses quickly when boiled, giving off the odonr of
nitrobenzaldide. Boiled with acids^ it jields nitrobeazaldide ^ud sol-
pburous acid.

5. Nitrobenmldide dissolves Teadily in alcoli^l^ and with tolemblo
facility in rtAcr*

Nitrobenzoic Acid.

Plaint AHOUE. (1839,) Ann, Pharm. 30, 349.

MULDF.R. J. pr. Chem, 18, 253; 19,362; ^ho Ann. PIiarnL 34, 207*

MiTSCHERLicit. J, pr, Chm. 22, 196.

MAjtciiAJ^D. J. pn Chem, 18, 254; 19, 365.

Abeu Ann. Pharm, 63 p 313; also Mem, Chem, Soc, 3, 445,

H. BLUMEifAu, Ann, Phnrm. 87, 127*

Bertagnini^ Ann. Pharnh 79, 250.

QERLAffD, Ann* Pkann, 91, 185,

Niirtfcinrioltdmrt^ NiirGbmzintUMrt, Bentaetatpeitrw^mit^

ForwMmn^ 1, By tbe action of nitroaulphuric or chromic aetd
oitrobeosaUlide. — 2. By beating nitrif! acid with betizoie acid (Mnld^
E. Kopp, Campt. ehim, 1849, 149), with cinnamio add (PJantamcii
MulderJi by continued boiliug of uitric acid with cuniol (Abel; ^
boiling dragon 'e blood with dilute nitric acid (Blumenan) - — 3. la iW
docom position of hjjjpnric acid by hydrocbloric acid, (Bertrngnini.) —
4. By the action of nitrosulphuric acid on benzoic acid or oliloride oi
benzoyl; in tbe latter cage, cblorine ie evolved, together witli anoilier
gas which excites a cop ions flow of tears. (VoiL)

1^

»ui^H

'4

1

Preparation, 1. Benioic acid is boiled with eicceflis of nitrie
till the solution, which is red at first, bocomefi decolyriie<l and givi
nitroua vapours; the nitrobenzoic acid cryatayises out un Doollng
may be purified by recryst alligation from hot water, (Mulder.)
only neee^sury to beat for a t^hort tinie in order to convert tbe wbiJt fd
the bcujcoic acid into nitrobenzotc acid; the nitrons funics arisn from i
further action of the nitrous acid on the nitrobcnioic acid, (Mitschr'i
lich-) It is only by continued boiUjg with fretiuently r^neweil portiaua
nitric acid that beQEoic »cid can be completely converted into nitmbcju
ftcid. (GcrUnii ) — 2 . Oil of vitriol is added with agitation^ to m uil<
mm of 1 pt> of bencoic acid with 2 pts, of nitre, the mi]ttur« ke«tad tif

m%)iibib K6fDr'

ISS'

it eoftenSj and the resulting^ nitrobenKoic acid purified by crjitalli^ion
from water. With smAll quaotibe^, tbe mixture may be h^Ated till It melci: if \t be
then left to cool quietly, the bbulphate of potnih ciystnlUses out first, and the nitro-
benxoic Arid decanted fnira it in perfectly pure after two cryst«lIiB»tiona* (Gerlaud),
Or, fused benzotic aeid is added by email portions to a mixture of 2 pta.
BiTong sulpLuric acid and 1 pt. nitric acid of sp. gr, Vfy and gently heated
for about half an hour; on subsequently adding water to the liquid, nitro-
benzoic aeid is precipitated in white flakea. (Voit, Ann, Pfmnn. 99, 100,)
— 3. When cumol is heated with fuming nitric acid for several hours,
Eitroben^ic aeid eryetaliises as the liquid cook, and may be freed from
ftdbering btoitrocumol by treating the solution with am muni a aud preci-
pitating with uitric acid. (AbeL) — 4. When dragon's blood is boiled
with exoe^ of nitric acid of sp. gr. i'34 mixed with an equal quantity
of water, it dissolves gradually with evolution of red vapours* When no
more %mpours escape, the liquid is evaporated to dryness; the cooled maa«
pressed between paper, and saturated with car boa ate of soda; the solution
purf^ed with animal charcoal and precipitated by nitric acidj and the
precipitate washed with cold water. The mass consisting of fine scales
contains a subi^tance which chars when heated, together with nltrobenKoic
acid which sublimes, (Blumenau.)

Froperi iei. Col o u rl ess, cry s ta 1 1 i ne 1 a m i use gen e ral ly grou ped t ogeth er.
In water it melts below 10d°> forming an oil which solidilies on cooling
in a bard, brittle crystalline mass; by itself it melts at IS?"", and begins
to sublime at 110- The pure acid sublimes completely and without

]

decomposition in slender needles; when coloured it leaves a small quan-
tity of charcoal. The vapours have a pungent odour and exciie cough-
ing. The aeid reddens litmus. (Mulder.)

Plantftmour. Mulder. M^rcbund. Abel, Bertagniui.

UC. 84 .... 50-73 ..„ 50*14 .... SO'42 .... h^lB ,... 60^30 ..,. SOSO

K 14 „.. 8-39 8*35 ... fl-36 „.. 8*38 .... 8*63

5 H S ... 2 96 .... 306 .... 302 „„ 2*99 ... S-UO ... 3*12

SO. 64 .. 37'9Z 38-21 38*46 , 38 32 _ 3? 95

C*^NH»a* 167 . lOOOO 10000 ,. 100*00 ... 100 00 ... 100*00

The ftdd ftimSysed by Plantamqur was prepared from cinnBUiiiT acid ,* that by
M uld^F, from benzoic acid ; that by Marchaud, from cjaimmit acid j that by Abel,
froita dragon's blood i aud liiuC by Berta|£itini from mtrubippuric add.

L

Decompomtiom, 1. The aeid when heated to Its boiling pointy
blackens and gives off combustible gases. (Mulder.) — 2. It dissolves in
atrong jiitric acidf without decomposition (Mulder); it is decomposed by
continued boiling with uilrie acid. (Mitsclierlich.) — 3. It is not altered
by sublimation in c/ilorine ga^. (Mulder,) — 4. It dissolves without
colour in oil of vitriol; on heating the solution, a small quantity of the
»cid sublimes without alteration, and near the boilinff point of oil of
vitriol, the liquid turns red without giving oiF gas; if a larger quantity
of water be then added, a few grey Hakes are separated, and the liquid
on being saturated with carbonate of baryta^ forms a solution containing
a peculiar substance not yet further examined, (Mulder.) — 5* By
peniacMoride of pko»pl^rim^ the acid is not attacked at ordinary tempe-
ratures; hut on the application of a gentle heatj a T?\a\6Ul y^Sx^"^ Wt.^

^ i'W^L— Xbt mrtioa of ti« aiad fa |

J to in'

^ ^WBtitj «f wtrabenol li gtTiNt off m ibi

jITi^rotoixMCf of Sidm^ — ¥ttfmi^ hj dknlTing ike add is fli«itiC
loda. DiliqvMQmt «a4 JiGenll t4> ajswUie. Bebmrei lik# t^o potei^
Mb wbeo iMtod. (Mulder.) Do« not ikU^oem k Om air. (Mit^

Ni^iAamaig ^ Margta. — W1i«a tLe aeid b Wiled witb wmlar aii
tx^ifl of oarbonale of bwyt^ llie aoLatioQ yields on coeliiig hgaalifit ^
akialag cr^Atala^ wltleb giv* off 10-12 per ccpl (4 At) of water al

C>l^«j/4#f(l. Mulder.

C»-KH*(F , Ui^ _ $f-3«

'B*0 „.. 7€*6 ,„. t«*31 28*10

4HO„ 3e0 . 13-31 *„...» 13 9*

C»*NM*BiO« + 4M .„ 3tJ0 6

lOO'OO

^^^^^^^^^ NITROBENZOIC ACID, 125

N'iiir^hmio^^ of Str&niia. — When tbe acid is boiled witli water and

carbonate of strontiop, and tbe solotion evaporated to tbe crjfita 111 sing

j pointy it yields on cooling feathery needlea united in tufts and destitnto

I of lustre. After drying in the air, it gives o^ d52 per cent. (2| At)

water at 150^ (Mulder*)

^b Mulder. 1

^^^ 2 cmmy .„„.„^ aie .„> 67 ge '

^^^^ 2 SrO 104 .... 22 36 19-22

^^^ 5 HO ,.,■■■,„„...,..„„,■„„ 45 .... 9-68 9-a2

H^ 2{GJ*NH*SrO») -f- 5Aq,.. 465 .... lOO'OO

^^ KiirtihenmaU of Lime. — When the acid is boiled with water and
earbonate of lime and the solution evaporated, it yields on cooling, small
white, faintly luetruus crystalsj which give off 9'09 p. o. {2 At) water
between lao^ and 1 90^ (Mulder.)

^^^ Crftfailittd, Hmlder. I

^^^L a^NH^ ^ 1&8 .... 77-45 i

^^H CkO ,_ 2i ,„, 13 72 ....... 1400 ^

^^^H 2 HO .... IB .„. 8-$3 ... 9 05

^^V C^NH^CiiO« + 2Aq 204 ... lOO'OO

^f When heated above 190'', it melts, blaekenB, gives off nitrobeniol,
^mnd finally detonates* (Mulder.)

^B NitrobenzoaU of Manganese. — A aolntbu of tbe acid In ammonia

^■lilixed with salphate of manganese yields by evaporation, white crystals

containing 4 At. water, of which 2 At. (7-16 p. c.) go off between 40^

and 70", and the rest between 115'^ and 133^ At 115'', the salt begins

to assume a yellow colour

Or^fMialtUtd^ Mulder*

C^^NH^OJ „. 158-0 „., 69-03 ,

MnO .„ , 35-6 .... 15-42 16-23

4 HO. 36-0 .... 15-55 U'78 1

C»*NH<MiiO' + 4A^ ........ 22y*6 ... lOO-OO

jrMUrdbemoate of Einc.'-^a, Quadtihasie^ — Acid nitrobeniEoate of
Dnia added to a solution of sulphate of ^inc, throws down a basie
■all in the form of a gelatinous precipitate. (Mulder.)

^ Mulder,

ai 130°.
i Ci*NH*0' -,«.... 158-0 .... 47*92
■ 4 ZnO 160-8 .... 520B 51*8
3ZiiO,C"NH^EiiO« .... 318-8 ... 100*00 1

h. Monobasic. — Tbe liquid filtered from a yields by evaporation,
laminar crystals which give off 18 61 p. c, {5 AL) water at 140\
^(Mulder.)

KSZfLEn: imio-iiTCMrs C*-iiA

MttJder

n>* (2).

»n

»5« »W

4-M

I'U

_ 1S7 _ 141

45-9t

__ 45-41 _ 4SII

tf-l?

Tli« WDfl mJI renmiu nndinolTeil wlieii b Is m%shed.

When nitrobetianc mdd k boiled witli wmter mud c&rbonatd of k

Infft ffoantitj of earbo&ic ^eid escapes, ^nd two salts &t« prodace^

of whim u Boiable wbile tbe otiier fomu in^oliibk fl^es. (Mubk^

&. Ji^ormfii. — Wben s boiling saturated ai|tteoiis wiliition
heniolc acid is mixed witb ba£i« acetate of lead^ till s permai
ptiate it formed, tbe liqaid on cooling, jblds even at 90^
CfTStak wbieb hood fill tbe eotif^ l^iiid^ eo tbat it soUdiGea into a

this moit be tbrowti on a filter and premised. A leta ootii
•olnUoii yields on cooling more dbdooi cr^italsp wbicb, wben
formed], arc Int^jluble even in tbe boiling litjuid. — Tbe su
prodaced wben m solution of a in aeetie aoid ii dropped into
iolotion of nitrobenzoic aeid.

14 C .- »»,„. 84-f _ 31-U

N „..^-^™ U^ ... a-19

4 H . _ 4-« _ 1-48

FW ni'8 ».. 41-45

7 0 , ..„ &e*0 .« 20 7S

C"Nfi<PbO» 2«f*8 „„ 100 00

,„„« 41-W

Ferric Kitrohmtoatt. — Obtained by precipitating a boiUog i
of tbe acid with aooeoui fetrio chloride* Bulky ilesb-colotirtd I
f&tolable even in boiling water* After drying in the fttTp il i
pre off afiy water oven at 135°. (Mulder.)

3 C*NH*0? ..„, 474

ri»0» „,...,,... 80

84 '65
n-35

Mulder.
15 23

W& 3C**1«H*C? .„ !>^4 ,. \^ Wi

N1TR0BEN20ATB OF METHYL.

127

N'tirohmmaU of Copper. , — When a hot solution of the acid is mixed
with acetate of copper^ the liquid on cooling deposits a blue powder
which gives oS water at 130°^ and part of its acid at the same time*

a^NHW «,...

CuO ,,..„.„„

HO

... 9 0

76*iO

19-24
436

Mulder*

18-96
5-53

P^NH^CuO" + Aq .... 206-8 .» lOO'OO

Nitroben%oQt€ of Silver* — Obtained by precipitating an ammoniacal
aolation of the aeid with nitrnpte of silver, and press inij t!ie precipitate.
It p»s#eij througrb the filter in washing » (Muldor.) The precipitate IS crystal'
Heed from Lot water, then washed and the crystals dried. (AbeU) It
crystal I laes from the aqueous eolation in laminm huving a pearly lustre
(Mulder):

Mulder, Plantamonr. Abel.

840
140

1081
640

30£&
5*11
1-46

30-69

aoe

1-57

3i'42 38-fl6

23*36 ..„„.. 23^Ba

40*37

30-24

LimprichL

39*a4

•^NH^AgOS „,. 274*1 ....100-00 10000

At 120°, part of the acid volatilises, the salt turns grey and continaes
i give off acid; at 250^* in close vessela the salt explodee^ with formation
*f nitrobeiizol and empyrenraatic products. (Molder.^

By dry dietillation, the salt yields a large quantity t»f nitrohenxol.
[Mulder, Abel) Heated on platinum foil, it melts and bums without
ietonatiom (MuldeTi)

KitrobeuKoio acid diflsolves in alcohol (Mulder) in les« than 1 pt* of
ilcohol at 20". (Mitscberlich; E. Kopp, (hmpL chim* 184fi^ 140.) It
iisaolyes readily in ether.

Nitrobenzoate of Methyl.

C"NH'0» = C*H'0,C'*XH*0^

Shancbl. Compt. chifa* 1849, 170; also J. pr. Chem. 47, li2; abstr.

Ann^Pharm. 72,274,
lERTAGHtPf I. Ann. Fharm, 78, 269; also N, Ann* Chtm* Ph^», 33, 473.

Fonnation and Preparaii&n* 1 , When hydrochloric acid gas is passed
_ b rough a boiling solution of nitrobenzoic acid in wood-epirit, till part of
%he wood-spirit is distilled ofi", the residue consists of two layers, the lower
^Df which is nitrabeuzoate of methyl, while the upper is a solution of the
^«me compound in wood -spirit, whence it may be precipitated b^ water.
■i*U« whole of the compound ether thus produced Is eUak^u >i^ -wv^ a.V^kV

in BEN2YLBNB : KlTaO-SfUCLEUS C»XB^

so! Q Mod of carbonate of &o4a, repeatedly washed with m\d wmter*
between paper, and orjstaUieed from alcohol or frnm a mixture of all
and ether. — 2. A solution of chloronitroben^oyl in wood-spirit
deposits crystals of mlrobenzoate of methyl. (Bertagnmi.)

Small, white, nearly opaque, right rombic priiots, « : w = 118' to
120^, melta at 70''; boils at 279". Uaa a very faint aromatic odour and a
fre^h ta^te.

16 C ^« 96 .». 53 04 ....... ^2 92

N. 14 ... 7-73 7-81

7 n ,.... »... 7 ».. 3*8e ....... 3 93

8 O .....^ ....... 64 ...p 33 37 ....... 35 28

a*NH"0* 181 .... 10000 100 00

Ita reactions are exactly similar to those of uitrobenzoate of ethyl,
tt 19 Insoluble in water, sparingly soluble in akohal aod ia Hk^^
somewhat more in wood-ipirU.

Nitrobenzoate of EthyL
C"NH«0» = C*H»0,C"XH*0'.

MiTscHBKLice, Lehrh. 4 Aufl. 1, 22 1<

E, KOFF. CmipL rfnd. 34, 615; also #. J. Phnrm, 11, 427.
Chancel. Gompl. ckim. 1849, 177; also j. pr, Chrm 47, 140.
BEnTAGKTHi. Ann. Fliarm 79, 269; abo ^V, Ann. Chim^ FhtfM, 30,"
hmt & LiMFBicUT, Ann. P/umn. 90^ 200.

Formation and Prtparutimk 1, An alcoholic solaiiou of nlti^
benEoic acid m continnously boiled with a »malj i^unntity of «it| ~
add, and the liquid ii mixed with ammonia and precipituted b^
(Mitscborlicb.) — ^2. Hydrochloric acid ga.8 la pAseed tb rough m botlti
alcoholic solution of nitrobenEoic acid, and the proceaft completed
the preparation of the corresponding methyl -compound. (Climiioel,
E. Kopp.) — ^3. Benzoate of ethyl id abided by drops and witb OdtMtaat
■Urring lo a mixture of 1 pt, nitric acid and 2 pt^, oil of vitriol, wkidi
must be kept cold; the mixture gradually poured into cold WAter; aad
the separated nitrobenzoate of ethyl filtered ofl* and cryat&llij«d from
alcohol. (List 4 Linipricbt) — 4. A solntion of chloronitrobetisoyi in
itrong alcohol yields by evaporatioa beantiful crystals of nitrobenioaee of
ethyh {BertagninL)

Proper iifi, Cry&talHges very beautifully in rhombic prlamfl. [Fii
6L L.] u : w =^ 122^ (Cbancel) Melts at 70^ (Miucherfiefcl
4r (E. Kopp); at 42" ^Chancel). Boils at 300^ rMitscbtfi
at about 298^, (Chancel) Has an aromtttic odour (E. Koff]|
tbat of strswbetriei (Chanc«2}; has a fre§h and sujuewhai bluer f
(i, Kopp, Cbaaoel).

liC,., ....108 .,.. 55*M ...... 55 l«

M .. « 14 ..„ f li 7-SO

§n^^, — » .... 4 61 4^2

S O .„ 64 . . 32-83 32 70

C»NB«0*

\n

100-00 10000

NITHOHIPPURIC ACID. -'' ^^ 129

DicompoiUiom. 1, With potatk-iey, it is resolved with tolerable
facility into alcohol ant] nitrol)en«oic acid, — 2. Wilh afntry^nia^ it
readily forma nitrobcnzarnido mid alcohol:

C'^NH^O^ + NtP ^ 0*N*MH)* + C*H*0*,

a* When treated with hydroitdphate (f ammonia, it forms amidobenzoati
of ethyl. (Ctiancel):

<?*Na»0* i^ 6HS - C>*NH«0* + '4HO + 6a

Nitrobonsoate of ethyl is insoluble in water, but diaaolires very eatily
in almhol, especially if hot*

Nitrohippuric Acid.

BenTAOjVTSd* Campi. rmtl, 31, 400; also J^. J, Pharm. Ifi, 351;
J. pr. Chem, 51, 25$.— Ann. Pharm. 78, 600; abstr. #. X Plutrm.
20, TK

FmTrmiion. 1. Bjr the action of nitroBulpburlc acid on hlpptirie acid,
— 2. Nitrobenioic acid is concerted into hippurjc neld in the animal
organism, and posses off* as such in the urine* C grammei of uitrDlwoxoic
acid mKj b« Calceii for lef creJ dajt 10 iBceeieioii without injmy^

Pttparatian* a. From Ili^purk acid. — The solution of htpimrie
id in cold fuming nitric acid is gradually mixed with an eqnal Tolume
of oil of vitriol, care being taken to prevent the liquid from getting hot;
the o*inveraion is completeii in two hours withont any percf^ptihle action*
The li«iuid is mixed with three times its volume of water, — avoiding rise
of tcmperudire, — and after 12 hours, part of the nUrohmptirie acid
(amounting to balf the weight uf the hippurlc acul used) ia deposited in
needles; on mixing the mother-liquor with carbonate of soda till it
liegina to show turbidity, an additiutml quantity of the acirl separates*
The still yel!owiah acid is washed with c*>M water, conrcrted into a
potavh^saU, then precipitated from the tnkewarni solution by hydroehlarie
a^d, and nseryetallis^ from water* --L From. Viinc after the ej-hibUton
of J^iirclmmic acid. — The strongly ncid urine remains clear when mixed
with hydrochloric acid after concentration at a gentle beat; if the liquid
he then shaken up with ether and a little alcohol, the ethereal solution
when left to evaporate, deposits brown crystalline nodules, whicb^ after
being freed from the mother-lifjuor and dried upon a tile, yiidd brov/niah
needles by recrystallisation from hot water These needles nre boiled
for ^re minutes wilh excess of milk of lime, the Ultra te decomposed by
hydrochloric acid, and the mtrohippurie acid recrystallised from hot
water.

Froptrtm. The acid crystallises by evaporation from the alcoholic
iolation in silky neefl!es, whtch do not suffer any diminution in weight
between 100° and I5u\ It melts between 150" and 160'', into a eolourlesa
Liquid which crystal lise a on cooling.
^ YOU xu* m

yj^\

130

BINZYLINK : NITRO-NUCLEUS C»*XH»,

fierUfAiiiL

48-21 4831

12-50 ..., 12^42

3-57 , 3'6|>

3572 35*fil

C»*I^H*0'* ..., . 224

100-00 ...,„,. lOO'OO

IIIOOO

IkoomposkiimM. I. Abov^G 100"^, it assunies a reddish eoloar Aod
longer eoUdifiee to the CTj^taUiuc form; tlie solutiou in hot ir&t«r #1
yiehh as cooling crystiils of the acid uppareotly onaltered- XVkuM
gradualty misetl to a higher t^^mperature, it gives off pungent coa^fc-
exciting vapours and sabltmeB in tho cryjatallbe form; when ii m fad*
denly er|K)ee<i to a strong h^t, the odoar of oil of ciuuamoti ba^m«
apparent — 5. When boiled with five tiiues iu weight of eonc«ntntd
hjdrocliloric acid, it u at fii^t not attacked, but after an hoaf it i«
reaolvLHl in la nitrobenzoic acid and glycocoL — 3, When nitric oxide m
tfl po^^ed thrangb a solution of the acid in strong nitric acjd, a lam
quastttjr of gas w given off; and If^ when no more gia# eecapee, tteu oq
tM application of heat, the liqnid be nentrallaed witb ammonia, wap^
rated, precipitated with solution of sulphate of copper, and tbe precipititf
deoompoied by sulphnretted hjdrogen, an acid is obtained whic^ if
difaraat from uitrobipptiric acid and prub;ibly consists of benaoglyojlie
^eid, — 4* Nitrobeiiioic acid dissolves with out' decomposition in euU mI
of vitriol i at a geutle heat, the colourless solution assumes a t^ddidi
tiage, and Ibcn oa addition of water yields tiilrobenxotc acid; at a
dfOliger ht>at, it turns brown and nitrobenxoic acid volatiliaet, ~
5, Heat<'d witb strong potash dey, it inirnediaiely assumes a yellow^iroini
colour, and gives off ammonia; at a higher temf^erattire, jt beconci

7, Sttlphurelted hydrogen has no action upon the a^jueous acid, but ti
mrtsa redd ish colour to the acid mturated witb ammonia; and if i
liquid Iw then supersaturated with sulphuric acid, a large qaaulity
sulphur separates uat. I'crhajii amiiJabeaioic »nd DUf t^ formed in tak

CbmbimtHans* Tho acid is somewhat more soluble m cold vatc_
than hippurio acid, and di^olves in 271 pts. of water at 23''; the tobM
lity is iuert^aited by traces of (otgI^ matter. In boiling water it dis^olfifl
niadily. the iwlutiou becoming milky on cooling and yielding oily dnfi
which' afterwwriN crystalli**. It dissolves easily in water ocmtj " '

pbiu'pb

Ult**t pi»
w hf'u h'
niftaU gtte otl

r

1

an If

i'wnff^ generally crystallise In needles mnd ar« for tki

in water and in alcoh'd. Those of tbe alkalies df>toBitt

i ,liflU*e an odour of oil of cinnamon; tho^ of tJi« hmtf

when heatiHlj an oil which smelts rery ranch tike oil *^

V ,%/ Ammf^nia, — The solution of the acid In ajnoMtii
. ^rid during the ^roeesa of eraporationp and leafw a
in water and alcohol.

/Vis^. — The hot conoentratod a<]ueoni aolataoa
4e*l with carbonate of |>oia«h, erapomted ©iw tbt
t^dna ashattKiail with alcohob which when wn-

I ipy

NITHOHrPPURlC ACfD.

poimtedj lenTe^ the salt m crystalline crusts. From boiling alcohol, it
separat^ in distinct crystub. It haa an alkali oe reaction, and dissolves
really in water and in weak alcobolj apiiringly in atroncp akoJiol .

yitrohippuraU of Sod*i, — Prepared like the pot^ah-salt The slightly
coloured cruets are washed with cold strong alooUoL The salt crystallises
D needles from hot alcohol. It has aa aikaline reaction, dissolvea veiy
easily in water, but is not so soluble in alcohol as the potash ^salt.

Nitrohippurmt of Baryta. — When the acid is boiled with baryta-
water and the excess of baryta precipitated by carbonic acid, the salt

stallises in needles as the licjuid coob.

Niirohippuraie €f Lime, — The acid is boiled for a short time with
iailfc of lime, filtered hot. and carbonic acid gas passed through the
filtrate; the Bolution on cooling yields white needles which hare no action
upon litmus. Between 100^ and 110°, itgiTes off 10^64 p, c. (3 At.)
of waten

wau

Piilk

C^N»H'0? ^15 _ ?9*63

^0 ^ 2% _ 10-37

3 HO..,. 27 _ 10 00

C'WH^CaO*" 2n .... lOO^OO

BertBgnint,

11-51
1064

N Urohippum(£ of Magnesia, — Wlieu maf/ttcm dlha is dissolved in
the hot concentrated aqueous acid, the solution yields a white crystalline
maafl easily soluble in water and alcohol.

Nitrohippui-ate of Zinc. — A tolei-ably concentrated acjueous solution
of nitrohippnrate of Itme mixed while lukewarm with chloride of zincj
hccotnes filled after a while with needles which must be recrystallised
from boiling water. Between 100^ and 110^ the crystals give off
17-S5 p» c. (fi At,) water* The salt dissolves sparingly in cold water
and alcohol, somewhat more readily in the same liquids when hot.
(Bertagnini,)

N itruhippuraU qf Ltad* — The aqneoua solution of the lime-salt
forms with nitrate of leiid a white heavy precipitate which immediately
hocomcs crystalline. The salt precipitated in the coJd gives ofT 12^30
percent. {^ At) wntcrat \Q\fi that which h precipitated at higher teni-
peratnres la anhydrous and very hygroscopic. (Bert^gnini.)

At 100'.
IBC .«,. ,^^, 108-0

2 N _ aa 0

?H ». 7 0

Pb ...... ..... 103*6

10 O .-.- flQ-0

C«»N«H^PbO>« .,„ 325'S

BertagninL

33"04 ...,,... 3312

6*58 ,......, 8^91

2 19 2-4a

31*76 , 31-31

24-43 .,.._ 24^21

lOOOO lOO^OO

F&rrk NUrohippurait. — Obtained by double decomposition. Yellow
flakes soluble in boiling water.

NiirohippuraU ff Copper. — Concentrated aqueous solutions form
with sulphate of copper a copious lighi blue precipitate; dilute solutions
solidify after a while in the crystalline form. May be purified by washing
with oold water and crystal J kation from hot water,

1B2 BEN2TLENE * NITBO-NUCLEUS C"XH*,

Berta^isL
C»«K'H70» ..., 215 0 .... 84- 18

CttO ..,,...,..... 39'tt .... 15*82 1&'S5

C^JWU^CaO'o .... 2fi4'9 ,. lOO'lW

The pale gr^en alcoholic salutbn deposits detiente, pal© blud, ailky
needles which give off 14 93 p. c. (5 At) water between 100^ and IW*^

Niirohiimurute of Silner^ -^^ The solution of the lime-salt mixed with
nitrate of silver g^mditally yields cryataU, or if highly concentrated^ ito-
tnediateiy forms a curdy precipitate whicli aoon becomes crystalline.
Slender needles which when moist qaiekly decompose on exposure to
lights but remain analtered if dry. It dtasolvea rea^iily in liot w^ter,
and with tolerable facility in cold water and alcohol*

18 C ,. .108-0 «.. 3262 32-39

2N 28-0 .... 8-45 »..,„. 873

; H .,.. 7*0 ..„ 2-11 ,. 2-27

Ag ,..,. 108-1 ..., 32'65 32^76

10 O BOO ... 24*17 23-85

C^Wa'AgO'** . . 33M .... 100*00 100*00

Nttrohippuric aoid dissolves readily in alcohol and eth^r.

Nitrobenzoate of Bibromophenyl

List & LiMPRiCBT, Jnn. Pharm. OO, 203.

Nitr&bfn%fiait t^ Bibromoearbolic acid.

Separatei m a resin when finely pulverised bensoate of bibrottiopheny]
li gradually added to nitrosulphunc acid which is kept cold; water added
to the liquid scarcely throws down anything more* Crystal I iae« froin
the hot alcoholic solution on cooling in sni^ll needW united in nodular
mus^oj}; from a concentrated solution, it separates as an oil »

Mi^lts between 90° and 100°, and (>therwise agrees in its external
propertied with nitroheuzoaie of blnitrophenyl.

Lift St. LimpHcbt.

26C 156 ... 38-90 ....... 40 n

N ..................... 14 .... 3*49

2 Br ..160 ..*, $9m ....,.„ 4Me

in „...«„ J *,. 1*74 2-04

SO U .... U-97

CJ»NBf*H'0^ _. ., 401 . 100 00

The b^nsoate of bibromophenyl used hj List St Ljmiiricht in tfa« prepArailoii of tb«
ittbflUncvs 4n«1]r»rLt« wns nut i\mte purr.

With alcoholic potaah the salt forms nitrohenioate and bibnitiiocu^
bolate of potaah . "

H m ifltfoJuhJe m water ^ and sparingly soluble in hot i

NITHOBENZOATE OP BJNITROPHEHTL*

lU

Nitrobenzoate of Bimtrophenyl,
C^Nm^O'* ^ C^»X'H'0,C**XH*0\
tiiST & LiMPSTCHT. Ann, Pkarm. 90, 200.
NUrohen^cmit t^f BmUr^earb^Uc acid.

Formation and Preparation. When finelj pulverised benzoate of
plhenyl is gradually tMided to a mixture of 1 pt. nitric acid and 2 pts. oil
T vitrioU it dii?fiolve« without evolution of red vapours, and if tbe acid
I in large cx^esa, the liquid remaiua perfectly cimr, but when gradual Ij
psmred into cold water, deposits a bulky yellow ieh precipitate. When a
eonsideiable quantity of btjuzoate of phenyl is added to the acid mixture,
the liquid becotnes suddenly minted with small crystals; and, if these
are drained on a funnel stopped with asbestos, the fi It rate still yields a
limilar precipitate on heini; ruixod with water. The crystaU, or the mass
preeipitaied by water^ are washed with water as long as that liquid
oontiauea to take up acid, and afterwards with alcohoL

Fmpertiss. White inodorous, more or less crystalline powder Be-
comes warm when heated, melts at 150° and solidities into a yellow trans*
parent glass, which becomes opaque after some time, or more quickly if
Wt«d^ or by contact with a sharp body. It may be sublimed in a
eurreut of air, without previous ebullitioii.

lift St Limprickt.

26 C .„, 15fi .,. 46fi4 47'61

3N-. „„., 42 .... IS-ei

7H 7 ..» 2*10 %$7

16 O, 128 .... 5B4b

C»K^H70« .,» 3S3 .... 100 00

_Thc substance analysed perhaps contained ft portion of a coropownd coutaining
[ At- NQ'^ and bence the amount of carbon and hydrogen appears too large.

Demmpo&itw^nM, L Th« compound bums on platinum foil with a aooty

e, leaving a small quantity of eatlly Qombuatible charcoah When
isd in a tube, it creeps up the mU^ and explodes, — 2. Heated
with oil of vitriol, it yields nitroben^oic acid and binitrocarbolic acid. —
3. With alcoholic potai^h, it forma ujtrobenzoate and binitrocarbolate of
potAeL. — 4. h dissolvpB with deep red colour in hydrosulphate of am-
momaj and the solution evaporated over the water- bath leaves a dark
Tiolei-coloured r^ainone m&^ which dLs^olve^ with tlfte^ purpk coloufj
while sulphur remaina behind. The hydrochloric acid solution evapo-
mted over the water-bath, leaves deep blue nodular crystals which dia-
solve m water, forming a yeUow solution and leaving an indigo-coloured
powder. When the sulphuric acid eolation is boiled with excels of
oxalate of baryta or the hydrochloric acid solution with oxalate of silver,
the solution yields browni^^h yellow needlo-sliaped crystals^ which aro
-*bUined with leas colour by recrystnllisatiun from hot water,

134

BEf

[JCLEUS CWH*.

Sulphide of Nitrobenzylene.

Behtagnini. N. Ann. Ohm. Ph^s, 33, 473; Ann. Pharm, 7fl» 159*

When sulplmretted hydrogen is passed through an alcoholic solution
of nitrobetiKaldiJe, n whitish powder separates, whicb must b© digeiled
in lukewarm waterj then washed and dried in tUo air*

Grejish white, light pov^der^ whi<^h m^jlts into opaque drops ia boiltof
water* InodorouB in the cohl» but when rubbed between toe fingen it ^
imparts an offensive and persistent smell When boiled ^itU water, *
exhales vapours having an alliaceous odour.

14 C

N

6 H ,...

2 S

., B4 ..
.. U ..
.. 5 ..
. 32 ..
.. 32 ..

.. 60 29 .

.. 2*n *
.. iyi7 .
. nil .

Bertftgnmt.
....... 4936

. B'50

...... 3-37

19-45

4 0 ..

...... 18? 72

C"NH*3^* ..

.. 167 .

.. lOO'OO .

....... JOOOO

Decompontiom* 1. By gentle beating with i^tAm^ry nkrk aeid^
is converted into a half-fnsed tnmefied mass, which gives oflT abuniliii
of nitrons vaponrs and soon dissolves completely, with fortnaiion
sulphnric acid and nitrobenzaldide or nitrobeuzoio acid. With red
fuming tiitric acid, it becomes strongly heated, even to explosion whea
considerahlo q nan ti ties are need^ as the solution cools, drops of bittef
almond oil separnto from it^ mixed with a small quantity of a jellov
substance. — 2, When ammotiiacal ^^cm i^ passed over sulphide of iitlii^
benzylenej a large quantity of sulphuretted hydrogen escapes;^ evem ifl
the cold, and ternitrohydrohenzamide ifi formed; similarly with a^iiioif
or alcoholic ammonia.

Suljihide of nitrobenjiylone is insoluble in water. — It dinolm
without blackening in wann oil of vitrtftlf wheaoe it is precipitated hj
water. It does not dissolve in alcolioj, but cakes together when boiled
in it. It is insoluble in ether, but becomes tough and translucent when
faiineried in that liquid.

Binitroben^oic Acid.

jjtnotJiia. N.Ann. Ckim, Pkp*. S5> 30; also/, pr. Chgm. 40,
Ann. Pharm. 6&, 241.

IMnittiihtnMtik «eirf.

When a mixture of fmnbg nltHc acid and oil of vitriol ia lueatfJ t«
betwmn 50° and 00", and fused benzoic ^^vi ttdded by small portion*, »

BINITROBENZOIC ACID.

13S

stnftll qtianiiiy c^f gas b immediaielj piren off* and the benzoic acid
dL?ao]ires* After th© solution is complete, the liquid is goatlj warmed
for about an hour^ and as soon aa it begins to show turbidity ^ it is cooled
and mixed with water, the separated yellowish flakes washed with water
till the wasli-water no longer shows any acid reaetioii, then pressed
betweett paper and recrystallised from boiliug alcohol. If the heating
with nitroHulphuric acid has not been continued long enough, the product
must be again boiled with it, (Cahours.) According to Voit (Ami,
Flmrm. 99, 100} the mixture requires to be boiled for six hours, and the
oonverHioa is known to he complete by the liqaid ceasing to give ofT red
fumes: if the solution be then left to cool, the bin itroben zoic acid sepa*
rates almost completely in shining crystals; but if the boiling be longer
continued, vapours are given off which excite coughing, the liquid acquirea
a darker colour, and the acid which then separates on cooling is also
coloured.

The acid separates from its alcoholic solution by sudden cooling in
iridescent laminaj; by spontaneous evaporation from a dilute alcoholic
solution^ in short prisms having a strong lustre. It melts at a gentle
heatj and when cautiously heated sublimes without decomposition in
~ ielicate needles. (Cahoum.)

U C 84

2 N 28

4 H 4

12 0 -.,......„»... 96

C^WH*0" .,,. 212

Cahoun,

39fiG a9'52

13^34 13*37

1-86 2-02

45*22 43 09

iaO-00 100-00

iinitrobenzotc acid is converted by sulphuretted hydrogen into
hianiidobenzoic acid, C"Ad^H*0\ — Heated with aleobol and oil of
vitriol, it yields binitrobenzoote of ethyh (Voit.)

The acid dissolves %*ery spari ugly in cold, more abundantly in boiling
water ^ and the solution yields delicate needles ou cooling. (Cahours.)
Less soluble in water than nitrobenzoic acid. (Voit) Dissolves with-
out decomposition in oil ^f vilHol; at a higher temperature decomposition
takes pJace. — It dissolves abundantly in bot nitrk add and sepaTates
on cooling in hard shining crystals.

P Mmitrohenwate of Amwoniu, — The solution of ihe acid in aqucons
ammonia yields on evaporation slender needles which have a silky lustre
when dry. Dissolves readily in water, especially when hot.

14 C 64

3 N 42

7 H 7

12 0 %

D^X2Ha(NH^)0^ ... 229

Cabonrs.
36^G8 ........ S6-55

18-34 18^52

3'06 ._... 3-14
4192 41-79

100*00 ., 10000

The potmh and so*Ich$alts behave like the ammonia- salt. (Cahours.)
The acid dtesolres with red colour in carbonate of soda. (Voit.)

196 BEN^YLIHl: NITBO-NOCLKUS Cwx*H*.

BinUrobfnzoatf of Barfftu. — When the s<?jd is WIed wHh wslerftod
carbonate of baryta autl tbe liqnid filtered liot, the barjta salt ftcpantei
on cooling in yellowi&b crjsballine nodules.

C^<K«a>0" 2030 ... 72 63

BaO _ 70*6 .... 27'37 27*27

C"X'H»B*.0* .... 279-fi ... 100 Oa

Binitroheniofite of Ltad, obtaSoed bj double deoomfiosiiioft, i*

eparixigi/ soluble in w^ater.

BimtrvbenzoaU of Silver. — Obtained from the ammosivrffalt by double
deeoni position.

Cilioiin.

C'WHK>»* 2U 0 .. 6S15

Ag imn ... 33-B7 33'7&

C**X*H*AgO^ .... 31S'l „.. 100 00

Bmitrobenioio acid dieijolre^ Vfhh tolerable facility in cold
and Hh^r, eaeil/ ia tbe eamo lit^uida when bot. (CahoniB.)

Binitrobenzoate of Ethyl

CAnoTjRs. y, Ann. €him7Ph^9* 25^ 30; J, pr, Chem, 40, 341 1

Phurm. 69, 241,
Voir* Ann. Blmrm. 09, 105.

«

When abBolute alcohol is saturated with binitrobenisoic acid,
Qep&mtes which solidifies on cooling* and of which an additional qiianitty
IB precipitated by water. The product is waabed with water conUiDbl
am TO on i a, a n d c r v etal 1 i sed fro m h ot al coh ol . (Cab ou rs. } — B i ti i troben ioie
acid heated witt alcohol and oil of vitriol yields the ether in oily drop
which solidify on coolings and nmy be crystallised from hot alcohol
whence it separates in a magma of long silky needles. (Voit,)

Long, Blender needles, having a strong lustre aud scarcely
yellow coiottr.

It C lOfl „., 4500 ........ 44 74

2 N ».™ 29 ... J 1*67 ^. iVm

8 H a .... 3-33 3*4i

12 O _..,., m ... 4000 40-24

C»»N-H'0'^ .... 240 ... 100 00 10000

By strong poiath-t^ift especially when hot* it ia quickly dt
ftloohul and btnitrobeiiJEoic ftcid. — By digestioo for ieveraldiji

CHtORlBl OF NITROBENZOYL.

137

In afmhoHc amm&nia, the ether h converteil into hiniiri^b^nzamid^^
C^*X'^AdH\0*. — Snlp/iurH(fd %ffrw?m fmssed tK rough the hot ammo-
DJacal saktion of tba ether, converts it, with eeparation of silver, into
hiumidobenmic add C^*H*Ad^O*. — When the ether is digested with siilphid*! of
Kumonium, A hir^ quantity of Anlphur icpitrRteit, and the filtrate Icivea on eraporHtioii
|L cTjilaUiue maaa fvbich is prohablf bumidobenxamide. ^ Voit)

Anhydrous Nitrobenzoic Acid*
C»XH*0' = C"XH*0,Ol

Geroardt* N, Ann, Chlm, Php, 37, 321 ; Ann, Pharm. 87j 158,

^p 8 pts. of dry nitrobenzoate of soda are hented to 150^ wlik I pt, of

^^ttlorophogpboric acid, till the odour of chloride of benzoyl is no longer

perceptible. After waahing with cold water^ there remaina a white maas

nearly insoluble in boiling alcohol or ether, \tm fusible than Ditrobenxoio

I ^ftcid, but quickly converted into the ktter when washed*

^^^^H Anhydrou3 Benzo-nitrobanzoic Acid.

^Rerbardt. N, Ann. Chim. Ph^9, 37^ 321 j Ann, Phai-m. $7, 158,

BentQk NUrQbfnzo&Ut Bm%ff-nitr^hms&it Anhydride, BtnzQtttt qf NUr^heHZoyU

Niirubenzoate qf Bmsotft.

5 pts. of ehlonde of benzoyl are heated with 7 pts, of dry benaoate
of aoda, and the syrupy prod net j which crystallises on cool 111^% is heated
with a small quantity of water, w^asbed with carbonate of soda, and
dissolved iu hot alcohol, whence the anhydride separates in the crystalline
form on coo ling. It is more stable tbaa the preceding compounds

p

I

Chloronitr<hnucleu8 C'*CIXH*.

Chloride of NitrobenzoyL

C"CINH*0* = C^*G1XH*,0' [= C^*XH*0^C1],

Cahoubs. #. Ann, Chim, Ph}i%, 23, 339; also J. pr. Of^em. 45, 138
Bertagnihi, iV, Ann. Chim, Phys, 33, 465; also Ann. Phai^nt, 79, 259-

Chloromirobenzfiytf Vkhrurt de btn^otle nitrique.

ForJUfJiion and Preparattofu 1. Nitrobenzablide exposed to the
action of chlorine gas in sunshine is quickly converted into chloride of
nitrobenzfiyL {Bertagnini,) — 2* When nitrobenzoic acid ie gently
heated with pentachloride of pbosfibornfi, a violent action takes '^\'aJ:ft,
^d a yellowish liquid passes over into the receiver, IW Wtoi!^ ^vblV

138

BENZYLENE : CHLOBONITRO-NUCLBUS Ci*ClXH^.

of this distilUte rises from lOR"*} at wbich temperature cliloropliciipliom
aoid distils over, till it reaches 270^ The last portion is washetl witJi
cold water, dried ovor ciilorlde of calcium and reotiHed. (Cahoura.)

Froperim* Yellow,
between 265^" and ms°,
(Bertagnini,)

14 C

N .
4H

a

60

mobile liquid* heavier than water. 1
(Cabours,) Smells like chloride of b«i3i

i4*0 .... 45-25 .......* 45*0(r

140 ..„ 7-63 7*39

4-0 .... Zn ».. . 2-34

35-4 .... 19i>8 18-40

48^0 .... 25'8S ....»» 26-81

C'^NH^CTO* 185-4 . ,. 10000

100 00

DecompogUhnv^ 1 . Chloride of nitrobenzoyl is insoluble in water, Irat
is frradually et>u verted into nitrobenzoic acid by water or moiit air. —
2. Wben heated with potftih^ it is tjuicklj decomposed^ yielding cblan<*
of potassium and nitrobenxoato of pctaeh. — 3. With amfnxmiaeai
it becomes heated aud forms a white crystalline mass posseeaai^
properties of nitfobeniamide. (Cahours, Bertagoiui.) The same
tiori appears to lake place with aqueous ammonia. (Bartagnioi.) —
4. With u'ood'»pirifi it becomes heated and forma a solution which sooi
deposits cryatafa ot nitrobcuJtoate of methyl. (Bertagnini,) — It 4»*
solves with rise of temperature in strong almhol, aud tlie solntioii wlit9
evaporated yields, besides bydrochlorie acid, beautiful crystals of nitT»-
benzoate of ethyL (Bertagniui,) — 0. With aniline^ it rapidly erolrei
hydrochloric acid gag, and forms a solid mass which crjstallifes from
alcobol in shining needles and doubtlesa consists of nitrobenzatiiLide.
(Bertagnini.)

The compound dissolves without alteration inrfA^r,ereii at the bodiflf
pointy and remains iu drops when the ether evaporates.

fl* Chloronitrobenzoic Acid.
C^*C1NH*0» = C**C1XH\0*.

Li MmicHT k T. UatAE. Ann. Pkartru 102, 201,

Cblorobeutoic acid dissotres slowly ia foraing nitric acid, and ibf
solntiou if mixed wilh water after a few hours, does not yield iij
immediate precipitate, but continues for several days to de|xmt tfia^
parent colourless plates of chloronitrpbenzoic acid.

The crystals dissolve readily in alcobol and ether, and from tbe
etli«feal solution the acid crystallises in prisms. In water it melts when
wmrtntdy and diasotvos at the boiling heat, but does not separate ooi agaia
ou ooolin^. The dry acid melts at 11 8\

ChhrtmkrottnMQitif a/ Baryta. — C'*ClXH*BaO* + SAq. ~ Vm
mhthle, nodolaf crystals whicb give off G'4 im. (2 At.) water *l im\ *

BEKZAMIDE,

Al im\

0*£XNHH^ ,..„ 2*MJ-# ..„ 74^5

Ba 68-G .... 25-5

LimpHcht

25$

a<cixmBao*

269 0 ..„ imrd

CMortmUrohemmU of ^^^per. — C"ClXH*AgO*4- Aq? — :N'itmte of
gilver added to the eoneentrnted sohitian of the acid, throws down small
shining lamiuee, whkh do not blacken when the Uquld la boiled, and
dissolve pretty readilj in water,

LlntpHclit

#L T. Pslir,

Ci*aNH»Q» „, ...„„..,.„.

.. 200^4 ,

... 63-1

Ag... ,.

.. 108'I .

.. 34 1 .

33-W

HO.. .„.

. 9^0 .

.. 26

C»<ClXH*AgO< -h Aq ..

.. 317-5 .

.. 100 0

Chtoroniiroben^oaU of Mth^l, — ^ ChlorobenKoate of ethyl (p, 115)
djs8oIv€s in a mixture of 2 pis. oil of vitriol and 1 pt. strong nitric acid,
and the eolntion mixed with water after 2i hours, deposits an oil which
erystaliisea after a while and doubtless consists of chloronitrobenzoate of
ethyl. It dieaolveB in alcohol, and separates from in iolution in liu'ge,
Iran&parentj colourleefl cryetal@p (Limp rich t & t, yslar.) \^

Amidogen-nttcleus C"AdH*,

Beaz amide.

WoHLKB & LiEBia (1802,) Afui. Fknrm. 0, 268; &bn J^o^g. 26, 465.

WiNCKLEft. liepert. 48, 20(3.

FBHX.ING, Ann. Phfirm. 28, 48.

ScawAHZ. Ann. PImrm, 75, 135,

La If B^ EI* T. Rev. scitnlif, 16, 391,

DegsAiGisEs. ^^ Ann^ Chim. i%*. 34j 146; also Ann, Pharm. 82, 234;

also J.pr. CJiem, 55, 432.
Gerbahj>t k CmozzA* Gerh, TrattL 3, 268,

Formation. 1 - By heating anhydrous benzoic acid with ammonia.
(Gerhardt, p. 95) — 2. By the action of ammonia on bromide, chloride or
cyanide of benioyl. (Wohler ic Liebig.) By the action of ehlorido of |
benzoyl on carbonate of ammonia, (Gcrharnt.) — 3. Benioate of ethyl
in contact with aqueous ammonia forms benzamide, slowly at ordiDary
temperatures, more quickly at 100'' in a sealed tube, (Dumas, CompL
rend. 25, 734.) — ^4, By boiling hippuric acid with water and peroxide
of lead/ (Fehliog)

Preparation, — 1. Chloride of benzoyl absorbs dry ammoniacal ^
with very great rise of temperature, and bocotnea CQuv^tWi m^^ b^ thNi\\»

140

BEHZYLENE: AMU>OGfiK-HUCLEUS C"Ad^,

solid maj^ of saUammDtime and benmmide, which muet be repeitodlN
corn minuted^ ia order that none of the chloride of benzoyl wmj m'^
enclosed within it and go escape the aetiaD of liie attmiooia. Th^ mU
ammoniac is extracted by c<jld water and the henxsiniide crj^ijilli^
from lolling water. Under certain circunmtatice6r especiallj when tW
chloride of benzoyl contaias excess of cbloriue, there is forwiedf on satumt-
ing the lit|iiid with animunia.. an oily body having the odour of hitter
aluionds, which ini|»arta to the henzaiulde the prt^I^erty of iiielting into m
oil before didsol ving when heated with water, and separating a^ia fttm
the sol ution in oily drops whtch do nut solidify till after some time. If
the quantity of ammonia passed into the chloride of benzoyl is not gaffi*
cient to complete the rea^tion^ the benzaniide, when treated with water,
is decomposed by the hydrochloric acid resulting from the decomponitiQit
of the chloride of benzoyl. (Wbhbr & Liebig.) — 2, When an ak^
holic solution of chloride of Itensoyl is laia^ed with aqueous ammoma, s
copious crystalline precipitate ia somewhat quickly formed^ coo^istiug d
beuiamide, which may be purified by pressure and repeatcil crystaJlitt*
tioD. (Laurent)^ 3. Chloride of beuioyl is triturated with excess of
commercial carbonate of am in on ta; tho mixture gently heated aiid then
washed with uold water; and the residual henzamide crystallised from
boilinsf water or alcohol. (Gerhardu)

4. Hitter aliDond witter h distilled with hydrocbloHc add i Ibe diMilUte mind ittti
■trong hydrochloric Acid ; arid llie liquid evhponttd over the w*ti;r-bath. The ftmim
i» a thick oil, which* on roolingg iolidifiea into a i'Oft ciys^talluie iiisi« ; find ihis, wbi
exhausted with cisld ether and seirer«l titntrs WHshed, leavea m grejbh vbite rc«id«
whtch i» obuined pure by crystal Li uttbn ffom hot alcohol.— Ben jtaniid« ntaj ak» I
obtoioed froin the residue of tbe difltilbtioii of bitter almoDd water with (ijd
add. CWiQckter.)

5. Ilippuric acid is boiled with water and peroxide of Iead« luid tk
reBulting bippurate of lead dc-composcd from time to time by dilute vol-
(huric acid, avoiding an cxce!?s* Whew the evolution of carbonie bM
as ceaaedj and the oxide of lead still in excess remains unaltereil, tbi
solution is filtered hot; the Bltrate decanted from any bippuric acid thti
may crysUiUise out before cooling, and evaporatetl; the white ^maabr
residue disbolved in water; and th» eoljjtlon filtered from aay hip|taraffifi
that may he present; the filtrate then yields^ on cooling and furthr
evaiioration, indistinct crystals of benzamide* (Fehliug, Scliwmrm.)

Properties. When a hot ai(ueoug solution of benzamlde ia lelt to oool
slowly, the entire liquid soUdifici^ to a white mass eansisting of fine se^dki
having a j^ilky lustre. After a day or more, separate cavities fi>na b
L ihii um^f containing one or more hirge crj'stald into which Iboj
'modification ha* been converted. This transforaiation extt^nds _
through the eutire wb^. When the boiliag solution ia dowly
the Itenxamide separates in laminoe having a pearly lustre. (Vv<>hl«r <
Liebig.) ^ — The finest crystals are ob tamed from a sol ution iti
WDifiODla or potash; aucb a solution, when aufHcieutly conceotrmt-.
diiea on cotding in a mass of blender needlee^ which graduallT i
into large shining crystaU. The aqueous solution yields only ibm ]

{Seiiwmr«.)<^Tniu>(parent ripht rhombic prisms having n strong
Qatre; Ihe obliijuo lateral Cflge^ are truucated by a fa43e to wh
cleavage plane is pnrtillel, and on whicli thtj be veiling- faces MXm iet al
right anglcA. (Wohler k Liebig.) Liirgo oblique r^etatignlar taUt
(Fig. IBS), i : t = lOr aO'; i : HI = IIT; l is rectangular &nd ft^^
mijamtet; i aocf m mm very narrow, ^Laitt^tic'l Inoiiorotyi, Mihi ■!

I

■ BENZAMtnf. 141

115° (at 100^ actjorditij^ to Schwar^), forming a. traoaparent colourless
litjuid which on cuoling solidifies in » crystalliDe uims composed of large
lamioffl and frefjiicntly penetrated witb cavitiei enclosing well defined
crystals, (Wbliler ^ Liebig.) — Volatilises a little aho^^e its meltinij
point, (Schwar?,) May be distil le<l without alteraiioti and gives oiF
vapours having a faint odour of bitter almonds. (Wohler & Liobig.)
The contents of the retort turn bruwn during the diiatilliitioii. (Sdiwan,) Its tacte
t faintly bitter aad aromatic. (Schwarx.)

Wohler & Liebig. Fehliii|. Schwara,

UC , 84 .... 69*42 ,. 68*92 .... 6875 »» 69*19

N ..*...,.,.* 14 _ ll*5fi n*5G .... 1102 ..., 11-21

7 H 7 „„ 5^/8 ....... 57^ , .. 5-80 ,,., 6-OG

to _„...... 16 ». 13-24 ..».,.. 1373 .... 14-43 .... 13*54

(?*NHW .... 121 ... 100-00 100-00 .... 10000 .... 100*00

- NIFjC^^H^O* -= ammonia la which I At* H U replaced bj benzoyl,

Decompodtiom, 1. Ben^mide is rery inflammable and burns witb a
sooty flame, — 2. The srapoiirs paasod througli a narrow red-hot tube,
pass over for the most part undecompcised, and without deposition of
cbarcoai; but the lenzamide which pasaes over is mixed with a peculiar
oilj which m lighter than water, and insoluble therein^ has a sweetish
aromatic odoor and very sweet taste, burns with a bright flame, and i&
not decomposed by acid S| alkalis, or potaasium. (W{)hler k Liebig.) —
The vapours of benzamide passed through a tube filled with pumice-stone,
yield at a moderate boat, hydrogen, nitrogen, carbonic oxide aud benzol.
(Barreswil & Boudault, iV. J. Pluirm. 5^ 268.) — 3. Benzamide disaoives
In strong acidti at the boiling heat, and the solution on cooling deposits
CTjEtals of benzoic acidj the liquid retaining the ammonia-salt of the acid
employed. — 4, By the action of pentachiorUle of phmpkonu on benza-

fide, be n zon i t rile is p rod uced ( Cah o urs, Cmnp L rmd. '25,725);
C'^NH?03 + PC15 = C^^NB* + Pa«02 + 2HCI.

5, Benzamide boiled with a<|ueoui potash givea oW ammonia and forma
benzoate of potash. (Wohler & Liebig.} Dilute alkalies do not act on
benxamide even when heated with it. (Schwarjs.) — 6. Anhydrous
baryta heated with btnzamide, is brought into a kind of fuision, and
Mpears to be converted into hydrate; at the same time amnionia is
given off, together with the sweetish oU produced in (2). (Wbbler h
Liebig.) — 7. When benzamide is fuaed with ptitassium^ no amnion ia is
evolved, but cyanide of potassium is formed together with the sweetish
Qil just mentioned. (Wohler <k Lit^big.) ^ — The formation of cyanide of
potassium in this case is due to a secondary reaction, (DumHS, Mislaguti
& Leblanc^ Compt. rend. 25, 6C0.) — 8. When benzamide is boiled with
peroHde of had and sulphuric or hi/dtochlonc addf a colourless filtrate is
obtained which when mixed with ammonia and exposed to air^ turns
trow n an d deposi ts a mo u 1 d 11 k e e u bs tan ce . ( Sch w arz .) ^^^ W h en ben za -
mide is heated with 2 At. of benzoic anht/dnde, ben sole acid and beniio-
nitrile are pro^luced;

C'^NH^O^ + 2C^^H^O^ ^ 2C^*H^* + a*NH*.

10. Benzamide heated with chloride ofhtmo^l yields benzoic acid, benzo-
nitrile aud hydrochloric acid. (Gerhardt & Chiozza):

142 BBNZYLEKE : AMrDOGBN-NUCLEUS C»*AdH*.

Comhinaiiom, B^nzamide dissalvea very Bparingly In eoH, Iwit

Mmzamide wkh Brnmifu, — C-*AdH*0* + 2 Br. — ^Banmmide diasohei
in bromine withoat evotutloii of bydrobromlc aeid. Afler 14 dajs h
winter^ tbe liquid deposits rabj-coloured crystals which grwiaiJlj
give off bromiDo on eiposure to the air, and are deoom posed ilowlj
by water, immediately by amtnoaia, with separatioti of beniaoii^a
(Laurent)

Laureat.

CMNH70> 121 ,... 43 06

2 Br ......»„,»„ 160 .». 5G94 .... 6e*3

Ci^NlF0P,2Br 281 .... 100*00

Wkh H^drochhrk Acid. — BeuxamUle dissolree readily in
centi^teil bydroebloric acid, and the solution tin cooling deposits \m{
fi^^egateJ prions, which exhale hydrochloric acid on exposure to tlH
sir, aud give off the whole of that acid in a few days^ becoming opaque at
the aanie tirne^ After recent pressing between }>aper, they contain 20'4I
per cent, of bydrocblorie acid; (the form n la C"NH'0%HCI reqaifw
23rl7 per cent) i (De&daignes.)

The aqueous solution of benzamide dissolves small qnantttiea of oxide oli
eopper and oxide of silver. It dissolirea nter^urk omde in lar^e qmitititT»
and the fiat u rated solution solidifiea in a crystalline mass. If the matfl
coloured by excess of mercuric oxide be treated with hot alcohol, ilitj
iolution fiUered from the mercuric oxide yields on coolings white ihimii|
lamins&j which im^y be washcil and dried at 10U\ (De3adgtios.)

DmdffMftt
C^NB^O .„. 113 .... 50-91

HgO 158 ..» 43-09 .»„». 4fll

C^NHmgC 221 _ 100 00

Chloride of bemtoyi acts on this com po and with great Tiideaee^ #^
if artiBeially cooled, prodncmg ben sole acid, benzonitrite ntid chloridi
mercury, (Gerhurdt & Chios^a)/

C**NH*HgO* + 0^<H*CI03 = C^*H*0* + a^NH* + HgCI.

Beu&imide dissolves readily in atmhol aud in boiling ether^ whtnet it
separates in beautiful cryt^tals (Wuhler k Liebig,)

I

Amidobenioic Aeid.

Zmm. (IBiS.) J* pr, Chem. m, 103,

CiiAmmh. Compi. Tfttd, 28p 422.

Gkhlakei. Ami. Phnmi* Kfi, 143; 91, 185,

Vom Ann. Phatm, 88, 100; €hjm. Soc. Qu, J. 8» tOd*

AMIDOBENZOIC ACID.

143

Ifmsmtie Atidf Cartfanilie acid, — Gerknd sbuwcd in 1853 that nmittobeiiKolc
and carbaojlie acLda are tdeatical, but differ frotn anthraQilic acid wbicb ia isomeric
with tbcED. — ^^Tiie term benianiict generaJij iipplied to tbi* acidi is inappropriate,
betaQw it i» not really the amidogeu-Hcid of benziiic acid ; in factt it is only tbe radicali
of bifcjaaie acids that can form amidoeen acida properly ao-called (¥id. Gcrhardt.
Train, W, f"""'

Formation and Prepamtm}, a, {Amidohmzoic acid,)^\. When an
alcoholic; solution of uitrobanjEoic acid is saturated with ainiiionia atiil
aulpliuretted hydrogen and then boilod, tbo liquid acquires ati olive-
greeo colour, tlieu becKinics turbid and deposits a \tvtgQ quantity of eulphiir,
and ultimately becomes transparoot and of a yelbiw ct*loar. In order to
decompose tUe nitrobeiizojc acid coinpletolvj tUe liquid js decanted from
the sulpburj again mixed with the alcoholic hydrosulphate of ammuaia
which has been distilled off; unce more saturated with sulphuretted
hydrogen; and several times distilled. This series of operations is re-
pealed two or three times till no more aulphnr separates. The residual
alcoholic liquid \& mixed with water; boiled to expel completely the
alcohol and sulphuretted hydrogen ; then evaporated to a syrup and
0a persatu rated with strong aeetie acid, whereupon it solidinea to a
thick yellow pulp, which is left to dritin on a filter, pressed between
paper, iiried on a tile, dissolved in hot water^ decolorised by animal
charcoal, and filtered at the boiling heat (Zinin.) — 2. Gerland dis-
solves nitrobenzoic acid in excels of at|ueous ammonia, saturates with
sulphuretted hydrogen, and boile the liquidi keeping U all the while
exylnded as completely as possible from the air, and passing sulphuretted
hjdrogen through tt till that gas ia no longer absorbed. The solution
decanted from the separated sulphur and neiitrali.^ed with acetic aoid,
det>osit^ nearly colourless aniidobenzoic acid, which may easily be ob-
tained pure by repeated crystallisation from water, — ^ 3, Nitrobenxoio
acid is digested with iron filings and acetic acid, whereupon a brisk
act] cm takes place attended with rise of temperature; the mass is then
heated for some time over the water-bath, digested with aqueous
carbonate of aoda» and filtered ; the filtrate neutralised with acetic
acid, and precipitated with acetate of lead; the resulting precipitate
of aniidobenaoate of lead decomposed by sulphuretted hydrogen ;
and the acid obtained in the e ry a taMine state as above* Ferrous
acetate appears to exert upon nitro-acids in general tbe same reducing
action as hydrosulphate of ammoniai (Bouiletj Compt. remL 43 ^ 399;
see also Schiff, Ann. Pharm. 101, 94.)

6, (C^r&a/iii*ciidrf.) — Carbanilamide (li, 303) ia boiled with strong
potash -ley asi long as ammonia continues to escape. If the liquid be
then supersaturated with acetic acid, the carbauilic acid Grystalliaes out
on cooling, (Chancel.)

y Properties. Small whitd crystalline nodilles and spherules. Has a
mther eweet and sourish taste and reJdens litmus strongly, (Zinin.)
Orange-yellow needles. (Ghanc€L)^The acid prepared according to
a, I, is obtained in needles by evapoiuting its solution to dryness with
potash and precipitating the redis^olved salt with acetic acid, or by
heating its solution or that of one of its salts somewhat above 100 ,
The acid prepared according to 6, crystallises in nodules from the
ammoniacal solution after addition of acetic acid. By tbe procesa
a, 2, it is obtained in hard crystalline masses ot tTaraa^ax^Tit n^^^^^.
(GerlandJ

144

benzylenb: AMIDOGKS-NUCLEUS C"<.VJH».

14 C ....-

N

7 H

4 0 . ,...

... 84 .,
.. 14 .
.., 7 .
,., 32 .

.. 61-32 ..
.„ 10-22 .
„, 511 ..
... 23-35 ..

Zinin* ■

6106

.».. lO'Ol ,

5-13 4

23-80 ^

C^AdH'O* .

. 137 .

... lOO'OO ..

lOO-OO

BeefmtpontiotiSs 1. Amidobenxoic aeid in the state of golntiomj
i|uicklj Jeconi]>osey when exposed to the avr und yields a. brown reiinoa
eubatancse, (Ziu)n.) — 2. When heated, it meltaj givea off white irritat-l
ing vapours having the odour of benzoic aci-l, and leaves a balky easily
corabustlble charcoal; part of the acid sobliuies undocomposed. (Ziain.)
— 0. Carbanilic acid heated with ^pon^^y platinum is resolved loto auilino^
and carbonic acid. (Chancel) — -4. It is not attacked by ordinary niiricT^
acid at the boiling heat; in fmumg nitric acid it dissolves with blood-rod
colour^and on boiling reives off red vapours, the liquid turning yellow and
being afterwards no longer precipitated by water The liquid ncutmlLW with
unmonim forms with lead-svalts, itii ocbre-yellow precipitate, with oopijer-Stilts, n gfecn,
and with iiUcr*j<»U» » red-brow q predpitatc-. (Zinin.) Fumiug nitric acid 0011*
Terta atnidobenaoic acid into picric add. (Gerland.) — 5. When n*trom
acid is passed into an aqueous solution of anndobensEoic acid, nitro-
gen gas free from carbonic acid is evolved, and a red aniorphous pre-
cipitate funned, which becomes scarlet when dry, is insoluble ia
water and alcohol, cakes together in resinous lumps when boiled with
water^ but is dissolved with red colour by caustic alkalies or their car-
bonates, and reprecipitated In Ita ori^^inal state by acids. This precipi-
tate contains from 58-0 to 59^ per cent of carbon and from 3-9 to 3 4
per cent, of hydrogen* lt« solution in ammonia forma with acetate ol
lead, eulpbate of copper and nitrate of silver, brown amorphous pecipj-
tates; the lead^compound contains from 38 to 4S> per cent, of lead-ox:ide^
the silver compound^ from 41 B to 51 vi of silvernixide. — The red pi
cipitate dissolves in strong acids and is precipitate<l without alte na-
tion by water, ^ — If the action of the nitrous acid l^e longer continued,
ooinptete solution takes place; and the red brown liquid^ which has an
uupfeuant, Bomewhat bltttr taste, yields after being evapoi-atefl to a
syrup, crystals of oxybenzuic aci<l (C^*H*0*) having a fine yellow colour.
(Oerland.) — 6. AmidoWnzoic acid forms with cold oU ff tnfrityl a
cobmrless solution, which turns yfdiow when heated, is decolorised by
addition of water, and when neutralised, yields with cupric salts a pr*>et-
pitate having the green colour of malachite. (Zinin*) — With oil of
vitriol it forms »ulphanilic acid. (Chancel, Gerland.) — 7. Amido-
l>enzoic acid boiled with water and per^Jf of man^ftneMe is converted
into benzoic acid* The liquid acquires an intense rod colour and gives
off nitrogen gas together with traces of carbonic acid : and if, after
sovomi days boiling, the colouring matter be precipitated by acetate ol^
]eftd, the mtered s(>iution deposits on cooling crystals of benioi.to of le.n^B
A aimilar action but nmcb more rapid Is produced by pfrmaM^nai9 ^^
^Mituth, (Gerland,) — H, A miittare of ehrmnaie of pnkuh and miphmru
acid acU with gr^t violence on amidoljenioic acid ; the evolved gas«
certain carlmnic acid. (Gerland) — 9. Hot aqueous wmidobenioic avi
absorbs <M<^rine fjas in large quantity, and tbe soluratcd liquid cimtDio
bydr^ichloric acid and benzoic acid. Amidobenioio acid dis^dved '
alcohol is converted by chlorine intft a black resinoua substance wUieb If
/itsolabh In water, diBsolvca with 'leep violet colour in alcohol, and foriM
Mparlagly mluhle saline compounds v\i\i tv^elaWk otlv^^^. (^Zinin )

i

AMIDOBENZOIC ACIDt

145

Aniidobenioic acid diasoliroa eparingly m coldj abun-

v'jiter* (Ziiiin,)

!(dobenzoic acid. -^ Dry amidobensoic acid diBSolves

heat in oil of Yitriol, aud forma a colourless liquid

h.ni to tho boiling point without decornposiug, and ou

II maijs considtiiig of need lea having a diauiond lustre;

illiaation from bot water or alcobol^ the compound

rol our less* It remains unaltered in contact with tbe

n has an intensely sweet taste. (Gerland.)

c ..,.. ,.».

_„. 84 ,.

,. 41-2 ..,.
.. fi'8 ...
.. 4-9 ...
.. 7*9 »..
, 39 2 ,

GerUtid,

N ..,,„,«*

H , »

S ,,._..,

.„„.,. 14 ..

10 ..

16 ..

...„..., 80 „

.... %b
... 4-9
.... 8'3

0

.... SBO

NmO^.SO^H + 2Aq .... 204 .... 100 0 .„.»., 1000

rat^r tt la gradnally reaolred into sulphuric and amidoben-
Witb bases it yields a sulphate and an amtdobenzoate.

* of Amidohensolc tmd. — Amidobenzoic acid dissolves in heated
' without evolution of gsm ; and on cooling, the compound
in small crjstallioo icales. The excess of nitric acid is e vapo-
ur the water bath and the residue repeatedly crystallised from
riiin lam in 10 permanent in the air, and easily soluble in water

■hoL The aqut.'oai3 solution gives with sulphuno acid and proto^

« of iroiij the reaction of nitric acid.

14 C

2N..„.. ,....

. 38 ,
. 80 .

.. 42 ,..
.. 14
.. 4 .„
. 40

Gerland.
417

8 H

10 0 ,.

.... 43

C^^NH-OSN0*H...

. 200 .

.. 100

lydfQchloratf, — On adding strong hydrochloric acid to the liquid

ined by treating nitrobenicoic acid with sulphide of ammomum, after

Saa been decanted from the precipitated aalphur and evaporated,

^Ifwjhlomte of amidobenzoic acid separates in needles united in

Jular groups* (Voit)^ — With bichloride of platinum it fomis the

laiinum^salt C'*NH'OSHCl,PtCR (Cahours, Amu Fhanti. 103, 88.)

AmidobenzoiG acid expels carbonic acid from its compounds. The

" iGbtntmih are for the most part soluble in water, and crystallisable.

amidoben;eoates of the alkalis heated with hydrate of potash or

mcj give off carbonic acid and aniline (^Chancel), and a large qnantity

' ammonia, (Gerland )

^. Amidobanoate of Soda. C^*AdH*XaO*. — The hot aqueous solution

* of the b^ry la-salt is precipitated by an equivalent quantity of sulphate

* of soda; tbe filtrate evaporated nearly to dryness; the residue mixed

* with alcohol; and I ho resulting white crystalline magma pressed between
paper and dried at 100^ When examined by the niicrosoope it appears

I Uj consist of needle-shaped crystals. (Voit.)

^L xou xn, li M

14fi

BEl^ZYLENE : AMIDOGIW-NUCLECS C'*AdH*,

Voit,

D*NH«0» 128

N*0 „.,.... 31

80-45

CJ*NH*NmO* ... 159

IDO'OO

Amidohei^oai€ of B(%ryta^ C**AdH*BaO*- — The aqaeoos eolntioii cl"
hjdrochlorate of araidobeazoic add \h digested with carbonate of Wjift
tnj the add reactioD diaappeara^ and the bot-SUered liquid \% eTap4»ral«d
ov^ertbe water-bath; it iheCj at a certain degree of eoncen t ratio n, aepcmti
large pale reddish prism si, which cannot l>e completely decolorisetl evco
by repeated crjstalli nation, but nevertbelesa yield a perfectly whit^
powder, (Voit.J

At 100-.

Toit,

uc ». «,

84-0 „.

. 41-07 ..

.... 41-12

N

14 0 „

. 2^93 ....

.... 3 51

6 H „.

60 „

.. 3350 ....

„„ 3^20

B»

68^5 ,.

6-04

4 0 ..,...,.

320 ..

.. 15^66

cmmj^o'

204-5 .,

. 100 00

Amidobmtoaie (tf StrmtUi* —C^^AdlVSrO*-^ 2 Aq.-^ The am^jm
Bolntion of the baryta-salt b precipitated with sulphuric acid; tlie nltni^
niixed with a sujncient quantity of liydrat€ of etrontia to prodaoe »
ilight alkaline reaction^ and evaporated. It then yields pHsmatie crf»-
tati which hare a faint reddish ci^lour^ but may bo dtjcolorised by rc^iyv-
talliaation from alcohoL They give off 8*78 p.c< (2 At.) water at lOfTt
and are ^sily soluble in water, sparjQgly m atoobol. (Yoili)

C»*NH«0«

SrO

^lor,

.., 52 .

... n-u

... 28^89 ....

VoiL
28-58

C"NH*SrCF ..

180 .

... 100-00

Ami<Joh(mtoaU of Limt. C^AdHM^aO*, — When hrdf^ebtofmlo
amidobonfoie acid h boiled with milk of lime and tbe filtrat* evap
the eonceiitrated liquid yietds delioato i%bite needles which tarn rf4
exposure to the air. They are purified by repeated crystaUimtiOB
hot alcohol, and pressure betwoen paper. (Voit.)

C*NH*0* ..„..„,^.«. W „^ 82*05

C*0 28 .... 1? 95 .... 17 61

C'*NH*C«0*;.... ., 156 ,, 100 00 ^

Amid^hmma^ o/ Magnesia. C^AdH'MgO<-K7Aq,™ Ofcfaimtil fcy
iMOilpOtfiiig the hfirylaftalt with enlpbale of nmguesia. hmig% tnuit*
Bnlr tiK-ftided prieniB with oblique truncated facea. After drviiyronr
iurie acid ihey give off 21* 36 p. c. (7 At- ) water at 100^

tMIDOBlNZOAtB OP MBTHTt.

147

C»NH«03
MgO ........

At 100".

128-0 „..

20'7 ....

s&-o$

1392

Volt.
13 54

C"NH«MgO' 148-7 .,., 100-00

The ga.lt deeompoaes rapidly wlien exposed to tbc air. (Voit) %.

Whh proto^idf oflead^ amidobenaoio acid forma three ealts; (a.) Pul-
Teruleot, insoluble in wat€^r; {b.) Sparingly soluble needka; (c) Sbining
needles which dissolve with greater facility.

Tbe copper-sdlt has tbc colour of malachite^ is insoluble in water and
aJeohalj bttt dissolves readily in the stronger acida.

Amidobenzoats af Silver, — Amidohenzoate of ammonia forms with
nitrate of silver a white curdy precipitate which soon becomes crystal-
line. It diesolTes in alcohol and ether more readily than in water,
aBsumea a bine- violet tin^e when initnersed in lotling water, but does not
diMolre (Zinin); it dissolves pretty readily in hot water, and crystal liaee
on cooling in somewhat elongated scales^ (Chancel.)

r The salt decomposes when heated above 1 00° (ChanceK) It blackens

' when heated, melts, swells np, gives off irritating vapours, and leaves

a carbonaceous residue which easily barns away to metallic silver.

(Zinin.)

uc ................^

.. 84-0 .
» 14-0 .
.„ 60 .
.. lOS'l .
.. 320 .

.. 34*41 ...
.. 5-73
.. 246

., 44-28 ...
.. 1312

ChanceL
.... 34^6

N

6 H ,-

2-59

.^:::;:::;;::;::

.... 44-11

C"AdH*AgO* .

.« 2441 .

... 100-00

i

Benzimic Acid<

LAiTREirr^ Compt. meru. 1, 37.

When An alcoholic foliition of bitter almand oil gaturat^d with ammonia, is tnlied
I with water fcfter atanding for 48 houns, the water takes tip benrimale of aamionia. On

d«euitiii| the Uqnid and tieutr^Hsing with hydrochloric add, beoKtmic aeid e^paratea on
I eootingt in beautiful, slender whitt silkj aeediea, whicb melt when beat^ and cannot be

diatHled without decoiKipoaitton.

^m Amidobenzoate of Methyl,

Chahcbl. C&mpL rend, 30,751,

, CarbaniimetkytaHK

^P Prodnoed by treating nitrobeij;5oate of ethyl with hydrosnlphate of
ammonia. Its properties are similar to thoae of amidobcnaoate of
ethjh

1 L_

1*8

BBNZYLENK: AMIDOG EN-NUCLEUS C«AilH*,

Amidobenzoate of EthyL

CeANCEL. Comjd. vend. BQ, 75),

B^nzamale qf Elktft, Senzaminvineaier, Ether carbaniU^Uf de taie&kid, 0^»

When a. ematl quantity of hydrosulpbate of ammonia ia add^ to an
alcoholic solution of nitrobonzoate of ethyl, a copious precipitallon of
anlphur takes place; and on adding^ water to the Irquld, after it bad h^m
hoatod to complete the decompositiowj amidobenzoate of etfajl le piwi-
pitated In the form of a eolourless oil, which may be purified by repeatd
solution in alcohol and precipitation by water. (Chanoeh) The «am«
reduction may be effected with metallic iron and acetic acid* (Scbtf,
Ann. Pharm. 99, 118.)

The alcoholic eolation treated with potaah yields amidobeaioKli of
potaeh.

Thiobanz^nide.

Cahours. Comjd, rend. 27, 3^9; alao /, pr. Chem, 43, 354.

Wtien a eolation of bentonitrile in slightly ammonia^^ aloc^bo) if
taturated with sylphnretted hydrogen, the liqnicf soon attsumee a browiyi
yellow colour; and if» after some hourSf it be boiled down to j^ and mxxfA
with water, it deposits yellow flakes, which disaolve in boiling wmter sail

crystaUii^ on cooling in long sulphur-yellow needles baring a ailkjf ]

14 C »......, §4

N_ „„ 14

? H 7

tS 32

C**NH'S» 137

61'30 „ 6l'2f

10*2t 10*54

fill 613

23 3; ...... 23*51

10000

100 iK)

H* Triben2ylamine<
C«NH*' ^ C"Ad(C»*H7H*,H^

CAlf!(lZZABO, Cimento, 3. 397-

When chloride of benseoyl, C^^H'Cli and alcoholic atniQODia ar^ beat«d
together in a scaled tube to 100""^ ammoniacal gas pn^oed into tho liqii
after cooling, the resulting precipitate exhausted with etlier, mx * ''
ethereal solution left to evapomte, tribenxylamino [(C^lfyj
oht&iued in shining lamimie, which melt at 91-3^ to a colourl^u 1

rAMTDOBBTfZOTC ACID.

149

and at 360** are 'partly ^^olatilieed, partly deeompoMil, The compound
m alkaline and forms with k^droeMork add a salt which is sparingly
aoluble in cold water, more soluble In boiling water, and crystaliises from
the solution in needles. The solution of this salt mixed wjtb bichloride
of platiauni, forms cAhroplatinaU of tribaniflamine C^*H^^N,HCl,PtCl%
which crystallises in orunge-coloured needles.

Triben^ylamine dissolves sparingly in cold ufaier and alcohol, more
re&dily in bet ling aleobot^ and still more in ctkei\ The aolutions have an
alkaline reaction.

If Amidogm-7tudtm C"Ad»H*.

Biamidobenzoio Acid.
C»NH'0* = C**Ad»HSO\

VoFT, Ann. Fharm. 99, 106 j Chem. Soc. Qu. J, 9^ 2T1.

^rmation and Prtpuration. By the action of hydroaulphate of
ammonia on biDitrobensoic acid (p«. 135). Sulphuretted hydrogen ia
pas^d for some time throngh a hot amnioniacal solution of binitro benzoic
&crd; the solution filtered from sulphur, evaporated over the water-bath,
supersaturated with hydrochloric acid and filtered hot; the crystals of
hydrochlomte of biamidobeozoic acid which separate on cooling, con-
Ferted into sulphate by digestion in sulpbnric acid; and the sulphate
deeom posed by carbonate of baryta. The filtrate, which contaios the
free bianiidoben^oie acid, is then evaporated, first over the water- bath
and then over oil of TitrioL

Propertiei. Small greenieb aoiiininateil crfstale, tasteless and with-
out action on vegetable t^loura; they melt and blacken at about 1B^°,
and cannot be sublimed,

Decomposiiw'm. BiamidubeiiKoic acid heated to 100'' In a sealed tube
with iodide of ethyl, becomes solid; but on adding hydrocblorio acid to
tbe aqueous solution of the solid massj white needles are obtained con-
sist ing merely of hydrochlorate of biamidobenzoic acid; no biamidoben-
loic ether appears to be formed, — Nitrous acid vapour passed for several
days iuto a hot aqueous solution tof biamidobanzoic acid, forms a red
resinous, uncry stall isable mass, which has not been further examined.

■ Ccmhinations. The acid disaolves readily in «Nifer, — Though called
an acid, it exhibtls rather basic than acid properties; for it does not
oombine with bases, but forms crys tall isable comi>ounds with acids. It
will be observed that amidobenzoLC acid, formed from benzoic acid by the
fiubstitution of 1 At- N H^ for H, exhibits basio as well as acid properties,
while in biamidobenzoic acid, in which 2H are thus replaced by 2 At NH*,
the basic character is still more marked,

f Svdpki^ of Biumidobenmk acid. — Wheu the hydrochlorate is dis-
solved in dilute sulphuric acid and the solution concentrated, brownish
tables and lamiuie are deposited, which may be obtained nearly ^l^utW^

«n1pbur takes place; and on adding water to the liquid, :
heated to complete the decomposition, aniidobeoxoate o
pitated in the form of a colourless oil, which may be pur
Bolution in alcohol and precipitation by water, (Chan
redqction may he effected with metallic iron and aceti
Ann. Pharm, 99, 118.)

The alcohol ic eolatton treated irlth pot^ish pelds \
potash*

Thiobenzamide.

C^*NH^S» = C^*AdH»,SV
CAiiouRa C^mpt rend. 27, 329; also /. pr, Chem. 43, 1

Wlien a solution of benJEonitrile in sHghtlj atniti
saturated with sulphuretted hydrogen, the liquid soon &
yeltow colour; and if, after some hours, it he boiled do«
with water, it deposits yellow flakes, which diasotve id
crystallise on cooling in long sulphur-yellow needles h*

u c

g4 .,

... 61*30

... 10-22

», ftll

. 23-37

. 1

N ........

2S .......

14 ,

..., 7 ..
, .« 32

C^^NH^S* ..

- 137 .,

.. 100 00

««^^

150

VZTLENE: AMID06EN-NUCLEUS C»A«PH«*

by oryatalliaattoti horn alcc^oK They 4i^f^v^ reaidily tn wa<fr, wm^
what less in alcr^lio); the solutlQti» decompcj@o verj easily, aad appear
broirnish yellow by trans raittedj grass -green by mdeoted lights

U C „ 84 .. 33*G0 ..» 34*aS ... SS^i^

10 H 10 _ vm 4-65 _ 4*^5

2N.„„..„_„. 2p .... ii'?p iy%^ ... la-si

eO .., ^.... 4S ... 19-20 17'4B _, 17*90

2 50" ..,. 80 ... 32-00 32-25 „. 326$

0*Ad5fH*0\2SCMH,.. 250 ... 100 00 10000 . . 100*00

H^drochioraU* — The impure eompDund prepared in tlie maaoirr
already described may be purilied by dbsolvjog jt in a email qDaiilHT of
water and adding strong hydrochloric acid, whereupon either w\jte
needles are immediately deposited, or a floccnlent precipitate is fortfi«d
which afterwards changes to the same needles: if these are Dot qmSe
pure, the op ration must be repeated. — The compoaad dj^siolree w^
easily in water, alcohol and ether; tlie aqueous eolution deeompo«^ on
expoeuro to the air, depoaitiiig black flocks. The dry coiu pound melti
when heated, then decomposes, and yields n ^u^bUjDate of i^al-^Linmonkc.

Ci<N5H»0< 152-0 ... 67-7$

2HCL. ....... 72*4 .... 32*24 31'8a

CWAd«a^O*,2HCl 224-4 .... 100 00

Tb© Milt for aDaJjsis was preised between paper and dried, ftrrt Otct oil of i
then At 60%

Chloroplatinate, C"Ad^H*0*,2HCl,PtCi«. — The aqaeowi M>liitlf4i <

the hjfdrochlorate is not precipitated by bichloride of platinam, erift i

addition of alcohol and ether; but the mixture, when left to evaponlf
OTer oil of vitriol, depoeitfi brown crusts which yiehl a greyish whiti
powder, and when ignited leave 2 48 p*c. platinum, agreeing nflarlj
with the above fonnnk, which requtrei 25 01 p. c.

NUraU^ — Obtained by deconipoBing the sulphate with nitimte of
bftryta; acparatcs in dark^coloured crystals*

Acetatt, — prepared by precipitating the sulphate with aeeAftte d
baryta. Tlu^ iolutiun deeompost-d durmg evaporatioD and depoiited « brown powder^
but hr further eTappratiDii^ th<! Altc-ird lipuidp browmHh priEiii> wtre obtaiiijetd.

Oxiilate^ — Brown needles, obtained by eyaporating the doloUoo of
the hydrochlorate with oxalic acid.

Sulphobenzamide.
C«5'H"^»0" = C'*Ad*H*,2S0'.

LutrmienT k 7, Uslab. Ann^ Pharm, 102^ 259,

CHLOROBENZAMIM-

ISl

Produced hj tbe action of amrooziift on eiiloroauJpliobenEmc aold
(p. 118).

D*H*S=0«.CT + 2NBP = C"H'S5o*^N^H* + 2HC1,

Strong aqueous ammonia, ia added by email porttoDa to cbloro&ulpho-
benzoic acid, till ao farther evolution of heat can be observed; the pre-
cipitate washed with a small quantity of cold water to remove eal-
ammoniacj and the reeidual amide purified by crjsta-1 ligation from hot
alcohol, with addition of animal charcoal. If the precipitate be pre-
vioiiAly dried and absolute alcohol bo used to dissolve it, the ciyatala
obtained are perfectly anhj^droua; but if hydrated alcohol is used, the
crystals which separate consist partly of the anhydrous amide and partly
of a hydrate containing 2 At* water.

Anhydrous sulpha ben zamide forms small ciystals haying a glassy
lustre; the hydrate crystallises jb small needlesi which ^ave off from
7*8 to 8*9 p. c- (2 At*) water at 100"*, but not over oil of vitriol at ordi-
narf temperatures. Tho amide melts at 170^, remains soft for a long
time after cooling, and ultimately aolldifies in a vitreous fissured mas«*
It remains unaltered at 230*^, and exhibits hut slight decomposition
between 270^ and 290"^, Even when it is kept for a long dfue at that temperature,
DO sulpboben^amide appcara to form; itideed the only well diaracteiriied itib*t«,i]o«
found in the fesldue was iyJpboben^oamide ittelf.

Anh^dr^ns*

Limpridit

& V, Uakr,

14 C 84

2 N 2B

8 H 8

2 S 32

6 O .♦... 48

.... 42 ...
.... 14 ...
... 4 ...
.... 16 ...
.... 24 ...

42-3

..... 14-2
..... 4 5
..... 16 3
22-7

CHj^H^SW ....,„. 200

.... 100 ...

...... 100 a

Hydroicds

Limpriclit

14 C ».... 84

fi N 28

1^ H le

2 8 ..*.. 32

.... 38-5
.... li'%
,... 4fl
... 147
.... 29 4

3^e

12*5

5-1

8 0 64

Th6

CUN^HSS^O" + 2Aq,... 21B .... 100*0
compound m&j be regarded ai

fH')",C**H^{S=^)0^ or nitride of aulphobeojoyl and hydro|«n ^ N^j Ht

waier^

Sulphobeoxamide is nearly insoluble in cold, but easily soluble m hoi
er; in ©old tdct^Ql it dissolves sparinglyj in hot alcohol readily,

^, Afnidochloro-nucUm C"ClAdH*.

CMorobenzaraide.
C'*NH»C10» = e*ClAdH*,0*,

LiMFRiCHT & T. UsLAR. Anu, Fkorm, 102^ MZ^

152 BENZYIiENE I AiUDONlTRO-NUCLKUS C»*AdXtl*,

Chloride of chlorobenEojl (p. 11 (J) disaclvea with grest erolutioii <>f
beat iu concetitratHeil aqueous ammonia, and the {solution depoiit* yellow
laniumted crystals of chlorobenzamide which naay be purified by recryi-
tailisation from hot water or alcohol. They melt at 122°, and Bublime h
email quantity at the same temperature.

Limpricht & t. U«Ur*

UC ..». 84-0 ..» 53 8 54*5

N U-O ... to - 8 7

6H„, ..._ 60 »» 3 9 ...... 4*4

CI 35-4 ... 23*0

2 0 . 16-0 .... 10 3

C"NH«C10> ,..p 145-4 .... 100 0

Ci*H*ClO»

Nitride of cblorobenioyl and bjdrogcn Ni U

Chlorobenzamide is sparingly soluble in oold wwifer, bat diitolfii
xeadily in hot water and ia ak<M. (Limpricht ^ v. Uelar.) ^ -

Nitrobenzamide,

JlELD. Ann. Pharm. 85^ 54,

CflA^CEL* CompL chim. ] 849, 180] J. pr. Chtm. 47, 1#S.

Formatian and Preparation . 1 , Nitrobenzoate of animonU kept
iome time id the state of fusion, yields a substance which ia innolubk \n \
€old water, bnt may be recryetalliaed from hot water. (Field.) — '^^

preparstioii !■ not ill ways eiiocesifulr ns iUe nitroben^qate of aenmonui toinftiaM
cxplodft*, (Field.) — 2. Njtrobcn^oato of ethyl is disfiolved m * fllte
large quantity of akobol, ihe ^otuilon mixed with as much «^it#oai
ammouia as can ho added without precipitating the ether, &nd tlii
mixture left to etand in cJo«e vessela (for 8 or lO days at a geutle heat,
for a longer time at ordinary temperatures) tilt a sample of the liquid no
longer becomes turbid on addition of water. The liouid is then evapa*
rai&d over the water-bath till it erystalliijes on cooling, and the oitit»-
benmmide is obtained pure by two or thre« crystal Illations from % tnix^
tuio of ether and alcohoL (Chancel.) \

Propertiei. Nitrobeniamide crystallises from water in yellow ueedlei
(Fitld); by evaporation from solution in wood -spirit, alcohol or #t^eft i.1
long needles, or by very slow evaporation In tabular crystals reeemblii|
gjpfltttD, derived from a rhombic prism. It melts at a tenipcrriture abovt|
100% mid solidifies in the crystalline form on eoollng. (Chancel.)

14 C.^ ,.,-. 94 .,.. &0-60

2N..« ..*...« BB _ 16 Bf

i B»„...,....«.™ fi »... 3 ei

go ^...> 49 „„ 28*0a

c'*N^H cp _... leo 100 00

FkLd.
5039

ChMOaL

AO'fta

li'ft

3-98 .... S*7S

2&8d

lOO'OO

mkitrobbnzaMtbe.

k

Dtcovnposiimig. L Nitrobenzamido heated iFith aquaons potash
forms nitrogen z«ate of potash. (ChanceL) — 2. The aloohalic soliition
is dccompoaed bj hydroaulphate of ammonia in a very complicated
maonerj but the a(|ueoua aolation yields sulphur and MiiiiaQ-QrBa*
(iaomeric with carhamlamUk, O^WWO^) .

C^N^HW + 6HS = CJ^NSH^OS + 4HO + m (Chamsel.)

Nitrobenzaniid© dissolves sparingly in cold, easily in hot wa'er;
easily in wood-spiritj alcohol or ether. (Chancel,)

^ Amidmitro-nudeuM C**AdX-H",

Bmitrobeii2aimde,

VoTT, Ann. PJiarm. 99, 105.

r VoTT, A n

^f Btnjtrobertzoate of ethyl (p. 130) digested for ieTeral day« with
' Hilcobolic ammonia, dissolves and forms a blood-red liquid which after
I concentration, deposits binitroben^saniide in prisms and lamiDDe harlog a
faint yellowish colour and fatty lustre.

The compound dissolves sparingly in eold, more readily in hot watetj
forming a solution which has a bitter taste and is neutral to vegetable
colours. It melts at )83^, and decontposes at a higher temperature
without subliming. The ammoniacal solution does not precipitate
nitrate of silrer.

Voit.

14 C ». 84 .... 3S-81 40-B7

tSH..^ 6 ...* 2 3? 2'S8

N .„,. 14 ..., 6-63 ,, 6 90

2 NO* 92 ..„ 43*60

2 O 16 ... 7-59

auaxm^os 2u ..„ loooo

May be regarded as nitride of binitmhofizo^l and k^drogai=-

N H %

I H

" * The nB4M« anfliDe-orai doei not, atrietly spcftking belong to the wmpound
C**N*HPO'* dcicribed Mt page 303, fol. it, ioAimuch aa that compouiid doe* not com-
bioe with acidf j where*a tlie Lioufnc body produced by tbe nction of h^rdrosulphate of
ttmmoTiia od nitrobtnKamide, docs combTtitf with add», and may be rtfarded Hi urea in
wMch 1 At. H i> replaced by pherayl [C'^N'H'OJ^ - C^N^(C'^H^)H>02J. (Ch«ici3h
CffmpL chim. 1849, 1112.)

IH

BBNZTLENE: CONJUGATED AMIDES,

Confu^ated Amides G/the B€myltm Serim.

Benzoyl-nrea.
C'*N*H*0* ^ C'Ad(N.H,Ci*HH>'),0\

Zraiw. (1854.) Bidkt. Pdmb. 12, 291,

Bmmylknmatqft Benzurnd.

Fortn^iofu By heating otilorlde of beosoy] with ur^ :

C'Ad(NH»)(P + C^H'O^Xl = C*AdCNH,C>*H*0*)0» + HCL

Freparatim. 6pts- (2 At.) of dry and pulvertBed area (the qaantiiy
not exceeding 12 to 1€ grammea) are heated with 7 pts, (1 At) rf
chloride of benzoyl in the oil-bath to 1 50 — 1 So""; the vessel remoTed fro«
the hath as eoon as the urea is completely melted, and the mixture wi?!!
stirred, whereupon it becomes hoJ, and coagulates into a soft kneA<Ubk
mwsSf which may he rubbed to small lumpa when the action is over, i^J
bwsomes tolerably hard when cold. The action i» not attended with anj Aiiliiii
of veight. — If tlie tempemlttre rbei above 160°* a fdtit odour of b«nzociitrtle bot^ooa

perocptiWc On washing the maas with cold alcohol, which takes up hjdith

chloric acid and area [hydrochl orate of urea ? L.], benzoyl- urea re maim b
the form of a CTyetalUne powder, which may be recrystallised from boil'
ing alcohol.

Properties. ColonrlcBa, highly lustroua, long, thiji> four-aided^ ofteo

acuminated lamimi^ united in broad groups.

M C ..*,,

JN.

S H ™

... 28 ,.
... 9 ,,
.. 32 .

. no; ..

.. 1953 ...

less

.... 4-d7

4 O »« .,..

..... 1M7

CHN'H'W.,.

... 164 .

.. 100 00 .,..

10000

Melts at abont 200% and forms on cooling a cry^tftlline mamf wUib
more soluble in water than the origiuat substance and orygtalliflw is i
different form. When the heat is raised some degrees above the tneltiBf
point, the liqQtd begjoB to frotli, and suddenly becomes filled witJi loBf
whit© needles of cyauurio acid; from the cooled mass, alcohol e;
benxamide:

3C"K^H«0* :^ C*N»H»0« + aC'^NH'C^.

Benioyl-urea heated on platinum-foil melts, gires off an odour of
niirile, and volatilisos completely, the odour of cyanic neid 1mm
perceptible at the last, — It is decomposed when heated with miiriet^^^
and the nolution on cooling yields crystals of henxoic acid. — Bailed will
p<m$k-i^y, it gires off ammonia, and yields bouxoate and Oftrbooait of
potash.

It dissolves sparingly to ttmiert even at the boiling heat, more eMily
h^f «n.i rather atroiig hydt-ochioric'^ieid, and crystalliae* onl m lil

in hot aud

BEHEANILIDE.

155

origmsl state on eooling. It disaolvea readily in cold pot&sh-Uf/i and m
precipitated therefrom by acids with out alteration, even if the solution
has b^een gently heated. —- It is not attacked by ammonm, — It diaaolvei
in 100 part* of cold akokolj m 24 pta* of boiling alcohol^ and in Bmaller
I proportion in ether »

Benzanilide,
C"iNH"0' = C^*(N,H,C»H*)H',0^ or C^(NH,C»*HK)')H«,

IOekhardt. (1S45*) CompLre^d. 20, 1038; also N, Ann. CMm. Fhys.
14, 124; N. J. Fharm, B, QO.-^N. J* FUnn. Q, 412; abstr,
[ J. pr. ahem. 38^ 304,^iV. Ann. Ckim, Phyg. 37, 327; aUo Ann.
I Phtirm, STp 164.

Avfiare ie phi»yte_f de hetit^ilt tt

N

FormftHon and. Pri^aratian, When benzoic anhydride IB dissolved
Id heated aniline, a formation of wat^r is obfierved, A slight excess of
aniline m need, and the product is washed with water containing a little
hydrochloric acid, and crystallised from boiling alcohoL — 2. When
chloride of benzoyl which baa been rectified over chloride of oalcium ia
dropped upon aoiline, gr^at heat is evolved and a crystallino mass ia
produced. This mass is exhausted with boiling water, washed with
water slightly alkaline to remove any accidental traces of benzoic acid,
and crystalJiaed from alcohol. If tho crystals ar© still colouredj they
may be purified by careful distillation.

Pi-Qpertieis Ci^&tallises from the alcoholic solution by spon tan eons
evaporation in lamimc having a pearly lustre. Melts when heated, and
jielda on boiling a distillate which aolidifiea in the crystalline form aa
it cook

Gerhardt,

0)^

(2).

26 C ..,

)56

.,. ^9-1 9 .

_ 79-98

... 78^7

N

14

.... 7-11

n H

11

.... 5-58 ...

.... 5-63

.... 5*9

2 O

16

8-12

C*NH"02,...

197

.... lOQ'OO

N,C^^HSC»*H*CF,H - nitride of phenyl, beai&jl uid

hydrogicn] »

Decomposes when distilled at a strong heat, and yields an oil which

loes not solidify. — It is not attacked by boiling dilute acids. When

' aed with hydrate of potash, it gives ofi* aniline and yielda benioate of

otasU^

It is insoluble in wateTj but soluble in ak^^koL

IffS

INE : OOKJUGATE0 AMIDIS,

Bibeazaiiilide.
C^'I^H^W = C"(N.C^H*,C"H*0»)H*0»orC»(X.2C**H"0')H*

GHttifARDT & CHIOZZ4. (1653,) Compt rmd. 37, 90.— 4V, .^IjMt. CAi*.
Fhy9. 46, 137,

pkinyie ft dt benzoUe*

When benEamtde ii heated with cWoride of beaioyl to belirc«li 1«0*

and 180% bydrocbloric acid is evolved in large quantity:

The mass, which la liquid at first but solidifies on coolings is digiiiii J
with carbonate of eoda to remove the excess of chloride of bensoj^ mai ^
the residue is dissolved in boiling alcoboL The solution on eoolin^
depMits delicate shining needles, sometimes a^gregateil In ifTmndir
masses. The compound meJts at about 137^ and solidifies in a cry*ti^
line maas on cooling. At a higbet tetpperature, it sublitne* 10
tufts.

40 C ...., i40

N _„...« „ U

15 H „.. 15

4 O ...„„.„„_..„ 32

C^^HiK**.., 301

79 7 ., 79-7

46 ^.»,. 4'fi

5*0 ..,.„. 61

10-7 10-4

1000 1000

- N.C»*H*,(C>*H*0*j>, nitride of fyhrayl md bibeotorl.

PiMolTes sparingly in boiling umter^ and eeparates on oooltng !l
amall perfectly white needier. Ammonifi dissolTes it some what matt
readily, and deposits it in white Bakes on cooling. It dissolTea ettiJy ii
ftbeolttte akolm and in €th€r^

J

BenzosnlphophenMfude.
C"NH"^0* = C"(N.i^,C^'H*S^O*)H^O' or C*XN.H,C"H*CP)H'SV.

OEJtHARDT k Ceiozjsa. (1863). C<mpL rmd. 37, 1S8 ; M, i5?7 ;
Gerh. TmUi. 3, 75,— J^. Ann. Chim. Ph^fn, 46, 145.

Whon cbloride of bc^nsoyl tind sulpliophenEmide aro healei! log«tlrr
In equal uunibc^rs of atoms, hydrochloric acid ee4;ape« in l*r^ qottali^
at liO^'j and the mixture becomes perfectly fluid. The terapfimaN m
maintained between 140^ and 145"" as long as hydftK^blorio «a^ •awit^
and the liquid is poured into a basin, wher^ it solidifies in Cm fvp^Uliat
ctate on cooling^ this tolidiBcation being attended with oootid^mUB rin
of temperatufe. It is purii^ed by recrystaUisatioa from boilta|t i

BBNEOSULPHOPH EN AMIDE.

157

aftar liavm^ Ueen freed from uny remit in hi g traces of eliloride of boDzojL
bj macerating it In the pulverised stale with ethen It ii itnportaat in tbo
prrpamtioii, to ketp die temperature vithin Ihe limita above Tnenti{>Ded» aod not to act
on too grtaX ^liiitiiticiez} at a tlmtf m otberwisfl a aecondarj action takes placfl^ attended
with fonnatiDii of benionitnle atid pbetiilitiLphurDUs arid.

CryalaHiaeg from baling alcohol, in beautiful needles or interlaced
pnamti^ colourless, shiniag and truncated. Melts between 1 35"" and 1 40%
and solid ifioa in a crystalline mass between 130^ and 120^. When
quickly heated in a tube, it burns and gives off rapours of benzonUrUej
and no longer ^solidifies on cooling.

26 C ,„,« 156

N „„„... 14

UH, 11

2 9 32

6 O ,. , 4S

C»NH"S=0« 261

Gerhardt & Chioxjca.
59 8 601

4-2 4-3

12-2 12-4

18'4 17*6

100-0 lOO'O

= N.C»5H*S^O\GiWOS,B, nitride of iwlphophenyb bentoyl, and hydrogen.

The componnd has an acid reaiCtton and dlstolres readily in alkalis*
— Ammonia converts it into ben^osulphophcaylamic acid.

It dissolves very sparingly in water^ somevrhat more readily in etftw,
readily in absolute aicahoL

Silver-salt, — When a boiling solution of nitrate of silver is added to a

beiling ammoniacal solution of benzosulphophenylamide, and tba liquid is

kept boiling for a few minutes, and then filtered, the silver snlt separates

on cooling in beautiful colourless needles^ nemo times aggregated in bemis-

L pherical groups.

^H Gerhu-dt & Ohioxza.

^^^^^ 26 C IftS .... 42-3 ........ 43*2

^^^^^1 N ......... 14 ^ 3-S 3-6

^^^^H 10 H 10 .... 2-f ». 3*0

^^^^B M ^(^8 ... 29 3 29-8

^^^^H as ,.. 32 .... 8-7

^^^^^ 6 O ,.. ... 48 ,... 13^2

^^^P C3*NH^»AgSaO«. 368 ,„, lOO'O

V / ^ V

^ ^ N,C^^H5S=0*,C»H*0',Af, nitride of inlphophenyl, benaoyl and wlTftr, or

benxosal ph oph eaargentamtde.

h Heated over a spirit lamp, it decomposes quietly, giving ofl* snlphupont
acid and benEonitTilej and leaving a black residue of metallic silver mixed
with charcoaK

It dissolves but very sparingly in cold water, more readily in boiling
I water; boiling alcohol dissolves it witb tolerable facility.

■ Ammmio^lver-ialL NH*,C^N H^^AgS^O*.— When a aolutioo of

"the preceding salt in a small quantity of strong ammonia, is left to

evaporate, this compound la deposited in splendid crystals having a faint

roiBe-colonr, apparently belonging to the oblique prigmatlo system, and

I approximating to the form of a prism witb rectangular baae, mcid\&^ ^^

158

BBNZYtlNEs CONJUOATEB AMIBES,

the «<iges parallel to the vertical axis, and bavins tlief r mimtnitif tmi
bj two faeea pftrallel to the longer dia^crtfaL When beaied, thmj
up and decompose^ ffiviag off ammo tim. They dissolve readily iu boitiir
water, and if the solution be boiled for some time, animoniiL id given off,
and 00 cooliog two kinds of crystals are obtained, viz,, needlet of
bon^osulpbopbenargentamidef and prisnis of the nnaltered ammcmi^
compound. — The aq.ueous solution mixed with nitric acid, beeaiBii
tnrbtd and doposits^ on agitatioai white flakes of benaosnlpbopbeir
amidd.

GerhardI & CbiooL

4

26 C

2 N .„..
13 H

2S

6 0

156
28
It

108

asi

49

40'S

260
12-5

40-5
3-7

H

NH^C*«NHi'»Af8'0* 3a5 .... lOO'O

« ^nitride of rulphophenjl, botiBoyl, illver and bydroita^

N^,(Ci*U'S=0*).(Ci^H*CM)»A^,E3, or nitride of idphophenyU bcaiojl isd

^ V

f - SulphophenylbeMamic Acid.

Gbreabdx & Chiozza. i\^, ^»n, CAiwt. Ph^i. ifi, 147.

Obtained by dlatolvini; benzosulphophenamide in aqtaeoud ainmonti.
The solution evaporated at a gentle heat, or better in vaono, yieliia ih§
acid ammonia^alt of sulpbophcnytobeuzamic acid in the form of a tliick
gjrup wbich ultimately aulidiBes in a radiated maaa

Add Amm&jaa-tAU*

S2C.

3N.
29 M.

48 .
10 O.

.. 312

.... 4a

.„. 29

..„ 64

.... 128

Gerhmrdt H i
MS ...... 54*6

113
22*5

G^N(H«,NH*)SPO» + C»NH"S*(y .... 575 .... 100 0

NH*

O* +

Tbe acid aramonia-imlt ii very eolnbla in wati^r and alcohol but

lubt« in ether> On adding an acid to the aqoeoas solntioiit tbe K.

lieoomee turbid and depoaitji an oil which soon changes into W«moMP
n««dle« of bcnxoflulphophenamide. — Wben the rndimted ami]Mmia*«Ul
b heated in un oil batii, it melt^ at S^"", gives olT tmem of aaiBiQn
belwten Hf and lOO"", and a con eiderable quantity at about Ua% b«i m

BIBBNZOSULPllOPHENAl

1«9

' water m depoatted on the sides of the tube. Thefeaidiie ia tm oily liquid,
which when dij^olred in alcohol und repr^cipiUited hy water, reseinblea
the substance preeipitaieil hy acids from the aqueous flolution of the

axumani^g^lt

Ben^acetosulphophenamide*
C*»(N.C*HH>*,C^H''0*)H^K)* or C*(N-C»*H*3*0SC^*H*0')H>0*.

Niiride of Snlphophenfft, Benmoyl and Actfyl, ^,am^&O*,0*HHy',CmHP.

Obtained by the actioo of cliloride of aeetyl (C*H*0',Ci) on henzo-
snlphophonargentamide. The two substances act upon one another
energetically without the aid of heat, and the product treated with boiliog
ether yields a eolution, which when evaporated depoaita the compound
iu small shiaing needles. { Gerhard t *& Chioaz a. iV^. Ann. Ckim. Fhm,
46, 150.)

^fe Bibenzosulphophenainide.

Gebhardt & Ghioeza. N* Amu Chim. Fhys. 46, 155.

^m Di&mzoykulpkaphffnylamide, Jmtnrt de ^ybph^nyk €i de diBtmoUe.

f Obtained by the action of chloride of benzoyl on benzoaolphophen-

I argentamide. Chloride of silver is immediately formed, together with a
viscid masi which dissolves in ether, forming a solution from which by
evaporation, bibeD^o&ulphophenamide is obtained in splendid crystals,
[Wbeu chloride of be&iojl i» brought m contact witb beaiosnlphophefiamide, hydro*

I chloric acid ii eToLTed, but the [troduct femainA Mqi^id after coolitig and contatns
bensonitrik together with a Bubstance which ia tranifornied by alkalis into beniom

i add and pbenjLEiiJ[»litirous acid. Thia fitibstaace h probftblf C^H'^O^ =

Large, brilliant, truncated prisms, modified with octohedra! faces.
The substance melts at 105 ^ and softens even at 100^ After fusion,
jt retains the viscous state for a lono; time, and can bo recrystalUied
only by dissolving it in ether* At a high temperature, it decomposes,
yielding benzonjtrile together with other products.

40 C .
N ,
15 H

2S .

80

240
14

64

G57&
383
4 11

1754

Gerbwrdt h Chiqaxa.

6579

4"12

4'3fi

9'(}2

...... 1671

C^^H^-'S'^O*.... 365

lOO'OO lOO'OO

s N,^C*^H*S^O*,CC"H*0=)^, DitHdc of lulpbophetijl and bibenioyl.

160 benztlene: oonjugatbo amides.

The <xtmpotitid k tUglitly soluble in 3ininoQt&. Boiling Hber dW
solrei H bat slowly under the ordioaiy atmospberic preaatii^ hut em«i1|
wX 100^ ia ft clo^a tobe, and the solution, when left to eTapormte, de|ioi'"
the (»>iDpoand in fine cry^t^^^ even with only small f|tiaiititie0

tobstance, ~

Suecinylbisnlphophenylbibenzamide.

C?(N.C^*H»S^O*,C^*H*0')*H*0* or C*(N*.(?H*0*,2Ci*H*0^>H"SM)'.

Gehhahdt & Cbiozza. N\ Ann,^ Chim, PA^m. i6, 161 ; CompL rmi.
as, 457; O^rh, Tmki. 3, 11.

Obtained hy b^kting S At. benzoaQlphophenfti^genlamide (p, 157)
With 1 At chloride of snccinyL

2C*NH»AfSW + C»H*CH,CI* = 2AgCI + C*N'H*'S«0».

The rem] ting nimss h exbansted wkh ether, and the solution when left lo
evaporate deposits small needlee^ which are purified hy wasbitig with
ether. The ether^l soluttiou i^till ret&inj an oiij- sab^tonoej which alti*
tnately crystal Hsea in needlea identical with the preceding.

The compound melts at about H^"". Heated with ether in a closed
tube, it dissolves, and the solution yields, by cooling an<I evaporation^ terj
thin elongated I amine, radiating from several distinct eentres. Undtf
the ordinary preaatire, ether diseolves tbe substance hut slowly
crystallised, but readily and in all proportions when in the ^ ~

Gerbardt ^ Chlatu.

«C 360 , 59*6 59*4

2 N. ......... 28 .... 4-6 I '3

24 H „,. 24 .^ 4 a 4-4

4 S .«_,,. 64 .... ia«

16 O..... ,.„. 128 ..., 21-2

C*»Nni'«9*0'* „ 604 _ im-Q

^

« N^C»5H«S»0<)*,(C»H"0»)»,C»H«0*, nitride of MinlplwpbriijU hib«iMrt.
tac^dnfl, tbe bstf C^LI'HD^ bebg m btttotnic r*dioil eqiuvakot |q H'.

T. Sulphobenzanilide,

LiiirRfcBT & T. UsLAR, Am. Pkaim. 102, 258*

SmipAQ$fngohpAfmyUmid*, BimiiHdt ^ Smljik^itm^pp^, phenyl, md kpdfVfn.

BENZON'ITRILE*

161

Produced by tlie action of chloroeulpLobeaioio acid (p, 117) oa
aoiJiue. The solid product after beiii^ wa^ibed with water, ia pariHed bjrl
crystiilli&ing several timea from alcokol, with addition of animal cbarcoaL

Small wbite crystals, wbicb become sliglitly brown on drying, Tbey
melt wbcn beated, and decoiiiposo at a bjgber tompenitiire, witb separa-
tion of amiine, Tbey are not decomposed by cold potasWey,

■ 38 C ...

K 3 N ,„„..

W 16 il

■ 2S ,

„.. 28 .
... 16 .

.. 6J»8
., BO
.. 4-5
.. 91
., 13'5

Limpriclit & r, UaUr.
655

,. 52

8^4

' 6 o ::::::::

.. 48 .

... 352 .

., 1000

^ N=.{C'nP)'.C'<H*SSO«,H^ or 2 At. Rmmonifl ia which 2 atoms of hydrogen ire
replaced by 2 At* pbenyl, and two more by I Att of the blatomic radical siilphoben^oyl

Tht differeacG between the oaftlyttcal and calculated resttlta is due to partial
decomposition of the crystals.

Tlie compouiid dissolrcs sparingly in hot imttf; but readily in hot
tdcofml and €iha\ ^J*

A^nudem C"NH«.

I

Benzomtrile. C«NH^

fciJLiNa. (1844.) Ann. Pharm. 40, 91,
LiiipRicnT & V. UstAii. Ann. Phmm. 88, 130; also J. pr. Chcttu
61,511.

Cyanide of Phfuytf Bii^isioftmLm^ SiicJtgi&fbenzt^sfh

Fonnation* h By tbo dry dktillatioii of benzoate of ammoiiia,
(Fehlin^, Laurent St ChanceL) — 2. By the drj distillation of hippario
^«€ld (Linipricht k v, Uslar,) or by distilling hippurlc acid with ^uartz-
P«and and dry chloride of zinc, (Gussman.) — 3. By treating beazoato
" of amaioaia with dilute tiulphuric acid. (Dnmas, Compt. rttid. 25, 384,)
— 4. By the action of pentacbWide of phosphorus on benKanilde.
(Cabours.)^ 5» By the action of benzoic anhydride or chloride of bcu-
xoyl on benzamrae"(p. 141). — ^. 6» By heating bcnmroide witb anhy-
drous pbosj'aoric acid. (Buck ton & Hofaiann, Ck^ut, ^oc, Qa. J, 0,
2.55,)— -6, By the action of chloride of benzoyl on sulphocyanide of
l>«iUssium. (Hugo Schiff, A7Uh Fhurm, DSI, 117.)

C"H*O^Cl + C^'KS- = C^^NH* + Ka + CO^ + CS^

7. By beating chloride of benzoyl with cyanate of potash :

C^ni^OXl + C'NKO* ^ C»NH* + KCl ^ 2C0».

After i\m action has been continued for some honrs, the mixture forma a
browD pasty mass, which solidifies on cooling and yields benzonitrile w^heu

I exhausted with ether. (Schifi; Ann. Pharm. 101, 1^3.) — S, B^ U^-4.U\v^

lit

BENZVLENE: AZO-NUCLEUS C^*NU*.

bensAtc anhydride with efiiQtte of potash or salphocjanide of pafMiui

(Sehiff):

Eensotiitfjltt !i not imidaced by besting $iilpbopb«Q|rlato of iMrjt* with cjRtiiile
potafluudi, (Ho&uQD, Ann, Fharm* 7^i 32)

Preparation. 1, The solution of benzoic ft«id in ammonia U evapo-
rated to dryness and beated in a retort; ammonia tbcn escapes, a sub-
limate forms in the neck of tho retort3 and water patsses over to^etber
with a small quantity of oily benKonitrile, tlio larger quantity however
remaining in the retort. The fnaed residue i« therefore covered with
water (to which a little ammonia may be added) and dietiUed to dryness,
and these operations are repeated as long aa any drops of oil pass over
with the water. By this process, 12 oz. of benzoic acid yield In five dayi
6 OK, of impure beDEonitrile. Thia product it wftshed with dilate hydro- !
ebloric or aulphuric acid and afterwards with water, then dried overJ
chloride of caletum, and rectified. (Fehling.) Buckton & Hofm«nn^ bj dis
tilling ben^oAte of rnnnionia ivith cMoride cif ztnc, and rectifj^inf the dtstiilale, obCaltia
i pruductj, onlj one-^^third of wbi<-h consisted of benzoDltnte, the mii&inin|if two-tbiri'

beiog bcMol 2. The distillate obtained by heating hippuric acid

240"' (p, 73) is distilled with water^ and the ben^.onitrile which

over is rectified over lime. (Limpricht Js v. Uslar,) — •]. 3. When

distils over, a small quantity of charcoal Is separated^ and carbonic aeid

gas is quietly given off:

SO grUDBiM of bipporrc bcatrd in tbU manner to a tempcrBturc not cxcwfilinf S50*, mink
the QtinotE posflibk exciu^ion of moittnrei fielded Ijetween IQsnd 12 $rtnm. of b^OAoniirUt;
m imall portion only w«« resolved into benzoic add and gljcorol [po*aib|| from tbefifMesev
af» trice of moiBtttre, (p, 71 J] imd from the de«oiiipoiinoD of tbe laUer a smtll qit«iitjt| ol
«aUammom»c»iyi produced. {Go^mmii, Ann. J'hamt. ItSO, CD,) — 4. Whfil
1 At, ehlorideof benioyl k mixed with 1 At* sutphocyauide of potM<
fiiuni, great heat h produced; the odoar of bisulphide of carbon beeomei
pereeptible; and on distiUing tbe product, a slightly coloured liquid pants
over, which, after a few rectificatious becoraesi ^lourlest, and exhibits thi
ebaraoters of benzonitrile. It is probable that auJ;>hoc^anidG of bcnioil
IS first produced and afterwards resolved into benaoniifUe, carbonio acid
RUd bisulphide of carbon (Sehiff):

C'*a*0',C^NS* - C»^NH* + CO* + CS».

5, According to Buekton ^ Hofmann. the be#t, though a tedious proeW
for preparing h^nionitriH « to distil bonsamido with anbydrouT diot-

#iErikA*»i«, f.l.*I> /t> ii X k ^'^ water, out rises lo Uie

WHOCYANOBENZYLINE,

163

D8, 373,) BoiU at 10T« (Pehliiig, Scbiff);
V. Uslftr); at 190 0^ with the barometer at
V^apour-deufiuy = 3 7. (Febling.)

V Feliliag. Chodnew.

•Z. Sl-55 .... BM9 ..., SO^S?
■1 1359 .... 13-35 ,.„ 13-52
^ 4-86 .. 516 .... 4-97

& T, UsUr.
........ SMI ...

- 12-42 ...

4-99 .„

Sdiiff.

. ai-0

. 13 4
. 5-1

BlOO^OO .... 99-70 .., 99-46

99-52 ...

Deatitj,

5-8240
0'9/OG
0-3465

. 99 5

Si:::::::= 5 ;::::::

apour of BctixoQitrile ..„ 2

7-1411

3-3 r 05

1. Benzonitrile burns with a bright eoDty dame. —

lUger ctcitjls it yielik benzoatc of aiDuionia, water bein^

thtj same time. — 3* With strong mlphurk acid, it yields

ind bieulphobenzolic acids, biauJphate of ammonia boiog

I me time and carbonic acid evolved, (Bucktou & Hof-

If; sii* 53-)

h'O^H + 2H0 - C"H«S=0>o + C^H^S^O^s + 2(NH^,H,2SO^) + 2C0^.]

^ilrosalphateofaramonia^itformasnlpb obetj zamrde. (Cahours.)

fe..^itim doea not act upon it iu the cold, but the liquid assumes

colour when heated. (Febling ) No gas is evolved in this

tnd uo cyanide of potassium is formed. (Dumas, Malaguti ^

yompt. rend. 25, 475.) — Heated with potassium in a sealed

eqnires m fiae carmine colour, and at 240'' yields ueedle-shajfod

w&ter extracts cyanide of potassium from the productj aud the

yields by distillation a green oil smelling like creo^sote, in wLich

,jitals again form and may be purified by treatment with alcohol

ad by Bubliraatiou, (Bingleyi Ch^n. Gaz, 1854, 329.)

t^momtrile diasolves in 100 pts. of water at 100% and separates out
« <m eodiog. With alcohol and ^her it mixe» in all proportions^

Appendix,

Sulphocyanobenzylene.
<?WH*S» = C"H»,(?NS«. 1

[

miLDKAT* Ann, Fkarm, 71, 13.

' SmhtkoeymUde qf Bensopl, [This appellation is howeTer Incorrect, the term
loyl danodng 0*UW, not D^H^.]

When bitter almond oil, either pure or crude, is mixed with ammonia
1 bitnlphide of carbon^ two layers are formed, the w^^t c>\ viVv^

164

BEXEVLKKE : AZO-KUCLIUS C»'Kll*.

exbibite m red tiDt gru^tiallj increasing in intensUj horn tka
eofiifid with ibe lower^ ^nd deposits a yellow TemnQnm iNvdy; mhm
nailed with ftciib, it^ives olTsatpkciretted bydro^en and depoiits « jiUsv
niinons body solubk in potani. The lower layer g^radn&lly becwnei
milky and deposits cmtab wbicb dis^ippear again after longer aundu^,
but may be (fbtatnfHi pure by draining off tlb« motber-Iiiiuor, ^rmmtg
between bibulous pajx^r^ and wafihin^ witli eiber. ^^ ColonHeas prt^ or
granules haying a bitter taste.

U C Ij6 ... C5-S0

K „ 14 .... 9-52

5H«« ^ & ... 310

gj » »„»., at ^. 21'r»

Ci*NH'SF ,, 20r ,,.. 100*00

65^2
9M0
Z-B7

2\'M

100-00

IJecompoiifions, 1. When exposed to the air for com© time, ii
f-xhalea a peenliar odour and turns yellow, Melt^ at 100^, witb itroij
i n t u mesce n ee an d incipient decomposition . A t 1 20 ^, it gi v es off am moo it,
bistilpbide of carbon and bitter almond oil. At 150, the yollowisli
frothing mass suddenly become« clmnged to a mobile liquid, oeaiff t»
froth, and doea not begin to boil till heated to between 210" and 2^0M^
few needles then subliming, simlar to Laurent's benzoylaxotide C*N*H'^H
The residue solidiBes on eoDltng to a yellow resinous mass, eontdnii^^H
a few needle -eihaped crystals which may be oictracted by «lc%»hal of 4^^
Tiio body insoluble in alcohol bebav-es very much liko Laurent*a benfOy^
lazotidft; it is however C"NH^ ( = C^NH'S^ - CS').

2. Sulphocyanobenssylene boiled with nearly anhydroua fd^i^M gtvK
off hydros ulpha to of ammonia and carbonic acid, the lit^nid ae<|uiriitg t
yellow colour and depositing white kmiuai as it cools. Th© tryt^

consist of:

1
QoAdnt,

56 C *, S36 ,„, 7110 .««». 71-W

2 N „.. .„., 28 .... SB8 .„„.» a-B5

24 II „„ 24 ,... 513 ,„„.M 5-23

5$... ..... 80 .,., iroa ....„„ ly-fs

C>*Nm=*S* .... Am .... lOfl-OO . 10000

Quidnt rri^rdt this bodr as a compound of thiobtni stnid« vHb bcfuasvl (OV^
sfi4 lulphur (C*^.V f I=*8* « 2C^*NH?!5= + C^^H* + S). [The two tides of tluB «q»-
tion do not »gr*t?, W.] —Compare l^iircfit (Cetiijal. cAim. 1850, Hfi).

3. When aulphocyanobensylene ia dissolved in hot ithoJk^l of 40
containing a little a^/imortia, and water added till permanent turbtdity i
prc^duced, the liquid on cooling yields a ciystaHino powder which '
insoluble in wuter, and cannot be purified by eiyetAltiiiation
»lcobd, because it decompof^jes when dissolved in that licjuid.

4. £ihtr likewise dissolves sutphoeyanobocsyleue with de^ooifo^l
bitiou, T

5. Su1pbocyanobcn%ylene Impurts to aqueona ^e^itkMotkit ^ «nM«
a blood* red colour, arti;iiu;^ from the formation of ferrte anlpboeyaaiJffi
on hetttiDg the liquid, bitter almond oil distils over;

aC'*Ml*&^ + FeCl» ^ 6HO - Fe«(CjS?)* + 3a*B«0> ♦ 3lin,

BiNZOSTiAKILIDE. 165

BenzoBylanilide.

C^NH» = C"(C»NH«)H» = C"N(C"H«)H«.

Lauhent & Gerhardt. (1850.) Compt chim. IB50, 117; abstr.
Compt. rend. 30, 405.

Benzotylttnilide^

Formation. By the action of aniline on bitter almond oil:
C^^HW + CWNH7 = C»NH" + 2H0.

Preparation. When a mixture of about equal parts of dried bitter
almond oil and aniline, water separates out and rises to the surface; and
after a while a crystalline mass more or less coloured is produced.
Sometimes the mixture remains liquid, but solidifies when water is poured
on it. . The mass is pressed and recrystallised from a small quantity of
warm alcohol; to render it perfectly colourless, it may also be distilled
after pressing; a colourless oil then passes which solidifies in a crystalline
mass on cooling.

Properties, Beautiful shining crystalline laminsB. Very easily
fusible. Distils without decomposition at a high temperature. Inodorous.
Tasteless.

Xanrent & Gerhardt.

26 C 156 .... 8619 8573

N 14 .... 7-74 7-30

11 H 11 .... 6-07 6-97

C»NH'i 181 .... 100-00 100-00

Decoinpogiltons. 1. Benzosylanilide is immediately decomposed by
bromine, with great evolution of heat. Bromine acts with violence on
the alcoholic solution, and the liquid, after a while, yields crystals of
tribromaniliue. — 2. With cold fuming nitric acid, it forms a dark green
solution, from which water throws down bitter almond oil, while nitrate
of aniline remains in solution. — 8. With oil of vitriol it forms a yellow
solution, from which water separates bitter almond oil, while sulphate
of aniline remains in solution. — 4. In contact with ^yc/^'oc^^-tc acid it
becomes liquid, and is dissolved by the concentrated acid at ordinarpr
temperatures, but appears not to be altered by boiling. — 5. It is
scarcely attacked by potash. — 6. Acetic acid causes it to liquefy, but
does not dissolve it m perceptible quantity.

It is insoluble in water, but dissolves very easily in alcohol and in
eiker.

101

BlNZTl

AZO-KUCLIUB C"NH*.

CTtteent & GffAKCEL. (1848.) L'ImL 1848, &5. — Compl.

115, 1G2; J.pr. Chtm. -IG, 51 L
Chakcel. Compi. rend. 28> 85.

Formaii&n, By the action of suTphureited hydrogen on Moitfo^l
henxone (p. 86) ;

C^N^HH)^'^ + 121IS - C»N3H>202 + SHO + 12S.

Preparaiicn. The proilact of the d^ diatUlation of beoxoati
linie (p. 39), after being freed from benzol and the last portions of lit|
diBtilUtej ifl hoi Led for seme hears with fuming nitric acid, and tlie li<|!ij4i
afterwards diluted with water. It then deposits a yellow oil wtid
partly solidifies in the crysstalline farm on eoolin*, and aft^r th« acid h«
iK^en poured off, ts washed with nlcohol and dissolved in a small qnaiilil|
of ether The solution Bolidifies after a few honrs, to a crj^faHiM
tnixtare of seveml hmiies diffitnlt to pcparale from one aootber; tKii
mixture is dissolved in ether and alcohol, and the liquid filtered. Tbe
resiilae on the filter forms with hydrosnlphate of ammonia and eth«r-
alcohol, a solution whichj in the course of 24 hours, becomes filled wilt
crystals of flavine* These are collected on a filter and dissolred b
hydrochloric acid ; the solution filtered to remove the preeipttalc4
sulphur and insoluble impurities, then precipitated with ammonb; llw
precipitate dissolved in hydrochloric acid; and the solution dilated mil
aleobo! and mixed with hydrochloric acid at the boiling lio&t: it then on
cooling depoaita slender needles of flaTine.

Propttiies^ Colourleas or jmle yellow neefllefl.

Laurent & ChB«»f«K
26 C „... 156 _ 73'S7 73 1

2K .....*,,, 2B ... U"t2 ^.,.,. a^6

12 H ,_.„ 12 ..^ 5-6fi ....... St

2 O ..„»..... 16 ... ?'&5 7'S

o^N^a^o^ ...... zn ,.„ loooo imo

Mftr be regarded ma urea Iti wbich 2 At. 0 <ir« repboMi W
CWrC»^H*)^H*0*. Ctfmp. GerbArat (Traii^ \, 430)

When heated with pota^^h, it gives oil' an oil which Las nn
feoetion and dissolves in acid.

It is abnoat insoluble in water.

H^drochloraU of Fin vine, — Pr^aratioii, rid. tup. — Long luniiis. By
dry diatiliation; it yields a scanty white subliniate ftod litt^aa m rtfj
bulky cbareoul. — It dissolves very easily in water, soinewhftt Um m
alcohol ^_

ChhmphtijmU qf Fhmne, — Obtnined as a pnlvenilent pi«ei|itei^|
on mixinj^ the dilate solatjona of bichloride af platinum and VydtodMl
mtif of JJnv/nc, After drying ai \5Q^/\l ^^tjtvx^vii^ S14 ^ ^^ p^*^--- ™

STILBENG.

167

I

agreeliig witH tlie foHDiila C^N=H"0*,2HCl,2PtCIV wUidi requires
31-43 percent.

Flavine k soluble in ako^iol and eiher.

i

Compounds cmiiainm0 two ot- more Atami of C^*H* or qf nuclei dmvfd

therefrom*

StUbene. C»H^.

Lapeent. (1843.) Compi, rend. 16, 856.^i?<rv. mmii, 16^ 373;
/. pr. Chefn^ 35, 418,^^ci?. acifji^. 18, 201,

The name tttWettf if derived from rr*>3t*v to #Aiiif .

Format wn^ By beating iiilpliide or nitrosulpliide of beDzykne.
[The resmotis tubsUncti produced by the actioQ of fluoride ot boron* &(,c,j or beozylic
Alcohol (p. i6), is probably stUbcuc]

Preparation, L The scales which first pase oTer during the drj
distillation of sulpbide of etilbeno (p. 168), are dissolved in boiling
alcohol; the solution filtered from the undissolved thiones^^^l; the mother-
liquor drained from the crystalline 1 ami use which sepamte on cooling;
iheae JamtUEe dteaolved in excess of ether; and the solution left to evapo*
rate.^ — -2. When the mixtnre of pieril^ sLilhene, thionesaal and lophinc
(p 2 5) j obtained by the action of hydrosulphate of ammonia on hitter
almond Oil, is boiled with ether, and the solution left to cool, etilbeue crys-
tallisea out first, and may be purified by two or three cryBtallisatione
from alcohol and ether.

■ Proptriiei. Colourless, pearly lamina? often joined end to eud, or
j&hort prisms belong to the oblique prismatic system (oP, aoP, ocPoo ),
Fig. 112, without the A -faces j i : ^ = 112''; t : i = 100°; « : « =
53^ 30'; u : t - IU° 45'; r:/= 133^ 30'; i :/= 6r, Inodorous;
solidifies after trantjuil fusion at llO"* or sometimes not till cooled to 100"";
but if agitatedj it solidifies at 118°^ forming a scaly crystalline mass.
Boils at 292^,andpa5fl over undecomposed, Sp. gr. of the vapour := 8^40

(by anutber inetbod ; S*2)»

Laurent.

se c »...».„»... 16B ... nzn ..... 93-28

12 H ....„ 12 ,., 6-67 ....... 6*66

C^W^ 180

lOO^DO

99^94

Vol.

€*Tit|Krar .* 28

H-fu ,... ,..

I>ensit7,

,,... 11^6480

12 0-8316

Vapour of «tilbeae. . , .

Hencei itilbeDC-TKpoQi' h f ^atomic.

l2-4r96
6"2338
8-3298

* Ai it ii impossible to claaiify theie compounds eixoctly accordlo^ to the ij'item
a«topted in tbiri Handbook, thej tktt arfai)g(Ml partly according to their on|ia and
mode of formation.

Au

witli

and tJierefofg

bitter mlmood

4'if tf.) If Ihe boiling witU nttrie

m Mistare is foniie<d conUbing t

. I Mil It foad 67*1 p. r., € wad 4*S H j

I hms^m \nSSmg^ aitntUIIiie maJL m ptodaeed ia idditlatt to the jtlbv
I, — S, Slilb^i# is Boi djeeaipoipd bj dilate ckpomie imd; mi the
eourentraled idd acts on it with tiolKioe, formm^ bitter altaood oil —
3> ^'ttb Awiag it gins of Tapoitn «f bjdnklirDcnle aeid and fannf
bydrobfWBata of bwiiiftlllie ne. — 4. ChhriaM goM Is at grst abaofbedhjr
fo^ ^tilbene, wilhoal crdatm of kjdiociilorie acid; if tlie ptinge cif
tlie ebtorine be eoatiBiied aad tie teMMstsre fmUed at tlie mm% liiM,
hvdroclilonc add fiiesptii^ aftd tbeveia ffonneda mixta n& fif « and ft lijrlnv
cLlnnite of cblorQ9ti1ieM;» bjdrooUotste af bixiiloniistilbefie and aa <>ilj
cbloriue-compoixii d.

(

BtaIb«M diM(»!rei Is itnmf oU of vitHol; ttitsalilM |
lfec]i» s soluble bu^-eatt

U dissolvei m etbei more readilv tban in aleoboL

Solphide of Stilbene. c^H^'^*-

Laurest. (1841.) N\ Ann. CA^. Pkf^. 1, 202 ; ^tn, tUm

38, 320.— i?irt. fdfwi. 16, 073; X |>r. CAf»- 35, 418,
KociitED£ft, Ann. Fkarm. 37, 346. i

CUHorns. C&mpi, rrwdL 25j 457-

Foi^irtixfion, By the aetioii of hj^drosutpbate of amtnotsiA on Kllif
ttlmoticl oil. (LatirGnt, Bocblederj p. 2 J.)

aC^^HH)^ + 4HS - C^H»^S^ i^ 4 HO,

or of mlphnretted bydrogen on Lydrobenzamide (Cabrmrs) ,

2C<^N-H*» + 12HS - 3C^H»^S< ^ 4KH^

Prfpardiicn, I. WLeti 1 vd, bitter almoiid-oil Is dbiolvinl in
10 ToL nlcobolj atjd 1 val. bydmsnlpbate of aunnonia grudyjUly
tbc Uauid, aft#r a few minutes dcpomU a mealy powder con£i«ti]^«C
i^ulphiae of itilbeno. Or au akoltoHc isolation of bitt*:r almond oi b
bf^ated to tbe boilinj; point, and mono- or bi hydros u I pbatr of amaifi^
added in bittrU quantities: the liqnid tben after a few Be<^cinds depo^Ui
wbite pre^ipJtate, wbidi may be purified by wasUini^ with aleobol 1^
'*okolk riolattoti coiitftini «iii«]i c|UAittitici of hydride of iq1[ '

1 dftc§ not alwsfi iacce«d< (Laurtat.) ^2, U^beu
lied In excess tbrougb an alcoboHc solution oi ii vijroiH-n£a.iiu^
l^uid afterwards ml at rest^ it dcpoeitf «ulpbide

on./

of

SULFnTDH OF STTLBENT,

169

Properties, Whito powder ( Laurent^ Rochleder ) consisting of
microscopic granules {Laureut), Softens bctwecu 90° and 95^ Wbeti
carefully heated to the melting point, it eolidifies oncooliti^ into a trans-
parent Qon- crystalline ma^s. It ta inodorouB, but imparts to the fingeria
a very persistent odour of odious- (Laurent*)

Laurent,

2«C. ...„*, UB .,. 6B'S9 ...p..*, 6871

12 H .„. , 12 .... 4-92 ,.._„ S 21

4 S 64 ■■■■ 26-19 25'fl5

C^n^S^ 244 .... 100-00 ...... 99; 78

^ Polymerio with tulpUiile of benKyleue (p. 49). [It i« perhipi C«H*«S* ; at leaat

till I formal^ htid§ to a asmpler eKpre^aion of ita formatiDiL from hydrobi^nzamidc i
C^N^H'-^ + 8HS = C^U'^S"' + 2NH^S. (L.)].

W I}ecomposithns. L Heated above its melting point, it turns roddiah-
yellow, and solidifies in a crystal lino tnasa consiitiug of decomposition-
prod uctg. (Laurentj Rochleder) Wlien kept for some time in a atata
of fusion, it gives off sulphuretted hydrogen and a small quantity of
bisulphide of carbon ; and if the beat be cousidembly raised after the
escape of the 5?ulpharetted Lydrogen, scales of atilbene sublime at firsts
an«l afterwarda needles of thionesj^al (Laurent) ;

2C^HJ'S^ = 3HS ^ 2CS^ - C^^H^- -I- C^^H'^S.

B 2* It barns with a rery offensive odonr^ and a bright sooty flame.
^Laurent, Rochleder,) — 3. fie com poses in contact with heated nitric acid^
with rapid evolution of red fumes and eeparation of *;ulphnr. (Kochledor.)
Nitric ucid acts violently upon it at a ^.fcntlc heat^ forming anlphuric acid
and bitter almond oil or benxoic acid. (Laurent.) — 4. It is not attacked
by cold oil of vitriol J but dissolves on tho npplicatton of heat, fomiing a
carmine-coloured solntiou (Laurent, Roclileder), which is decolorised,
with seimration of flakes by water. [Was bcnajltc sciJ formed? (L.)] —
5, With immi/4(?, it forms an oily mass J while hydrohromic acid is given
off. (Laurent.)^ With iodittf it melts into a brown mass which dissolves
with yellow colour in alcohol. (Rochleden) — fJ, When boiled with
hydrochloric acul^ it gives off a small quantity of sulphuretted hydrogen.
(Laurent) — 7* With melting ht/drat^ of ^yotmh/ii furms a red maa?,
whence thick fumes are evolved, which sublime in fern-like groups of
crystals like the products obtained from the compound by dry distil lation*
(Rochleder.) It is slowly decomposed by alcohol ic potashj and water
throws down from the solution a reddisfi oil, whieli forms with nitric
acid a body apparently different from benzoic acid. From tho alkaline
solution free acids evolved sulphuretted hydrogen. (Laurent)

Sulphide of stilbeue is in.'joluhlo in water and in alcolmL (Laurent,)
When boiled for some time with hydra ted alcohol, it dissolves ah u ai-
dant ly, formiug » yellow solution which does not yield any deposit on
cooling. On boiling it gives oft' sulphn retted hydrogen.

With fther it quickly forms a transparent liquid, which disaolves in
small quantity in the excess of ether, and is recou verted into a mealy
powder by alcohol (Laurent.)

iro

COIfTOtTKDS OOKTAIKniG TWO OR MOEE At. C"fl*.

HydrobvoiB&te of Bromostilbene.

0»H=Bi* = C"BrH",HBr.

BrQmurt it tHthine*

Frodaced hf the action of lirDtniiie aa stilbeoe — witii eTolntioo of
kydrobromic acid — In tbe (otm of a white powder, whicb b iiuioluye b
icoLol and etber, and may be puriEed bj waeJiing with ether.

28 C

2 Br ..«»«...
12 H

4941
.., 353 .-

.», 48-2

C»H«Bi*_..

.. 340 .

^ 100-00

According to Laurent, th€ fubfUnce ui^fied donbtleat eooCamed hfd
of bitrrOinoAClIbeae C^Br* H '*, H Br, * sappotitLoQ which iccomiU, oot onlj for tlM it
ferencc bet wet n the uimljticjl And csleulated resotU, but dso f&t tint tf^lwtlm tf
bjdmb ramie idd wbldi »cTOinf unics thr formAiioti of tbe uromj^oiid.

When healed; it girei off bjdrobrQinic acid and a ?erj «mM ^mfilitf

of free bromine*

CMorostabene- C^CIH".

Lafbent. Efv, tdmL 16, 373j J, pn Cltem, 35, 425.

Frodaced by tho action c»f akcrhalic poist&h on hjdrvjelilofilt
chloroitilbene} and like the latter, faring two modi B cations, a wad ^

n. Hydrochlamii: of chlprustUbene boiled with alcoholic potask, yiilii
chloride of jiotaa^imn and chlorogtilbeQC «, whii!lj in jmcipilmM bf
watnr ofl an oii ciipuhlo of being dietiUed without deconi|Kmitjatu SnUm
in alcohol and ether.

2ec ...
CI ...

11 H ..,

......,„ 168 0 _ 7S25 ..

...„„ no . . &-13 .

Luitreiil.
?J 0

C«^IH^*

214-4

99-90

ft. When liydrochlorat© of chloroattlhene p is botlcd witb
potaih, an oU is produced which disiila tindecomposcd, and tuia dotti
the ftame conipoaitlon a« «,

Brmnidt f*f ChhrottUhm€,~0^m,W. ^ a. CWoroaljIlica^ « .
biaeii directly with bromine, forming a eoJid body» which ia ohtatn^d
.l&o ci/«talJine #tate by solution iti boUuv^ cilicr and i(|>otitaiuKiiit 6Tifi»-

HYDROCHLORATl OP CHLOHOSTILBINE,

17

ratiot). Forms einall six-sided prisma with dihedral euramiti. Dissolves
fiparinglj in akoliol and ether*

p. When brant me is poured npon chlorido of stilbeno ^, a lolid mass
IS farmed; and on dissalving this iu boiling ether and leaving the eolutioit
iu evaparate, indistinct crystals are obtained, which yield Ly distillation
bromine^ hjdrobromic aeid, and corapouiitls wbich crjstallise in needles*

r fgC ,

«. 168 0 .
... 160-0 .
,. 85*4 .
„. lia -

.. 44-87 ..,
. 42-74
9*45
,. 2*94 ...

Lnqrent.

.., 43*5 ,. 4G-30

f s Br .......

^ CI

11 H

.... 30 .... 3-05

C3"Br2ClH» ,

... 374-4 ,

.. 100*00

Hydrochlorate of CUorostilbene*

C^H^'C? = C^H^'aHCl.
UcRENT. (1844.) Bev. sdent. 16, 373; X^r. diem, 25, 422.
Chhfmre df wHlh^He,

Formation. Obtained in two isomeric niodificatians by the action of
chlorine gas on melted stilbenc*

o. When the product of the action of chlorine gaa on melted stilbcne
(p. 1G8) is treated with cold ether, o- hydrochlorate of chlorostilhena
remains nndiseolved, and by Bolution in boiling ether and elow spon-
taneoua evapomtion of the solution, may be obtained in beautifnl crystals
Irelonging to the oblique prienialic system, (P, co P^ odPoc) Fig, 114,
without t ; a : jn=106^ 3\; u : m=:lO0^ May be partially volatilised
without decomposition^ but at a higher temperature yields hydrochloric
acid and an oily substance. Boiling alcoholic potash converts it into
a-ch!orostilbene, — It dissolves sparingly in ether, and it qnite iiisolublo
in aJcohoL

ft. When the ethereal solution separated from a is mixed with
alcohol and left to evaporate, it yields eight- sided tables of /J-hydro-
clilomte of chlorostllbene and dull lenticulu^r crystals of hydrtichlorato
of bichloroatilhene, while the oily compound reauiins in solution. The
octagonal tublcs arc picked out and recryijtalliscd from a mixture of ether
and alcohoL — Colourless, transparent table.$ belonging to the right
prismatic system and having a faint pearly lustre. Fig. 48, without the

narrow face and with the ;;-faco prcdoniinuting. (P, Poc^ o F)* p * ^
about 103'^; p : i about 112°; p :a about 110^* Boiled with alcoholic
potash it yields fi ehlorosalhene. Dissolves readily in atcohofj and still
more in ether.

i 28 C

f 2 CI ...,

16S 0 .

70'8 .

.. 4-78 ...

Lattrcut.

0.
... 66-32 .... 66-82

12 H »..

_,.,. 12*0 ,

4-84 .... 4B3

C2^fH» ,

...... 25a*8 ,

,. lOO'OO

*1

— r.-L : :ii "iier. ::/,i .0 .-ir..

-::r» "A •.'■2 j-nV-irccL- — .:*
::r. " ■: •, .;u::-. .' :.

Nearly insduble in water, dUsolvee more readily in ulcoUo). still more

^'HmstUtaie of Sihft\ — Obtained by precipitating tlie ammontacal
solution of the acid with nitrate of silver; contains 41 0 p> c silvorf
agreeing with the formula C'^Xn'^Ag^O^*^, which requires iVQ p. e.

Beuzcia. a*H^^O*.

loBidCET* Amh Chim. Ph^s, 21, 254; iV. Ti\ 7, 235,

'3BIQCET ifc BouTRON CHAttLARu. Ann, Chim, PA^i. 44j 36i; 40, 204 1
OKASTUE. J. Pharm. 16, 519; N. Tt\ 23, 2, 184,
rbHLEB ik LiEDiG. Amu Pharm. 3, 27Q; Fogg, 26, 4?4.

b*A0itENT. Ann. Chim. Pht/s, 50, 402; Ann. Pkarm. 17,381; Pog^.
BQ, i07*— Ann. Chim. Phyg. CG, 1D3,

SrNiN, Ann. Pharm, 34, 186.

Iehhardt, Mev. ment, 10, 371,

Slfaroptene nf BUier Almond OU, Bitiettmtndci&tcajripher.^ — Fiwt (^o^.'el!ilf
allied b| WiJiif'EA k hiEBiain lfi32.

Famiation. 1. Occurs sometime togetber mih benzamido in crude
bitter almond oiL ( Laurent ») — When bitter almond oil conUming prmsic acid
H expoaedl to the air, \t form^, besides benzoic acid, a jellovr cryBtalline substance not
poucssing acid properties. (Eobiqiiet.) Bonastre, iti diiitiiled bitter aUnoud oil vtitU
fpring-watfr, found In the residue, a resinous subatance wUkb, according to Laur&at,
cc^nsUtcd of bitter almond oiU benzamide and benzoin.

2. By aqueous or alcoholic potash, especially in presence of oyauida
of potassium, or by pure cyanide of potassium, bitter almond oil id
eQUTerted into benzoin {comp. p, 21),

Prepfiration. TLe benaioTn wbieh remains beliind when crude bitter
almond oil is rectified with jiotasb or lime, is purified with hydrochloric
acid and crystallised from alcohoh — 2. One pt. of crudo bitter almond
ell i$ tihakeu op with a solution of 3 pta. hydrate of potash in 1 2 pts. of
waterj in a stoppered bottle, coiupletely filled with the liquid. After
three days, very small crystelline lamiose are deposited, but are redia-
iolred by the oil on agitation; after fourteen days, the liquid is so
kiaded with it that it becomes thick j and after four weeks it becomes
quite solid* The separated laminae are removed from the liquid by
til nation. (Robiquct *fc Boutron Lharlard.) — 3, When water is satu-
rated with crude hitter-almoud oil aud a small quantity of potash added,
tb© liauid after a few days deposits benzoVn in slender needles* (Wohler
& Ltobig.) A solution of the oil in baryta or lime-water behaves in a
giniilar manner. (Zinin.) — When hitter almond oil containing pruiisic
apid ia dissolved in a hot saturated solution of alcoholic potash , the
niijctore solidifies in a few minutes into a yellow crystalline mass of
I benzoin merely cou taminated with a little potash and a resinous msitter,
I and easily purified by crystallisation from hot alcohol. The quantity of
benzoin thus obtained is nearly equal to that of the bitter almond oil
used. If the proportion of byarocyanic acid is too great, the mixture
I reniains fluid for a long time, turns brown, and solidifies in a curdy mass,

174

COMPOUNDS CONTAlNl?aG TWO OR MORE At. C>*H*.

potaah yielda too little benzoin, it is better to prepare pnr« bUlor i
oil, and treat it as follows. (Zinin.) — 5* Piinn bitter almond oil m eon*
tact w(tb a weak alcobulio solution of cyanidG of potaasiain or wil^
alcoholic potasb containing a few drops of pra&iio acidf la mton oesTtttod

into beniom. (Zinia.)

mmg S^

Fmperites, Transparent, bigbly lustrous, ren^nlar 8i3c-si^ed |».m
soractimea witb three rbombobedral faees. Melta at 120^, forniinf
colourlesd liquid wbicb solidities in a broadly laminated, radiating maMi
Boik when strongly heated and rolatilig^s undecomposcd. Tastdesc
SDd inodorous.

WtJhIer A U«big. LBoreaL.

28 C

12 H

4 0.»

,, 168
... It .

.,. 5-65 *..

70-118 ...

560 ...

... 1523 ...

.... h'7J
... 15'5S

C»HWO* ...

... 212 .

... 10000 .

.... 100-00 ...

100*00

Iiomeric with 1>eDxoate of benzol and potfmerlc vith bitter alaidnd oU.— M4| bt
reg^arded as the aldidq of benziltc add (Lourcnt, MiiMde dc CAf'miV, 108)»

Dccojftpositiom, L The vapour passed through a red-hot tote
converted into bitter almond oil {Gerbardt, Tniif^, B, 277.) M J. L
— Burns in the air with a clear Inmiuous flame. — 3. Heated in < ^*
gas, it yields beuzile and hydrochloric acid. (Lanreut.)

C«H'^0* + 2Cl -^ C^ll">0* ^ 2HCb

4. In contact with bromine, it becomes heated to the boiHng point i
gives off a large quantity of hydro bromic acid; and after tbe exceM i
bromine has been expelled by beat, tbere reniains a browD viadd lp|ty
which smells like bromide of benzoyl, but does not solid ify like tto
compound. On diiii^olviug it in alkali and adding bydrochloHc aeitL
Sakos separate eonj^istinj? uf delicate needles, whii^h are tieitfa«r bt«fDti
nor benzoic acid. (^A ohler ^' Liebig.) [ Probst bly bifnEUe. L.] 5. HflltA
with strong nitric ucnij it yields bensilo, with evolntiott of nitric aeii
(Zinio.)

C«H'-0* + NO* = C^H^OQ* + 2H0 + K0».

0. It is violently attacked by pentachtoride of pbosphorntt wilb .
tion of chlorophospUoric aeicl, and of Tarious products ditfietili lo (
ill the pure state. (Caboun, *V. Ann* Chint. /%«. 23, 351.)—
7* With oil of vitriol, it forms a violet-blue solulion, which soon txrs*
brown, and when heati^d, first becomes green, then black atnl gifw «£
sulphurous acid. (\V(^hler k Lcibig.) — 8. Benxom is not alt«i«4 hj
boiling pf>ta»h-le^, (W^iibJer A Liebig.) Boded with akoholto potidit
it yields beudlic acid [together with a volatile body havinj^ lb# mimi
of naphthalin. J. L.], (with evolution of hydrogen, nt^ordiug to Qm*
bardt, Tnnii 3, 277). Fused with hydrato of potash, it forma lifil
acid and gives off hydrogen, (Wohler A Liebig,)^8. In coniMi will
aqueous ammoTitrt for t^o months, it forms benzoVnamido; villi mltiihaKi
aiumonta, it yield*) b^^nxomam, benzoinatuide, ami vhtious prcNiiiQli dffciH
to obtain in the pure stat«. Laurent fmssed amuioniacd ga« taio abiAhili
aliohol in which benxoTo wai immersed; after 4 or 5 moniha, Um ttialui
effotmitt^: T. Ben:6o'itiam ; t. k Widy QrYtULlisiD^ in rlioibiwi

ACETYL BENZOIN,

1T3

and soluble m 800^1000 ptg. of alcobol; 3. Microscopic ooeilles wliich
appeared to be benzoin amide; 4. Crystalline grains, which dissolved with
tolerable facility in alcohol; 5. A soft resin which dissolved easily in
alcobo), very easily m ether; 5 and pirt of 4 reiiiam dissolved in the
liquid. — Hydroaulpbate of ammonia does not appear to act upon ben^oiiii
(Laurcat.)

Comhinatiom. Benzoin is inaoluble in cold water, but diasolves
sparingly tn boiling alcohol, and crystallisea in elender needles on
cooling, (VVdhler & Liebig.)

It dissolves in hot alcohol more readily than in coldalcoboL (Wobier
A Litibig.)

^^ Acetyl-benzom.
C^H^*0* = C*H'0^C^H«O* = C*"H"(C*H»0')0*.

IiwiN. Ann, Fharm, 104, 120*

J^otmaiton find Preparatton, By the action of chloride of acetyl on
benzoin, — When oldoride of acetyl is poured upon benzoin (3 pts. of
the former to 4 pti. of the latter) the action begins but slowly at ordiuary
temperatures; but on heating the mixture to 40^ or 50^, tho beiizuVn
dissolves, with evolution of hydrochloric acid. The heat moat not bo
misled above 50^ till the solution la complete, as otherwise the mass turns
black and becomes difficult to purify. If the solution be then boated
over the water- bath till nothing more is evolved at 100^] the product
(whose weight amounts to about f of thai of the benzoin used) filuwly
solidifies on cooling to a crystalline mass wliich dissolves readily in
alcohol and etherj and may be r eery s tall ised tberefroin.

Properii^i. Crystallises from the ethereal solution by slow evapora-
tion in large rhombic prisms and six-^ided tables; from the hot alcoholic
folntlon in thin shining cryataU, Melts below lOO^j forming a colourless
liquid wbicb thickens ou cooling, and remaius viscid for a long time, but
afterwards solid! fiea in a gummy mass, and slowly changes, especially
in thin layers, into a white cry^jtalline mass.

Zinin.

3a C __.,,,,.,., li>2 ,.. 75 59 756a

14 H... „,. 14 .,. 5*51 ....... 5'5S

6 O 48 .... 18-90 IS-Sa

C*^HWO« ..... 254 .... 100-00 100*00

Tbe snbiitance aual)!jed was recrystalUaed from alcohol and etber.

The compound is not acted nyion by sulphuric or hydrochloric add*
Jtrong' nitric acid produces with it a mixture of two nitro-products iu
"be form of a viscid, transparent, nearly colourless masa, insoluble in
rater, but dissolving easily in alcohol and still more in ether; the ethereal
olntion deposits a nitro-compound in crystalline crusts. — Acetyl- be n^o'iu
^'^ act acted upon by aqueo?is potash, but with alcoholic potash it yields

< , *"ire of acetate and betizciate of potash.

I 1 b'^ ^^ water, but dissolves readily in alcohol and fther^ warm
1 I 1 1* *\ ,. iQaHy twice its weight of the com\>ovv'n4.

COMroUKDS OOXTiUNING TWO 01 IfOU Al«

170

^- Benioyl-benzom,

Zixiif, Ann. I^kmrm. 102, 11*1.

^orpMtflMl amd Fr^ata^R, By iLe »ciiou of clulorlde of Wni
c^n betkjioia^ N<» fteti^n takee place at ordinaiy tempemtore^, but if
niixttire he heatetl ttll the WaioTn Is eompletclj disfi^lTcd and no a
lij«lrocblonG udd i.^ erolTed, erenat & tempemture near the bailing poiil
of chloride of benfayl^ a eliglitlj jello^^ish oil}* liquid is obtained, wbid
on coaling de|H)6it3 benxoTl-Seiixotn in wartj,^ Jamtnar, cry^t&Uine itia«ii.
I .Etad if tbe proportion of cLloride of benzoyl ig not too great, ike aotiit
liquid sometimes folidi^es into a white mass. To parify tbiA pitKtiaet.il
h poured while yet liquid into cold alcohol of 75 per eetit, (in which It
di^olves bat aparinglj) and diffused through it by brbk a^iution; it h
thereby obtained in the form of a crystalline powder, which is oeparatri
from the liquid when qnita eold and washed on a filter with coM alooWl
— Th* fjQAntitj of tKnrofl-bcmom obtained i% ftlwaji the sa^me, tii* 1 At., wberW
U 2 or 5 At. cUoride of benzoyl be used to 1 AL beoioin ; bcit if enl^r ) Au chloric ^
hmaojl be used, it U necc^arf Co heat tbe mixture mare itilHiflf and fbt ■ kflCff tma,
md It h thtn apt to turn dark jdlow or erea bro^o.

Frop€rtia, Crystal Uses on cooling from boiling alcohol in Ihii
cotuurlees needles re'Fembling benzoin^ and from ether by apontaatow
evaporation in large shining rhombic prisms. Afelts at 125% fonolaf i
colonrless liquid which on cooling becomes riscid and tenaeioue and tna
BolidiHes in an aniorphous mass^ which becomes opaono and oryttaUte
etowjy when left to itself, more qnickly when rubbed with a hard hodrf
a-iid ftUll more when warm alcohol or etber is poured upou it,

Zluln.
42 C .„..»„„„.. 252 .... ;0r4 ........ #0 79

16 H .....,...^. .. 16 ... 5 06 ....,.„ 618

6 P.. .,. 40 ,... 15 20 ...... 15 03

C*?H"0* 30g _ 100 00 ... 100*00

iJrcompositiomn The compound is not acted upon by hydrochloric tf
by dilute laulpburic acid, but strong sulphuric acid decomposea It with l&t
aid of heal< Chlorine ha^ no action upon it even in the melted slate.—
With nitric acid it forms nitroben^oyl-benzoio, C*H**XO** Ai|i
potojih does not act upon ben^oyt-benzum, but alcoholic notaak **
It with violet colour, aiul when the action ;uiBi«ted by boiling ts c
a mixture of benzoate and hen si late of potash la obtained.

tcr, tery q>arin;cl/ aolabld in e«U
it^ weight of boiling SQ per Nttt

VemhifmtitmB, Tnsnluble in water,
Xmkohtylt but diasolvea in e^ix times _ _

Sleohob Dissolves readily and abundantly in ^h^r^ eepeeaallj
heuted^

Dlinoires without decomposition in chloride of bentoyl.

TraOBENZOTL-BENZOm.

\>

11^ Nitrobenzoyl-benzom-

Zjifjpr, Amu Plmnii, 102^ 118.

" FoTTnatlon and Freparatwn* By tlie action of filming nitric acid on
henioyl-benzoiti, — Wben benzoyl-benzom is added to nitric acid (either
colouriesa or yellow) of sp, 15 1, heat is evolved tind the Bulstance
meits; if only a i^nall qnaatlty of nitric acid is present, the benzoyU
ben £01 a diesolvea in It on the applii-ation of heat, and eeparntes out
again in its original state on cooling; but if 1^ pts. or more of nitric acid
be added to 1 pt of bcn^oyl-benzoiiij the latter diasolvea without external
beating, and with scarcely iiny evolution of red vapours; and on pouring
the yellowish solntion into cold water, a resinous body is deposited which
13 hard while cold, but inoltfl easily in hot water* This subBtance is
washed with water as long as the water thereby acquires a yellowisb
colour and acid reaction, and the washed product {amounting to | of tho
Lenzoyl-benKom used) is treated with cold ether, which dissolves a per*
tion and leaves nitrobenzoyl-benzoYn in the form of a crystal hue powder
amounting to rather more than half the weight of the benzoyl-benzoTni
it is purified by re crystallisation from boiling alcohol, — The ethereal aolit-
tion kares on evaiioraCion % thick oil, epannglf soluble la alcohol, which nppeara klso
to be a ujtro -com pound*

Properties, Cn^fitallisefl from boiling alcohol in wbit^s shining scales
composed of rhombic plates aggregated in scalariform groups, ^lelts at
137"^, forming a colourless liquid^ which fiolidifies at 110% in agranular
mass like starch-sugar; in thin layers it solidifies to a gummy mass, whicb
however quickly becomes opaque and crystalline when rubhed with a
hard body^

42 C ,

... 252 .
.. 14 ,

,., 15 .
... 80 ,

.. 69-80 ...
.. 3*S8 ...
.. 4a& ...
,. 2217 ...

Zinin.

»,* 6577

N .„..

13 H

10 o „,

.... 4^00
.... 4 22
.... 22-01

C«NH^O^« .

.. 361 .

.. lOO'OO ...

.... 100 00

The compound is iBSoluble in water. Strong nitric acid dissolves it
Pifeadily and in large quantity, especially at a gentle beat, and without
decomposition; but on boiling the liquid , a new body is formed, which
dissolves pretty readily in ether, but is less soluble in alcohol than the
ijitrobenKoylbenEoin, and separates in the pulverulent form as ths
eoltition cools.

Nitroben^oylbenzoTn dissolves in 12 pts. of boiling cdcokol^ and sopat
rates out almost completely on cooling: it is insoluble iu ether* K*

VOL. xn.

1?8 COMPOUNDS CONTAtKlM TWO OR MOfifi Ah CmK

StUbousAcid. C«irw?

RoBiaOTT & BouTKON CnARLARD, (1830.) Ann. Chim. Fkjfi. 44, 371.
LiEBio ^ WiNCKXEE. An7i. Pkarm. 18, 324; Fogp. 41, 389.
LiEBio & Pklouze. Ann. Flmmt. Id, 289; Ann. Chim, Fh^s, BB^ 145.
Laurent, Amu Ckini. Fhjfs. G5, 193; J. pr. Chcm, 12, 416,— jV* Aufi,

Chim. Fhy9. 1, 309; Ann. Fharm. 38, 035.—Jieu. Mci<mi\f. 10, 120;

X pr, CAm. 27, 310.— /i\^. #cmii. IB, 370; /. pn CAem. 35, 4$^—

Cbmyj^ r<f7i£/, 22, 789,
Laurei^t & Geruardt. Comp^. cMm, 1850, 117-

hxn biCQ flnt obflerv^d bj Sunge {lU^pert. U, 36!)) In bitter almond oil m\k\dh bnd
been tzeited with cbloriae gasi but wa« lirtt recognised oi a pecoliar tubiUiice cLij^nut
from b«i^ofii by liebig & Winckler«

J^o/Twoium, By troitSng bitter almond oil, cLerrj- kernel oil, or Ifttrrel
oil, containing pmafiic acid with moist cbloriuo gaa (Robiqnet & Boutroii
Charlard, Liebig t Wincklor, Lnurent), — or witb fuming oil of vitriol
(Lani^eiit), — or witli cblorido of eulpbiir, (Laurenu)

Preparation. L Moist oLlorine gas is absorbed by bitter almond oil

(or laurel oil), with couflidorable rise of teniperatufe, ntid tbe cl«Ar
greenish yellow liquid saturated with chlorine de|>osits, after a few
hours, small crystals which often cause the entire liquid to assume tbe
form of a compact solid ma^s. On treating this mass with ether, a
white crystalline powder remains nndisaolved. (Robiquet & B, Cb&rlard,
Liebig jSb Winckler.) — 2, When three raeaaures of eommercial bitter
almond oil are mixed with one measare of fuming oil of vitriol, gr^At
heat is evolved; and the brown liquid tbiekeos and eolidifies in the
cold to a crystalline mum, which, on being shaken with water, separates
mio two layers; the lower consisting of sulphuric acid with a small
qaantlty of bitter almond oil, while the upper ia semi-eolid aud yieltlfi,
when treated with a small quantity of cther-alcohol — which take* up
any bitter almond oil that may have remained unaltered — a white i
talline powder, which, when rocrystalliaed from hot alcohol, forms T
rectangular prisms or alender needles. (Laurent) — ^3. Bitter ml
which did not yield any product when subjected to tho procofi jlit
described, was, after being treated with oil of vitriol, immtdiHtetj aih»d
wtlh ether, and gradmtlly neutralised with mnmoniii ; an oily layer ib^ti
Mmmted, which solidified after a while, and yielded reetanguliur privms
when boiled with alcohol (Laurent,) — 4, Bitter almond oil lK»comoi
ttrongly heated in contact with chloride of sulphur, ojid evolves
chloric acid; and if tbo oily product containing a few needles, be I
after a few hours with a mUtare of ether and alcoholio ammonii
li^erfi are formed^ tbe lower of which is a thick masa chiefly coo
of ^oiphur, tbe middle an alcoholic solution of sal-ammoniac, m
upper an ethrroal iolution of unaltered bitter almond oil and stilli
aeid (Laurent)

Frtparaiifm. Crjitillitea in two difierent forms ; the
i, B&nd 4j and iumetilliei ftlao S, crystallise in dazzling white.

STILBOUS ACID.

179

rectangular prisms^ wbose terminal faces are replaced by two faces
intersecting one another at an obtuse angle and resting on the horizontal
edges of the prisms; one of these faces generally predominates and gives
the crystals the aspect of an oblique rectangular prism. (Liebig <fe
Winckler, Laurent.) The crystals ootained by (2) are small rhomboidal
prisms whose terminal faces are replaced by two faces intersecting at an
acute angle and resting on the edges of the prism. (Laurent.) The
two forms cannot be made to pass one into the other by recrystallisation
from hot alcohol; but if the rectaneular crystals be kept for a few
seconds in the melted state and then dissolyed in hot alcohol^ the solu-
tion on cooling deposits the rhomboidal prisms. (Laurent.) The salt
melts when heated at about 160*^ (Robiquet & B. Charlard) without
volatilising; and solidifies on cooling in an opaque radiated mass or a
transparent gum. (Laurent.) Tasteless and nearly inodorous; without
action on vegetable colours.

Formula and Calculations according to :

L

Liebig.

IL

Laarent.

42 C.

18 H.

.... 252
.... 18

75-45

5-39

19-16

56 C

24 H

10 O

.. 336
.. 24
.. 80

70-36
5-46

8 0.

... 64

1818

C«HM08.

.... 334

100-00

(J66H240»0...

. 440

100-00

IIL

Laurent & Gerhardt.

IV.

44 C.

... 264

76-30

5-20

18-50

30 C

12 H

. 180
. 12

,. 48

750

18 H..

... 18
... 64

5*0

8 0..

6 0

20-0

C**fl«W.

... 346

100-00

C»H«0« ...

. 240

100-0

Analyses according to :

Liebig.

Liebig &

a. b.

c.

d.

•

c...

H...

74-59 71-86

5-42 5-66

74-92

5-69

75-27
5-64

Laurent.

C

H

e.

74-2
5-6

.... 74-4 .... 74-6
.... 5-4 .... 5-3

.... 750 ....
.... 5-4 ....

t.

75-82
5-47

76-20
5-45

For the analyses a, b, c, d and i, the substance was prepared by (1); for
«»/f 9t h and i, by (2) ; the analysis i, was made by Laurent eight years later than the
reft. — Calculation I, is founded on analyses a ... A, and regards the substance as
benxoate of hydride of benzoyl, 2C"H602,Ci^H«a* : II, is founded on the analyses i , k,
and assumes the formula, 3C^H«02,C»<H«0*. Laurent & Gerhardt observe {.Compt.
ehim. 1850. 117), that these views do not explain the formation of the compound by
the action of oil of vitriol, and they suggest that its formation takes place with the
agency of hydrocyanic acid (like the formation of mandelic acid) as represented by the
foHowing equation (Calculation III):

3C"HW + CNH + 2H0 = C^H^G^ + NH';

1*^

ISO COMPOUNDS CONTAINING TWO OR ilOKB At. C**!!*,

]

si tbe same time they direct ittendon to the decotiapoiitio& (4)*

u^rrea better viUh the (greater Dumber of tUe nnalvsea* Accordinf to tliis

nctiorj of the oU of vitriol, or of the hydrochloric acid restiKing from C]i9

LOivverta the liyrirocyanic acid Jtito formic acisl, trhich unities with 2 At*

oiL or 1 Al bctizotn, wliile 2 At. water are Ecparated (compu% .Deeoa^miiSm 4^

the potash -GompcQiid) ;

C^RUQi „ CMHO« « C^'O* - 2HO.

The formation of heozoie acid on heating the compound with dcuholic potii«h iom
necestltate ttie auumptton that the compound actuallj contains benxoie add^ tELAitner]!
aa tbftt add i» prodncedp under tbe same drcumstanccs, from bitter almond oiL (p.^I,

Becompositkm. 1. Stilbotis acid yields by di&tiHatton firet a yd-
lowiabj then & greenish oil, wliicb dissolves in ether, leaving elongstfil
laminm, (Laurent ) — 2. Chlorine gas passed tlirougli fused stiibaiis jbdd
forms liy<3rocbloric acid and an oil which solidifies partial ly after m wfcile^
and is partly dissolved when boiled with water j the solntioa on c^ooUii^
yields small rigbt rectangular prisms, which crystaUisa in tb© same lona
after fusion, burn with a flame which has no green edges — tbcrefott
do not contain chlorine — may be volatilised witbont deeompoatioQ
(therefore are not nmndelic acid, L.), and form with nitrie ftcid, a «ola-
tion, yielding by evaporation a substance which dissolves in alcohol mi
other as well as m ammonia^ but docs not appear to be a definite ooan
pound. The portion of the oil insoluble in boiling water diasolTes in Alcohol ud m
ether, and for the mo>t part also in boiling pot«ab. The etill hot potaih^aolntkpii forai
when saturated with acids, a laminated crystalline precipitate, vhicb molls mhea. lieitalt
soltdifiea in a jibrous mass on coolingi dissolves in alcohol and ether, bul 4<w hI
consist of benzoic acid [st liberie add? L»] (Laurent), — 3, Stilbous ad<l H
slowly decomposed by boiliui^r nllric acUf; the solution does not coatiii
benzoic acid. (Lanrent,) — -4, Heated with oU of vitriol, it mvm iti
carbonic oxide; and the residue treated with water yields a tbtcX brow
moss, which smelb like bitter almonds, and dissolves partially u
nmmonia. — 5. Boiled with iilcoholic potaJt, it yields benzoate of pof '
(Liahig,) — Op In contact with alcoholic ammonia it remains unali
(Laurent)

Comhinalioiu. tS'itlbUf of Fcta^, — Fomieil by the action of
strong pot ash- ley on stilbous aeid^ as an oily-liqui*l, which, when eri
to the air, gives off 8 or 10 per cent of water, and eolidiBes in a fil
mass, which at a temiKjrature somewhat above 1 0O'^j giTes off S5 p, e<
(about 10 At.) water and leares a solid tumefied mass oor*-— -"
17*1 p» c. potaslu

C»H»W ...... 231-0 ..,. 8304

KQ , 4^*2 ... 16-96 ....... 17t

C?ftH»iKO* .... 278 2 .... 10000

If the compound were C^W^KQfi (aeeordinf to I), it tbonld eoataia lS*n nfrfiit^
of p<»taahi wberitaa tbe formiiLa C"H»1K>« (according to il), or, mco
C»H»KO*. recimrM 18 28 p.c KO, and the formalm C**K''KO» (»
requiitJi 12 p. c. KO,

Siilbous aoid k insoluble In cold alcoboli but diseolvefl abttadantiy ia
lioi ahoMf ftEd readily in c^cr*

STiLBEsrc Acro.

Stilbesic Aoid.

I

L.irBE.NT. J?^f* sci^tt l^j 387; J* pr, Chmi, 35^ 430.
Xaurent & GehhjuRdt, Compt* ddm. 1850, 117*

AmdM MtilbtKurf SaroMde de sHl&he^

Whetj bitter almond oil w treated with cblorino gas, aided by heat
towarda the end of the proceaa, the whole solid ifi eg on cooling into a
crystalline mixture of benzoic acid, stilbesic acid, a body crystaUiaing in
slender needles, and chloride of benzoyl; and if the chlonde of benzoyl
be allowed to drain on a funnel stopped with coarsely pounded glass, the
mass pressed between paper and treated with cold ether-alcohol, stilbeaio
acid remains behind, and may bo crystallised by solution in boiling
ether and spontaneous evaporation,

Obli<|uo rhomb ie prisms. Fi^. 84, without / and i; Z"^. 84 without
/and m; i : m ^ 126' 30'; m : u = ISB^^ u : u = 96'; n : m = OQ.
Melts at HS*^, and if tho whole baa not been fused^ solidifies at the same
temperature, but after completo fusion, not till cooled down to the ordi-
nary temperature^ forming a tranispareut gum which when carefully
Ilea ted, slowly crystallises in opaque radiated nodules.

2BC 163 .... 71-80 71-58

10 H 10 ,.., 4-28 4^33

7 O ,.. 5G .... 23-92 ..... 2409

C^Hi^W 234 .... 100 00 ....... lOO^OO

I*aurent sapposes that, in tlie forniatioti of stilbesic acid, 2 Ath bitter almond oil
baTC taken up 1 At. oi|gen to form etilbous acid, and tbat la this eompound 2 At. 11
are replaced by O, water being at tbe aame time decomposed ; for althongh the cblorino
lucd was dr^, tbe bjdrocbloric acid vapours tibovfi tbe oil bad nevertbeless condensed
moistisre from the air. ThiB view takes no account of the decomposition by oil of
vltnol- Accordbg to Laurent & Gerbardtf tbe prusdc acid contained in tbe bitter
almond oil exerts an inrtuence on tbe formation of stilbesic as well as of stiJboua acid.
I Any more definite eanclniion a[tpeara fur the present unattainable.

' Stilbesic acid yields by distillation an oil -wliicL on cooling depositg
crystals, apparently a product of dccom posit iou. (Laurent.) — Heated
with oil of vitriol, it gives off carbonic oxide gas; water added to tlie
residue separates benzoic acid. (Laurent k Gerhard t.) — It dissolves
in jwtask and in ammonia and is precipitated therefrom by water*
(Laurent.)

JStiibemiie of Silver, — Tbe boiling amraoniacal solution mixed witli
nitrate of eilver farms Bhiaing scales* (Laurent.)

Laurent.

C^MKfi ....,.*. 2n .... 51-79
2 kg ..„.,. 216 ..., 48*21 487

C=»H«AgSO?.....,.. 448 .... 10000

The acid dissolvea very sparingly in alcohol and in ether. The soltt-
iion does not roddoa litmus. (Laurent.)

18S

COMPOXmBS

)R MOEl At. CWfl*.

TUe solution in etlior-alcohol obtained in tbo preparatiOB of ^ift
acid y^ields l>y evapora-tioii, benzoic acid atiJ eleader ueedW.
when freed from benzoic acid hy dilute amtnonia and purttied by reerp*
tal ligation from cold etber, form lons^, shining, needle-shaped erjitoii^
united in tafts; after fusionj they solidify in an amorphoaj ma»^ whicf '
when gently heated crystal! iaes in microscopic spherical ucMlules. Ihm
CiyBtah dissolve in boiling ammonia and arc precipitated therefrom h
aeids. (Laurent.) When distilled, they yield another eub^tanc© wli'
cry stall isei in distorted needles.

BenBilic Acid.

LmBio. (1838,) Ann. PhnrTii, %5, 25.
ZiNiN. Ann. Fharvi. 31, 329.

F^rmathn and Frfpamthn, Hot alcoholic potaeh is added to betmls
or [belter, J. L.] to benzoyl, till a fresh addition no longer i^uae* laj
blue colouring; the alcobol is then driven ofiT, and the aJkaline lif|ai<i
diluted witb water^ mixed at the boiling- beat witli excess of hydrocycoie
acid, and filtered from any oil or resin that may he separated. Tfc*
filtrate becomes milkv on coolin*^ and deposits crystals of the acii
(Liebig.) Benzile or benzoin is dissolved in boiling and tolerably con-
centrated alcoholic potash, in encli qnantity a^ to leave the liqnid dis-
tinctly alkaline. The mixture is then boiled till a portion of it mw^
vrith water without turbidity; the liquid evaporated to djryuem otet ikb
wat«r-hath; the residue exposed to air rich In carbonto add till th$
potash \s completely «^turate<l with that acid [the eonTerstoti df tbt
caustic potash into carbonate may however bo better effected by :
carbonate of amtnonta before evnporating; J, L], the mass treate

ti^|M

alcohol 3 the solution separated from the carbonate of potj^h, mixeiiT
water; the alcohol distilled o^, the remaining liquid iKJilod with animal
charcoal till it becomes colourless or retains only a slight yelbwi«^h tiatr
and then filtered; the charcoal washed with hot water; and the «riluiiwo
left to evaporate to the cryfitallising point. The erystallised potiuli^i
is dinsolved in water; the solution poured into an exce^ of btnljng tad
largely diluted hydrochloric acid; and the mixture hoiked till the tnM*
dity produced on mixing has eompletdy disapi^eared. If llio Vt^uH It
then left to cool aIowIj^, it becomefi i»pftle0cent and flUed wjlh bog m90m
of hen xoic ac id . (Z i n » n . )

Fr^perim* Hani, shining, transparent needles, loo^loroua. Hm •
flourish, bitter/motallie taste. Melts at r^O"^, forming a eotatLrlcas 1m|«I*
(ZiDin.) Ha» & strong actd reaction*

L nc

% n H

lis

„,..- 12

lii^bif.

**Mi.*« 6 "33
2\U

Zinin.
... 73 H
., 6 31
.., SI fca

1

6 C . ._

40

*

C»U'HJ«

L

....... 228

.„ imm

....« 100*00

J

BENZILIC ACID,

183

I

Be^miposUims. L Heated above tbe meltiD^ point, it turns red,
aud emitsafjeculiar odour and a violet -red vapour, wliich condensei into a
brown-red oil having a burning E^liarp taate, distilling without alteration,
insoluble in water^ bat dissolving easily and with red colour in alcohol and
ether; the solution is rendered turbid by water, but not decolorised, it is
decolorised by potash ammonia and nitric acid| but not by hydrochJorie or
Eulphurie acid. (Zinin.) — 2, To oil of vitriol, benzilic acid and its salts
impart a fine carmino colour, which is not easily destroyed by heat; it dis-
appears on addition of water, but reappears on evaporation. (Liebig,
Zinin.) — 0, ^}^^ pentachloride of phoepborns, it yields phosphoric acid,
chlorophospboric acid, and chlorobenzilo. (Cahours.) — 4, fienzilate of]
|H)tash when strongly heated, gives off white vapours which condense to a
Golonriess oil, smelling like naphtbaliUj having a rough burning taste, dis-
tilling without alteration, easily soluble in alcohol, and precipitated there-
from by water. The residue contains charcoal and carbonate of potash*
^ (Zinin,)

Combinatwm* The acid dissolves sparingly in cold, more readily in
boiling water.

It dissolves in hot nitric aoid, and is precipitated unaltered by water,
(Zinin.)

I> BmxU^e of pGtmh. — (PrtptaraUtm^vld. mp.) Colourless transparent
crystals, easily soluble in water and alcohol, insoluble in ether* The
|U(oeous solution, evaporated at a strong heat, solidifies id a mass con-
mating of narrow tables. Melta above 200^ forming a colourless liquid,
which solidifies on cooling. It is decomposed at a high temperature
(piJ. #ii;^.). ^ AnhvdrouB. Contains 17-5D per cent, of potash, and is
therefore C^^H^^KO*. (Zinin.)

^m Senzilate &f Lead, — Obtained by dropping a solution of neutral
acetate of lead into the aqueous acid as long as any precipitate is pro-
duced. White powder, unalterable at 100''; when heated, it melts into
B red liquid and gives off violet^red vapoura. Dissolves to a slight
extent in hot water. Contains 32 87 per cent, of oxide of lead, and is
erefore C«*H^TbO*. (Zinin.)

r

SmniaU of Silver. — Obtained by precipitating nitrate of silver
ith the ammonia or potash salt. White crystaliine powder. At 100"*,
it assumes a snialt^blue colour, without loss of weight, but after some
time becomes brown -red and begins to decompose; at a higher tempera-
tnr€ it melts, gives off violet- red vapours, and leaves metallic silver.
Slightly soluble in hot water.

• 11 H

6 0

... 108 .... 32^24 _.,„
.... 108 .... 60' 15
.... 11 .... 3-2fi
.... 48 ..., 14-33

Liebig,
32-25 .

Zmia.

... 31^38

49-53

3-37

15' 12

C^lFAgO'* ,„, 335 M„ 100 00
The acid dissolves in alcohol and in ether

100-00

1S4

ODM70C5DS COCTADCme T»0 01 HOdl AK« €fV^

CAHorsii. {IS49,> X Amtu Ckim. PhfL. 23, aSO | X pr.

P«alacliloriile of pkM|ifco«a a^ett riol^itl j, witli the aid of Itealp tpoa
Imslie aod, a li^|e qwotitj ^f liirdroeiilonc meld 1>ein^ evolre^l, and tlis
jifodiel, wifeev ^iitUled, jieidiBg dilorapbospboric ^cid At 1 1 1 ""^ And (^n^
SSO** upvaidfl, ddarobes^le^ wEkli is imbed witb cold wmier^drid
b^ cblortiSo Cif dlciiuB sad rMtlfied.

CoJoinleB limii^ fc»^ier Ikia wmter. Wiling si abottt Tttf, aal
Ii»riag » poir«cfiil «dtmr.

?8e .

1] H ,

a.

40

lSS-4 ^ SS*10

11-0 »* 4*l€

3i'4 _ 14*35

32-0 ..^ laoi

. 68-39
4-43

1113

c^H**aa»«« «4S'4 ^.. iwKHi ««

10000

Tti contact with moijt air, it is qnicklj c<>nTeri«d into liydi
and benztlic acid. With hot strong pota^h-ky^ it qoiekly yields
of potassium and bcitxiUle of potash. With ammonia and a
forms crystalline prodaets (bfniiliinwic woA betuUuulidc ?)*

BenzUe. C*H'^<.

[iJiirimiiT {!%%$.) Ann, Ckim. Phfi. 5$, 402^ Am. Fkitrm. 17, fti

Po^. 36, 501 ; /. pr. Tim. 35, 46.
LiEBia. Ann, Pkarm, 25, 25.

ZofliN. ^nw, Pkann, 34, 188.— ^ j>^*, C5W^. 33, 35,
GnEGQiir. €^Mi^. Mm. 1S45^ 30S.

Formfition, By the action of chlorine or tiitrio add upon _
GirfonTj on one ocosiotii obtiii»«d bcniik, in «tl«)aptifif to pfcpain ^rfttctn hf I
bitter dinon4 qU with bf drpejinic actd Ami tlcoboUc potaili.

PrepoiXiiion* 1. By passing chlorine gas over fused b«njoTp, aa loog
as hydroehlorio acid is evolred, and crystaUiatng tbo pfodncl 6w
alc^bd, (Laureat) — 2. When 1 jst of dry benioTta k Avotly Im ' '
with 2 pts. of strong eolonrleat mtrio acid, nitroiis acid la copic
€voIve<l, and the bcnioTu melts into a clear yellow oil wfakli tiai
the Aurface of the li<iuid and consists of pore Sanitle. (Ziiiiti.)

Pt^Hrtm^ Volbwisb, nearly eolonrlees. CtyBtallJaea
boliG or«Uitreal ^lutioa by apontaneoiia eraporatioa in

185

fideJ prisma. (R a>R oP or R. «R,) (F^. IB7, fii. 140.) <r : if
— 120^; ri and r= : # = 134"; r* : ^ = 152, The crystals COUH
moTilj have in the middle a hollow epaee with m% sides paraHel to the
faces of the prbm. (Laurent.) Conchoidal fraijture. After fu^iion
between 90° and 92°, it solidlfiea in a fibrous maas- Volatilises Without
decompoaitign. Inodorous and tasteless*

2a c

4 O

.. 10 .
.. 32 .

.* f^O^OO ..
.. 4-76 ».
,. 15-24 .

Laurent*

7901 .

„.,, 4-84 ..
..... 13'&5 .

liebig.

., 79-29
» 473

.. 15-9B

C3*H»"0^ .

..210 .

,. ioo-00 ..

..... 100-00 ,.

.. 100-00

Decompodtion. I, Burns with a red sooty flame. (Laurent.) —
2. It is not altered hy boiling with nitric acid* (Lanceut) — 3. It is not
decomposed hy boiling with potash*ley (Laurent); but when boiled with
alcoholic potash it turns bine and forms beuzilic acid. (Liebig'.) — i
4. The vapour passed over rod-hot lime yields an oil and a small quantity
of charcoal, (Lanreut.)— 5. When au alcoholic solution of bsnzila
Is mixed with acjneoiia ammonui^ a white fiue-grained precipitate of
arobenzOe (C"NH-*0') h produced ; at the same time benzoato of
ethyl is formed, and a aabgtanoe which disaolyes readily in alcohol,
and crystallises in small needles. The latter substance Is formed
in larger quantity when the alcoholic solution of benzile is gradually
mixed with small quantities of aqueous ammonia, and kept boiliug all
the whilcj till the liquid becomes turbid. (Ziniu.) When an alcoholic
iolutiou of benzile saturated at a high temperature, is saturated while yet
warm with dry ammoniac d gas, and sufl*ered to cool during the passage of
the gas, a white sedimeat is produced^ which ^ in the course of 24 hours^
becomes covered with small needled^ while other products ri^main in
Boliition. The products thus formed are iraabenzil, benziUmide, benxilam
and an oil very soluble in alcohol. {Laurent) ™<J. Sulphitretfrd
hydrogen forms, with abundant deposition of sulphur, a yellow oil
emclling of garlic; this oil, however, is more readily formed hy distilling
benzoyl with hydrosulphate of ammonia, (Zinin.). By the action of
hydros ulp hate of ammonia on benzile, two or three diflerent substances
are formed, among whicJi hydrobenzile (p. 185) occurs. (Zinin.) —
7* Benzile fused -wilh. potassium giY^E o^ yiolet Tapours and leayea »
^ carbonaceous residue.

™ ComhirmtimiM, Insoluble in water. Dissolves in hot oil of vitriol
and is precipitated therefrom by water* (Laurent.)

H lltfdroeijamiUof Bemili. — When to a solution of beuEJle in boiling

^^ alcohol, there is added a quantity of nearly anhydrous prnssic acid about

equal to that of the benzile, the mixture, on being left to itselfj deposits

white shining rhombic tables produced from a conibmation of the rhombo-

bedron with a right prism. (Zinin.)

^^^H

32 C

„ 202 .

.. 73-72 ..

.... 72*96 ^^H

^ 12 H

.. 12 .

.. 4^38 ..

^^H

F 2 N .„,.... ,.

„ 28 .

.., 10*22 ...

^^M

^ 4 0

.. 32 .

.. 11*68 ,..

^^1

., 274 .

. 100*00 ...

Wk^m ^^H

1B6

COMPOUNDS CONTAINING TWO OR MORE At- C^H*.

Molts and decomposes when lieated, letkvmg a residue of Wniila
Heated with nitric acid or ammoiiia, it jielda benxilo. The alcoli&lj^_
solution mixed with nitrate of silver foFtn« cyanide of silver^ and Jjeniile
crystallises from the solution. The a!coUo3ic solution heated with
n»ar<:iiric oxide reduces it, and at the same time, 'he preBenee of benio
of ethyl becomes perceptible. The compound is not altered bj boilia
trith water or with galta.

Ben^ile diseolvos nmdilj in alcohol and in ether.

Appendix to ^etizUe.

HydrobenzUe. c«H«0*,

ZiKiN, (1844.) J.pr. Chem. 33, 35.

When benzile is treated with hydrosulphate of ammonia,
three diflerent bodies are produced^ one of m hich forms crystals in
shape of concaro-convex lenses united in spiral ^ode«. Melt« at 4,
forming a colourless liqmd which may be distilTed without alteration _
and eolidi6ea in the crystalline foim at 42°* Smells like bitter almond"
oil and has a sweetii^h burning taste.

ZiniiL

28C.« «, 168 ..., 85 71 .^.», %hn

Uri 12 .... 612 ..„,,„ 6-27

2 0 16 .„. S-I7 ». y-9§

c»H»*o* 196 .„. loooa „„.., imm

Boiled with nitric acid, it forma a yellow resin ^ which la uoi!
pletely precipitated by water*

It is not altered by boilini^ with solution of potash. It does not i^
aff ammonia when fused with hydrate of potaeh. Jt diasvlves in aicohoti
potash, and appears not tt* be altered by boiling.

It is b u t ^ I i 4j h tly attac k ed by c h 1 ori n e gas .

pissoUes readily in oil of vitriolj and is precipitated by water In fti
original a^tiite,

Jnjiolublc in water^ but dissolves readily in tUco^toi and ether.

Piciii,

C«NH«0* or C«NH^* (= C«NH>»0\0'), I

Laurent. (1844.) Mn?. mfnt 18, 201; J. pr. CA^m. 35, 448.— i^, in.^
Chim. Phjs. 1&, 3(J9; J,pr Chtm. 40, 407; Ann. Pharm. 6t^ lOa

Frepamtwn, The ethereal liquid from which omd© stilbene (p. II

hfti topamted on cooling, yields l>y ipontaneons evaporation a very dai_

colour^ dl and brown cry^jtalJino g^rains which, nftcr the add it ion of L

icinall <}uantjty of othor, nui^t be scpnrtited quickly froin the liquid. TIj<^

mqIuUou aiUl yieldA by evftpotatioa a few more crystallioo granulce^ which

picRHi.

1B7

may be washed with a mixture of ether and alcohol; the mnlher-Hquori
ia a^LD left Iq evaporate as long sa any crystal lino granulos separala, f
Tho tryutallme granules, when tliesolveS in ether and eereral times
recrjBtallised, yield very beautiful colourless crystals.

Colourless octohedrons belonging to the oblique prismatic system, and J
having their summits and the smaller edges of their bases truncated,
( + P : — P on the lateral edges = ll2"j — P ; + P on the edges of
tho base = 117"; + P ; goP =^ 1S9' 30' : oP : -f^ P :^ 133" 30;
oP : P = 12P 30'.

Melts at a gentle heat and solidities into an opaque gummy mass on
cooling.

Cftkoktioa I.

42 C _.. 252 80^80

N... ,„ U , .... 450

14 H,___ ,, 14 _ 4*50

4 0_ 32 10*20

fC*^H"0* »».... 312 100 00

Ana

C .., eo'80

K « 476

B .-... 4*59

O 9*B5

Calcnlodon 11.

42 C .». 252 80*52

N_. 14 4-4f

15 H 15 478

4 0 32 10*23

C^NUiiiO* ...».., 313 lOO'OO

6 C 8 •

eO-45 80-27

I 7

470

477

^
^

lOO'OO

Pfora analysis a, Laufent formerly deduced the foTmula I, accorJmg to whiehj
pietit might be li com]M)UDd of benzolone aud cjajiogeti (C^^NH'^O* — C*H*^0^ + C'N) ;
•nftljsis 5 wiu aftenvank mjide vrith fomewhat y alio wish a7«tols| c with perTectlj
oolotirlasf cry&tals.

Decompohitlfms, Pulverised plcril itnmcdiately forms with brommc
a gunnay mass, a small quantity of hydroHromrc acid escaping at tho
tame time. The product, after being purified from free bromine by
washing with water, then dissolved io ether, reprecipHated by alcohol,
and freed from adhering ether and alcohol by gentle Leatiug iu
vacuoj fonus a colourless, trausparent, brittle resin, which contains
61*36 p, c. C, 3'33 p. c, H, and 24 30 p. c, Br. and according to Laurent,
u a mixture of C*»NBrH»*0* and C«,\ Br^H^*. It appears to be capable
of djstiliing partly without alteration, hut at last a small quantity of
Lydrohromlc aeid is evolvodj and charcoal also io email quantity left
behind, — Chlminej aided by heat, acta like bromine, evolving hydro-
eklorle acul, and forming a soft resinous mas« which dissolves readily in
ether and is precipitated therefrom by alcohol; it contains 68*2 p. c. C
Slid 3 8 p. c, Hj and is therefore a mixture of C**NCiH**0* and

3. Picril boiled with nitric acid is at first converted Into a yellow
resinous muB^j which, after boiling for some time, didaolvea and isconreded
into nitropicrih — 4, Wljen picril is boiled with aqueous chnmiic add^ a
brown mixture la produeedj partially soluble in etlicr. The insoluhio
portion may he sublimed in white lamia oe at a high tem^mtut^.

^^r^* ^j

188

oourainms coFTAmncG two 6i

—$.i

Nitropiciii

L^imE^vT* £d€. Ht*

When picril m boQed witli niiHe acul till tlie whole U dj«olr«4 tW
iolution on coolii^ depoeits s yellow fiooiewlist cijilmtlia^ powdtr, a
Utile more of vrh^ek wepuamteB qu adilitioa of wmttr.

C^*H"0*' „, 417

100^00

42 C

4 N

12 H.

IfiO

2S2

If
128

«^ 56-25
.«, 12S0

_ 2S-57

it<io

f8«23

C«K*H'«0» «„ 448

lOO-OO

lOeiNl

When L^ie^ it decompose wttb emission of l\Ai-

It difl®oH*e« very spariiigly in ahih^tl^ very reidfly tn fCler.

ThiouessaL
C»*H^S = C»H*S,C«H«.

Laubejit. (1844*) ^tfVp ici£fil, IS* 107; J. pr. CT^w. 35, ii.

Formation and Frfparfiiym, lo the dry distill ailon of suIpUdtt

ittlbene or of tbe cm do product of the action of bydroeulpM&e «P

unnaonia on bitter almond oil, after the etilbcno Iiils paased mrcr uil

eolidified in scales and the bent haj9 risen, needle- shaped crystals conteM

in tho neck t>f tbe retort, and may he purified by builmg tbem In tl«

ffiato of fine powder with ether^ which dissolves out the eiilbcne mix«^

witb them. Tbe ro^idual white powder ii boiled with a Um Mualiiy

of etber. till it i^ completely diaealved, and the ethereal iol^taoa dgptiitf

^yunc^seal by coo I log or by ^ponlaiieoiu evmpef&tioa» in loboitot Iftt

tab gronped in tufts or spherieai masses. It \m bow«v«r wm

^tigeoui to reerystalliMe the product from boiling reetifi^Kl fockn

irkieh tbe tbionesaal separatefl on cooling ia iiotdlott *

hml

NITROTIllONESSAXi

189

Prepfriki. Colourless, inodorone needles liaving a silky lustre.
Melts at 1^°, and solidifies on cooling, in a epoiigy mass, whien absorbs
the «tiU liquid portioa and swells up. After slow cooling, it fiften
remains anjorphousj and does not crystallise till gently heated, Tho
vapoara have a faint and not ^ulpliarous odour.

' 7- - ' -^^^

26 C

15fi .

... 86-18 ..
.. 4*98 ...
.„ 8-84 ...

Laurent,
...„ 8G-35

9 H

S ,...

9 .

15 .

..... 4^90

..... 878

Ca»H«S „....

181 .

.„ 100*00 ...

100-03

I vapoa

Bams with a reddlsli sooty flame, Witb bromine it immediately
becomes beated, gives off vnpours of bjdrobroraic acid and forms bromo-
thioaessaU It ia but slowly attacked by boilinjr nitric acid, witb formation
of n i troth ion ess al; the liquid does not contain sulphuric acid. Jt is not
deoomposed by boiling alcoholic potash» Heated witb potassium, it yields
sulphide of potassium and a largo quantity of eharcoal.

It dissolves very sparingly iu boiling akokQi^ with difficulty in boilbg
ether, most abunduntly in boiling rodt-oi/, from which it separates again
almoat completely on cooling.

Bromothionessalp C=<Br*H^S.

T. ioc. ciL

BromitAion€t9iUw

Obtained hy treating thlonessal with bromine. Hydrobromic acid ia
then evolved and a solid mass formed which may be purified by boiling
with ether.

Pulverulent J melts at a high tomperaturej and solidifies in rhomblo
tables on cooling. Volatilises without deeom position.

i 26 C

7 H

.*.. 156 ,
7 .

.. 46*02 ..
... 206 ..
,.. 47*20
... 4-72

Laiirent,

...... 49*S

2*2

i 2 Br

' S

... 160 .

.... 16 .

C«H^Bi3S ....

,.,, 339 ,

... lOO'OO

Nitrotliionessal. C^^X^H^s,

Lauhent, lo€, ciL

KiirilhioneMiU*

When tbionessal is boiled for some time with nitric acid, it first
'softens and ultimately forms a yellow porous friable crust, which ia
ijbe4 with water and with alcohol, and ultimately boiled with etheri

190

COMPOUNDS CONTAIKINO TWO OR Mom AU C^n\

whkh dis9olTes bnt little of il^^ and on caollng deposita it all in ihe ttm

of a flocculeut powder, Tho residue formi a p^ilo yellow, tolenbl]
fui^ibltj powder, wLicti on cooling solidifies in a yellow %t
amoqihous mam,

LanreflL

2e a ise ,..* 57 se „...„. si-s

2N 2g »„ 10 S3 10*7

7U 7 ..M 2-58 2 7

S .-.. 1$ .... 5*91

8 0 .,». 64 ..„ 23 G2

C^WmsCF ,». 271 .... 100 00

When heated to the boiling point, it iakea fire and learea a

q^uantity of cbarcoaL It is not attacked by potaah-loy.

Bibenzoylimide.

RoBsoN- (185h) ehem. S&c. Qu. J. 4,225; Ann, Fharm. 87, !«;]

J. pn CA«K. 55, 245; P/^a^m. cmfr. 1852, 209.

JH&mzoylimide*

Formation and Frepfiratimt. Ammoniacal gas parsed into an ale
Bolution of bitter almond uil, is abu u dan tly absorbed, and aitet r
tours a granular precipitate of bcmoylaxotide eeparatos out, mixed
a resinous body, which is dissolved on treating the precipitate willi
alcohol. The residue obtained by evaporating the alcohol ic aolutioc,
aasunies a tight red eolonr after several hourfi bolting with polaab-l«yi
and beoomea brittle and reainoua* Boiling h3^drocbloric ncid extras
^from it only a small quantity of amarine, and after t^he residnc baa been
edwitn boiliDg alcohol, bibenzoylimide remains boliind.

J?rope)im. Y otto wish powder conaiating of feathery crystals^

28 C 16« .., 75*$t

N , 14 .... SeO

laH 13 ..,. 616

2C -. . IG .,.. 7 '62

*.„ 79-66

.... 6^49

.... 6-43

.. ^41

tP^B^H^. 2U .,„ lOOOn .., 106 00

{2C^*H*0» + NH» - C^H^C + 2HO.)

). It is not altered by boUfog with hydroobkrio cciil
continued boiling with uiwholk p^ioMh^ it j- '*-
bitter aimotid oil 'and ammonia. -^3, It is di£«olved by Wiliog i

I1YDR0BEN2AMIDE.

101

acid an J crygL^llises ont nnalter^fd on cooling. After seveiul hours boil-
ing, boweverj it do loBjjer crystalHses, and water tht^n tbrowe down from
tlie solution a body which hae a strong yellow^ coloufj is dissolved by oil
of Titriol and reprecl pita ted therofrom by water; dissolves with yellow
colour in potash or amraonia; disaolves also In hot alcohol, and separates
in the crystalline form on cooling- — 3. Bil>enzoylijnide dissolves with
fine red colour in oil of minol and is separated therefrom by water. —
4. On distilling it with mdm-Hrne^ a small qaantity of a yellow crystal-
line non-a^otised body sublimes, wliich dissolves with fine violet colour ia
oil of vitriol, and is insoluble in wood-spirit, alcohol and ether.

BjbeQ!^oylimide dissolves re^ily in boiling teood^pirit und tdmlwl^
btti is nearly insoluble io tlher*

Hydrobenz amide,

C«N=H^» (= C"AdNH^« ?)

I

H J, pr. Chem. 9, 130, — Ann. Chim. Fh^s. eSf IB. — N, Ann. Chim.

^ Fk^i. 1, 300; liev. $cimt 19, 48; X pr. C/w^. 35, 408. — PAa?m.
cenir. 1836, 215; 1838, 245.
RocJBLEDER. Ann, Phm^m. 41^ 89. — Ffmrm-. centr. 1842, 57*
FowNEB. FhU. Tram. 1845, 263; Ann. Fharm. 54, 363.
BEttTAOKiNi. Ann. Fhaim. 88, 127. — Fhurm. eentr. 1852, 70.

Axittuire dt hm^n€^ Hydrure d'&z&tenzHkj Niirure dt pkrGmyte.

Formation. By the action of ammonia on bitter almond oil (p.24 ).
3C"H«03 4- 2NH* " C*2N^H»^ + 6H0.

^P Frepm'niion* When tbo portion of rectified bitter almond oil whick
' boib at 180° k covered with aqueous ammonia and left at rest for
14 days, ^ of the oil solidifies in a crystalline masa. The rem arn tug
liquid 19 poured oif, the crystals broken up, quickly ehaken with a ^mall
qaantity of ether to remove the adhering oil, and diaeolved in boiling
alcohol which leaves a email quantity of white powder undissolved; the
filtered aolutmu yields by cooling and spontaueous evaporation crystals
of bydrobenzamido. {Laurent.) According to Rochleder, bitter almond
oil covered with ammonia eolidiliea in 24 to 48 hours at ordinary tem-
peraturca, or in 6 to 8 boars after being heated to the boiling point of
the ammonia, into a yellow reainous maaa. which, beaide^ hydrobenra-
mtde, contains -^ of a yellow-green, fetid, volatile resin; the hydrobcn-
xiLmide m%j bepurificdby washing with water and cryatallizatioa from
boiling alcoboL

Commercial bitter almond oil forma with aqueous ammonia a yellow
resinous mass; and when this is freed by ether from adhering oil and
repeatedly exhauated with boiling ether and alcohol, the decanted liquids
yield several crops of crystals of hydrobenzamide, ben zhy dram ide>
azoWnzoyI, a small quantity of ben zoylazo tide, and a substance sparingly
soluble m alcobob From this mij^turci the crystals of bydrobenzamide

*^=iar- «^«^ifr; «^<=s^jr. ife

— C Wl«

«r kuQie Mid. (FtfVM.) — i. Wit^

k jiel^ Utter mlaiaj oil ani tl«
FWM,)— ?. BoiMwilfc^

Sjii&Snl«aMr^ Utter slMod oil Wi^mhtd. (Fimii.)
B«9«d wkk aleohoiic polMk, il gmt «ff ft smU Mulilr of aansoM
wmA Vatr w^mj oiL (iMMt.}— flL WWn it it 6aed with It jdnOa ii
poiaAp Ihi SMS htoomm irtt ligU vtOow, tiM ibric jelkw, s»i
sllbHiltIr Imn mi bbek^attd If dmljheiitod gtra off ootywUl

inistera of dbonl 4 ir»L 117^111^0 gmi lo 1 vol. aiftet«tled fcjdiy,
n« Uftdc evMdoi olMiyuiiA cuiNMiate 0I potMb, eymmA& of firjIiWM,
biBJotaiM, umI m Em&lt qu&ntitj of m Tellov oil, vU^
boeoinai Tiadd on exposure to the sir; IM oaM wUeli lii
beeone dark jellow, containa noUiiii^ bat bensotttltiiii wxl m «•*
aU&gMm qmLUilir of the yellow oil. (Rodiloder.) ^ — t. Heated vilk
potftmium, it jkfds a red fosibb m&ie and a emaU ^uaatity of ciafeoiL
(Laofeai.) — tO. Whea Bolpbaf^tlcd bjdrcaeeii k pawtd tJiliwgii lla
atootiolk iolatioDp fialpEiide of fftilb^ne U pr!>diioed. (Cthimm^ pw lilL)

HjdmbmiiEaitiJtlo diiiolv^ witli facUUj In a^^»M Mid in ilAp%

BEKZOSTfLBni*

ws

Appendix t(t Ilt/clrohenzamide^

Benzolone. C"H*Ol ?
iLESER. (1842.) Ann. Ffiatm. 41, di.^^PMtm. Ceriir. 1842, 57-

W

Produce*!, logetber with Leozoetilbm,
fitronglj heated with hydrate of pataali :

when hjdrohcDzamide U

2C«N=H^» + 6HO = CPH»03 + (^B^Q* + 4NH'<

An intimate luixture of hjdrobcnzamide and hjdrato of potash 13
heated in a silvor hasin till tho mass assumes a black -brown coloor, and
the product after being nibbed to powder is treated with water, as long as
the water es-tracta any thing from it; the residual powder h then washed
on a iilter with cold hydrated alcoho!, till that liquid do longer aaeumes
a yellow colour, and tho residue ia added to warm oil of vitriol. The
blood ^red solution thua formed j when gradnally mixed with dilute
alcobol, becomes greenish yellow and deposits small crystals of benzolone,
which, if not yet eufficiently puro^ must again be treated with oil of
Titrioh

Small crystals which melt at 2iB% and suhll me almost without decom-
position when strongly heated.

22 c .
20.

132
8

le

84*62

5 13

1025

Rtjchledcr.
... 83*50
.^ 5-21
.., 11 29

C^^a^. 156

100^00 ......,, 100^00

It is dissolved with reddish yellow colour by strong nitric acid, and
precipitated therefrom by water in it^ original state; hut fuming nitric
acid converts it, with evolution of red vapours, into a yellow resin. It is
Dot attacked by potash -ley*

Insoluble in water and alcohol

Benzostilbin. c?m^O'^

Hochleder. (1842.) Ann, Pharm, 41, dd.—Phamt. Centr. 1841, 57*

Formed when hydrobenzamide is heated with hydrate of potash* At
a strong heat, the moss blackcus, and ben^olgue is formed at the same
time.

The yellow alcoholic liquid obtained in distilling benzol one contains
bcnzostilbiD contaminated with a yellow oil which renders it more soluble.
From this it may be freed: I. By recrystal Using the residue left after tho
evaporation of the alcohoL — % By adding to every pound of the
alcoholic liquid 8 or 10 drops of hydrochloric acid, which colours it pale
red; after standing for some time however, or on boiliiig^^ it loses tliid
colour, and at tho same t me^ the beusoBtilbin separates m yvi\^\\^t^r,'^^^,

VOL, XIL Q

I COJ(

I:

188

col

>S CONTAmnfG TWO OR MOM ku C>*H«-

5. PicTil ia decomposed by polamum whb tbo aid of h^t^ and etbfl
extracts fraiu the product a body which cryBtalliaes iii rbombs. — €. '
ia not decomposed hy hoilitig^ with alcoholic potaEsh.

Ficril digsolres very readily in etktrj mucU leas readily m tUeohoL

Nitropicril*
C«NX'*H"0* or C*^NX^H*^0*.

JiAWmxT, io€, eit.

When pieril ia boiled witb nitric acid till the whole is disaolred, tbti
solution on cooling deposits a yellow somewhat crystalline powder, i
little more of wbicli separates oa addition of water.

42 C .*,

.. 252

.... SG-SQ

4N

., 56 ........

,„ Ml f Ml*,.*

.. 128

..» 12 50

n H ,„„!..

2 45

16 O

..» 28^75

C*>N*H"0^8

.. 447

... 56*25
..., 12-50
..» 2-68
.... 28-57

.... IOU*00

42 C ,

252

ae

12

128

Laurent,
,_.. SG'SO

4 N *.....

i2^ea

12 H »»....

........ 3e-ar

16 O „ ...

28-23

C«N^H'^0« .„.

44S

... 100^00

, 100 00

When lieated it decompoaee with emission of light.

It dissolves very sparingly in almhol, very readily in ^er.

Thionessali

Laubemt* (1844.) Sev, sctmt. 18, 197; J* pr. Chfnu 35, #4,

Formatiofi and Freixtration, In the dry distillation af snlpbi4« d
stilbene or of the crnde product of the action of bydroenlpb&te td
atiLtuoniii on bitter almond oil, after the fitilbeao has passed orer tiA
sol iili lied in &eale3 and the beat lim risen, needte-sbaped crystals con^enn
in the neck of tbe letort, and inay he purified by boiling tbem m tli
state of tine powder with ether, which dissolves out the slilbene mis«d
with tbem. Tbe reaidual white powder is boiled with a large qnaattty
of ether, till it is completdy dissolved, and the ethereal solution depoiili
thionessal by cooling or by spontaneous evaporation, in aabeatoiJik*
etjstaia grouped in tufts or spherical masses. Tt is bowerer ncff
adnmtiigeons to recrystallise tbe prodnet from boiliug reetifiod roek-oi^
from which tbe tbionessal separates on cooling lu needlei gioaped in

NITROTinONESSAL,

189

Fr^ertm. Colourless, inodorotjfl ucedles liavin|nr a silky lustre.
Melts at fW^ and solklilies on coolitig. in a spongy rnasa, whicli absorbs
the still li<[iiid portron and swella up. After \\ow cooling, it f>ften
reinains amorpbousj and does Dot crystallise till gently heated,
vapoors bare a faint nnd not eulpburous odour.

Tiio

.0"

26 C.
S .

156
9

16

4-98

e*&4

Laurent.

4-90
B7B

C^^^H'S IB I

100^00 .„ iaO'03

Bums with a reddish sooty flame. With broiuino it immediately
becomes heated, gives off vapours of hydrobromic aeid and fu rms bromo-
thionessal. It is but elowly attacked by boilinff nitric acid, with formation
of nitrotbionesfal; the liqaid does not contain sulphurie acid. Jt is not
decomposed by boiling alcoholic potash. Heated with potassium, it yields
sulphide of potassium and a largo fjuautity of charcoal.

It dissolves very sjianngly in boiling alcohol^ with difficulty in boiling
€ihtf, most abundantly in boiling rock-oil^ from which it separates again
almost completely on cooling.

Bromothionessal. C-"Br'HU

loc* ciL

BromM ione»nie.

Obtained by treating thionessal with bromine. Hydrobromic acid ia
then evolved and a solid masa formed which may ho pari fled by boiling
■with ether.

Pulverulent, melts at a high temperature, and solidifies in xhombia
tables on cooling. Volatilises without decomposition-

26 C .„. , X5fi _ 4G'02

7 H 7 *,„ 206

2 Br _ ISO .... 47*20

S 16 .... 472

C^H^Bi^S ........ 339 .... lOO'OO

Lfturent.
,.. 49 3
.. 22

Nitrotliioiiessal. C^xm'S.

Lauhent, fo^p cit.

NiirifAioneaHU*

P When thiontssal is boiled for some time with nitric acid, it first
softens and ultimately forms a yellow porous friable crust, wliich is
waished with water aud with alcohol, and ultimately boiled with ether,

190

COMPOUKDS CONTAINIHG TWO OR MOEE At. am\

which disaolTea bafc little of it, and on cooling deposits it all ia the for
of a floeculeot powder. Tho residue forms a pale veliow, tolerallj
fueible powder, whicH on cooling solidifies iti a yellow tmaepnirQ'
amoqilioiifi umm.

LtttureaL
Pia.«„.™.. 156 .., 57'5G 57-9

aw 28 .... 10-33 la-y

7H ...„ ,.,... 7 „,. 2 m ,-,„. 27

S _ 16 ,.,, 5*91

8 0 64 .... 23-62

C^^N^IFSO' .... 271 .... 100-00

Whon heated to the boiling point, it takes fire and leaves a 1«^^

<iuautitj of charcoal. It ie not attacked bj potaah-ley.

Bibenzoylimide,

RoBSOW. (1851.) OAm, Soc. Qu. J. 4, 225j ji«n. Fhurm. 87, l^i

J. pr. Chem. 55, 245; rhm^m. ecnlr. 1852, 209. — "

Forpiaiion mid Prep(rr€Uion, Ammoniacal gas passed into an alcoholi
solution of bitter almond oil, la abundantly absorbed, and after a feif 1
hours a granular precipitate of benzoylazotide separates out, mijced ttilIii
a remnous Lody^ which is diasolved on treating the precipjiate witlif
alcohol The residue obtained by evaporating the aloobolic solutlott
aaanmes a light red colour after several hours boiling with potaahdcy,
and becomes brittle aud resinous. Boiling bjdrocbloric acid e^tiw^
from it only a small quantity of amarine, and after the residue bas beia^
treated with boiling alcohol, bihenzoylimide remains bobind.

JPr^periUs. Yellowish powder consisting of feathery crystala,

RobeoD.

28 C 16S .,.. nS2 ....... 7g'66

N..., H .,.. 660 6-49

13 H 13 ... ei6 .„,_ 6-43

2 0,.., U .,. 7 62 .,. 7*42

C*^H"0».. „. 2U .... lOO'OO lOO 00

(20<H'O* + NH» = C»NH»*0* ^ 2H0.>

IkcompoiUiom^ 1. It is not altered by boiling with hydroeblaHo »ei4
Of |K>taah-ley^ By continued boiling with al^kcdk poiask, it yictdik
Sitter almond oil and ammonia. — 2. It ia dissolved by boilbpig miirP

HYCR0BEN2AMIDB,

101

a^id aai] crystaiHses out uDaltcred on cooling. After seTeml Iionrs boil-
ing, however, it no longer crystal I isea^ and water tLon throws *lown from
tlie solution a body wLich has u strong yellow colour, is dissolved by oil
of vitrioi and repreci pita ted therefrom by water; dissolves with yellow
eoto»r in potash or ammonia; diaaolTes also in hot alcohol, and ieparatee
in the cryatalUne form on cooling. — 0. BibeniEoyUmide diesolTes with
^ne red colour in oil of mtrlol and Is separated therefrom by water* —
4, On distilling it with todadime^ a smiiU (quantity of » yellow crystal-
line non-aaotiaed body subliTues, which dii?solvcs with fine violet colour in
oil of vitriol, and is insoluble in wood-spirit» alcohol and ether.

Bibenzojliniido diaaolvcs readily in boiliug WQod-$pini and (dmholf
but is nearly insoluble in eihtr*

Hydrobena amide,

C*^N'H^* (-^ C*^AdNH^« 1)

Ladrent, (1836.) Ann,Ckm, Pki/s, 62, 23; Ann. Phartn.2]^ 130;
J, jir, Chem, Q, 130. — Ami. Ckim. Fhtf$. 66, 18*^ A" Ami. ChijfU
Phtjs. 1, 300; Rev. sdetd. W, 48; J. pr, Ch^n. 35, 468, — /'A/im.
mdr. 1836, 215; 1838, 245,

BocnLErjEB. Ann, Phann. 41, 8ii, — Pharm^ eentr. 1842, 57.

FowNKS. Phil. Tmm. 1845, 263; Jnn. Pharm. 54, 380,

firnTAGNtiti. Ann. Fha^mt, 88, 127. — Fharm. cmtr, 1852,70*

Formation. By the action of ammonia on bitter almond oil (p,24 ).

^f Pref>af^iion. When the portion of rectified bitter almond oil which

^^ boils at 180° is covered with aqueoua ammonia and left at rest for
14 daya, ^ of the oil eoiidiHes in a crystalline mass. The remaining'
liquiil h poured off, the crystals broken np, quickly shaken with a small
ijnaDtity of ether to remove the adhering oil, and dissolved in boiling
alcohol which leav^es a fmall quantity of white powder undissolved; the
filtered solution yields by cooling and spontnueons evaporation ciy^jtals
of hydrobenzamide. (Laurent) According to Roobleder, bitter almond
oil covered with ammonia soHdiliei lu 24 to 48 hours at ordinary tem-
po?aiurca, or in 0 to 8 hours after being heated to the boiling point of
the ammonia, into a yellow roMinous mass, which, besides hydrobenza-
mide, contains -jV ^^ * yellow-green* fetid, volatile reain; the hydroben*
^amide may be purified by washing with water and crystallization from
boiling aleohol

Commercial bitter almond oil form.? with aquooua ammonia a yellow
resinous mass; and when thia is freed by ether from adhering oil and
repeatedly exhausted with boiling ether and alcohol, the decanted liquids
yield several crops of crystals of hydrohenzaraide, henzhydraniide,
azobenzoyl, a small quantity of benzoylazotide, and a substance sparingly
soluble in alcohol From this mlJtture the crystals of hydrobouzamiJe

192

CDl^l POUNDS CONTAINING TWO OH MORE kU C'*H*,

maj be picked out and porified bj repeated cryetalUaatloQ from alcobuLl
(Laurent.) Wlien the last portion of liquid wbieh passed over in thti
distillation of bitter almond oil was dissolved in 4 or 5 times its tolumil
of aleobol, and mixed wtlh 1 vuL hydroaulphate of atunionrnt an oUfi
mass separated, whicti in 24 hours solidified eouipletely in the form 0(*
hydrohenmmido, mixed only with a few erystaU of hydride of sulpho
benzoyl,

ColourlesB rhotiibio oetohedrons, truncated on tbeir greater kliisl
odiros. (Fig, 41). a : «' = 130 ; « : a = 122^; a ; a"= 84^ 30'. The
crystals generally exhibit wedge-shaped elongations. (Laurent) Tasl^-^
\msj the alcoholic solution has somewhat of the taste of bitter ali]iolid&
Inodorous. Melt^ at 1 10'' to a thick oil, which bad a eweet tftBte^iaA
after some time solidifies into an opa<^ue brown mass.

42 C .,

2N

18 H

.,. 252 .
.... 2B .
..,. 18 .

... 84-56 ,.,
„. 9-40 ...
.., 6'04 ...

Lftureat*
.... 84-40 .
. . 9*00 ,
.„.. 6-38 .

... 83-91
... 1001
.. 6"08

..„ 84-Bfi ■
.,., 9' 13 ■
.,„ 6 01 1

C^N'H^'.....

.. 298 .

.., lOO'OO ...

.... 99 ?a .-

.. 100 00

.... 100 00

BecmnposUi&tts^ L Hydrobenssamidc when beated m the air, taJci
fire, and burna with a not unpleasant odour. (Laurent.) — 2* Betwecij
ISO^'and ISO*^, it changes in three or four bours into amanne. (Bertaf*j
nini.) — 3* By dry didiUaiion^ it yield a lopbino and a ijtrong-sn]olliii|1
volatile oilj leaving a small quantity of carbonaceous matter. (LaurvaL)J
— 4. When the alcoholic solution is continuously boiled, aramoaiai
escapcsj and on evaporating the alcohol, bitter almond oil remain*. 1
(Laurent, Rev. sckaL 19, 448.) — 5. Boiled with at^ aeons cla-QmU <i6dt\
it yields a large quantity of benzoic acid. (Fowaes.) — 6. With iic»aX
even at ordinary temperatures, it yields bitter almond oil and tk
ammonia-gait of the acid. (Laurent, Fownes.) — 7- Boiled witb ijot^nk-
lt\j^ it changes gradually and without perceptible decrease of weigLt, iai<^
amanne, only a faint odour of bitter almond oil being evolved. (Fown««.)
Boiled with alcoholic potash, it gives off a small quantity of ammoaja
and bitter almond oil. (Laurent.) — ^8. When it is fused witb bvdmto ot
potash, the mass becomes first light yellow, th^-u dark yeUow^ sod
ultimately brown and black, and if slowly heated i'ivos ofl^ uotbinglnit
ammonia; if the heat be continued, there is given otf, besides aramojiSi, i
mixture of about 4 vol hydrogen gas to 1 vol. carbu retted by<lrog«&
The black residue contains carbonate of potash, cyanide of potaflstmi,
benzoatilbia, hcniolone^ and a small quantity of a yollow oil, wbietl
thickens and becomes viscid on exposure to the air; tue mans whicb liift
then become dark yellowj contains nothing but beuEostilbiQ and a eoiH
fciderablc quantiiy of the yellow oil. (Rocnleder.) — 0. Heated with
poCamumg it yields a red fusible mass and a small quantity of cbajvoti
(Laurent.) ^ — 10, When sulphuretted hydrogen is pa^ed ihrougb tli«»
alcoholic solution^ sulphide of stilbene is produced, (Cabouit, fi* W^)

Hydrobenzamido dissolves witb facility iQ o^o^ and in cther^

BEN^^OSTILBIK.

193r

Appmidh to Il^drobtnmmidt^

Benzolone. C^HW ]

tocBLEDEB. (1842,) Aun^ Phw-m. 41, 04* — Phaim. Centr, 1942, 57*

Produced, to^fether 'w^itli beDzoatilbin, when hydrobenzainide is
ftronglj beated with hydrate of potaab;

2C«NSH»» + 6H0 - C^H«0» + C«HkO* + 4NH\

k .. .

r An intimate nuxture of bjdrobenzamide and hydrate of potash h

Ilea tod in a silver basin till the mass asanincs a bhick-hrown coloar, and
the product after being robbed to jJOwUer is treated with water, aalongaa

f the water extracts any thing from it; the residual powder is then waelied
on a iilter with cold hyd rated alcohol, till that liquid no longer assumes
a yellow colour, and the residue is added to warm oil of vitriol. The
blood-red solution thus formed, when gradually miiced with dilute
alcohol, becomes greenish yellow and deposits small crystals of benzol oue,
which, if not yet auffioiently pure, must again be treated with oil of
Titriob

Small crystals which melt at 246^ and iybli me almost without decom-
poeitloa when strongly heated.

22 C ,
8H.
20,

Eochleder.

132 .... 84^62 83^50

fi ..,. 6*13 521

16 .„. 10-23 ,...,.,, 11-29

C^H«CF,.

156

100^00 ..„_ 10000

It is dissolved with reddish yellow colour by strong nitric acid, and
"'pi-ecipitated therefrom by water in it^ original state; but fuming nitric
acid converts it, with evolution of red vapourSj into a yellow resin. It is
not attacked by potaeh-ley,

Insoluble in water and aleohoL

Benzostilbin. e'H«0*J

BoCHLEDER. (1842.) Ann, Pharm .41, t>2.—Fharm. Centr. 1 84 1 , 57-

Formed when hydiobeoaamida la heated with hj^drate of potash- At
n strong heat, the mass blackens, and benzolonc is formed at the same
time.

The yellow alcoholic liquid obtained in distilUng benzolone c<>n taint
benzostilbin contaminated with a yellow oil which renders it more soluble.
From this it may be freed : L By recrystallising the residue left after the
evaporation of the alcohoL — 2. By adding to every pound of the
alcoholic liquid 8 or lO drops of hydrochloric acid, which colours it pale
red; after etauding for some time however, or ou boiling, it loses this
^colour, and at the eanio t'nic, the bcuzo^jtilbin separates in amalWt^^VvwV*.

VOL. XII* Q

ICOJoij

L

COMPOUNDS COKTATNIHG T^'O OR MORE Ku a«H*.

3, By passiog cWofloe ^ into the alcoholic liquiil, whemby It ia i)
dlately deeolorised, beeoniiDg at tlie same tinie almost of tbe coar-
of tar, from tbe preseiree of the separated cvystab. The stnall c
obtajDed by 2 or 3 are free from eblorinej ftad when immersed m
are gradual) J coov^erted into larger crystaifl*

Melts at 244'' aud subiliues at a higher lemperature^ for the mo^ fm
deeomposed.

62C ...»„ 372 .

2% H .,„„„« ,* 22 *

.. 87 32 .-
„. 517 ..
». 7 51 ,

AO 32 .

,.. s-as

C"H«0* 42$ ,

. 100 00

.,_ 100-00

Dissolves with pale red colour \n <^U <ff viirufi.

May he boiled without deeomposition^ with potask^hif of sp. gr< 1'2T*

DissolTes sparingly io al^oM.

A mixture of benzol one and henzostilhln healed in a retort wit!

■trong potash-ley and hydrate of potash, till the mass 13 diy, yieldi I

^imall t|ii3ntily of an oil smelling de^eptiTely like gemnmms, (Rocb*

Amarme.

rmiENT, (IS44,) CW;j|. raid. 1% 353; N. X Phmm. e, 11
Campi. chim. 1845, 33; J. pr. Chem. 36, 1, — *¥. Jnn, C'Am. i%ft^
1, 300; PhiirvL Cmtr. 1845, 828.
PowHBs. PArl rran*, 1845, 263; Jnn, Phurm. 54, 063; *T. jm

C/nm. i^Ayj. 17, 483,
Bertagnini, vlnn, Pharm. 88, 127.— P^crr»t. CiW/r, 1852, 70,
GJteHAKH. J«n«. Pkarm, 93, 320.— PAflm. Ctfw^r. 1855, 266,

SttmUne, H^drure ^«o£inro{(iDtf.^ Discovered at the tame time by Laaml i
b; Fownes.

Pofffwiliott* K By heating the ifotnerlo body hydrobeniami^
between 120° and 130^ (Bertagnini), or by boiling it with a^jiieoatl
alkalis. (Laurent, Fowne^.) — 2. Bv heating iiilphit« of hensoAyl mJ
ftiUDonium (p, 27) with hydrate of fiino. (Gofi«mami.}

Pffpar^iion, J , When Lydrobenjsaniide U heated for thrtd of

hoars to a temperature between 120' and 130^ the cookd Titreom „

diMolved in boiling alcohol, and hydrocliloric acid add^d in esreat, whllal
crystab eeparate consisting of hydrocblomte of amartne, which ittay hi]
pnritlcd by one recry«tal ligation from hot alcohol. (Bcrtngninl ) — ]
^ Hyd robeujsamide h boiled for several hours with poUsh !er ; ihi

llim^ fake of resin dissolved in dilute iul^hnric actd; t)i« ^iitittt

AMARINE.

ns

ipr^dpit&ted hy ammonia; and the precipitate waalied witli water and

IcTjiJtallueJ from Lut ulcohoL (Fownes) ^3, An alcoholic foluticn of

[bitter almond oil saturated with amnioniacal gas solidiiies, after 24 — 48

iBourfl, into a crystal lino mass composed of several eu1)staiicea which caa^

[ not h<? purified by treatment with ether. This maee is boiled with a little

* vater to expel the gnj^^ter part of the iJuoliol, and saturated while etill

hot with hydrochloric acidj whereupon an oily masa separates, and aome-

times also crystals of amidobenzoic acid (p, 143). If sufficient water la

prciseat and the liquid is hot enough, the whole of the bydrochlorate of

aanarine remains dissolved. The Hqnid is decanted j any hydroclilorate

of anmrine that may be contained ia the oil is extracted by boiling

water; and the solution nenlralkcd with ammonia^ wherenpon it deposits

while microscopic needles of anmrine^ either immediately or after some

miuuteSj according^ to the de^^rce of concentration, Tlieso needles are

collected on a filter, washed, dissolved in alcohol, mixed with a little

bydfochloric acid; and the solution neutral ised with ammonia; it then

on cooVuig j^ieMs crystals of perfectly pure amarine. (Laurent,)

4. When a mixture of the dry sulphite of ben^osyl and ammonium
with three or four times its volume of very dry hydrate of lime contained
in a capacious retort, ia covered with a very thin layer of hydrate of
lino and cjuickly heated over charcoal to hctwcen l^O"^ and 200^, the
neck of the retort becomes coated with an apparently amorphous mas^
which, at a stronger beat, flows downwards and into tlio receiver, whilst
needles of lophiuo sublime in the upper part of the neck. The amarine,
yart of which occupies the lower part of the neck of the retort, thereat
being contained in the ammoniacal liquid in the receiver, ia wa^^hed with
sicohol, dissolved ia alcohol mixed with hydrochloric acid, and preci-p

pitated by ammonia, iRatead of the pure sulpliitc of ben^osum and ammonium,
tte mass xn^j \x used which i« obtained wheti an alcohoUo solution qf bitter almond oE
■tilxed witK an eqttivaleni ^uaritity #f a wturated solution of bUulphite of immonia, h
quickly ef jiporated to dvjness. ^G5ssmann.}

PropeHi4i. Crystallises from alcohol in shining six-sided prisma whose
terminal faces are replaced by two or four faces of a rectangular octoho-
dron. (Fig. ea.nithour the face ;;0 (Laurent.) Melts at 100^ (Fownca,)
Solidifies on cooling lu radiated rosettes (Laurent), in a vitreous trans-
parent mass* (Fownes.) Inodorous, tasteless at first, then slightly bitter.
Slightly bines red litmus paper. (Laurent.) The alcoholic solution has a
atrong'alkalinercaL^tion. (Fownest) — Yields a strongly electrical powder*
(Fowues ) — Introduced in small quantity (3 grains of the acetate) below
tbe skin of do^s^ rabbits, and gninea-pigs, it causes convulsions and"
death; when introduced into the stomach, it also produces convulsions
e^nd other morbid symptoms, but the anit.ai recovers in a few honr3.
The isomeric body^bydrobenmrnide does not exert any such potsonoas actloi^
(Bacchetti, Gimenlo, 2, 76; Litbi^^ K(y}.>p*t Jahrt&erichtj 1855, Mi.)

42 C ».»

... ut .
... 2a .

.. 18 .

,. S4'56 ..,

„, 9-40 w,

. 6-04 .

Laurent.
,... S4'G6 .... 84*20
... 9-70 .... t'70

Powmcs*
.... 84 22

2 N

18 H

.,.. 910
_ 608

C«NW«..„

,.. 2S8 .

,,. loooe .,.

100*49 .», 9^-87

... 9&-40

Ivomeric with hjdlfob«nt&m]^«»

Q^

IStf COMPOUNDS CONTAIKIKG TWO OR MOM Af Ci«H».

Demmpoikifms, I. Atnarine sulijectctl to dr^ dkttilaiimi, i
almost completely, leaving- only a small residue; ammonia is er^lve^lj an 1
tjil smcHinj^ Hkc WdzoI distils over, aud pjrubeiisolino sublimei izi Hia^
neck of the retort (Fownes,) — 2, Amarlue is briskly attacked h
throvilnfff apparently with formatioo of hydrobromate of amanne an
bromamarine; nrntmrnia poured on tbe product cob verts it into a solid wm
the alcoholic solution of which yields crystals of amarine ou cooliDg and
deposita small radiating Bpherulea. (Laurent.) — 3. When it is heated
ln-ith aqueous chromk acld^ a very brisk action takes place, a lari?© <[uaa-
[tity of benzoic acid being formed, A similar actton but ]ess violeot if ^
[produced by nitric acid. (FowueaO — 4. Hydrate of potnsb io the'
melted state does not act on anarine excepting at a very high tempe-
rature. (Fownes.)

Coniihmaimu. A marine js insoluble in water. ( La n rent, Fownes*)
TEio amannt saitf are formed by direct combination. They are fcr
the most part sparingly soluble.

Sulphate cf Amanne, — The solution of amarine in snlphnrle mli
1 yields by spontaneous eraporation small colonrless crystals reaemblliig
] e^alic acid.

HydrocMotHiie of Amnrme. — When liydrochloric acid is poured upon
[ amarine, a colour! ees oil ia formed*— formerly regarded by Laurent u uotttfHe
rith bitlEr altnnni] oil and called Hydrtrre dt bmzuUme — which becomes mom
[ml id when dry^ and may be drawn out into threads wh^n lieated«.j
{(Laurent.) Crystallises from the hot aqueous solution in Bmall, coloof-j
riess, highly lustrous needles, which effloresce in vacuo, giving' off 2 "4 |i.e*
{1 At.) water. (Fowncs,) Maybe distilled without decomposition afli |
passes over aB an oil which solidifies without becoming opaque. (Laiii«et*^|

42 C.

19 11 .
CI.

Drg,

2&20
28*0
ISO
S54

;5*37 _. . 73 20 .., ?^15

6 37 .,....,. r*B3

5-68 5*77 ... 5*62

10-58 9*89

C^3H«,HCl ,....., 334-4 .... 10000 ,h 08-68

The «alt combines directly with bromine, — It is insoluble In wstfff
but disaolres readily in alcohol and ether.

A^itfoft of Amari7i€. — ^ A marine fonns with hot dilute nitric acid s
«oft n on -crystal lino mass^ which diss^^lves in a sufficient quantity of
boiling water, and separates in microscopic crystals on cooling. (LanreQt)
Small crystals having a faint lustre and remainiug unaltered in vacuo;
they diasolve very sparingly in water. (Fownes.)

4

42 C.

253
42

19
48

09-80

11*64

6*20

13*30

FOWTlftf,

, 69-70
. 5-30

C^K'U^HO^KO*... ^61 ... lOOOQ

TEHKITROHIDROBENZ AMIDE.

197

With hichlof\da of pliUmumj hydrooUl orate of amarine forma an luso-
[lubleyellowisli floublesalt (Fownes), wbicl cx)atams 19 S p. e. platlnuui;
tlie formula C*>N»H^^HCI,PtCl\ re^juiring 13-58 p.c. (Gosfimaiin.)

K Afdate of Amanne. — The solution of amanue in acetic acid ytckk
™ Ij evaporation a gumnjy noo^ cry stalling ma^Sj which di^dv^ very
easily in water* (Fowces.)

AmaJiDe dissolves readily in Qlcohol and «^^%

I

Ternitrohydrobeiizamide.

Bertagkinl (1851,) iV'. Ann. Chlm. Fh^9^ 33, 476; Ann, J'^mrm,
7U, 272; Fl^rm. Cenir, 1851, 68.

llydrohens^midc Mnitiiquf.

P

Foj-mathn. By the action of ammouia on nitrobenzaldido (p* 1 21) or

sulphide of nitrobenzylenc,

Prepat^atwn* I. When 1 pt- of pulrerised nitrohenzaldide la mixed
with 5 pta* of strong ammoniaj the liquid turns milky; the undissolved
portion acquires a flocculent consistence, ami changes in the course of
24 bours, into ternitrohydrobenzannfle. If the nitroben^aldjde need iu
the preparation is not quite pure, the product is red-hrown, but is easily
purified by washiisg the powder vrhli cold and digeatiog with lake^
warm alcoboL — 2. When nitrobenzaldide is mixed with alcobolic am-
monia^ a solution is obtained which soon deposits resinous ternitrohydro-
benzamide.^ — 3, When ammoniacnl gas is passed over melting nitroben-
zaldide* a large quantity of water is given off, and a transparent vitreoua
mass is formed which becomes opaque when immersed in boiling
alcohol.

Pi-operties, White light powder, or after fofion, a transparent
vitreous mass. Separates from boiling alcohol in flakes composed of
ehining needles. Inodorous* Tasteless,

I 42 C

.. S&2 .

.. 6619 ,»

58^3r

P 5 N

. 70 ,

... 16-lG ...,

lfi-27

15 H

.. 15 ..

.. 3'4G ...,

3-67

12 O ,.

.. se .

.. 22 19 ».

21-69

C^-WW'O'^ ..

., 4B .

.. lao^oo .,.

100*00

B Decompimlims. 1. The compouud heated to between 12ii^ and
~ 150% is converted into ternitramarine. — 2. Similarly when botled
with dilute potasb'ley* — 3* When boiled for some time with hydruted
Lalcohol, it la resolved into nitrobenzaldide and ammonia. — 4. Heated
fwith dilute acids or in contact, even at ordinary temperatures, with strong
rhydrochloric acid, J t k cou vetted almost instantly into nitrobeniiildjd<^-'
R»nd smraoniacal salta It dissolves easily and with ris<3 of t^m^^\^V\i.t^ '

IM

COMPOl-NBS COHTAIKWO TWO Ol MOIE Ai, C**H*.

ciTstallijw mmss of ciltnlitiiti^ ftCuL * '

It M tMoliibto m wHer, tcij ipizngly waM^ in iMiilirg %lmhol
imidMt m ether sad eil of lupentise.

Temitramariiie.

AGxixT. (I SSL) M, dmu €km. I^y$. 33, 47^; ^ra. Ami..

7^. tT5,

Fran ie?uiiio1ijiirob<fum]iij<le, b^ heftllag It ta kol«««^
lis* and 154f J or hj boiUu^ ll wilk fti|iieotti poM.

PHporailML men temltrobjrdmWdismiile h lieatod wHli i
mixtiire of 1 n>eMgre ol potasli-lej of 50' Bm. asd 50 m^i^aj^ «f
w&ler, the ponder eakee tcgetlier ftsd forms m bfown e-emi-Huid ma.'*
wliieh becomes briltle •■ cooliii|r sad ii i inixt«i« of tern itmni art ne ind
m brown enbeUuice. nb pt^vet m dimilrfd in hoi sttting bicobol
nixed with & titde etWr, ind kydroelilorie aeid u added to the folutioa,
whidi then tmmedktelj deposits sBall, wblte. shining needfei of hjdfo^
cbionte of temitimm&ime. These erj^taU «Te pnfiGed hy di^eetioo ii
Inkewarm alcohol and diecoin|»Oied by alcvbolio ammonm; the alcoholic

tolution is CTaporated; ibe reeidia freed from eal-ammoniae bj iriabiQ|j
wilb water, h dbsoUed in ale^ol; and ibe solatton is lefl to evapomte,*^
2* TefnitrobTdi^beiiwiiido It h«aied in Ibe oal*batk to bet ween If 5* iili
ISO""* wherea'pon ft BNlle into m gnnnij mmsm wkidi beeotntA bdllle M j
cooling*

CrjstaJli^es from Ibe akobolk eolotion bj ipontaneons evaponti
in white bard nodale^.

u c _.._ tat » 11

& K ...... , 7t It-lft ..^

— IMS

nil. .. •« „ tilf

c»N*ii«w* m . . i«t^

ItooMffe vltb terotoiob}dfob«aiaaud^

Ternliramariiie tof^ens in botlitig wat^ and imotrm to m rerj ili/clil
exletit, fonnbg ^n alkaline solmioti* ^

The ff-mifrtfmifnjie iafr# &» rcrr ■fatsngtj eolnble m water. H

ffpdrothhmi^ if TrmitmmMrw. — Obtained by adding bydiDcblom ,
lotd to the alci^bfilic fotntion of temil^nsaTine, whiVb then dep^^lU mu"
^iniog tired U*s. It i^ ncarlr infolable m cold, ipaMnglv aolol^ i
mn$ boiling alcohol, whence it cTVEtallifca in infU of ncMM i

tOPHlNB. IW

42 C ,.. 2520 ..,, 33 6S

kN ...» 70*0 ,„. 14*91 .,».... 15*03

Un .»* 16i> ..,. 3 41

110 « .„. 960 ... 20M6

CI.. 35-4 ,.., 7-64 ....... 7^11

C<Wai*O^^HCl. 469^4 .... 100 UO

.^^ttraie </ TifmtVranktnne crystallbee in neeUles from boiling dJcuHoI.
It is JDSoluble in water.

Ifercunc Chhfide forms with an alcoliolic solution af ternitramanne
A some vli Lit crystallioo precijiitate; bich/orltk of plat iniLU fiiviu^ smM
[leavy yellow noilnlea insoluble in alcoJiol.

Ternitramarin© dissolves sparingly in strong boiling aJmhol^ the

^dissolved |>ortioii eoparating in the amorphous state on coolm^^ It dis-

olvee pretty readily iu ether ^ very easily in a mixture of tth^r and akohoL

Lopbine.

(^WW or C**N^H^*.

I Laurent. (1844-) Rev. &cunU 18, 272; J* pr, Cft€m, 35, 455.—

^\A7ln. Cklm. Fhf/s. 19, 360; CompL rend. 20, 11 11 ; Ann. Phafin.
62, 103; J. pn Chent, 40, 40T; Pharm. Cenir. 1844, 335; 1847, 383,
tAS»N, Ann. Phamu 93, 331; Pkann. Cenir. 1855, 266.
iHAKN & Atkinson* Ann, Pharm* 07, 283 ; CAm. jS'of. ^ t/^.
0, 220.

^ Formaimu J. Bj the dry distillation of bydrobeniamide, benzoy*

riazotide or azoanlpbide of benxylene. (Laurent,) — 2. By heating

sulphite of benzosyl and ammonium with hydrate of lime, (Gossmann,)

Preparation. L When hydrobenzamide is heated, ammonia escapes
together with a mobile frajfranl oil [benxol? L.]^ and there remains a
fused ma^ which may bo distiUed at a high temperature, but ia more
ad%*antageously treated by pouring it out, pulverising It when cold, and
digesting it in hot ether, which extracts a small quantity of a body
crystallising in shining larainn; aa the solution cools. The residue
\e beated with alcohol to the boiling point, and hot caustie potash a^tded
to it till the whole is dissolved; the liquid on cooling deposits threadlike
crystals which may be wai^lied with alcohol. It is better however to
boil the residue insoluble \\\ ether wtth alcohol containing hydrochloric
acid, mix the solution at the boiling heat with ammouiji, and leave it to
cool. (Laurent.) — 2. From the mixture of lophine and amarine ob-
tained by distilling benKoylazotide, the a marine h extracted by boiling
with rocK'oiJ, or the lophine by boiling vviih alcohol containing hydro*
chloric acid, (Laurent.) — 3, From ihe dii^tiHate obtained by heating
aiiisnlphide of benzylenej the oily products are extracted by ether, the
elilbene by boiliu^' alcoUol, and the thionessal by rock-oil, and there^^idue
consisting of lophine is dissolved by boiling with alcohol and potash or with
jijcohol containing hydrochloric acid, A similar process is ado^tjti ^^J^^

^ ulco:

200 COMPOUNDS CONTAlfilKG TWO OR MOUE Au C^RK

the product resulting from JifitilUog the mixture obtainod by tr«*Uii^
bitter almond oil for two or three weets witb hydrosulphate of ammuaij
which mixture also contaias picriL (Limrcut,) — ^4. The needle-d

cryatab (p, 195) which sublime in the neck of the retort during tbei

lation of sulphite of beazosyl and ammoniutii with hydrate of lime, i
dissolved in hot alcohol and recryetalliaed after being treated witb anim
charcoal. The formation of the lophine ia fftcilitatcd by beatiiig tl
retort very (|uicklj and covering the upper part at the cemmenceDieiit t
the distillation witb red-hot coals (GSssmann). IT The best mode
conducting the process is to add a quantity of quick lime equal in weigl
to the hydrate, introduce the mixture into a mther sbaJlow gbWli
retort coated with clay, and cover the retort as far it is Slled with ll
mixture, with live coals, from tho very beginning of the openttion. Otf(
emuU quantities should be operated on at once, from 10 to 13 ^ntmmeafl
the sulphite with about four to m.v times the quantity of the lime-mixttiTf
When the operation is thus conducted, only a small quantity of am
forms at Brst^ and when this has melted down, the upper part of the i
beginf to be covered with radiant masses of lophine, and the fomutki'^
of eecondary products ceases, nothing being formed hut lopbin© sod free
ammonia. At the commencement, a small quantity of an arom&tk o3
accompanies the lophine, apparently resulting from tbe decompodttioa of
the araartDG into lophine and other products, the priucipaJ of which Is
amarone. (Goesmann & Atkinson*) Furificaticm ai in Loureut's method (l).

Pmpatm. Colourleas needles often an inch long, grouped in titHi
and having a luitro similar to that of caffeine ; they heconie opalaiCioL
after a while hut retain their lustre. At 2o0^, the compound subltiiiei
gradually but completely, without previous fusion and without decontpod-
tion. It melts at 265^, forming a transparent liquid which at fW
Bolidifie$ in a radiating crysialline mass. Tasteless and luodurouB, witb
£earcely any alkaline reaction* Tho alcoholic solution exhibits flaora^*
cence like quinine, but not in so high a degree* No Action upon poUnvil
light* (Gosamanu & Atkinson*) IF. ^y

Calculation T, Cal«iiktion II, ^^

46 C.. ...276 ..,. 8625 44 C... ». 264 .....,..„„ wn

2N 2S ^,.... 8-75 2N ^. 28 „ _ Hit

16 li 16 5-00 16 H.... 16 ,.„„ rH

C**N'H« ..,. 320 10000 C^N^H*' ..., 308 ,„._..« lOOiM

^ Calculation III*

42 C ,., 252 „. ...„ 84-84

2 K 28 , 5-73

17 H , 17 ».,...»..»... 9-43

C«N«H»^...... 297 .*.„* 100 00

A H a I if * t 9,

C 8S59 86 Oa .p.. 85 69 ...„».,.., 81*73

N....... 9*24 8'g3 S*47

H.., ....... 5-38 , 512 .,„ 550 ........... &*$S

loqai leo 00 gi^^a

LOPHINE,

201

•arent firat pri>po?ed the farmula C^N^IV\ Tor which Uc fifterwurd* snbBtituted
IC^N^MW. GciUflrdt [Traiti, 3, 13y) regarded lopliioe as iJcntical with Fowrit?s'*
bjroWnioliije C*2N-I1^^ (p. 204). Giiasmatsn (AniK F/imfn. 93^ 331) Adopted
Laurent's earlier fartniiLi. — Calcubtion II ngrees better with some of the anatysifs ttf
lophuie and its compounJi, and ejcpkins the formatiaa of lopbiue ffom fajdrohciusjimide
^Hiply according to tbe eq nation i

4Q«>jjms ^ 3C*WH"= + SCm*'^ + 2NH^ [L,],

{G^MDiaiiii & Atkiaton iu^^evt that the diacrepaticiea between the aeTcral aaalyi^^ of
■ophine may arise from the prtseiice of saiaU qoantitSes of amaroiie (p, 208) jn some

lif the preparationi analysed, Tht^y regard lophine as identical with pyrobenzoline, and
bropOBc a foraiuk differing from tbe don hie of Fownes*s ori^nd formula (C?'NH*}
Ij onJy I At. hydrogcTi, Tlie fonuula C^-N-H^^ is bowcTer sotnewhat improbable on

iccount of the ttnefen nmmber of hvdrogen*atomi. The correct formula ia more

Bfcompositiofu, Lophine boiled with nitric acid fryrms nitrolopbine*
Laurent.) It ia dissolved bj bromiiie without ovt>Iutioti of vapours of
Jydrobronijc acid. Wben tlie mas^ is dissolved in eilierand the solution
aixed \^ith alcoliol and abandoned to spontaneous evaporation^ beautiful
ellow prisms with rectang^uiar base eepanite out; these crystals give off
tronilne when heated, and when water ia poured upon them, turn white
acd fall to powder* (Laurent.) Lophine in contact with iodide of ethyl doea
not forin any substitation compound, not e^en vhen the two hodiea are heated together
ta 1 0Q° in a aealed tube for aeteral weeks. A portion of the iodide of ethyl is decom-
posed Into alcohol and hydi-iodic add, which combiaet with the lophine* (Gijs^imna £c
AtkinBon.)

Lophine does not dissolve in water,
the

FComhinaiimtB, ^ , „ .

It dissolves with the greatest facility and without decompoi^ition ia
hailing alooholjc potash, (Laurent)

The ktphine-saiti are for the most part insoluble in water, and spar-
iugly soluble in alcohol, — They are nither instable^ h living a tendency
when recrjstallised to give up part of their acid and form basic com-
pounds; this is particularly the case with the sulphate. (Oossmann k
Atkinson.)

Stdphaie of Lo^ykuie. — Lophine ia Iieated with alcohol, with addition
of sulphuric acidj and tbe solution mixed with hot water, whereupon
crystallisation ensues. — Small shining rectangular laniina?. The
aJcoholic solution reddens litmua and is precipitated by waterj a portion
however remaining in solution, so that on adding ammonia, a precipitate
of lophine is still obtdtned. Laurent found in the dry salt 115 and
13*2 per cent, of sulphuric acid; the neutral salt requires 11-21 percent,
of sulphuric acid. (Lanrent.) — -^ When a solution of lophine to which
excess of sulphuric acid has been added is left to evaporate slowly, the
hulphate separates in broad transparent tables which become opaque
and ciBoresce on exposure to the air* Wlicn crystallised more rapidlyj
the compound separates in largo needleSj which, if left for some time in
the mother-liquorj chaii^o into small white opaque needles. At each
ystallisation, the ealt becomes more basic, and by frequent solution and
crysLallisatioUj the acid may be almost entirely removed, (Gossmann &
Atkinson,)

Ilf/driOff(tle of Lophhe* ^- Prepared like the li yd rochl orate. Crystal-
lines readily in lirge needles, which are more soluble in ako\id a.u4 ^^]a^x

202

COMPOUNDS CONTAINING TWO OR ilORE At. C**M*.

tban tbe hydrochlorate. From a reiy acid tolutioii, it eepaimtM
granular crystals- It dissolves very easily in iodide of etiiyl. In M
jreapecta it reaembbs the bydrochlomle. (Gusamann ife Atkinson*) ^,

fff^drocMorate of LopMne, — Separatee quickly on cooling fjroiSj
goluLion of lopliine in boiling alcohol containing hydrochlonc acid* If |
solution in a enfficient quantity of boiling alcohol bo mixed with i
quantity of hot witter that no immediate precipitate Is formed^ theliii
on cooling yielda well deHned crystalline lamina. (Lanrent.) — %, W
hyilrochloric acid is added to a hot saturated alcoholic solution of lopbfl
till the mixture exhihita a decided acid reaction, the hydrochh>rate »ep
rates on cooling In \'±vm traa^pareat needles very mnch like the erf
of pure lopbinc. If left for some time in the mother- iiquor, they m
into small white opaque prisms, an alteration which is probably datl
toss of water. Several other lophine compounds exhibit a etmiliircliaiigf.
WhsQ lofiLuiie h treated with strong hydrochloric acid, it beci>tije» i^naiii, utl dfl
only be reitored to ibe crystulliiie sUte hy rcmovluf \ht tcid and cryjtiaibiof ftop

RlcohoL (Gossmaun Jt Atkim^on.) Nearly Insoluble in water, butdi»s(4y#
pretty easiJy in alcohol. (Laurent.)^ IT. Has a &Hght aoid
Dissolves more readily in water and alcohol than the pure
esLhibits stronger fliioresceDce, (Gossmanu & AtfeinsoB.) W,

Calcalatioa L
CJli _ _ 36-4 10-21

C«N3His„

Calculation IL
,... 308^0 *„

36-4

— i*-^

C«N*H^C1E 35G'4 ... 10000 C^WH^CIH ... 341 I

Cnlctilatioa llL

GS.

42 C
2N

19 H
CI
O

252"0
2HQ

35*4

leo

735/
SI?
554

1036
236

100*00

& Aclciaios.
73*7t

9*42

Ci'-N'tlir^HCt + Aq....... 350*1

loa^oo

Nitrate of Lophuie, — Fine li^rljt lamina?, devoid of luetic. Whi
beatod till they fiofteo, tht*y give *jli* 2 At water, (Laurent-) — Fram
concentrated alcoholic soluiiuu of iopliino acidulated with nitric ac»*l, (
salt erystalliees in small plates whieb if covered with slroug iiiiri^ ■<
which is free from nitrons acid^ ar6 converted into ati oily mm99* (Gi^
itiatm ^ Atkinson,)

1.
46 0 ..

17 U .
6 0 .

Amhjfdrom*,

„..„ 27a ....

..,. 42 „„
..... 1? ....
...... 4f ..«

7207

1095

4 44

1253

IL

41 C ....

a N

17 H ....

GO

AhA^dromt.

264 ..

..- 42 ,,

...._ 17 „
......... 48 ..

1132

Ij ■..;

.1^

C«N«H*«,KO*U 383 ... 100 00 C*'N^a'^NO«H* 3J1 .... lOOOO

16I7-,

C'5^'*fl«JsrO'H + Uji 401....100&0 C* K H5».N0*H + 2Aq 389...100*M_

n^9* J

LOFHINB.

203

When lieated to complete fnmoD, it swells op, gTves off red vapours
and perhaps ako a little water* Tho rcsitJuc contaios 785 p. c C, 85 Nj
50 Hf anO HQ Oj wbicL is nearly tlie composition of 1 At. Joplune
mnu$ I At. nitric oxido; it is pcrliaps only a mixture. (Laurent*)

T. Lophim unth AVitruie o/ StViw. — a. C*^N'H*\KO°Ag* — When a
iicutral, niDdcratcly coiicentrated alcoLolic fiolution of nitrate of silver la
mixed with a hot saturated alcoholic fiolutiou of lophiue, the mixture
«clidi£es on cooling, in a inasi of crystals; and on disBolving these in cold
ftleohol and leaving the solution to evaporate, the compound a eepanttt*©
in tolerabl^v large white needles. — L 2C*^N^H",3NO*Ag. — On attempt-
ing to purify the conipounil a by recrystallieatioUj it chanf^es by boiling
into a pulrcrulent, crystalline, i*pariugly soluble aubatanco which ^oLtles
down with a slight violet tint It contains 29- Ql p* e. silver, the for-
mula b recjuiring 29-06 p. c. — c^ 2C^^N'H",N0*Ag. Separates iu
brillbnt white needtejj, after the compound 6 has beea removed uml the
solution further evapontted. Contains 13 92 p. c. the ca! cm dated <]uantity
being 14'11 p. c* The change produced in a by boiling is represented by
tho cf^uation:

4(C^=N=HTT^K0*Ag) = 2C^^*K4P^3KO^Ag + 2C'3fKmi^NO«Ag.
(Gosamann & Atkinson,) — [A sunilftr equation wUI of cutirse hold good if lophtiie
b« regarded as L*^N^H'*, f>u this hypatlie-iii ulso the ^ompoQnd b should contain 2&"40
p, c. and c f^bould pontam II '17 |J.^ c. silvei',] ^.

l^phina mth Blrhroride of Platinum. -^ 4C*^N^H>^3PtCP — When
a concentrated alcoholic aolution of lopbirie is mixed with a concentrated
neutral alcoholic i^olutlon of bichloride of plaLinum, a compound separates
In clear, omnge-yellow, microscopic crystals containing 17*38p*o. phitinum.
The above formula requires 17*45 p, c. (Gussnianu & Atkinaon.) V,

Chloropialuiate uf Lophhit. — Wben solutions of bjdrocblorate of
l^pbine and bichlondo of platinum in boiling alcohol are mixed together,
the platinum-aalt cryitaltisea in a few hours, provided the solution is not
too etroixg, in long, pale orange-col oared rhombic tables, which may he
washed with cold aleohoh (Laurent.)^ — On mixing a dilute aleohollb

I eolutiou of bichloride of platinum with a warm moderately couceutratcil
Bolution of lophine containiug excess of hydrochloric acid^ crystals wJiith
are often needle-shaped, sepurate aa the liquid cools, and sometimes after
a while crumble to a crystalline powder of a fine orange colour. This ,
gmlt ia more soluble in alcohol than any other compouud of lophine.

L (GSssmanQ 5c Atkinson.)

k

1

%t c .,.„

2 N.,_
17 H .....

Cakulition L

276*0 52*46

28*0 ... 5-32

. _ ,.. 17-0 .... :^23

CalculatiQH IL

44 C 264-0 ....

2 N 2B'0 ..„

17 11 ....„ 17*0 ....

Pt 990 ...

5 1 -34
544
3-32

3 CL

,„ ,..„,.._.,. HW't . ., 20-18

-20*65

Pt,.,...

_.......„... t9 0 .... le-si

19-25

^1^*W

UCUPECl«„. 52ii*2 .... lOO'OO C«N'HiSHCl,PlCF.... 514-2 ....

C&kuktion III.

42 0...... 252-0 ........ 50 08

■ 2 N .»,..-- 28*0 3'5ft

lOO'OO

i 18 W

._ 1B*0 ,.,..... 6*56

n

^ 3 CI

Pt .....^ ^.........

.... 106*2 ........ 21 16

„„ 9U-0 ........ 19*62

t

C^'l^H^?,HCI,PtCF ...

.... 503-2 \QQ-Qft

204

COMPOUNDS CONTAINING TWO OR MORE A». C»«H*.

Ana

lytet.

Laureat

G5f3raaDD-

GiSssiDsnn Sl K

c

41^22

H

395

€i

19*73

PI

18-25 ....

». 1889 .

I9*rf

If u doobQUc eolation of lophme be beA&ed for some tiixie with exoe» of Lk^t.\fi!« af
jjihSaiUiii tli« bvte Womea eflsentmlly altered ; i^latmum seponttei out m « frUU of
TPrTfincdiTiiion, a»d Lbe Altered liquid is very difficult tQcrjBtallise> Tllcbodf wW
■eparates oat ii geaerallj very soft^ ad hen tig together in a rciitiisiu QiMi, n4 Ifo
quanlity of pktitium in it b les^ than in the crystoUited doable sdt^ {Gilhaaak
atAtkinMii].}

Lopbiue dissolves very sparingly in boiling' alcohol ^[id In c^A^r, uA
c?y stall kes in needles a;9 tbo eolution cools, 1 1 dissolves ta alioiil tli
same amonnt m rock-oii and oil of turp^Rtinef wbetica il sepam^tes on Mol*
in^ in the form af a white crystalline powder. (Laurent,)

Appendix t{i Lophtne.

Pyrobenzoline, C«N^H»

row;NES, (1845.) ^MWi FhrniYi, 54, 3C5 and 368.

Passes over, tagetKer with an oilj in tLe distillation of am arise, lad
erystallises in the neck of the retort. It may be freed from oil hf
pressure between bibulous paper and then crystallised Jrom tioiU^f
alcolioL

Melts when heated and sublimes, even below itm \m\mm paln^ ii
feathery crystals resembling those of benzoic add. Tho fnsed mm
solidifies in a radiated crystalline mass on cooliDg* ToJiteleai.
alcoholic aolutlon has little or uo alkaline reaction.

42 C ,

2N,

16 H.

252
28
16

B513
5 41

Fown^s,

34^4

911

5-43

C^*N^B*« , 296 .,., 100*00 ,....«, 09 48

Mo«t prob«bIy identic*! witb lophiae.

Insoluble in water, acids, or alkalis.

Diasokes sparingly in cold, readily In hot atcohaL

NITROLOPHINB*

205

Nitrolophine.

Laubent. (1844.) Sev. seient. 18, 272; J. pr. Chem. 35, 450.
NUrolopkjfle.

Lophine boiled with nitric acid forms a yellow oil wliich solidifies on
cooling and may be pnrified.

Orange-yellow crystallino powder. Melts when heated and appears
to Tolatilise partly nndecomposed, then suddenly becomes red hot and
leares a large quantity of charcoal.

. I. Anhjfdroui.
46 C 276 .... 60-66

5N 70 .... 15-38

13 H 13 .... 2-86

II.
44 C

5N

13 H

Anhydrous,
.... 264 .... 59-59
.... 70 .... 15-80
.... 13 .... 2-93

Laurent.

.... 6000

.... 15-70

3-14

12 0 96 .... 2110

12 0

.... 96 .... 21-68

.... 21-16

C«3PN«H» 455 .... 100-00

!• In vacuo,
46 C .......i 276 .... 56-22

II.

44 C

5N

17 H

16 O

.... 443 .... 10000

Jn vacuo,

264 .... 55-12

70 .... 14-61

17 .... 3-55

128 .... 26-72

.... 10000

Laurent.
.... 65-0

5N 70 .... 14-25

17 H 17 .... 3-46

16 0 128 .... 26-07

.... 14-8
.... 3-4
.... 26-8

C«X»N»H» + 2Aq 491 .... 10000

C«X»N5H» +

4Aq 479 ....10000

.... 1000

Nitrolophine dissolves in caustic potash, forming a mahogany-coloured
solution, which, when mixed with water yields a reddish precipitate
turning yellow in washing; the wash-water when boiled again yields a
yellow precipitate. Both precipitates appear to consist of unaltered
nitrolophine.

It diBSolres rery sparingly in boiling alcohol, and the solution on
cooling deposits flakes which under the microscope appear to consist of
iggre^ited laminas*

AzobenzoiUde. C"N»H«

UuRENT. (1844.) N, Ann, Chim, Phys,
ZZ, 331.— jPAarw. centr. 1841, 501.

Azoturc d*azottilbase.

1, 304.— ilnw. Phamu

Bitter almond oil was shaken up with potash and chloride of iron,
tod the first | which passed over was covered with an equal volume of
^monia. It then after a few days deposited a crystalline substance, and
iQ three weeks half of the oil solidified. Ether extracted IKq le^l oi Wv!^
^ and left BZohenxoHide,

^00 COMPOUNDS CONTMNING TWO OR MORE At. C"<H«-

Dull v^ilite powder composed of microacopic rbomUic or irregmlj
six sided prisms. Inodorous. Solidifies after fusion , and forms an opaqui
mum, which, under the mierosoope, oxhibita rhombic Bgu res with two,'
and £lx*sidod. figures with three diagonals.

'

Lauretit.

84 C .„,.

504 .

... 8303 ..

..... 83^0

5N

...» 70 .

.. n-53 ..

120

33 H ..........

... 33 .

», ^-44 ..

..„., 5-6

C»*N*H38 „

.„„ m .

.. 100*00 .

... 100 0

Isotnerif^ with imobenzcride and ^oh^Dzoidine (Laarsnt). Iti re>1aUofi to ^
almoTid oil ntid ammonift it dpretsed by the equntion :

6Ci'HW + 5NH3 = C*<N*I1* + i2H0 + 6H [L.].

Appears to he altered bj continued fusion, inasmuch as til e cooled
ma$a crystal Usee less dii^tinctly aiid forms onlj a few rhombic priiiQS with
a black rhombic ept>t in the centre; it remains soft after cotiUng. — It
diasoh^ea in hot nitric a-cid witliout evolution of red vapours; and the
^luiitin on cooling, yieldi microicopio four-sided prisms with dihedrtl
enmmitH, which appear t^> be undecomposed azobenzoilide. — Willi boil-
ing sulphuric acid it forms a yellow solution, in which ammonia produces
% white precipitate,

It j^ iiiEolnble in alcohol, and Torj uparingij sol able in etlier.

Benzoylazotide.
C^X^H" = C^CyAdH»\ 1

Laurent, (183T.) Atnu Chlm. Fh^i. 66,187; Pfmrm. Cbilr.

2^i^, — Rrv.Bcitnt, 1 », 207; J. pr. Vhenu 35, 483. — V^ev.

19,447,
Laurbitt k Gerbaudt. Coupi. chim, I850p 113; Oompi, rmd,

aa, 404,
RoBsoN. Chtm. Sm, Qtt. J. 4i 225; Ann. Pitarm. Sl^ 127; PJmm'

Centr, 1852, 209.

Foj-niatmu By the action of ammon'm on bitter almond oil oooUln*
ingprnnsie acid:

2Ci*UW + NH* + emu = C>»N^Hi2 + 4H0.

Frequently produced by the action of hyilroaulphitte of
bitter almond oil^ either with or without tUioben^aldin,

rr^parittion, L Tho yellow resinous mlituTG obtained fram 1iitt«r
ahuona oil which bad stood for four weeks in contact with an enu^
Tobme of ammonia (p. 25), h treated with hoilinj^ eth<*r, which dtamn^
liydrobeuxaini<lc, bi^n^hydramide, a less soluble body, und % small <ii
1*1' MobeniEoyl, whilst a mixture of ajEobenjsoyl and benioyli
remains undissolvel Thii mixture is boUed withdoobuJ, wbich'*'

EHit tl^ azobenzoyl and a email qtiantity of tFio l>enioykKOtide, ami tUe

residiiD is recrv3tallii?ed frcini lioiiin^ alcohil. (Laurent.) — 2. When

fitter almond oil aaliirated a.t 100^ with dry ammoiilacal gas. Is dissolved

' 1 n mixturo of ether and alcohol, a cryatallme deposit forois in tho course

f 24 hottPs and continues to increase for three or foordays, On treating

his deposit with boiling alcohol, benzoylaxo tide remains behind. (Laurent

Gerhardt.} — 3. The mixture of benzoylazotide and bihenioyl amide

rod need bj passing amnion iacal gas into an alcoholic solution of bitter

Jmond oil (p* 35) is treated with alcohol which dissolves the bibetwoy-

aide* (Robsoii.)

' PropeHies^ White crystalline powder composed of microscopic &bort
^bt rhonjhic prisma entirely wittiont modificjUion. Melts when heated
ad solidifies on cooling in a vitreous inajsa, in which a few oblique prisma
eparate« Inodorous; tasteless.

aoc

2K
12 H

ISO

28
12

81*81

12^77

542

Laurent. LaunKit & GerluFdt. BohaoiLp

61*77 81*55 . 81'2l

13'0S _.„. 1290
5' 10 b-n .„.......*. 5*55

C^N^Hi* 220

100-00 „ 99'95

nm

When mtUer strongly heated, it givea off an oil, afterwards a sub-
Lte of lophine and amarone, and ultimately leaves a carbonaceous
aidne. (Laurent.)

When immersed in strong potasb-ley^ it is gradually converted mto
bombic prisma and other products. (Laurent.)

When boiled wUli alcohol containing hydrochloric acid^ it gives off
hydrocyanic acid. (Laureut Sc Gerhardtj Robson.)

It is insoluble in water* ^

It dissolves in 300 — 400 ptfl. of afcoAof, but is insoluble in ether.

Quadi-at's Compound reBembllng Benzoylazotide.

jtnii* Pkttrm. 71, ^^*

Formation. By hcatitig sQlphocjImobeflJEylMie (p, IfiS).

2D'^H^S- • C^N'H" + 2CS . ?

Prrpatation. The re^iirtoua mats prodaced hf beating falpboc5ran&bcnrflene t^
nliAUtted with alcohol and the need lea fortning llie reiidue are washed wiUi

PrQptrtieM. Sir ndcr needl«if p^rmftnent at 100*,

QHidrat.

50 C. 180 ..., 82-57 .... 82-53

2K...,. 28 . 12B5 12'&3

10 H 10 ... 4-59 ...> 5-2e

C^Najiitt 228 ..,, 100-01 100*32

The compound it not decomposed by nitric acid*

It U insoliible in water &Qd ncTf ipuringlj' aobible ui ilcoWA,

208 COMPOUNDS CONTAINING TWO OR MORE A^ C'W,

Amarone, C«NH^^

LAimENT, (1845.) Rt^. icietiL iS, 207; J. pr^ CRe»l. 05, 453; Camphi
rend. 18, 1018.

Fcrtnathn and Prtparalion* Tbe sulistance which stiblimes In iht

neck of the retort wlien ben zoylazn tide is Ji eft ted (p, 207j, is freed from
adhering oil hy trc^itnieut witli etber^ and boiled witb nieobol containing
hydrockloric acid to dissolve lophine; the residue is washed witb alcobd,
dried, and dissolved in boiling rock-oil; and the needles which crystalline
on cooling are washed witb ether.

Properties. Small colourless needles. Inodorous, Melta at 233^i
and solidities in ^ radiating m^^ on cooling.

Laureot.
32 C .»,..«......„ 1D2 .... BS^ie „„.,, 88-36

N 14 ,.., 6*4?

11 H... U ... 507 5 16

C^NH",.......,.. 21 r .... 100-00

Amarone is not decomposed by boiling witb alcoholic potasb^

It ii insoluble in water,

II dissolves in oil of vitriol, witb a splendid bIood*r^ colour whick
ininiediatcdy disappears on addition of water: a concentmted solution in
hot oil of vitriol deposits crystals of amarono in proportion as it absorb*
moisture from the air. ^m

It dissolves sparingly in boiling nitric aeid and solidifies in sbinio^f
noedlea on cooling.

It dissolves very sp:uiiigly in alcohol, somewhat more readily in ether.

Lauhent, (1S37.)
1«30, 294

Azobenaoyl- C**K'H'*

Ann. €him. Phy$. 68, 185 ; Pharm* Cmii

Formation. By treating bitter almond oil containing hjdjrocy
acid with ammouia (p* 25),

Preparation, The alcohol wLrcb has been used to separate benitiy^
laxotide (p. 20G), from the admixed ar.oben^nyl, is evaporated, the residnff^
■fain boiled with alcobol, and oo forth, till the crystals of aziibenioyl arc
HO longer mixed with bonzoylaaotido*

Proprrtia. Whiti? isblulug powder reseiublmg starch, and com
ef very jf/uail smooth gbVu^uti tbomVic Ubks or somowbafc eloi

BENZlIYDMMIDfi. ^^^^^. 209^^

irji^uLu dx-sideJ tables?, Inodorotis. MoU^ wlien heated^ forming a
thick l^uid whicli solidifies to a tmu^parent gum on cooling.

I.

42 C

UN,...

IS H

» 252 ,
. 2S .
, 45 .

,. 85-43
.. 9 49
,. 5^09

IL

44 C

2 N

16 H .»,.,..

„ 2C4 .
„ 26 ,

.. 85-71 .
.,. 9-05
... 5^20 .

... 85-24

&'23

C*^>PH^....

.. 205 .

.„ lOO'OO

C'WHi*

,. 308 .

,. 100 00

n

L^urenfi ftirmwia I, aCii'ila no ei|)1nn:ttioa of the formation of Mobcnioyr; ac*
cording to II, its forraation i3 repressnted Uj the equation :

3C"H802 + NHS + HCy - C*WW^ + 6HO.

I tlie compound shoiild peihapjj be regarded m C^'Cf NH" [L.]*

Azohomoyl Is decomposed at a high temperature into an oil^ a solid
E>dj, aad cliarcoal.

When boiled witli alcohol containing hydrochloric acid, it gives off
kydrocjanic a^id. (Lauront <fc Gerhardt, Compt chim, IS 50, lli.)
It 18 insoluble in water.

dissolves in moiQ than 300 pis. of boiling alcoholf macb tiior0
illy in €tk€r.

Benzhjdramide.

o*N-H»^o' = c*^cyAd^^^o^ t

^AintENT. Ann. Chhn. Fhjs. 6^, 1S4; Phamu CmU\ 1838, 29*.
Laurent k Geuiiaiidt- Comp. chim, IS50, 114j Compt. rend. 30,404«

»

Farmation. By the action of ammonia on crade bitter almond oiK
*{Laurent.) By the action of cyanide of ammoniuni on pure bitter
almond oil. (Laurent k Gerbat dt) i

3C»*H«03 + KH^ + C'NH ^ C**NHiso3 4. 4H0,

Pr^paraimh The yellow resinous moss obtained by the action of
ammonia on commercial bitter almond oil ia repeatedly boiled witb alcohol
or ether,, and from the crystalline mixture which the liquid deposits on '
coolings, the crystals of benxbydramide are selected by the aid of the
microscope (pp. 25, 101), They are difficult to separate from another
substance which crystallises in needles, (Laurent.)^ 2, The liot alco-
liolic solution obtained in Laurent k Gerhardt^s preparation of beuzoyla-
eotide (p, 206), deposits by cooling and spontaneous cTaporation, small
needles mixed with drops of oil; they must be quickly washed witb a
tmall quantity of etber-aJcohol, and recrystallised from hot alcohol.
(Laurent Jb Gerhardt.)

Pro I'^rt ki. Col 0 u rleas, m i croscopi c, re ctan g ul ar pria m s w i th t w 0 <
Btiial fm^s intersecting at an obtuse ani^lo, (Laurent oL GerKa

SIO IMPOUNDS CONTAINING TWO OX MMI as. CV.

$o4tteiriiK9 two Utoral oilircs aro truncat-ed.. «■:■ iiiL'i k:l-s»si*: prisms an
y?\\;^c\\l ylauTvnl,^ Melts without dectrLjoijiii-L iz?£ j-i^iSfa in i

4*0 . -f»4 .... 80-98 £3-?^4 ^-i:

*\ 2S .... 8-59 ^-SO "JI^

:< u IS ... 5r.2 G-i«; .. : *i

iO lii ... l-IU 1-10 «?2

v^Vr-X-^ o:; ....10000 100-00 IK-iV)

*jM.vf." ".y- :."* .■•- i-'-u)*':*. whirh, accordiog lo L&iinr?;' x Gerlurdt, vu
•»* •>>*>»> ti.*,v • ' •• - . > .. >:.;v..v. iliHliuvd the formula C^'-H'S according M
« Vv> X'l- -i.-- * «. -c 5^'. -. - .V :>*>a'.«i:j with Uyilrobciizaiuide.

/•■■«. -^ .>«.• . : >. ' 1^ - :• : ". >■ -'i rr. ir. ule 1i ea ted abo ve i i ? melt i ng point
;^ *-.-^ .?«>.-,; •■ ." "• " .'v/.r/ii' ;;oM, and yields an oil, a cn'sttl-

i4,v --. *. .»••' •■ '■ > :.,'...::;.• »f L'harcoal. (Laurent: Laurent i

■•• -,-.1 J-y iHild liy»lrochloric acid. (Lac-
. . vi .: l.y.lroclili»ricacid, it yields bvJro-

\"Vi %. *v-» ^ "

>c

K%

• » ■ '

: .t A Gerliardt.)
^.!:l^lo ia cold^ more readily in

. ., ..... ,.> ■■■■" -r'^r jljaken up w::H

: :: ■ r-idiio di^soWeJ

> ::. r: aiiii tbr n^

■ . ;. : :. 11- ii..ir"-li

. ■■ •_ :"!•.■: v.'.^

-.;- ^l.:-:lL^•i.3

: . -- ..'•■ :-\z\.:v ii iv'

* .ji **^t*

AZOBENZOIDE.

m

Bte^ipomtiom. BcDzamil ilistik apparently witbout alteration, but

be diatiilaie is easily eoluble in etlior. With nitric acid U forma an oil

rhich crystallises on cooling. It La decoinposod bj boilings with Uydro-

liloric acid or akoliol; a small qimntity of white powder tben remaining.

|t is readily dissolved by alcoholic pota^jli, and the li<jnid on cooling

leposits a crystalline body.

It is nearly insoluble in alcobob ether and rock-eil, even at the boiling

Azobenioide. C"N-h^j

[lACHENT. (1837.) Ann. Chim. Fkifs. 00, 100; Phsrm. Cenir. 1838, 2^5,

Formati07i and PreparatiQn, By the action of ammonia on bitter
DOndoil (]>. 25).

Frapertim, White powder, which does not exhibit any crystiiUine
rncturo when examined by the microscope. After fusloOj It aolidifies
crystalline granules.

^■i

^H_

.... 504 .

.... n ..

..... 3S .

... 83-03

... n/53
.. 5-14

8S C

5N

s; ff

aifl .

70 .

3? .

... 82-62
. 11-24
.. 5 94

LauTTut
.,., 82-96
, , 11 76,

C?"N*H» ....

... flOf .

.. 100 00

C»N*HW ....

fi23 .

... 100-00

.., 100^32

Isomeric with azobenzmdin^ aad fiecording to LanreDt (T) with Bzobenioilidc* \l.
c>benEoide and sj&obejixoidin, a«> supposed by l-aurent & Gfrbardt (Cumpt. eAtm.
fSO, 113)* owe their on^ln to the actioo of prusslc ndd, thdr formalion may be
DSl fiimpljr expressed hj the equhttioti :

6C**H«0» + 4N11» + CyH = C^nm^ + 12H0.

je referred to the ben

Tlie fonnula C*^*H^ (?id. Cffknhiion II) mAy be referred to the benaylene lerie* in

■ A<

I

^H Kof-mathn and Freparaiimu From crude bitter almond oil and
^■Bwonia (p. 25). Purified by two crystallisationti from ether.

^^ Proper ( la* Colon rlesa, microscopic, eiic-aidcdt oblique rhombic tablea
I with dihedral summita. Inodorous* Melts when heated, and i
^■ta cooling into a tLon-erystalline transparent m^s«

L ^

Afohcnzoide when heated yields an oil and a fiolid sublimate.
Insoluble in alcohol and eihen

tuWitT* (1841 .) K Ann. Chim, Phjs, 1, 002; Ann. Fkarm. S8, 32S;
FMm. €mtr, 1841, 50.

212 COMPOUNDS CONTALXING TWO OR MOBE At C^UK

Laurent.

C ,.... B3-32

N , ,.„. 11*50

H 6*55

100-37
T^omeii^ ^ith axobenxQidiC (and uobenxoilide ?},

Nitric acid dissolves it with de com position; and tlie solution on ebol^
Ing depoaits &mM needles whJeb are nearly msnlnble in watcFi but tn
drssolvcd by ammonia. — It dissolves witli yellow colour In hot eulpbiinc
acid, and ammonia- added to the solntion throws douti a wbite eubstaiice*
^ — It is decomposed by boiling with bydrocblonc acid (with evolution of
hydrocyanic acid? comp. Laurent & Gerbardt, Compt. cAim. 1850, 113)*

Nearly insoluble iu aJcoholj eporiDgly soluble iu etber.

Benzimide,

Iaure>^t. (I83ff.) Ann. Chim. Pftyi. 59, 307; Jnn. Pharm. 17. U;
Fogg, ae, 497. — Ann. Chmu thys. m, 103. — iiTetr, Mcia^. 1% J20|j
J.pr. Chem. 27, 300; Fharfn. Cmtr. 1836, 127; 1842, 242, |

Zim^. Ann. Pkarm. 34j 188; Fharm. Cenir. 1640, 4a0,

Gregouy, j^fiH. Pharm, 54^ 372. ,

Laumbnt & GEnHARDT, Vm/ij^t chitn. 1850, 116; Compt.rtnd^ 00, 404,

Formation, By tbe action of hydrocyanic acid oa bitter Alaiotid oiL
Occars ju crudo bitter almond oil ^^WincVlcrj RfperL 02, 328).

Frepantilon, I, Pure hitter nlnioud oil mixed with one- fourth of _

volume of nearly anhydrous prussic acid, is shaken up with an «^vll

volume of concentrated alcoholic solution of po!a?b diluted with 6 pti^ ftf

ulenbo), tlicn gently heated «nd left to BLand for some time; a^nd tiwr

white, curdy, floccuient precipitate which then fiills down, is e^pamted

from the oilj boiled with water which extracts benzoyii, uid purifidd hf

•olulion in alcohol* (Zinin,) Gregory pbUmcd benzimid« by leamg cTads linir

ftlmond oil in contact witb potasJi-lej for ten years* Accordinf to Ziniii, bitter ■IniiM

I oil cti^nUbim^ a very larg« t|aauiity of pruBz^ic ndil, nlwiiyj )ictdi bentimlde \nhUmi> ftf

IbitinjlT^ when ircAtcd with potaah^ey.^— 2* When tlio re^iinous iDaas cliioftf

COHBisting of benioYn aud beniimide, which remtiins in the retort wita

1^ titter almond oil is rectified, U dissolved in boiling alcohol, il solntiott ti

obtained which on cooling yields benximide, to be purifed by aertnl

f^n stallieatjoji* from hot alcohol (Winokler.)

J

■5f

A

BENZIMIDE.

ProperiUs, Colon rlt7«:$, li.s^lit^ si^mewLat pearly fljtkea compoijed of
microscopic ucedles atid laminse. (Lfiurent.) White or i^reeniBh white,
looaely coherent inassj ^vhich loares u stain when ruhbed or pressed.
(Zinin.) Lijrhtj microscopig, yellowish white crptale, which are destitute
nf lustre and leave a eta in. (Gregory.) MelU when Ueatod and solidifies
in a radiated mass at 1G7°* (LanreaL) Melta without decomposition at
a high temperature, (Gregory,) Inodorous. May be volatilised without
decomposition. (I i^inrcut »)

46 C
2N

18 H
40

^1G
23

32

77-89

7*93
5-08
D Q4

Littrent. Zmti. Gr<*goty.

. 7S'.|5 .„. 77-28 ... 77 'GJ

7-00 .... 7-76 ..,. 8^20

A'U .... 5 09 .„. 5*17

U'Gia .... 9-8;'|...- 8-96

C^^U^SO*.... 331 .... lOU'OO lOO'OO .... lOO'OO „„ 100-00

^

Becomposktom, I. Wlien strongly heated, it turns brown, and
TolntiliseSj leaving cliarcoal- (2inin.) Decorn poses at a strong heat, and
emits the odour of bitter almond oil. (Gregory,) Burng on platinum foil
witli a red sooty flame. (Laurent,) — 2, Dissolves in hot rtitric acid
without evolution of nitrous vapours, and is not pieci pita ted therefrom
by water or ammouia* Heated with uitric acid and alcohol, it gives off
red fumes and yields ammonia and hcnzoate of ethyl. (Laurent,)
Pissolves in uitric acid with decomposition. (Ziuin.) — 3. Dissolves
with decompoaition m hoiiiug hf/drochlorie ncid^ and yields an oil having
the odour of bitter almoud oil. (Laurout.) Boiled with hydrochlorio
acid, it yields bitter almond oil and Bal-ammoniac (Gregory), probably
also formic acid (Gerhardt, Traill 2, 1 94 j compare CmnpL chim*
1850, US);

Vmm^Hi* + lOHO - 3a*lPO' + 2C3H»0* + 2NH^

4, When heated with oil of vitrloi, it yields an emerald-green solntioa
which afterwards turns yellow and then black, while benzoic acid
lub limes. (Laur«ut») When perfectly dry, it dissolves in fumiug oil of
vitriol with dark indigo colour; when somewiiat moist, with emerald*
green colour, which afterwards changes to yellow, (Laurent.) It dis-
solves in oil of vitriol with emerald-green colour which soon turns to
red, and is precipitated in its original state by water. (Zinin, Gregory,)
— 5. He^ited with strong bases it yields benzol, (Gregory.) Heated
with hydrate of potash which is moistened with a little alcohol, it yields
ammonia and benzoalo of potash. (Laurent.)

CotnhinaUcnM, Insoluble in water. Dissolves sparingly in boiling
ohol and ciAtr (Laurent, Zinin^ Gregory), better in wood-ipiriU
l(Lanrent*)

214 COMPOUNDS CONTAINING TWO OR MORE Au CWfi*.

Thiobenzaldin.

C*=NH^^S* = C*^AdH»^S* or C«AdH^*S^2 HS.

Laurent, (184L) N, Ann, Chm. Phji. 1, 295; Ann. Pk&rm.
38, 023. — i^fv* icknL 10, 393, — Com/>i* iwrf*3l, aj?; i*hmm

Caitr. 1841, 498.

Su^ahnsftjflnfMt^gtqf, HtfdruvB de jfui/azo&enzotift Sut/&z'>ture ie kemii^e.

formation. *By tlie action of hyilroeulphate of nmmotib on litter ^
almond oil, tlie first stage of the leaction being probably tlie farm&tioi
of gnlpbidc of at il bene :

Preparation, L Gone rally produced in t mall quantity in the pirejift-
/ation of euJphide of stilbene from litter almond oil and bjdrosuJpliiitt
of ammonia; cryafcallises from the filtered alcobolic solutioti by ^poa-
taueoua evaporation (p, 1G9).— 2. To a aolutiou of 1 vol. eriid« billir
almond oil In 4 or a vol etbcr, 1 vol. Lydrosulphate of anuaonift m ftdtUd^
and tbe crystal line crust lAbick fonn^ in the course of tbre« or f^ir
weeks is pnrified bj rccrystallisation from eiher. — 3. Wben I ©r2 ?«!.
liydrosulpbate of ammonia arc poured upon 1 vol. bitter aloiond oU, th»
greater purt solidifies lu 4 — 8 weeks, gometimeg in a re^inoua, BomatiiMi
in a crystalline masSj wbicb may be freed from adhering oily subituAS
by washing with ether, and repeatedly cry^tajli^ed from boiliog eiber. -

Jn tbij$ re&L'tifiii ^tyetitl qunipy^und>( are furou^il (p. 2b}. Bf Uie Ikjrd fr^cei
Laurent on one oecasloei obtaineU bc^tZfi^'Uxotide <tnd a thi-k oil ; Bomt^timca b«ox«]
nzotide or a white powiler insoloble in eLher is formed, in addittoti to tliipb^U£4ldi
Ju one in&taoqi:, rhomMicdroDi refeisbUng Lulc^puriiDd imcluble ui eihca' were
produced.

Ffop^rlied. Colourle63 laminm with a pearly Jnstre^ or when ob-
tained by spontaneous evaporation of the ethereal eolutionj mtii#j
large oblique rectangular prisms belonging to the obli^ju^ pri^iumtj
fiy&tem. Ptg. U7, without / and h and with the m^facea prodouiiudiitf
[oP. » p€6 . (sc Px .) tcT] i : t nearly ^ 129", in oiUcr cry*ti
= 98 ; u : u= 121' Wi p : u = 122'* 30\ Kxbibits tjuee di«iiac*
eleavageji, the most distinct being parallel to m. Uelts ^t l^^\ Ux?upei
dnotile on cooling and gondiliefi to a guntmy moM, Jt iiup«rt# to tbt
fingerB an offensive odoar^ like eulpbitle of stilbene.

4

mumm

bitUAS I

ru£4ldi4^H

42 C ...........

N :....

IQ H

_ 1* .
... 19 .
.. 64 .

... J2*ai ...

... 401 ..
.. 644 ..,
... 1834 ...

..... 72-31

..... 3-2a

•PP., &'3l

4 S ............

.... 1800

C^-NH'^S*.....

... 349 .,

... 100^00 ...

..... 98^62

TKil compound occupies in tUe bt^nzjIeHe icrtes the flamr plice «• tbltldla
ellijIcTt^ icriri. Lnurcnt, from tbe wbovii aniilysii, ilcduivd ibe Tartiiillji €**NW^^
for wbkb he after wanJi (O&mpL rend. 3)i li52) aubstlEuUd tbe oii« ^boYv gitoii k
mc€ordmace with a aev Diirogcu-dettrmiDatiou.

HYDHOSULPHATE OF AZOBEKZOYL.

215

pecomposkions, L Thiobenzaltlin when etronglj leated becomea
MuUli, then re<Idiah and gives off amnionm; on cooling, the rnasa solidifies
with a radratirig structure, Wht?ii tlistilietl, it ytelde an oil and raost of
the prod acta of decomposition of sulplnde of stilbene. - — 2. It is decom-
posed with eflorvescence by hruminey foFTniiig Uydrobronint<3 of amtiiotiiiiy
and an oil which may bo extra.cted by etbor and crystalliaeg partially
when its solution is evaporated.- — 3. VV^'heti trmderately heated witL
fiitnc itcid, it b violently attacked^ an oll^ wbich appeava to be bitter
ahiiinid oil, cullerliiig on the surface. On boiling the liquid^ benEoic
acid id ]irodueed. — 4. With hot o// r/ tv/W^^ it fonns a solution of a
beautiful carmine c(dour* Water d^^trfsys this colour and tlirows down
yellow flukes. — 5, Boiled with alc^^holie potaih^ it gires ofl' ammonia;
water uddcd to the solution separates a a oil which crystallises on expo-
sure to the air^ and acida Dliminate sulphuretted bydrngen. — When
cQiitinaously boiled with alcohol, it gives olV sulp Lure t ted hydrogen.

It disssolrcs in 20 — 30 pts. of boiliag ttUisr.

Appendix to ThiohtHmMiiu - *

HydrosiUphate of AzobenzoyL

Laohest, N. Ann. Chbn. Fhji, \, 300; Ami. Phmm. 38, 327; Pharm.
C^fnlr. 1841, 500.

Thr^atitin and Preparation. A mix tare of I voL crude bitter
almond oil, I YoL liydrosuljdiata of amiuonia and 1 voh ammonia, left
to itself for a tj^uarter of a year in a closed vessel, solidifies for tbe moat
part, and on IreaitinjL: the resultiii^ ma^^a with boilmg ethefj & small
Huaiitity of hydrosulphato of azobeuzoy] remaius behiud,

Wbitij crystalline powder consi.'stia^^ of microscopie rhomba -or
rhomWid^j often baying their acute ed^os truncated. Inodorous,

Laurent* ^

42 C ... ..... 252 .... 72*84 ........ 71^2

2N 2B .,„ 8 00 8-7

18 H ., .... ' It ... &'2fl .,.,..., 5*1

Si .., .. 49 ...» 13'8T U'O

QU^mm^ 3i6 .... lOO'OO ........ 57-1

As Iho atiultsis ihowg « !o&s of 3 per etnt, Laurent ptucvd but little i^on6de^tice ia
the formula deduced from it. ^TUe oo»j» pound h perhaps C*^"*H=iS» =^ C«Ad^H 1*8,2 BS,
ad produced ia tbc tnatinef represented bj tLe erjufltion ;

aC"U**S* + 4NH* = 2C^N^H«iS> + eHS [L],

|l la nearly insolabla la ak^hd and dissolved hat sparingly in boiling

2i&

COMPOUNDS COXTAiSlSG TWO OR .MOKE Au C**U^

Benzoylureide. C^N«H<^»-

Laurent & Gekharut. CompL chlm, 1850^ 110; Compt rend.ZOAMj^

Formation. By the action of urea on bitter almond oil ;
3CWH&03 + 4C^-H*05 = C«N8H»0« + 6UO,

Preparation, A mixture of 5 pts. of pulrerisctl area and 2 pU
bitter almond oil becomes perfectly liquid when lieatcd to a tetnperanire
oven below 1 00"", and eoon after wards eoiidifies into a compact mas*.
It \b best to place ihe mixture in a basin on tbe sand-bath^ and atir it with
a pestle. The eolid mass is pulverised , freed from any cxee^ of hhttt
almond oil by treatment witb ether, boiled with a large quEn^ty of
water till ao more urea crystallises from the filtrate by evaporatioo, mA
dried at 120",

Fropertm, Amorphona white powder destitute of taste and smtU,
Separates from the aleoholie eoluti(>n by evaporatioa in amorphous cristt.

I^nreat flt Gerhsf^ti

50 C »„,

... 300 .

. 59S2

.».»» 50* ;a

8N _.

. 112 ,

„. 22 22

, « 21*68

28 H .._.

..* 28 .

., S'Sfi

........ ^U

B 0

,.. £1 .

... un

1308

(^^*H^« ..

., &04 ,

... 100-00

........ 100-00

Dtcmiposiliom. \. Benzoyl ureiJe turns yellow at 170% and griti
off bitter almond oil at a temperature a fe^*^ degrees higher. By dij
distiUatioD, it yields bitter almond oil and water containitig ammt»mi
and leaves a yellow residue which difisolYes sparingly jn alcohol an
ether, and disappears completely when more strongly heated, ^2, Whet
boiled with dilute acids, it is resolved into bitter almond oil and urea. —
3. It ifl gradually decomposed by boiling potash-ley, bitter almond oil
and ammonia escaping together with the watery Yapours. The eolatioQ
contains benzoate of potash.

Benioyluretde is insoluble in water.

It dissolves m ctlcQlid^ but not in ether.

'4

letV

Beazomaia.

Laurent. (1844) C^ipt chim, 1845, 37; Pf^arm. Cmir^ 1845* Sl^
Fuimation, — By tbe action of alcoholic ammonia on ben iota :

It is sometimes produced by the action of ammonia on crudo Mtlif
almond oil, probably because thai subsiauce almost always contmiM
btazovh

I

Prfparqthn. "VVIicn the mixture Dbtahied from benzoYn znd alco-
holic ntnmotiia left to atand quietly (p* 174), is exliaustc<l by boiltng
with alcoUol, beiiKoYuam remains together with the crystal 1 me boily (2)
(p. 174); on boilings this mix t tire with alcoholic potash, the body (2)
dis?iolve5j and the liquid is then some ^vh at dil'ited with alcohol aud
fii teredo The filtrate mixed with water yields a prprlp state, whkh Iiowever docs not
couaiat of tlic compouud (2) in its orijjiixaJ state, Th<} beniuTuain remaining on
the filter 13 dissolved in boiling alcohol containing a small quantity of
hydrochloric acid, iind precipitated from the solution by aramonia/

White microscopic needles, Inodoroaa, Melta when heated aud
crystallises partially in needles on cooling*

rThe compound docs not appear to be decomposed by potash.
It diBsolvea at a gentle heat in oil of vitriol, fonning & reddish
aolutlcn from which water throws down orange -yellow flakes.

It diiisolves readily in boiling alcohol containing hydro chlorio acldj
and the solution, when diluted with water^ deposits a portion of the
beuioinam^ the rest on addition of ammonia.

Benzomamide.

""liAURENT. (1837.) Ann. Chim. rhy$. 60^ 189; Phami, CeiUr,
J838, 205.

, 2a c ,

...., 14 .
..... 12 .
..... 8 ..

... fiSO ..
„. 5 90 ..

.. 405 „

Laurent,

1 N L...::
r 12 H .....,,.

...., 7^4
3-8

CP'Nli^O .,.

...,. 202 .

.. 100-00 ,.

, 100*0

Frntnaiitm, By the action of aqncons ammonia on benxoTii :
aC^^E^O^ + 4NH^ - C«N^H« + 13HO.

forms in 8 weeks a white powder which may be freed from unaltered
benzoin by boiling with alcolioL The residue is recrystaJUsed from
boiling ether.

J^ropaiies^ Whit© powder consisting of microscopic^ very slender
needles, having a silky lustre. After fusion, it solidifies in a fibrous
mass. May ho distilled without decoai position.

Laureoti

81 C .-...504 .... 84"56 83 45

4N 50 .... 0*40 .„ 8-04

36 H 36 .... 604 5*65

^^^ C«*N*H^ 596 .... 10000 DTDl

^^ Foljmene or l^^inertc witU lijdrobsnTamldi}.

^f Insoluble in water; very sparingly soluble iti alt^h^l ^vA dltcr.

218

COMPOUNDS CONTAINING TWO OR MORE At. C^H^

Imabenzile.

C^NH"0^ = C«AdH«0* or C»*NH",OM

Laurent. (1843.) Mev. scimL 10, 122; 19, 44i; J. pr. Of»i, 27^
35, 403; Fhmn. Cmtr. 1843, 243.

Formathn, By the act ion of timuionia on beusUe;
C^Wm"^ + NH* - C2^H^^0=^ + 2HO.

Frtparatlmu Benzile is dissolved in warm absolute alcoboK
ammonlacal gm passed ttimiigh tbe stiU wurm solution^ and the lif^oi
left to cool J while the pajsaage of the ga& is cmi tinned. After 24 hatii _
the li<iuid, together with the sediment which has fonned, is beated t« tlif
boiling point, and tiltered at the same temperature* Imabenzile tlien
remains on the filter and may be purified by washing with other,

F roper tki. Whit© inodorous powder. Separates from ita solntion ii
boiling ether-alcohoh in uiicruscopio right rhombic priems with dihodfil'
Eumnnta who&o facee rest on the ohtase Jaleral edges. Melts «t ii*f,
reoiaina soft and glutiuous on cooling, and then solidifieis wilboul
crystallising.

I

2S C

N .,.,

.. 168
.. 14
. 11

.... eO'38 _

... r-65 ....

Lanrent.

.„, 80^0 ... 80^34
7*3 . . 6*^0

U H „..

2 O

5-3 ... 5'l*i

-.,.. 7-4 .... #'68

C=»KBi'0-..

.. soa

.... 100-00 .„

..... lOO'O .... 10000

Decomposiimts. 1 , Imahenzile h partially decomposed during fiiiid
When eubjeeted to dry diet illation^ it neiUior gires olTga^ nor kar^ai
carbonaceous rcaldne. — 2. When gently heated with nitric acid, it gifci'
off red vapourSj and yields a yellow oil, which solidifies in the cryst^iim
form on cooling, dissolves in alcohol, and crystallifioa tberefrom in fxnall
needles united in tufts, but h insotuhle in ammonia, — 3. It is not
altered by boiling with bydrochlnrtc act J. It dissolves in gently b«tte4
oil of vitriol, and the solution mixed with water deposits betizilan^^
4, It dissolves readily in boiling alcoholic pat adi; and water ft' ^
the solution throws down bcnzilimldo, while nothing but ixitasb
dissolred.

ImabeajGile is perfectly insoluble in boiling aleobol and other.

BanzUiin.

LACaiKT. (1845). ffcv, icimt n, 442; J. pf\ Chtm. 35, 463.

BENZILIAL

219

Formation, 1* By tho action of ammonia on benzHe:

% By boiling imabenzile withakobolic potaab.

P Preparation, Tbe bot filtmto obtained in the preparafcion of iinal)eii-
z\]c {p. 218), depoaits on cooling slender needles of benzilini, mixed with
a few thick crystab of benzilauL The iJefanU'd mutUer-liquor yielded hf ipon'
tuneous ernjKirBtloTi s few mort; crystals af I emilirtJ togfi^bcr with crjgtftls of Wtitilam^

The ben ill im is pun6ed bj several recryiitallifiation:* from boiling alcohol,
2. Imabeo^ile is dissolved in boil log u.leohultc potiiBb, and tho solution
mi iced witb water^ wbicb thrown down beiuiUni.

Pmpa'ites. WUite, silky, extremely slender needlesj wbieb, nodor the
uitcroscope^ appear to be united in tufts. Melts at 130% become*
gammy on coolin^% and eolidities aL ordinary tempera turesj without
crystallising.

mc

£2 H ,.......».,

... 336 ,

.... m .

,. 80^38 ..

C-n ..

.. e^26 ..
7-65 ..

Laurent.

...... BOO

..... 7 0

5 6

4 0

.. 32 .

...... 7*i

C«N^H"0* ....

... 418 .

... 100 00 .,

..... lOO-O

Polymeric for isomeric) wiib imabfnaile, — Laurent {AiHh^df di ckimif^ p* 108)
regardt it is ibe nttrile of bcAxULc Mid ^ C^KH^^Ov

Demmpo»kkm* L ^Vhcn fu&ed, it yields llie ^ame products of
deconi position a« inialienzile. Distill apparently wiihcmt decompositionj
but the distillate dissolvea very reiidily in ether and cryetalHscs therefrom
in needles by evappration. — 2. It iw oa^^ily decomposed by hot nitric
acid, with evolution of red vapours, and yields the saino products as
imabenzile. — 3. It disaolvea in gently heated oil of vitrioi, and the
Eolution mixed with waiter deposits benzilam. — 4. Jt ia not decomposed
by hydrocbloric acid,

It dissolves sparingly in alcohol and tther.

LAUBE^T, (1845 ) Uev, ment, 19, 443^ J. jr. Chem, 35, 404.

51 FormatiotL I. By the action of ammonia on beoEilei
f C^W^O^ + NH* = C^H» + 4HO-

S* By dissolving imabenzile or benzilim in oil of vitriol;
PrqmraiUm, 1. The thick crystals obtained in tbe preparation of
benzilim are purified by repented crystallisation from cold ether-alcobol,
— 2, TIk3 Boliii mass obtained by the nction of ammonia on benzile la
iva^hed with nleohoJ; tho resulting mixture of imatenzile and benzilim

220

COMPOUNDS CONTALNIKG TWO OR MOIIE A*. C"!!**

dissolved in getitlj teated oil of yitnol; and tli6 solution diluted i
water; tin oil tlion separatea out which solidifies aliisost inimedtiitcl|
Tbis product is washed wiUi water, then quickly with a small qaal
ti ty of alcobolj dissolved in ether-alcoLol^ Atid the solution it IgftJ
evaporate,

Froptrtm. CoIourlesSp right rectangular prUtnSp F^, 69 m\
p and ij and very narrow { oo poo , qcPqo , Poo), y : y = lOS*^
t im =i 90''; t lu zz.llS", Cryst-allisea from aleohol in pmms an incli
or two long; from ether in short, rather thick prisma; — Melts at 105^
and if not perfectly faacd, solidifies a-^aiii in needles at a tempemta^e
very little lower; but after complete imi<m^ it remains fluid foraloflg
time at ordinary tempenitures, and gradually sol idi ilea without ctry&til-
lisin^, but if it be then gently warnaed, becomea opaque and crystallr '

2B C

N

9 H

168 ,.

14 ..

.. 87^94 ,..

.. 7-3a ...

Laurent,
..... 87'C3

7-00

5*00

C=«NIP „.,.

...... Ifil .

... 100-00 ,..

..... 9963

It 19 quickly deoomposed by nitric acid^ au oil being produced whicli
cryBtaHisee in needles on cooling and is insoluble in ether.

It is not decomposed by boiling alcoholic potash.

It di^olves readily in oU of vilriolj and is precipitated in its ^npM
etate by water.

It dissolves very easily in alcohol and in €fJWr.

Azobeiisdle, C*^XH^*0*.

ZonK, (1840.) Ann. Fhamu 34, 190.

lACREiVT EnK met4. 10, 445; J.pr, Chestu 35j 46^.

FcrmaUon and Preparation^ When an alcoholic ^lutlon of
uot too concentrated is mixed with aqneous ammonia, a white g
precipitate is formed, which, after rqmainin/]f in the liquid for 10 bamSiii'
washed and recrystallised from alcohol. The liquid wbicli hu de|»o9iUd tit
AzobeiiziLe^ contuiDj* bcnzunte uf cttiyl; and aiiparently, u body which difsolves ttti^
iti alcobol and cryatiilliees in fiwall needles [probably beiuilam. L.]. The mtm wA*
■tanc« h more abunchLOtly produced whetv an akohoUc Botution of beniile is fradmUy
tnued with ammonia &t the boihng bc&tf tiU tbe liquid, still kept boitieig, lal^btfi i
milky turbidity*

Properties, White, highly Inetroug^ iridescent^ ibm, emooih nmdk^
and laminae*

I,

i2 C ..«.,

15 H

..... 252
..„ 14
..... IS

.... 87-20

..,. 4-84

.... 5-19

. 277

n.

42 C ,.,........*■

„. 8j2

.... S4-33
4».« 4*71

Si'3l

N

2 0 ...........

... 14
„* 10

O »

.... B

.„. iTI

^NUm ...

... 28t

.,. lOO'Oft

C^^W^O\..

.... vkl

«., 100-00

,.. IW^

I

METIIYLATE OP EEKZTLESJE.

221

Laurent, adopting Zimin's formula (I) give* for the formation of Mobcuzilc Uifl
ecjuotion :

5C3*H^W + 2NH3 ^ SC'^'U^^O t A0*n^O* + 2H0,

whk!^ likewUo takes acdount of the simultaneous fonmitiaii of benioatfi of ethyl.
According to formula (II), tlie formjition cf azoheniile takee place trraultaueouslj witli
that of bmzoic ad J aticl benzikm, as represented by the eqtiatioas

4C=«H^"0' + zmP ^ C*=NH»*0^ + 2C^NHi« + C^^HW + lOHO [L.].

Azobenzjlo h nearly ini?oluble hi ^ater, potasli and ammonia*

It dissulres in alcoholic potasli, ammoniap and liydrocbloric acadi

whence it crystallises without alteration. The solution Is not precipitated

by aleobolic nitrato of silver.
Soluble in aleobol.

% Addmdii to the Btniyla^ Seria,

Methylate of Benzylene,

C* WicKK, Ann. Pharm, 102, 363.

Mcthyhlfnt&lic Mer, Mfihyibmiordtker.

EFormatmi. By tbe action of metbylate of sodinni on chloride of
beniylone:

2NiCl + amXC^H'J^O".

Preparatlmi, 2 At. sodiam are dissolved in pare nnliydrons tnetbylic
\loobolj and t be sot ut ion boiled for aome boars with chloride of benjsylene.
A large quantity of chloride of sodium then separates; tbe excess of
methylic alcohol is removed by distillation at the heat of tbe water- bath;
the residue mixed with water; and the metbylnte of benaEylene, which rises
to the surfacei ia removed by a pipette^ then dried and rectified.

Fropertui. Transparent, colourless liquid, heavier than water.
Boils at 208^, leaving however a brown residue arising' from decompo-
fiilion. — Has an agreeable odour, resembling that of geruaiums. — Inso-
luble in water; easibly soluble in wood-spirit, alcohol, and ether.

Ethylate of Benzylenet

^ff'icKE. -Intl. PAam, 102, 364.

MihylohmxQiic ether, AHhylhtiRt&laiker,

222

ADDENDA TO THE BlINnXENE- SERIES.

Prepared, like the preceding compound^ by tUe action of etliykio of
sadiimi on cblorkle ^f benzyleoe.

Transparent colQurleas liquid, laeavier than water, and emelling ULi
the methjl-compoand* BoUa at 222°,

22 C .
40.

132
16
32

7333

8*88
1779

C*5H«0*

180

100*00 ..... 10000

This and the preceding compound innj bft rej^arded

ethers derived from the [unknown] biatomic alcohol

chloride of bonzrlene C**H*,CP, in iho lanie manner as WiirtiV gljeol

C*H*i
or hydrate of ethylene h4*^*' ^^ related te ciUloride of etJijleMr

these alcoliola being formed from 2 molecnles of water, vrif 0^ by Uie

renlaoement of 2 At, H bj the biatomic radioala C**H* and C*H*, The

ethers nre formed by the replacement of the other two atoms of bydrogili

by 2 At methyl J or ethyl, &c.; thus €th]fhite of hen2^l^n^ ^ rC* H*^'l
This compound oceapiea in the benzylene series the same place tfaii
acetal {cifiapfO* occupies in the ethylene lericB, m

Eth jlate of benzyl one is Insoluble in water, but dissolves readily la

tifood-s^irii, alcohol and t(h€t\

Amylate of Benzylene.

Afm^hhtmalk M^r, AfnyUfuistfliUAir,

Produced by the action of amylate of sodium on chloride of benxylci
It must be heed from adhering fuaol*oil by fraotionai distillation, thil
liquid not being sufficiently soluble in water to be removable by w«^iikf<

Slightly yellowish oil, lighter than water, and having an edow
somewhat like that of fusel uil. Boik, with some deeompofiitioiif U
abont 292""*

34 C ..*...
28 H .......

204
2S
32

2U

77-27
1060
12 13

100*00

Wjcke.
7C90
1037
12-73

ACETATE OF BENZTLENE.

223

^

Acetate of Benzylene-

C*»H"0*^ = C"H*tC*H'^0')'0*.

WicKE. Ann* Pharm, ]02, 360,

F<^rma&tm. By the auction of chloride of ben^ylene on acetate of
fiiHer:

0m\a^ + 2(^*^J^'}o^) ^ 2Aici + (cwo^)'}*^*-

I

^p Preparaiimi. Perfectly dry acetate of silrer (rather more than
"2 At,) is triturated with 1 At. chloride of benaylene, and tijo searcely
moii^t mixture introduced into a small flask. On tlie application of a
^nlle heat, a violent action takes place^ attended with evolution of white
fames j licnco it is boat not to use more than 10 graminDs of t!ie arlver-
saltatatimei hut oven then the product falls considerably below the
calculated quantity* The mass^ a,fter cooling, la treated with successive
portions of ether as loug as that Hquid diitsolvea any thJDf^ out of it]
the united ethereal extracts distilled in the water-bath; the residual
TcUowish oil freed from adhering aeetie acid by washing with weak soda-
Icy and then with water^ and Unally rediseolved in a small quantity of
ether; and the solution is left to evaporate. The acetate of henjjylene
then remaina in the form of a viscid oil, which deposits small made*
crystals in the course of 24 hours, and after some time soHdilles completely*

Pmpfrim, Small, perfectly white, shining crystals, very much
resembUiig the so-caUod swallow-tail crystals of gypsum and apparently
belonging to the oblique prismatic Fystom, From solution in alcohol or
ether it se|>arates hy spontaneous evaporation, a« an oil, and is likewise
pfecipitated as an nil on adding water to the alcoholic pohition. This
oil often remains liquid for a considerable time, but suddenly solidifies
on being touched with an angular body or ou agitation. — The compound
melts at l^S"* and solidifies in the crykalline form on cooling.

22 C , 132

12 H ....,..,.„ 12

8 O U

O^H^^O* ,. 20S

Wickc.

63*5 ,.. 63-6

58 61

30^7 30-3

lOe^O , lOO'Q

Decompogkions . 1. Acetate of ben xylene cannot be volatilised with-
out decomposition. When heated in a retort, it begins to boll at 190^,
the boiling point gradually rising to 240^ The distillatei which ia acid
to moist litmus paper, is a mixture of anhydrous acetic acid and bitter
Imond oil;

(c*H>o^)^}*^* - (c^H^o^no^ + €m^o\

224 ADDENDA TO THE BEXZTUCNS-SKBISS.

2. Heated with aqaeoos potash to 100^ in a sealed iqbe» it jriddi
bitter almond oil and acetate of potash:

<C*HHW>^ + 2HO => C«H«OS + 2C«HH)«.

Tha reictioQ is not exsctl; aiulogo«s to that of leelile of ethyieae fC*H>w}^

with aqxieoas potash* vhich jislds gljool or hjdnie cr cthjIOM HSI ^ ^ rfafltf
deeompositioii of aceUte of bcniy Iras woald jidd bmielir afeohol or hfdbraia of ta*

*f^ H'» ^.-a Acetate of benxjiene heated to 100'' in a aeakd taVe
with aqneons ammonia^ yields acetamide and hjdxobenaamidfl^ the foWMT
of which niaj be extxacted from the mixtnie bj adntioii in water.

*^CWCK/J^ + 8XH» « eN(B.H.C<H>0>) + C«N«H" + 12H0.

4. Healed to lOO'^ in a sealed tnbe with dilate «dplinfie and, it it eoa-
Terted into bitter almond <hI.

Cfomimaiitnu. Inaolnble in water, bat diadlTea rmj leadBj ii

Valenta of Ben^jlene.
C^ffW = C^ff(C»HW)W.

WicKX. Amm. Pkarm. 102y ^9.

Prepared like the acetate, bj the action of chloride of benijlene ti
xalerate of stlrer. Afker the action is completed, the mast is not aiU
bnt Tixld, and ether extracts from it an oil, whidb, when the iolYeit
is eranorated, remains rtscld and jellow, and cannot be indaeed It
crjstaUise.

34 C.
SO

WlAft.

.-04 -.. 69S

^7-9

24 — J5-2

7-«

64 ... 22-0

M-5

C«U-H>* .- S?2 . lOO-e 100-0

The dufereae« hec««ett the iiu!5ticAl and calcalatad raahs anaea from
prcaence of uceta of chlohik of b<aniene» vhich coald not he i

The compoand is decompoeed br distillation, apMurentlj in the MM
manner as the acetate: for the distillate treated wilb nthoMto if
soda> slowlj gire^ np ralertanic acid, while bitter afaaottd eO lemataf

behind :

BKNZOATE OF BEXZYLfiNE,

225

BeEzoate of Benzyl ene.

k

WicKE. Ann. /*/ki*T«. 102, 3*0,

When chloride of beniylene Is triturated with benawKito of silver, tlio
IT) I suture becotiics he:ite(l, ac^uircis a kneadtirhlc consist euce, and must h^
ijtiickly introduced into a fia^k pro vide J with an escape -tti ho to carry
uway the intensely tsufl'jeathig vapours f^f chhirido of beuzylcne. On
treating" the cooled mass with otliL»r, a brow a extreict is ohtaiued, v.dtich
whf^n evaporated, yields a viscid, brown, un crystal livable tua^s. Thin pro-
duct iiiixed witli alcoholic pc^ta?!* immndiately yields a solid mnx^ of
betiEoatd of potn^vh, together with bitter ahuond oil.

EBenzylciie likewise unites with bibiisio acids, furnnng compouuds
which m^y be regarded &b bcnxoUo alcohol in which the SJ At. of bnpio
hydrogen aro replaced hy tlic radical of a biba^ic acid.
} Siilj^^tts of Jlemiflme. — ^^qi j 0*f t^btaiucd by the action of cbUiride
of beujsyleno on sulphate of silver, la a red-brown, u n cry s tail i sable oiL

Succinate o/ Bentf/lcne. — ^^,jjiqjJ'0*j appears to be fovuicd by the

action of chloride of lenzylene on suoeinato of ailvor. Thr« ethereal
extract treated with dilute sodadey, yields free succinic aerd suid hi r tor
almond oih

The action of chloride of bcnzylcne on o^calato of silver t^ m violejit
that no ilefinite protluct c^u be obtained ftoui it

k

Chloride of hen xylene hoatod to 100' in a i^ealcd tube wUh i^tvti^
aqopous or al<^oholio potash (most qnickly by tiio latter) yields rMondi*

k

of potassium and bitter almond oiK

Om\W + 2K0 ^ C'*HK)«

2KCL

The statenftttti of Cnhotirs Cr» ^^) '**»t ^his compound i* not acted upon Ly potash, (4 (
Uierrfrtpe ini^rrCct.

Heated for some tbne to 100^ with acjueous or alcoholic ammonia lu,
:i sealed tube, it ytebk sal ammoniac nnd bitter almond ojK At oiJInafy ,|
temperatures no action tnkoa j^lace. Chloride of U^nKylenc may also ho
cUstilled without change in dry antn^oniacal (,^as.

Heated to lOO"* in a scaled tube with an alcoholic solution of sulpho-^
cyanide of potassium, it yields chloride of potiissium and an oil buving thai
odour of muetard-oiL With dry cyanide of potaeifium at lOO"", no docorn-
poMtion takes place. (Wiokc.) ^.

rnt. XII. tx

TOLUXirB: raoi4Ri kuclius c«h*.

T^um€ Serim,

A. PROtART SbBIBS-

Toluene or ToluoL e'H^

PAj«, 6T, 2m;

Pkli^etikr k Wai^teiu (1S3T*) Ann,

U, 81; Fharm, Cmin 1837, 551.
CoUKRBE. Ann. Chim. Pk^. M, 184] /. pr. ChmL IB^ 65.
Dktillk, y. Ann. Chhm. Fh^s, 3, 152, les; X pr. Ck^m, 25, m;

abstr. J. Fhartn. 27, 636, 640; PA^itn. e«i&-. 1842, 194,
Gl^sakb k BotJDAtrLT. X vIrh, Ciliw. PA^«, 4, 274; abstr, OMi(>t*

rend, 17, 503; alao J. pr, Ok^m, 31, 111. — .V, J. Pkarm. $, t50j

abstr. Compt. rmd. IB, 505; J, pt\ Chem. 33, 466; I*kmm* C&Ur.

1844, 155.
LTTH ^ Hofmahh: .i«i. Fkttrw^ B2f 325

losptLiTT & HoFMAim^ litn* Fianm. $4, 9; Fftarw^ Ctnir. 1845, 511.
KoAD. jlfw, PAarm, 60, 305,
E, KOPF. Cow/*/. cAw. iS49, 14».

lAmamsk. den. ^be, <^ ^« 1, 3$6| aln> .Inn. PAdfvi. 69, 47d.
^AMOVMM. OmipL rmdL 28« 3S4; bIio /, |7t-. Cktm. 47, 423 ; (Wi^

rend. 30, 319,
Wrtaow. ^ii«. Fkarm. 77. tl6; CAm. iSd<s. Q. J. 3, 154*
y^iXIKKL, Ann. Fkarm. 86, 334.
CA}n«^24KO. Anu, Fkt^wu dO, 353; 9$, S46.
RrrxHACMBf. J. pr. Ckem, 61, 74; Fk&rm. Cmir. 1854, 850c

F<rjinaf»Ofi« K By tke aetion tif potaili on b^nsjlic aIooIioL
(Cannimro):

SC^m^ ^ EO,HO = C"H*KO< + 3C»*H* > IHO*

2. By he&ting tokjlie acid wiOi exc«s of lime. (Noftd):

4

3.

By the dy distilktioB of toln balsam (Deville^ Muepmlt k Hdii>M% 1
■* ^ >f dMifon s blood (Gl^oard A BandauU^; of die resia of J'JiMii

C»H«<M « C»'H* + f COS,

melilMi (PftUetier * Waiter); ©f BarrooBe naphtha or Rangooa ter
(D« la Rue a MiHlar, Plw. J^^^y. ^oe, 8, til).— 4. In tbe prBpamlloft rf

UlumiiiiitJBg gaa fnm nsm or of rather lat oiK (Conerbe.) 5. In tW

dry dlftillation of wood (Yolckol) and of eoaL It ooemm mbttniknlty in
ooal'tar oU. (Mansfield.)

Ftyrian^tiam, 1. From Mn^/Ke aitokol, — Whea beti^lie
i« dintitlcd with four or 6r<> tiittes it^ volamo of eonctvtfmlfifl a.

Claith in an aftpamttis whtdi alloin tbo l^M Toimlih pr*idneU
ok af^n, all tha alrohol p^mem orer at ^rsU then waiter witli a
maiiiy of unalter&d Uni^o mlooh^^l, and at laei, wIi^q lie t^i^

TOLUOL.

£S7

i:

^Sfiome eelid, a mixture of toluol with benzyl lo alcolioL Tbis mixture
is distilled by itaelf; the portion which goes over at 116'^ coHected
apart and shaken up with oil of vitTiol, wbereby the ben gy lie alcohol is
resinized and dissolved j and the decanted liquid h waelied with carbo-
nate of potash and twice reetified ov'er anhydrous phoaphoric acid.
(CannrzKaro*)

2. Fjom Toht balsam. — The baleaxn freed by distillatifm with water
from toleue, einnameia and a portion of tbe benzoic ncid, u heatetl in a
copper boiler to remove the water, till it no longer froths up, and then
subjected to dry digullation in a retort filled only to one^fourth* At
first it boils fjiiietly and gives off nearly pure benzoic acid (b^naoic add
with a Utde cmnamio acidi which solidilj tn the rtceiver ia the crystalline form, atid
yield n considerable quantity of lyluol ivhen distilled with water x Muapmtt &
Hofmanii}. Tlio heut tnu&t then be increased to maintain the ebiillition,
which becomes irregular, the iMasa frothing op strongly and therefore
rec) airing frequent agitation; at a later stiige of the procesSj howeverj it
again boib (|uietlj. The product of the diijtillation ia — ^ besides carbon lo
acid, carbonio oxide and a little water — a heavy oil, which is a mixture
of beazoate of ethyl (more prohnbly ben ^o ate of methyl according to Maspratt &
Hofmann, abo according to Seharling, Ami, P/iarm. 97, 83), and toluol. This
mixture is distilled by itself, and the portion which goes over between
130*^ and HO" is rectiiied over stronoj potaeh-loy and dried over chloride
of calcium; the product ia very smalL (Deville, Mu^pniit it Hoftnanii.)
— E. Kopp purifies toln-balaara a« completely as poiisible from ciunamie
acid by repeated bo ill ug with carbonate of soda, boils the residue with
strong soda-ley, and distila the brown solution (which solidifies in a
brown mass on cooling) at a gradually increaaitig heat. The oil wMch
pa&ses over with the water increast'S in quantity till it aniounta to a
tenth part of the distillate after decantation; it is reetiftedj dehydrated
over chloride of calcium^ and agaiti ret^tified,

3. Ft^om Dmgon*& blood. — WJiea the blauk- red oil obtained hy tho
dry distillation of dragon's blood is rectified, a njixture passes over cou-
aiatiDg of toluol and sty rol (dracouyl: Glen^rd db /ioK^au^/) which bo-
domes colourless after being twice diatiJled with water; and when thi^
mixture is repeatedly distilled at ihe lowest possible temperature,
and without ebullition, in order to convert tho styrol into nietastyrol
(or* to retdin the tlracoayl, according to Glcnard & BoodauU), the toluol
dtstils over. According to Gl^nard k^ Boudault, the toluol should ulti-
mately he boiled several times with solid hydrate of potash to retain
the dmconyl; aecording to Blytho & Hofniann, the styrol is merely
converted by the heat into metaatyrol^ and coniidete separation might bo
effected by heating the mixture for an hour to SOO*^,

4. In the digtillation of remn-oii (x^ 411), toluol passes over after the
oil C'^H* {]£i, 378). {Coucrbe.) — 5, When the brown oil obtained in
the preparation of illuminating gas by the dry distillation of the resin of
Pinui marUima (hnii ^f*?.), is subjected to fractional diBiillation, there
paaees over between 130'' and 100^, a yellowi^^h red oil which has a
strong hut not unpleasant odour, reddene Jitnms^ and when rectified
leav^es a carbonaceous residue, while an amber-coloured distillate passes
over. This distillate is freed from the enipyrcuniatlc acid by agitation
with tolerably strong potash-ley, anil distilled in the oil-bath; the portion
which distils over at 160^' is shaken up with oil of vitriol; and the deonnted
oilifi washed with potash- ley and rectiiied. This treatment with oil o*"
TilTiol an<l potash-Icy is re|>eated 15 or 20 tinier, till lU^ i'a?\(lu'aX iJ

z:^> TOCxxsi: rwauMi xtcleds c?v.

3 r Lo^&n^ SIT talnQx s» ske «Q •£

h p«dmrr '2r:£«L. ^WMkr A Water.)
*> Witt •

v^ick iww #««r WcvtcB IviT aL»l 150*, h tmUsl wilk «a«l
aai dke «»&»9^r««i wraM » sbwctcil to frirriiil dktiDMm. Ihi
pcrawwkxk &Qk Wcvvcn U9r wd IW* ii tohol. (VWU)
— SL TW jqgMtt < (xL 135) rf Ae Ighl fhthi nWiiiBa tw gcJlB',
vUA«&cu»«T«rWc««nlW'»iilS«%cnHMte«ltolMl. (MaiiiJi,
Ri»ki82SCTL> — TW ^^::at vksk c«ce oTcr between IIW ftwl IM^ il
tz«i^e\i viik hail :» wix^ ef cci ef Txtiiel. vkenftj i
f^CDfvs aw reH»»T<«i aakTa ciTitiel peJact aove iWMfllj oMi
fMTi^Hi': jee sl^ KLLkeacjoi^ Joa. J^lam. 95, M; Ckem. Ok

'\

e<bN«ttI oc::sr T«rr xw^ £ke ^t&at of WaaJ, ud a

Sji. ST. 0-5?? .Pea^r 4. AVah«?V <k-S21 (CoMtM, Oiff at IS* (

0 $«4 a& :^>^ G.^fffiKra £ FoctlashV Terr vMUe; doc

--eO\ ro::^::xfr x Wa:»r: a>«a:d < BoaJaah). Boik at 108°

t!fc^ b Lr.w:cr jar^is ii i^:,? c*:. , PXIesier k Welter, DeriUe); et 16**

a^»a^r^^l* . a: vV?" »G:tf--rI & B^Niiielf, at 114= (Gcrbaidt, If. Jm.

Cli^, r'jr>\ U :o:; /. : *. riflfi. c^\ SOO: Cumixnro), at lOO'.bar.il

1>-T»>:> Ta^r:^ :!^e K>I::Tr p*.<": nsfcur rraieallT to 110-5* (NoadX ft*

9. 2.^^^ Vclak:ilije$ witWc: tieoMOpCk^uoo. It W«omw yrth^y «mhI
dkrlaL^ w:s;:ir t:icc. -i \.x< -nrcors- \:i Ae Vfr^vr sart of the Rtott VeroM« kettv ttoi tti

boiix* ikit:^. Ci^rft.^ — Varccr Je&sltr = 3-23 (Pdletier 4 Wellii)
r**jK^ GVrsanl ^ _._

U C S4 *l\.U> „ SOvi: „ . 4;-;i j; i^ • ^1-35 _ 91.55 _ M^J _91-tl
:! H S SM >:*>> Si: S-v6 „ «:8 .- 9Htt .-. f itt ^ f-??

c-H ?i i'H>w *»\;r s^-:s :,\v:« uhs-^i-^im-ss^m-h ^9H)

C-x-'pittT 14 ... .- 5*S?40
H-rw S e-W**

D::*^iiyysUwHK I. Vap--r.r of tolsol m not altered hf P***>4
thrv'u^li ;i rvJh'U t^l^ filled with iw>:d.-b-lime. (DeTille,^ — 3. T«la3
nv}i.rn< ur).ihemi wlxa left in contact with pola«h in raneb

HVDJUTE UF CRESYL.

229

*

I

air, or witli platinum-black la vesads coutairiiog oxygon t (Deville*) It
barns with a sooty flame, — 3. To!uol absorbs thhrine gas^ with ev^olution
of heat. (Gienard & Boudault.) When cMorhio gaa is pasfied iu the
dark tli rough toluol kept at a low temperature, the action cloea not
terminate La four hours. (The liqniUj after being freed from excess of
chlorine by passiDg a stream of carbonic acttl gas throogh it at n. tenjpe-
rature between 50° and 60°, contains only 13-87 per cent, of chlorine.)
After the action of the ohloriuo haa been continued for a week, the liquid
contains 14 At. C, 7H and 2 5 Ci; on distilling it, chtorotoluol, C**C1H^
l^aaaeg over first, without evolution of hydrochloric acid, hut afterwaida
that acid m given off. When chlorine i^ passed into t^iluol in broad day-
light^ as long as hydrochloric acid continues to form, bydrochlorate of
terchlorotoluol C"C1*H*,HC1 ij produced; after a etill longer passage of
the gas, liquid hi bydrochlorate of terchlorotoluol C^*CHiV2HCi isfoniied,
together with crj$talsof terh yd rochl orate of terchlorotoluol C*^C1*H*,3HCL
(DcTjlle,) — At ordinary tcmpffniturti, toluol absorbs chlorine gaa without bdng
decomposed) but whe» chlorine b passed into toluol heated to the boiling poinl, the
toluol U <:ouveited into an oil resembling chloride of benatoyl, ifihich npi etos to bu
C*^C1^H*, bnt cannot bi: eamittetely pari fie J by water from chlarmc and bydrocbloriti
add. (Pdletier at Wnlter.) ^ 4 . ' Fuming iiitiic at^k/ converts toluol at ordi-
nary temperatures into nJtrotoluol C**XH^ and at the boiling heat^ into
bin itro toluol C^*X^H^ Dilute nitric acid at Is shpwly upon it, but ulti-
mately yields the same products as the fuming acid* (Deville.) — j
Cold nitric acid docH not act scnsibty on toluol ; but on didtilUtig the litjuid, nitrous
Viponrs are given off, tOi^etUer with a large qauntity of bydrocynnic acid; and in tljo
retort there remains a warty moss Ti'hich when repeatedly boihd with akuhol, forms a
wbit« ^ronntar powder, which reddens litmnSj dissohea in fllkajis, U pre<:ipitated
thererrotn byaddSfOnd sublimes whfu heated, loaiting a carbonaceou* residne* (Pelletfcr
It Walter.) According to Glcnard & Boudault, lolnol (dracyl) fonviswitb fuming uitrio
^^d^ when it acts in small qoantity only, nitrotoluol (nitrodmcyl), but hi larger qimnLity
sud at a higher temperature, nitrodracylic acid C^^XLlK)* [?], theactioo beuig attended
witll evolution of carbonic add and red fumes, ^ — ^5, Toluol IS icarcely attacked
by boiling oil of vitriol {Pelietier & Walter); it dissolves in fuming
sulphuric acid, with rise of temperature and formation of sulphotoluic
acid and sulfitoluoh (Deri lie.) — Potassium and pota&h do not act upon
toluoK (Pelietier & Walter, Glcnard k Boudault,) Toluol digested with
eodium in a closed vessel for 1 4 days, violds two substances boiling reapec-
tirely at 97'' and 11 2 \ (Church, Fhil Mag. [4], l), 256,)

Comhinatwm. Toluol is insoluble in water, but iraimrU ita odour to
that lioujd. {DevilJo, Gienard k Boudault)

It aissolvcs io^/uif at ordinary lemporaturcs with ambor'Tcd cnloufj^
and at higher temperatures a Tnrge qunutity of 9ulphm\ which separatca |
in fern-like crystala on cooling. (Pelietier & Walter.)

It dissolves sparingly in alcohol, more readily in tthtr (Deville,
Gienard St Boudault); it is eohiblc in oih both fixtd and voluiih^ and
dissolves noost r^rjm* (Pelietier & Walter, Gl6nard & Boudault.)

Hydrate of Cresyl C^*H*o^

Williamson Sl Fatrlie. Chem, i^oe, Qiu J. 7, 232 1 Ofienu Gm.
1854, 37 G; J^ pt\ Chem. G3, 204,

Crrt^ift aft*}fi*ff*

330

imctsus

r ^mmi^j ia €Tmma^ ftnta eoal-tefg sad k obteiM

, alwipglj fe£iieliaf ti^aki, vkidi bolk o4 203^ Itt Um iir
f if I^WBgca.

UC-

nB —
to

t «

I€ „

TM7
Ml

14-a

C'^H'W _ 1«

Tke eaHi|M«Bil » ^eeanfaosd ¥f repeated dktilklioii m Ibe ordtmj
'war, a pottiaa sapearinf to be mYetud bj the oxidi^g action of &
I air into ijdfata if pbeajl; Wt io an ataui^lieie^of Lydr^eo, it m^y him
dlstUle^l aay aKmher al ttmes wkkoiti akeialiooT — Xiiric acid aX ut^J^
I aarr tempetatiovs at^dcs H with e^oiiTe TioJeiice; bat whm tmtel^
witft w^ ooakd itflm ae^ It jMds a md eolation contaiiimg Urniif^
MfttyiU mid D'X^HW {s\ *t8> Dilitte mtric aeid forms only a brtWl
lafiy tsas^ — With oil p^ »ift^ ii beeotnee rose-coloured, and hsim
l^pkocrm^tic 0eid 0*^BW,2SO*. Thm batyta-eali ol this acid jMM
Ij aihdjtii M'47 p. cl baiTta, wbile th« IbfiBnla C^^H^BaO^,2SCK t«<iiiii
t ft* W p* c — Wilt |MiiAieiliir»dle ^ pitmkonu h jtelde cklortde of cf
I (irldeb boHed al 197*} and |ilio£ptiate fu ercayl, whieli latter b ooare
I hf doable Ueconipoeitioa vitb ncetate of potash Into acetate of ccwrl^

[COBififtrc tiie tteii« «l rc^ «o Jijilratt ef piicarl (ni, U9, 1 TS.)] Mlaed with ia
' e(|anl balk of stroe^ potnab-lejr. It ^Nnns m the conree of 14 b#ifi^
I a few email czTStale, apparentlj conekllirg of crmrlate of twtaaitM

Salpliotdnlc Add.

Pefille. (1S4L) 3". Jiia, CTiJu. Fky*. 3, IT2.

Atidt mttfuioht^ifme, AeiiU t«#Mieee4*Jfar.

F&rmaiion, From toluol and fntnloi^ otl of vitriol {f^ StS),

I Fnpamii&n, doming oil of ritriol ia eatnrattd with tolnol; tie
vsaM whleh ^lidtfies rm cooHog h treated ^ith water; the eolation iltifi4
frcim the Mil^toltinl, h neutraJised with carb<m:iti3 of lend; Ibe UlefiJ
Hqiiifl defonijj^srd l»y hy^lrosalphuric acid; utnl the 61lrat« «»
jimt over the WAter ba I h /after w aids in vacuo. (UevilK)

Fnopertki. Small white cryaUUitie laminso. (DoTiUc.)

14 C ,

SALIRETIN.

,. B4 .„. 44*22 ....

.... 44*35

10 H ,.«...*.,*
2 S _......

8 0

.,.««...-.. 10 »t.* 5-27 .H>

32 *... 1682

64 .... 33*G9

„.. 5 85

SSI

CHIPS^s + 2A^.... 190

100*00

I

Dtc^mnmUimi^. Blackens quickly when dried over oil of vitriol ia
vacuo. When heated, it yields sulphurous aoldj empjreumatio produota
and charcoal.

Comlnnaimiu. The acid quickly absorbs moisture from the air.

The mlphotolnfiUA do not euffer much alteration by exposure to the
air Their solution does not precipitate nitrate of copper or nitrate of
sil?er.

BtdphoioiucUe of Ammonia crystaUises pretty readily in stellate
needles. (Oeville.)

Sulpk^^ohmif of Potaih. — Indistinctly crystalline lam in® contain-
ing 15*3 p. c. potash and no water. [The formula C"H'K,2S<>' requires ^2*55
per ctnu of potash; the formula CiHi?K,2SO^ requirea 15 72 p. c. potash. L,]
Very soluble. (Deville.)

^ui^hototuaU of Baryta. — Obtained by saturating the solution of
toluol in fumiug sulpbunc acid with carbonate of baryta; the solution
yields anhydrous crystalliuo scales « (Deyille.)

B Does not deliquesce on exposure to the air, Dissolres very eaaily in
" water. {Deville.)

The lead-mit ia rery soluble in water.

Stcondm*^ Nticki if Toluene.

SaUretin. C^*H^O^

Bracoknot. (183L) /. Chim. mM. 7, 17, Pogg. 20, 021.

PiRiA. Ann. Pharm, 2% 300; Compt, rend. 7, 935; J. pr. Chmti,

U, U2,^Ann, Pfmmu 30, 178 and 189; Ann. Ckim. Phys.

m, 281; J. p}\ Chem. 17, 241* — Ann. Phai^. 56, 45; ^. Ann.

Chim. Phijs. 14 J 268 J P/wim. Centr. 1839, 370; 1845, 75 S,
LiEBfQ. Ann. Pharm. SO, 186; Pharm. €mtt\ 1830, 463,
Geruardt. N. Ann. Chim. Phjs. 7, 215; Mev. sdent 10, 216; Phurm,

Cmtr. 1843, 160.
KosER. Ann* Pharnu 74^ 184,

^ UC

m 7 H

,.. 68-6 .
.. 840 .
... 7-0 .
... 320 .
... 48-0 .

... 28-68 .„

.. 8506 ...
... 202 ,..
.,. 1336 ...
... 2003 ...

.,... 28^40

34*48

816

■ 3S

lS-80

m oo _.

..,* 20*21

K ■■

C"H^Ba,2S08 .

... 239*6 .,

.. 100-00 ...

.... lOO'OO

333

TOLUENE! OX\GEK-KUCr,EUS i:mm\

FijrmaikiH. By tixe actlou of moist a€uh, even iu tlie very tl)lut«1
Huti?, on saligmiiii or saliciu. {Piriii, Bmcomiot.) Dy tieatipg a» ^ica>
Uolic ^solution of ^tilicin witb chlorine gas. (Roter.)

PvfpaviUiim. Sdiciu or sdigcnhi is troateJ for same timo wit1
tlilute giilplindc or liydrocbloi'ic aciil. — Tho mliretin collects on ibo
Kud'att} of tl]o li^jiiiil. TlifT more dilute the ficitK llic ptin^r and whiter is
flie prod net; wlieii galicin i^^ ui?odj ^flucuse reniulod in tsolulioii. (Firisi.)
Consent rated ^ulpliuric nr Lytlrocliloiic acid coaTcrts silieiii into a re^iof
wIjIci^ ou aJdilinn of ^vatr-r, is tlcposiied h\ lIjo form of a white powder^
(Bracoonot.) The dccfjmiJo.sUion of ealiein Uy dihite aclda takes a very
long time and ia not itimXy completod, m iWt the quantity af Bugar
obtniucd is very variable, (Ruaer,) — Gerhard t dissolves the pFecipitated
Baliretitt in alcohol aud precipitates it with water.

I

PmpfHm. HesinotiSt white, often somewhat yellowish, Fn^tbkJ
It enn only he dehydrated hy hin^' con tinned heating in a current of dryj
air. und it i« only when it has become perfectly trans|Mirent that ib

^v eight reiiiMina constant*

b.

GcrUartlU

20 10 ...

1511 ...

... &Sl ...
25 J 1 ...

21*20

.... e^
.... n-2

C^'U^O*.. 105 ..«

100-00 ...

. ... lOO'OO ..

100*00

... 1000

Tli& ftmmila C'*H*^0-j wlikh ivprf«-*nls Falirctm as i»oincrie with bUtcr i
iiiit U'lixt in, \^ iidaptrd by Piri?!^ bfcmi^f, in the sclion of <IUutG ndJ* upoa ullgtaEn^
the u«!y protluct oblajncd b«dile« ^alirttiQ, U a ^ cry small cjuaritity «f a bitttr lieli^
i|ueicrnt ?itb«UnQe; itid tlie dilTereiu-e of I5'1^9 p. c. betii^eeti tbe tsligmiii u^d i iid ibi
*iitirrJj« o1it»«iritJ moy be accounted for by the addition of 2 At. wuUt (Calc. 14'5'ii f.t^.J
TiiC iwj iiui^dt's a aiid A formerly ei 110 in c J were pmbably iiot mrfiydroiw {A^n. Ph^r
h\u -i*')' r^ b^ uiiuh'ics liowc%f I' enbibit, ft lied coiitpaicd Willi llic c^iLcuLitpd compo
li(i*i, un r.\ct.*« t>f Indtitgcn nrj-J osygen in the ratm, not of 1*8 but of 1'12 {L.)J
G^hjirdt %M^^i*i^t^^ tbeil die s.iiireMti whit:h be biuaacirnTinlyscd wni ai«o Hot ijnile ) nil
[lh(j t^cfis ol levdrogrri ftud ojiygrn wUicb be fuund b tn the rtstio of 1 : ^'fi (Li)]j
Itfi Twoft rceiMiUy doubled the fonimh t-f sdUreim, mfikiiig it L'^H^-O* (7V<ii7#, 3, SIO)<

ikcomimMiom. 1. By dry distilktlon, it yields carbolic acid,
and a rcfeidtic rich ia cbareoal, (Gerhardt.) — 2, Ikiled witli Moratf
poffTAh ttnd hiiJrocfdmiG art J, it d^^e*? not yield ehloranil, hut a y«lloi
untorphoui mass, insoluble iu water aud alcohol (Hofniauni J tin
rimvnu 52, 64.) — 3. Boiled with strong nitric mid, it first yields
yellow reitin and red vnjiourif and ultimately forms a solution irhle
ap|ic:ir^ to contain picric acid, (Piria, Gerhardt.) — 4. OU tif tittiot^
colours it blond-rcd, — 5* It dooa not yichl Fal icy Ions skcid when
lioiled with cbroniatc of potaili and sulphurio acid. (Piria.)^6. It m
lusoinblc in ammonin, but di^^olvcs in aqueous Hjccd alkalis, whence it u
I^rccipii'itcd a^ a wliite Jelly by aclib, even by carbonie acid. (Ptria.)

Sail ret in i» injgoluldo itt vvatcr^ but di-i^^oU'es in strung uerik <fc*</, ta
alcoltol and in clfttrt and Iei t'l^ctpi^^^^^^ ^■''^^u ^^ eohttton hy

mm.)

ns

Saligenm*

PmiA. (1S45.) .V. Atm. ChwK P%^» 14,251; Amt. Ph^fmu 5Q, 5^;
J, pi\ Ohtm, 36, 321 J abslr. ConqH. rend, 17, 186; Pharm. Cniir.
1845, mi^.—Ann. Fhttrm. 81, 245; Phmm. (kntr. 1852, 151.

Pormntlon^ By the action of dilute acids or eiuiilsin on flalicm :

C3aU3S02» + 4 HO = 2C»H''0^ + C^'H^iCF*.

Let^ordbjg to Pirb, it h contained in po|julin in conjunction \^itl» Leuxolc
cid and glncosCj but cannot be sepamted tbcrefrom hy diluto ac-id& or by
"iiikin.

Preparai'an. An aqueous solution of salicin acidulated vvitli sttl-
^Buric or hydrochloric acid i.<? heated till it juist boils up, the liiiuid then
saturated with chalk, and the filtrate shaken with ether ^vhich taket* up
the E^ali^eain* a HQHiS^ldeiabU^ quinUity of fi&lirctin is iilway» fi>rmccl at tbe same time
— 2. When oQ pie. of finely pulvcrie>*id t^alicin euspendcd in 500 pts. of
water aro shaken up i^ith 3 pts. of Robifjuct's emubin, ami heated in
lukewarai vvuter to a temperature not exceeding 40^ the salioin dissolves,
being decomposed in the course of 24 hours into glucose and ealigeuin,
AVben no more than the prescribed ipiantity of water is employed, part
©f the paligenin crystallises out; and if the J [quid he then twioe shaken
up with an eqnal bulk of ether, and the ethereal liquid evaporated over
the water-hath| the residue soHtlifies in a white masa composed of pearly
lfiraina% which mny be prest^ed between paper and repeatedly crystal lit*eil

from boiling water: H almond- milk is used iiiatead of emalsin, ihe i-ther Ijke^
wijse extracta nii mif and tite f^rodact obtamed by evaporation u Impure and more or
ltE& coloured. The emubin U likewise coagulated bj the ctber<

^H Ft'^erti^^. White rhombic tables having a pearly lustre, or small
^■^lourless rhombobedrons. By spontaneous evaporation of the aqueous
r solution, there is forujcd a white opaque mass composed of microscopic,
r shining, iridoecent lamina\ Saligenin is unctuous to the touch. In
Tacao over oil of vitriol^ it docs not ^'ive off water, but partly volatiliaes,
I in conseqnencc of wliich the oil of vitriol becomes covered with a crimson
j emst, — Molts when heatedj forming a colourless, transparent liquid,
which sol id i lies in a crystalline crust at 82^ When heated for some
litiie to 100^ it yieldii a iublimate of delicate, white, shining, iridescent
Iftmioa). — Tho aqucoua solution imparts a brif(ht indigo colour to ferrlo

► 14 C

I 8H

, 6i .

8 ,

» 67^74 ...
., G45 ..

.. 25 til ..

Pirk,
, 67-47

.... e-oj

4 0 , .....

... 32 ,

... 25^01

C"IFD*,.....

.... 121 .

.. 100-00 .,,

.., loo-oo

Tb<? nlcohul of tbt sukne'Sen^^^

SS4

TOLUENE: OXYGEN-NUCLEUS C"H<CP,

DgcoMpmtim^. 1. Saligc^nio iieated above 100\ giv«a off tqieoot^
vapour and ealicyloaa acid, Betweea 140* and 150% it becomes fwy
vismdj uDd solidifies on coolbg, in a mom which is lees crjet&lUno
the nioro atroDgly it has been h^ted, and at length tlieT6 is forraed sn
am her-co loured, traoslncent reein baving the properties of saliretin. —
2, Exposed to tho air in cODtaet witb platinum blacky it m quickly coo-
verted mto salicylous acid; at higher tempera turee, the same conrenioa
is produced by mere contact with the air^ or by chromic aeid, oxtde cif
silver^ &0.1 without the formation of any other organic sulietaaos Of of
carboDic acid^

C"H«0^ + 20 = C'^H<0* + 2H0p

Mercuric oxide does not act upon aaligenm, — When salig^nin is bsat«d
With sulphuric acul and peroxide of manganese, carbonic acid as!
formic acid are produced, wilhont a trace of salicyJous acid* — 3. CW^
rhu gai acts violently on dry Ballgenm, giving ofl hydrochloriis acid aad
forming a yellow reginj which gradually turns red, and uUimaiel/
solid) tiee in a ma^ composed of email crystals, which melt and tarn
red when exposed to the further action of chlorine^ Bmmine aeta in i
iimilar manner, — The chief product formed by the action of chlorine
gaa on a concentrated aqtieoua golution of salt^nin, is lereUlorocarbalie
acid (xi, 182)* — 4, With iodine and pho^phmtti^ saligenin fofiof t
brown liquid which appears to contain C^*H^G*JH, bnt is very unstable
(Limpricht, private communicadon) » — 5. Saligenin heated with dUute adds,
J9 resolved into aaliretin and water : C"H*0* == C*^11*0^ + 2HO, —
decompottitioa hj b^drochloric acid, the liquid filtered from the ffsljretla
er^poration onlf 06 per cent* of 11 hard, very bitter, deliquesoemt ert^act^
restiltinj^ from the action of the hydrochloric acid on the saliretin prrriausl; fci
6. Hot concentrated nUrk add decomposes ealigenin, giving off niJ
vapours and carbonic acid and forming picric acid* Dilute nilHo
at ordinary temperatures coloura f^aligenin dark red, and at the
time, em ail reainous drops rise to the gurface of the liquid^ and ifs
increased by mixing it with water^ the odour of sal icy loos acid aba
becoming perccptibTe, The lic|aid tientralified with carbonato of H»t
imparts a violet colour to ferric salts, and yields by di§ti)laiioii a milkv
water, which smcUs of Balicyloua acid, nut likewise depoflile mmk
yellow needles. — 7. Oil of vitriol dissolves saligenin wiUi ^Mp itl
colour. — 8, Sal i gen in is not decomposed by poimJt^le^^ Vih^m
with hydrate of potash, it gives off hydrogen, and the rosidaa
salicylate of potajs^h, — 9* The solution in aqueous amnwnm mm
the course of a few honrsj a green colour which is changed lo
by acids, and restored by alkalis; it disappears on boiling, and
aa tbe solution cools.

0. Saligenin is attacked by ckhride 0/ hemoyU wilfc
hydrochloric aci<l vapours, a compound C"irO*,C**H*0\
tho compound ethers, appearing to form (Limpricht, pHvsiv <

Saligcnin dj^solves in 15 pti* of water at 22^ and in nearly all
portions of boiling water*

It disaolvos in ammonia. It appears to combine witH
Inasnmeh a» no more faligenin can be extracted from the aqueous
tlon, arier tltt^ addition of a drop of |K»tash'ley. Aqueous saligesia iim
not preoipitute the solutions of bary tarsal ts, Hme-salts, neutrml ao^talirf
leaii, copper-salts^ corrosive sublimate, nitrate of silver or tartar-vmitiej
iu b^ic acetate of lead^ it tonaa ^ ^isai^iy ^r^i^iiate of variabia

I

SALICYLOUS ACID.

235

~€iiioti. Ferric ealta imjmrt to Uie aqueous solution of saHgenin a Wight
iodigo-colour, wbicli Ib mpidly destroyed by beatiug or by tbe action of
chlorine or of acids, TJio ulcoholic and ethereal golutioJiB do not exhibit
this colouring.

—

Salicylous Acid.

pAGENfiiEcaEH, (1S34,) Mepert. 49, 337> 51, 364; Ann. Chinu Phi/s.

09, 331; Fkarm, CenU\ 1835, 137.
L^WIG. Pof^g. 36, 383; Fharm. CenU\ 1836, 58.
FlRlA. Cmipt. tend. 6, 620; 7, 935; Ann. Fharm. 20, 300; J. pr. Chem.

14,285; 16, 412.-— Further : Amt. Fliarm, 30/153; Ann. Chim,

Phy^. 69, 281; J.pr. Ohm. 17, 241; FhMn. Centr, 18-30, 370.
DtTMAS. Crmpt. ixnd. 7, 940; Amu Chim, Fh^&, 60, 326; Ann. Fha^^^

29, 306; J, pr, Chmn. 16, 418; Phirm, €enti\ 1839, 375,
LowiG & WbidmaNx'^, Fofjf/, 46, 57; Fhat-m. Centr. 1830, 120.
ExTLiNG. Ann, Fhami. 29, 309; 35, 241; 53, 77; F/un-m. Ctntr.

1839, 376; 1840, 837; 1845, 324,
WoOLEB. Ann, Fharm, 39, 121.

MjiRcnAK0. /. pr, Chmi. 26, 394; Pharm. Cmlr. 1842, 885.
Bbrtagnini. Ann. Fhann, 85, 193.
PiKiA, Ann. Fkarm. 81, 245; Fkarm. CefUr. 1852, lat.

Salic^tiffe Suure, Utmaraiiuref SpiraaOh Spiraa-iaurft Spiff^^Hfft S^r^t
^JSatwyiii^omerAtqff', Aiidutn apirQsujrti llyilntre de Salicylt,

^^L^ £bnrcfi. In the flowers of Sj^irma nlmana {Pagenstecher); —
^^■Hpditig ta Paget! stechcr, howevc^r, it cannot be extracted by alcohol
^B^M Rppearg to bo formed by tho action of water (Dumas; compare also
Bucbtier, A\ RtperL 2, 1); — also m the hautm, especially of the double
varietyi and the rootstock of Spir(^a uhianfj; in tho haulm of Spitwa
di^iiuta, lohata and Jiltpendula; but not iu the shrubby spirasas ( Wick©i
Ann, Fkarm. 91, 374); in the warty secretion of the larvaB of Ohrysomela
popuU (Liebig, Schweiaer, #. BtapeH. 2, 1; 3, 212),

Formation, 1, By the dr^ distillation of kinic acid. (Wnhler.) —
2. B^ tho oxidatiou of saligenin, either in the free state, or as contained in
ialicin or populin; therefore by the action of chroinate of potash and
anlphuric acid (Piria), or of aijueous oamic acid (Buttlerow, */. p^\ Chem,
56, 278), on fialigenin. salicin or populiu, or by the action of bromine or
iodine on salicin in water containing potash, (Lefert.) — ^3, By tho fer-
mentation of salicin* {Ranke, J. pj\ Vhan, 56, L) — 4. In the decompo-
«itioQ of helicin by fermentation, by scids^ or by hca,ting with alkalies,

Pr^aration. a. From the foi(}er8 ofSpirw^ idniaria. — 1. The dry
flowers are distilled wilb a sy&cient tjuantity of water, till a quantity
of liquid has passed over equal to the weight of the flowerst, and
the transpareut, colourlo^, ^trong-fimellinc^ distillate is redistilled till ±
has passed over. Tho second yellow i,^h distillate, at the bottom of w
are numerous oil^drops, h neutralised with lim^^w^lc^T u^^ \M^'i

k

336

TOLUENli; 0XYGEH-NUC1.EUS C»H«0=.

distlUcU oir, and tUe residue te mixed with sulphuric ncid and distiUeMlfl
liquid wliich then passes ovcr^ exliibita ttie Ei^me cljamcters ns the I^^H
clistillaty, excepting that its odour is purer and milder. (Paj^eitstecftctB
The oil obhiiiietl by Pageustecher is a mixture of two or three UidiaJ
wliicli solidifies completely at — 22^ or — 23\ Between ^18° and<|^^|
it deposits, after some weeks^ large transparent crystals of sal icy leolBIH
wliicb melt at ordinary tempura tares; it like vise cont'^ma a caia^lifl
wbieli crystallises in pearly scales and remains solid at ordinary tanifieeiM
tures, and au indifferent uil wbicb passes over wbeu the tnixtim^ U
distilled wjtU potaali-lcy of sp, gr. 1*23. (EttliJig ) — 2, Tiie w^U
diMt tiled off, with cohobiition, from the flowers of ^jut/ccn uimm-iiM
repeatedly shaken up with ether; the decrvuted ether agitated wid
]»ota6h; and the potash-solution supersaturated with phoBpliork ft^id ;
distilled* At first salicylons acid passes over, and afterwards salicjll
acid subUiiies in long needles. (Lowig' & Weidmann.) — 3. The dr
flowers are di^itilled with water till the distillate is no louger cmJoup
yellow by potash ; the distilled liquid i.i then neutralised with potj
(or with carbonate of potiishj as directed by Bernelius in his Lehrhudit)*
nnd cvai>orated nearly to dryness in a distillatxsry appaiatns, to keen onl
the air. The residue is slightly supersatnrated with i>hi>sphoric add 19^
distilled, and tbe salicylous acid which passes over, partly ws a<{aeo«i
solution, partly in aiUdropSj is purified as in the second iiiethod, driii^
over chloride of calcium, and distilled* (Lowig, Lthrh. 2, 7-l7j-
b. From Saltdn, — 1. Salicln is dissolved in G pts. of liat water
tained in a tubulated relortj and an aqueons solution of 4 pts. of chron
of potash mixed with 3 pts. of oil of vilriol, is added in small portioi
through the tubal u re. At each addition, a bri^k action take^ place, T
mixture becomes green, and water passes over containing $u^»(^titl
globules of salicylous acid, (Piria,) An intimate mixture of 2
aalicin and 2 pts. chromato of potash, Is shaken up in a retort wttL
76 pts. of water, and a mixture of 3 pts. of oil of vitriol and 8 pt^,
then added. A slight evolution of gas takes place, lasliiig for \Mi
three quarters of an hour, the liqnid at the same time becr^miug be
to between CO^ and 70% and assuming an emerald-green colour; ii i
then bo gently heated, as long as drops of oil pass over. — 250 gnaaj
salfctQ yield about 60 grnis, of lalicylous acid- Towards the
of tbe distillation, there is formed a brownish resin which floats oo
water and amounts to abont a fourth part of the Baticin* With the ^
portions of material recommended by Piria, this resin is not produced;'
on the other hand; the quantity of salicylous acid obtained is much I
if sulphuric acid is nddcd to Piria'^ mixture after the distinatioPpan td
tional quantity of salioylons acid is obtainedj amounting to not quM i
the largest product. — The formation of the rosin appears to be <3cir^"
wiKi a decomposition of the salicylons acid; if this acid be boil
a mixture of sulphuric acid and chromato of potash in an ap
which allows the condensed vapours to flow bacK again, a similar i
may be extracted from it by ether. (Ettling.) Mart^hund takes S pls>^
Kilicin, U pts. of chromate of potash, 36 pts. of ^vatcr and 4| pu,
of vitriol, and after 20 pts. of liquid have passed over, adoj S
iimre of water, — 2, A decoetinn concentrated as mucli ws
willow^hark rich in salicin, is strained through linen and cv»fH>rali
thin extract, which is then mixed with an adeqnato quantity off'
of /K)tasli and sulphuric acid (2 pts, chromate of potmh to 3 p
riirhl) and distilled »« long a^ awy i)\\ ^ast©* *i\^x with the watrr/

SALICIXOUS ACID-

257

EilicyloDs aci J thus obtalnpd is purified l>y conibmiiig it witli an alkalij
eyijccntratiu^ tlie gijlution by evaporation j and distilling wjtli tiilute
flulpliuric acid, (Wohler.)

P roper im. Colourless oil, ivlildi eoHdifies at — 20*, fornitng litrge
tmosparent crystals. (Ettlbg.) Boils between 100^ find ITO'' ^LowIg
& WeidmannJ, from ISS"* to 185^ (Ettling), at 196^5, with tho haroiuoter
ftt 070 Tii0t. (PIrbO Sp. gr. 1-173 at 13"5^ Vapour— density =
4'27* ( Piria.) — Has a pleasant aromatic nJour somewhat like tliat of
bitter idmonrls (Piria); posse^^^es iu the highest degree the odttur of tho
flowers qI Splrma ulmaria. (Ltiwig.) Its taste iaburDin|f and aromatic.
— The aqueous fiol lit ion first reddciia litmua-paper and tben decolorlsea
It completely; litmus-paper is bleached by the vapour* (Lowig.) It
doee uot redden litmus. (Pager* steelier, Ettling, Piria-) — The ar^ueous
eolntion colours ferric salts violet.

lie.... 81

C U .. 6

4 O ,. 32

f

4-92

2G-23

"100 00

L6 w ig. Pit i a , Luwif & Weid man , E t tliu gf . Marchand*

0G'17 .. G8*37 .... G13'2fl C8*f;y (^8 65

5-55 ..» 4-»4 ... 4-87 ........ 501 .... 5'20

2S 26 ... 26*69 . ., 25-83 ...... 20-10 „., 26^5

300-00 100-()0

100-00 ....... ioa-00

100*00

The acid aMitle of tKe sal ene- series. It li rpfardcd by Gerhardt fts the liydride of
ttlirjl, C^*H*0*,H, llie esteraal atom of hjdr^^cn Mn^ repluceable by metalt^

Becovipofilioni. 1, The acid turns red when exposed to the ftii% but

does not undergo any fartber change. (Piria.) It may be rendered

CMilourle^s again by one distillation. (Gerbardt, Tvaiti 3, 204.) It doea

not alter in oxygen-gas either moist or dry. (LowigO — 2. When

Tap© II r of Bal icy Ions acid is passed through a- red-hot tabo filled with

platinum black, a dark viscid mass passes over, the greater part of which

dieaolves in potash, leaving a solid Mihstance, which volatilises with tho

iratcry vapur?, in the form of an oil which solidifies in needles, and has

Wk peculiar agreeable odour like tbat of bonzoL The tame body is

c»btained in smaller quantity, when salicylous acid is dislillod in the oil-

bath with an equal weight of lime or baryta. (Anderson, N .Ed, I*hii, J,

\ 41, 2fla) — 3. The acid bums with a bright eooty flame* (Lowig.) —

4* With dry vhhrmtf it becomes bifated and gives off eidoroBaliejIons and

I hydrochloric acids* (Lowi^j Piria, Ettling.) Chlorine gas passed info

I the second distillate obtained from the flowers of Spirwa vlmutia (p. 235),

I fif^t renders it turbid, and afterwards causes it to deposit delicate whit©

I lamimc, which are coloured yellow by a greater quantity of chlorine.

^^^n decanting the reddish water from the precipitate, the latter is ieen

^^^ consist of a red, viscid, strong -smelling substance and white crystals.

^(Pageustecber, Lowig ut Weidmanu, Ettling; vid^ thhrmaliciffaut atid,) —

I Chlorine-gas passed through oil of spirioa, colours it violet at first; but

the colour soon disappears and crystals of chlorosalicylous acid are

formed, (Dumas*) — When chlorine gas is passed through salicyloa??

neid shaken up with warm water, the acid first becomes solid, tben liquid

n^rain and yellowish red; when set aside overnight, it solidifies into a

light scarlet, crystallo-granular mass, which when pressed with paper,

^^cives up to the pitper a scarlet oil, while a crystalline mass of lighter

|K[>Iot]r remains beliind (v. chhiGMtitfeyhus add). The water fr->iu which tbe

PKrrfitals have been deposited contains a large quantity of hydrocLloric

acid, and after a while deposits yelbwish crystalline "laminae [nf $

mil Ul (Ettliug*)

^*;iQi]

TOLCXyiS

of S^mmm

\^1 Tfke ifirtabte bom the
whtu noxai w^ hnmtoe^ loss aearij^ ill its odoiir, and

wyeli ^mdwmwtm&fmwhoAal m^mh&p, nd erjatellm theniiM
llimrit tmb&m hmnmg a latter simmg odMf of braniiiiL /tP^oif
[y ■(fully «oJo«fi H yd]ovi& ted md dMmti a niddisii «3 wiih«al
I ritcprfinii of the gd<wr, ^fmto^er.) SuK^jiofv aeid dlsnlrei mmGm

S. SalicjMi acid aodezatelj haaled iriih ailr*0 ^omI of ordiaii^
latRSigilt aiM n<»i m exoeat, fbcisf aitroepbiiTloas aetd. (Pa^^eiuteto;
jifdwia^ & Wetdiaaaii,) — Wliea It is ti«aled vilk a cold mixloivif
I aittse add and oil of Titriol, a atixtsre of mvmrml olIn^-fmitMitiids h
(LtmpndiL) Faiau^g nitric acid acts v^tt -rioleattj «■
Dss mmd^ tdtrotM faaiei belaid erolY^d, a&d a Tellov viaeid mmm

[micflai

faoed, wlii^ maj i>e dktillcd and emeOs rwrj macfa like fratli balM

klactei werj bitter, and imparu a jeltow ooloor to tbe skia, oaill ttJ

[ aaKva^ wEea diitiUed witb water, it fvan oTer partly ia oolittioat F'^^X

a |»oirder. The fendae of tiia diblilbtioa yields by erm^w^m^

\ iiattifareat coloari^a pcufne of aa aeid wlireb detoamtes wbea bmloi

(Irilvig^ — Salicjtoas aeid hestei for mme tiDie with nilr»c aeid, yiclli

[piem add and carWoic acid* (Piria.) Wben it is gently lioalad will

[ vedflfntely ditute niiric acid, red fames aie giTen off and Mtkyttc aeU

ii prodoeecL (Low'tg.) — 6. Boiled witb bydrocbloric acid and *^*-^''

«f potash, it yields chloranil and carUoutc acid. (Hofntano):

om*o* + loci ^ 40 = c«cTO» + eoH + sec

Bialel^l

6. WhcQ salieylons acid h contirtiioualy boiled with biehrociale
potash^ milphoric acid, ttad w^ter^ in sncb a manner thai the «ietf
Tapoure msij be cotidenaed and flow back a^tn^ there retoahii^ aUttT tli
dlitiUation of the nnaltcrcd saticylous aeid^ a greeti resldoe^ fimn wWl
ether extracts a brown resin and salicylic acid. (EttLiiig.) — g. SiiXkf>
lous acid in contact with oU of titrioij tunis yellow and bepomes covtm
with a cnuit (EttJing); it fif^t ttirng brown and then black (Pif«-
iteoher, Lowig). When vapours of anbydrotis finlphnric actd mim pMHi
ovor diy Balicvtous aeid, a neutral insoluble body is fomod, wlrieh
eryitallisos in lar^ priamaj has tho fame composition as fialieyloas mai,
and b^ra to that acid the same relation tha^t btniicoTn boara to Ullb0
almond oIL (Piria.)

11 . ^Mien sallcylons acid Is heated with mpric oxide or witk fnivii
^icide and potash, «alycilic acid and cupmns oxide an? . -^ - *■

(Kttling.) — ^10* 0£uh of sitwr is reduced by jsalieylnys ncid [«

aeU tutmriij U] On mixing conceutmted solationa of mLiicyiite of j
and nitmto of fiilvur, a yellow prccipiiate is formed, wbtch i

nand afttrwardji black; if the aohition ia very diluie, lao pnc)|
iriDsd, but after 14 hours or immr^diatety on hentiii^, ibo sides of i
teossl boooms athered. (Eitling,X/bwtg 6: Weidnianu.) — ] t . Witli|;aMi
pr aqu^oUM ammoftia» salicylQua Wil Ivitras i^alh^dranitde, C^N'I "

SALICYLOUS ACn>#

239

It

(Ettling.) — Alaowith hydroflulpbate of ammonia. (Lanrent.) — 12. Heated
witb excess Gf hydrate ofpota^, it first turna recUbrown (rufin [»- M^iein}
he'mg perbaps fomiGd, according to Mulder), tliea becomes coloorlesi
aod gives oW a large qoantitj of hydrogen ga.s ; the mas? tbeu coDtainff "^
ealicjUte of potaaU* (Piria.) — ^13, Salicylite of potoah expoaed to the
air ia the Tooiat state, becomes covered iq a few mioutes with green
and afterwards with black specks, and gradually becomes black through- <
out; after three or four daya, it is coropbtely convertedj with absorption
of oxygen^ into acetate and melanate of potash (xL 163). (Piria*)

Combinations^ Salicylous aoid diHSolvea abtindantly in water; the t
solution has the odour and taste of the acid, and imparts a rio let-red
colonr to ferric aalts, even when very dilute*

Salicylous acid disaolvea readily in aqueous alkali 5, with riae of
temperature; iu alkaline oarbonatea, with evolution of carbonic acid; if the
solution ie strong, the salt aeparatea out.

The Salkiffitrs or S^licjflifk$ geaeriiUy contain only 1 At, of base,
tbeir forraube being C^*H*MO*. The salioylitea of the alkalis dissoWe in
water witb tolerablo facility; most of tbe others are insoluble. They are
yellow and contain M^ater of crystallisation. The solutions impart a
violet-red colonr to ferric salts. In the moist state ibey are quickly
decomposed^ emitting the odour of roses, and turning brown and nlti*
mately black.

SalieyUi^of Ammonia. — The acid in tbe free atate readily absorbs
ammoniacal gas; the resulting compound contains 8*»32 p. c. ammonia
and 91- 168 acid, nurnberi which correspond with 3 At. acid to 2 At
ammonia* (Ettling.)

a, ^onnal. — The oUy acid covered with concentrated ammonia, is
converted, with rise of temperature and conaiderablo increase of bulk.
Into a light yellow, thick, pasty mas^i, which mast bo washed with cold
alcohol The salt crystallises frcmi solution in hot alcohol, in delicate,
light yellow, transparent needles united in tuft^. It does not alter at
100% inelta like wax at 115'', and at a somewhat higher temperature,
volatJHsea without decomposition in the form of a yellow smoke. (Pagen-
fitecherj Lowig, Pirittj Ettling.)

NH' ...,„. 17

L»w%.
IS'52

86-48

C^^H^'CNH*)©* ...».., 139 . . 100*00

100*00

With aqueous potash, it emita the odour of ammonia, but only after
eome time or on the application of heat. (Pagenatecher, Lb wig, Ettling»)
rOw thii account, il U regarded by Gerhardt ( Traii/-, 3, 2t3) m SJilh jdr»mide ; neirerthe-
leM. liecordiiis to Pug^inslecher, LSwi j & Ectlmjf, acid* immediately precipitate s^UcyJoua
scid from it. aiid» occnrditjg to Luwif a»d aha Lfiwife' h WeiamAmi^ it dfcoJBpo^s with
tJie nJeUiUic Baits of tlie stronger acids into the aminoni^-satt of the slrongfr arid and a
Mlicjate of *He metallic oxide, (L.)1 — The alcohoUe aolntion e^^aporated with

Bolve Bpontaneously in fiye or ten minutes without riao of tenipeniture,
ftnd in five or ten minntea more the liquid aga\n Wcow^a \.^it\s\^ ^^^^

IW TOCXDE : OXTCEaHniCUn

I irLen expoaed to the air «ir IB
lt»mg mlic^bwi aei4. (Pint.) — 1& t&e

ryhafJBg tibe fcsetntiag ^doar •£ mI of VMca. (i
It is inoUbie in viter, «»ik{t mMUm m oU

k Acid. — Ohtauweii Ij iILsoItib^ m in
Miiejlow add; ojitailitts* tm caeXmg m
•gfcgtfgd Dccdlea. It dLkioIves in alcohol
■— 111 naltered at 100", aKlta at 115^, airi
ala k^ber tonpeimtne. (Beneiiai, L€M^A,95Q.)

StOk^lmu Acid with BimdMu ^' AmmoMa^ — hM MMawarialMi
a UMl^ute of asmoaia, of 29' & auxci mifilj m7 witk lin rf
teaipeRiarr, with an equl rdnme of Mlicjioas aeil, iMMnig a jdbv
oilf liquid which after a few hoars, solidifies in a CTjiNHfti aMK. Ihe
aoMtiea in a tmall quantity of warm water deponta^ on ~~ _
jraUowiafa needles, which, when exposed to the air for a few daji^i
mo a toogh rerj iHtter moss. (BertagninL)

Salieyliie of Pogatk. — a. Xoraud, — Potaannm dianlTes in the
aqoeoos acid, with cToIat'oa of hvdmgen. (Lowi|^) — 2. Wkok mIi*
erlons acid is mixed with potash-lej of aboat 45' Bm. the whole aoKdi*
MS in a jellow crystalline mass, which separates frmn the e»cem o(

-lej; it m»t be qaickly pressed between hibaloas papsr, aal
distolred in a small qaautity of hot absolnte aieohol, whence the «k
erjitallises on cooling. (Piria.) — 3. The acid is dissolred in three tistfi
its bulk of 50 per cent, alcohol, ao i caastic potash-sol ntion added till *J»
mass becomes e<ili<l; 1 vol. more of the same alcohol is then addedpand ibe
whole i^ently warmed till the solid mas? is dissolred. The erystals whick
separate on cooliu;^ are washed with a small qoantity of eold stnsf
alcohol, whereby they aro readcred lighter, then pressed between btbohMi
paper and immediately dried in vacuo over oil of vitriol. (EtUing.)^
Small straw-eolonred prisms. (Lowig.) Golden-Fellow, square taMi%
with a pearly lustre and unctuous to the touch. (Piria, Ettling.) ADb-
lino reaction. The salt conLiins water of crystallisation which cannot be
completely expelled. (Piria.) Assumes a dark straw .yellow eolonr it
100" and given off 10'72 p. c. water (2 At.; calc. 10-17); and no noi«
at 120\

At 100'. Sttlinf.

KO 47-2 .... 29-60 28-33

c>4rc>^ 1130 . . :o-40

C»I1*K0* .... lCO-2 ... 100-00

Decomposes quickly in the moist state, yielding melanie and aedit
acids. — When heated, it decomposes with appearance of fire, bnt with*
out separation of charcoal. (Lovrig ) — S];arincly soluble in water.

h. Acid. — The free acid is added to the solution of a in hot alcohol,
till a sample of the liquid on cooling no longer yields tables^ bat speeahr
crystals; it is then loft to cool slowly, nnd the resuUin>r orystalsar«
washed till the vollow colour disappears. — AVliite needles united ia
inft^. (FAiUng.j

SALICYLOUS ACTD.

?4l

At lOrl^

KO,, ^ 47-2

C"B*03 113-0 1

Cmm* 122-0 J

83 2;

C"iPKCH,C'*H<0* 2H2 2

100 00

n

Smnewliat less alterable tlian a m mmst air: tlcconipo^es witli waiter
into Uio Deutml ?alt which dissolvea, and frco sdicyloua acKl. (Ettling )

SaU(fl/lom ncU with BimlphiU o/PoiasIi, — 1 . Salicylou^ acul ^Imken
up witb an aqueuiis solutinij of bi^uliiliito of p^Usli of 28'' Bin. dissolves
without colour, and the eatiiratcd solution stdidifies in a few second:?,
forming a wbite inodorous crjstallhie maee, whtcli luaj bo re crystallised
from alcobob — 2, Dry sulpharoua acid gas la passed into a cold-saturated
alcoliolic solution of sal icy lite of potaf^b Gt a temperature between 40"*
and 50% till tbo yellow colour disappearn. — If tbe lifjuld be tbcn left at
restj it soon becomes filled ivltb j= lender needles arranged in spberical
groups. ^ Wbite, with a pearly InstrOj and a faint odonr of enlicyloua
acid. Dissolves abundantly in cold water, easily in warm aleoLol, less

ily la cold alcohol.

KO ....» 47^2

14 C 840

7 H 7^0

2 S 32^0

ft O , 72 0

C»HlC0*,K0,2S02 + All..,. 242-2

Bi^rtagnmL

19*47 10-62

34-71 34-76

2'8» ..»»„ a-ia

13-22 12-72

2&-71 29-80

100^00 .., 100-00

When heated, it gives off sulpbnrona and ^llcylons aeidj leavinjsr a
residue of sulpbite of potash which afterwards changes to sulphate. Jho
aqueous solution when heated ^ soon becomes turbid aad deposits sal icy lent
acid; heatod with acids, or mixed evonin the cold with alkalis or alkaline
carbonates, it turns yellow and yields a salicylito. The solaLion takes
op iodine at first without colouration; when it begins to show colour, tho
whole of the sulphurous acid is converted into sujpb uric acid, and the
cslicylous acid is mi free, With bromiuej the solution forma sulphuric
and Vromosal icy Ions acids. (Bcrtaguini.)

I

Salki^iUe of Soda, — Acid. — Prepared like the potash- gait. Crystal-

es more readily than the latter in delicate white needles permanent in

e air. ^ Gives off at 100^ only 0*CU7 per cent., at 135^ iu vacuo, 4-036

\t cent, altogctiier; and at 140% at which tetnperaturo drops of oil are

sitedi 4-35 per cent.

Atr-dtitd.

O^H*NaOSC**HW + A^ .... 275

N«0

HO «...

31 .,..
1131
122/"'-
9 ..„

Eetling.

11'27 11*55

e5'4G
3*27 4^30

100-00

245 TMTDn: irrr-i^-yTCLirs ci*h«o=.

■:5 12-05

rr:3

..*.'. -J

I: i:-rr - :: rr-r 7"t "^ i* ' - ' - : -• -" i - r^=^r t-:?3iperature, it yieldj

>- V .; .-■•■: .' f. -. — r-'H«0•-^XaO,2SOl-

X- fciLiiL* >: l: r :: ": .f_- i :-■ : 5-:»ia :f 27' Bm. dissolres a small
czLTiJTx :•: ^ rr-.-M.? l: i t li li-j-fr -::ii:::t:es a white crystalliBe
r-i.'T i? rjTZL'i'l LTi'.T L '..'.-^z L^zL'^.z. i^T £ If iL:s mass be redissolred Iw
ifti: :z :if tl :i-:r-. :-::. ■■-:i:l:::i1 rl:i'.r.j crrstals are obtained whia
LiT-- 4 ?Llr"ir*.::? lt"^ zzz-z-iz.' ZLr:-.. L^>:Wr readUr in pure water, and
Ilif-w-lftr Lss.L^f v.:l TiLTiJ^ Lr r MIT •;«:!: 0^ in boiling alcokoL (Bct-

>i -I --

5 :-/- :. — ^il' : t' : zi i^! i ^liaken np with baTyta-water
-. -:r: li!: - ^-J i '•Veiimann) ; the salt cmtal-
I;s?5 :- :•:■. r.^: :r. n ViT7-i "^iter fai-riiri wbile hot with salicylow
ac.i T.T.^^ sjlL j-TJir-t:-^ Li & vill-a- p:wJer on mixing taHcvHte of
pcti>":: :r u.tlt:..z.^ v -i * :• l>: iriiri ?-:l3i:on of chloride of barinm.
vL:"= J. r.r:i. — Yi^.v --:-£-I'f? iri::! a; 1^0' in a cnrrent of diy air,
g>e :f > > T. :. ^a::: £ A: ; «kl*, Sf7 - <^riria.)

I.:»-x\

?^ :- " . > ^4 r>i r"So ... 3304 ... 3293

Ui !^-. ^-. ' -.- . : :-. S4'? . 40-46 .... 4ais

JH ■ . - .' : : II ... 7».> .... 837 .... 3"4l

4 0 :: :i^ :?■« ■: *^ . 4?-^... 2313... SJ-w

C'U T*kO' >: . :.' .; • .A;; .. JOrG .... 100-00 .... IW-iW

A" err >: ^i.-; i-.^" r > . y . ; 1 -^ it ;. : . r .

v^.v".-; ' .' ' }[■ • • - ':..-:'. : ;- :*:a::=g ihe ni^neons aciJ viti
hr,!r.ito .f :•.:.-..:•..- : : - ; :. "; :.::.« a c. •neon tra led sulution f^
olV-.-r .1.- V f •.. .. ; ^ :.-. ^ . ■ ■ : : cvr.. : ia. ia the form of a \v^^
vol . .' w 1^. rt ^-. r . :. I ..: . v ^ ..^ . . .u " .. : : r I. ■•*■ : ■ »

.'^.;"..; .".:: • .7 •. — T: : ;* . . :.^ ;. *: 1 •;>-k;ves zinc with evoluik'B
of hy,l-.^^v:- T..^. -: ' .: ^■.^ .:. :... .: . .. j-..^!.! is shaken upwitii
oxM:^ . ;' . -...•. :i \;:; . > ... ■.. - ■ : . . I -.. ■ .y.. \s\:ki\ Lft to ovnporuie
in v:i.-.:.\ .lv*y *.:- ..•.'..: ' :. :*... >.;:. ; r:o:i»iiato is also funuftl
oM nj ■ \ i :- ;: :u\ : .; : .-- ^ ;' :.:.: %...!. ^.* . . v •. . . ;t v : anmi uuia, ( ra^en>tcchtT,
htiiini: )

'':■..' " .'■ '. — >.:.ir.i:c5 .1: :.::x:r.j il:o aqueous or alcoLoiir
»i'hi\ ^w .•:','..•■.: \[ \^ :\\ > '.::. v. !" :. .:r..'. .-...:.r.o of lea«l, with aaiiiiK-n
;''":»'■:; ;. ; • .i:":^: i V •'-■-.::: .:.i-;i::y has n>nnod; on heai-

ini: JIs • i: [•■■• : : * ; :. .* ; .:...:. '.>. .-. * :.:: '. Mpnratt\< a^'ttiii on aH^Wv:
in 1! .i\ V :.:.r.; '. - . :' .. vir.j' v. '.. w c " .:r ihe }'roci|iitate which U*rvis
in the i\'lJ :.- lI.'v\'-./.c"..i a* ;;rt*»» V'i\ ^t^Iwa'Av yiUo become* ffooMvbi*

SALICYIOUS ACID*

243

granular* (Ettliyg.) Formed on miscm^ aolufcion of neutral acetate of
leail vvitli fteid [? L.] salicylite of aiiiiuania, ai a li^lit yollovv preci-
pitute insoluble in watar. (Liiwig & Weidinaan.) After drj^iag in tlie
mr, it doea not eoEtain any water.

t

Etlling- L5#S^ •

2^0...*.... 223G ,... 664S ..„ 66B1 ... 67.69..,. GS 02 .... 655;

HC»... 84-0 .... 24-99 23 96

|#[L,„ SO .... 149 17 1

;|o 24 n .... 7*13 8-C6

C*m*0^2PbO .,. 336-6 ...- 100-00 lOO'OO

n was precipiutf d hot from basic acetate of k^d j h cold ; & FrQin tlie neutral
■ceUte by limmooTa,

When (be aajicftoiaa acid is in e^cmi, deep yellow trafitpnreiit cryttal^ form in tli«
prrdpHatc (Ettlitig,) Wbeo the aque^ius acid ia ibaken up with bjdrnted oxide of
lead, and the mixture left to stand for sotae timei imalli ligbt jrelLow^ abmlng lanunai
form in Uicm (Ltiwig).

Ferrous Saliei/lile. — Aqueotis jprotocliloride of iron forma a dark
rioht precipitate witli salicyious acid on addition of ammonia, (Pagen-
itecher, Ettling.)

F§rnc Sidi^Vdf. — Aqueoui sesqiiicliloride of iren mixed with
■a1ic3Hofi« actd acquires a tim^ dark eherry^red colour. (Pagenstoclier,
Ettling,), violet-red (Piria), witliout forming a precipitate. Tbo colour
does not alter when tlie air is excluded^ but on exposure to tbe air it
gmdnally disapiieara as tbe acid evaporates (Pagen'^tecber, EttHn^) ;
iddUioti of acids or expofjure to tbe air cbanges tbe colour to drrty
yullow. (Plria.) Water wliich contatnB only tj\ws ^^ ferrio oxide and
does not yield a perceptible blue colour witli ferrocyanide of potassium,
acquirer a di-^tmct violet colour on tbe addition of sallcylous or salrcylte
acid. (A* Doiftisfl.)

HydrOcblorate of cuproui oxide forms a light brown precipUai© with
the aqneoua aoid on addition of animonia. (X^a^enstecberj Lowlg.)

Ctipric Salic^lile, — I. Recently precipitated cnpric oxide shaken up
with an excess of l!ie aqueous acid, acquires a grass-green colour^ antl
after wuijljing witb a small quantity of alcoboJ, forms a liglit green
powder. (Pa^enstecher, Lowig, Piria.) — 2* AVben a solution of 1 vol.
salicylous acid in ^0 or 00 vol alcohol^ is mixed with an aqueous solntioa
of cupric nee tat e, tbe liquid acquires an enifirald-green colour, and forms
after a few minutes a large number of sbining crystals, wbicb increase
when tbe free acetic acid is neutralised with potash. (If tbe liquid wcra
neutraliMd witb amiDoma, tbt; sltgbtest ext^tss wotdd^ive rise to the formation of nitride
of fl»licjl and copper.) Tbe crystals are washed witb alcohol. (Ettling.). —
0. Wben a solution of cupric sulpbate is mixed with sal icy lite of ammonia^
a bulky, some what crystalline precipitate is formed, containing a small

auantity of eulphuric acid. ( Pagen^^techcr, Lowig.) ^^ — Large green
elimini

ing crystals, from 05 mm, to 1 mm. in length, and exhibiting a blue-
green colour wben dry. (Ettling.) Light green powder, having the
taate of copper, witb a scarcely perceptible aromatic charactet.

^^

2il

BUS cMiro*

La ft iff* ririo. Dumni^

Cn,
U C

5 H ,
40 .

31-3
Bt 0

320

20'Bl

3-27
20'9S

22'fl9 ._

51 J 8 ,_

311 ...,

22^20 ...

2021

3-44

21*76

21-5
54 1

3-2
21 3

LBwtf ^

WcJdmiinn*

... 21-82 ^. St-4

Ci*n*CuO^ 132-8 ..,. 100 00 .... 100-00 _* lOO'OO .... 100-0

'M

100*00

When Iieated to 125% it los^8 3 '022 per cent, t!io oJonr of tlie acM
tlio same tiino bcfjoming perceptible, Becomc^a blfickiali grcco at ii^
then dark-brown, afiil acq u ires a dark kernjes colour at 220% At I
sinic time tbat the brown colour appears, gas begins to go off, conaiAttJ
tif carbonic add and carlionir. oxidoj ami a niixttire *Hstilg over, consist-
cif falicylonsacitl, nnd benzoato of Balicylous acid, which mny he ec
hy pot^k&h. T[ie salicyloits add must be reproiluc'^d, b»«niuch as tbc tdt d&m Mt
contain ttateff the soLudon containa also another body tvhicb causes it to ■««■• i
iftlendiJ scnrfpt colour when miied writh oU of vitrinl, but e.mnnt be sc|iNrated bf ftifr
tional distillation. Thf? regiduo cootaing cuproMS aalicylata. At a ht|^li«r
temperature^ a black-brpw^u oil paaacs over, having an enipjFeuiititlc
odour. (Ettlin;^.) — Chlorine passed over the salt forms chloride of copp*r
and chlorosalicyloua acid. (Lowig.) — Wljcn the salt is heated w»ii
hydrate of potash, the whole of tbo salicjloua add Is converted ijiia,,
saliejlic acid, (Ettling,)

Insolublo in water and alcohol.

Mtt^ettric SirUef/l{(e. — The ammonia-salt fonns with a very ftronjr
solution of mercuric chloride, a bulky precipitate of & light straw-yelM
colour, (Lowig.)

I

41

Salici^lU^ of Siltf}\—Oxiiie of silver dlssolveg slightly in m
ealicylous acid; and the yellow, bitter, metallic-tasting solution yie__
©yapomtion in vacuo^ a bfown residue which detonates in the flaoitift
candle. The snmi? phenonionun i^ exhibited by the iindissolv^ pofttoo
of oxide^ wbich aUo ncquirej a black -brown ccdonr, (Pageti«|ddMf ^
Ltiwig.) — Nitntte of silver forms with acid sal icy lite of ptitnshf 1 ligll
yellow precipitate, which becomes grejsr "when pressed, and deeowpoiti
completely after a while; if the preeipitate i^ heated with wmtoft ^
decomposition tiikes place immediately and the vessel tieoome^ coTCwi
with a speculum of silver. (Lowig A: W'eidmaan.)

Salicylous acid mixes in all proportions with alcohol and tth^^

Benzoatc of Salicylous Acid.

Ettlikq* (1845.) Anth Pharm. .'53, 77.

Cauouhs. Comj,L raid. 32, 62; Jnn, Phmnn. 7B, 22S.

PaT&MdUtyti Bentonaar^ M^ie^Ufft SHMret Saik^fur^ tie £nti&i|#..

Formation, L By the dry dietillatiou of ct)pn<3 Balicjlite. — I
iht nctioQ of chloride of benzoyl on salicylous acid :

ACETATE OF SALICYLOUS ACID.

245

P

Prfpamllon, L Air-flried sal icy lite of copper is stiLjectcd to dtetil-
lattoa till the residue oxUibits a uniform kormea- brown colour, and yields
no more distillate fit the same temperature; the oily distillate, in wbich
crystals liiive already separated, is treated with potash-Iej, wbich leaFca
uixdiBSolved the crystallised bcnzoat^s of Balicjlous acid, and likewise tho
portion which was dissolved in the oil; and the compound h crystallised
from warm alcohol or ether, (Ettlingp) — *2. Salicylous acid is treated
with chloride of benzoyk (Cabours.)

Properties. Colourless four-sided i^Hsms belonging to the doubly
oblique prismatic system, and obliquely bevelled. (EitlinsTi Cahours,)
The largest crystals arc obtained from the crude distillate, When
obtained from the niothcr*Hquor, they lose their lustre, and become coated
with a white crust. (Ettling.) Mdta at 12?'', forming a pale yellow
liquid, which solidifies in a radiated mass at about Uii^* At 180', ib
eublimes in long needles, nadecomposed aud without previous obuUition.
(Ettling, Cahoursp)

28 C ,

10 H

60

16S

10
48

4-42
£1-26

^P C^K^^O* 22a .... lOO 00

^H FolyEQorlc with fa ouzo ic aabydride and oreosebne*

^^ Decom

74-12

4'52

21-36

100*00

Decompodtiom. The compound dissolves in hot stroiig nitric acid,
nitrous Tapoura being given off au'l picric acid formed. (Ettling.)—
2. It is not decomposed by boiling with poliish^ either in aqncou,^ or
alcoholic solution, or even by fusion with hydrato of potash, uader
which circum&taneei indeed it volatilises. (Ettlin^), [ ? L*] — 3* It i&
Dot altered by cold oil of vitriol, but dissolves with yellowish red colour
on the application of a gentle heat. If the liquid bii strongly beated,
it assumes a dingy red colour and givei off sulphurous neid; it may bo
tuixe<l with water without turbidity, and yields a soluble salt with
carbonate of baryta. ( Ettliug,) — 4. With chlorine or bromine in sun-
shine, it yields crystallised products. (Ettling.)

It is insoluble in waler^ but dissolves readily iu alcohol und ethtr.

IF. Acetate of Salicylous Acid,
CAnouns, Compt f-end. 44^ 1252; Ann, ritaim, 104, lOOi

^K Obtained by the action of chloride of acetyl {C*H*0*C1) on salicylout

^■ftcid. On gently healing the mixture of the two substances, an cucrgetiei
actton takes place, hydrochloric acid is evolved, and ac«?tate of salicylous
&eid is obtained in the form of a beautifully cryetalUne and perfect! j

I Eeutral body.

^m Crystallises ixDin the alcoholic solution In ^m oeedlet.

K 1 i

246

TOLUESB: OXYCBN-NUCLBUS C"H«0'.

IS c ..„ „ ,.
g H

lOO .

3 .

... 29 37

_ 65-81

.„.. 4*85

6 O .......

..... 48 .

.... 29 34

C^«HW

IGI -

.. 10000 ,.

.... lOODO

Hetimeric with benzoic acetate or Awtic bcDzoflte (p* 96).

Th<5 conipouTid is remarkably stable, scarcely oinlergoing any i
tioti wbeo distUled over anbydrous barylaat a dull red herit a
thm treated jielded after dbtilktifiu tifrOS p. c. carbon and 4*1*2 bjdrL*geii. Jf^
IS it altered by beating wi Hi solid hjdrdts af pQta«h or witb an ak
eolation of pota^Ii, — Chlorine^ bromine^ ttjid /umhtf^ nkric Uf:*^ ict
it powerfully, forming crystalliJiP products of siibstitutiotj.

Insoluble in water, also in dilute aqueous amraonia or potaslu
solves sparingly in cold^ but more abundantly in bat alcobol. ^.

Salicylic Acid.
C"H«0- =1 C»H*OSO*,

PiHTA. Ann. l^hmmh 30, 165; Ann, Chim. Plt^s. GO, 2D8; j; pr, Ckmjl

17, 241; Pimnn. Centr, 183.9, 373.— Furtber; Ann. Pharm. m,iStl

Fharm. Centr. 1S30, 373*
LowiG k WEinnAKN, J.pi\ Chtm. U>, 23G; furtber: F&g^, 1% 80,
MAitciiAKD* J. pr. Chem. 20, 305^ tharm. Cmir. IS 12, 885,
ViioctEH. A\ J. Pharm. 3, 275; J, pr ChtM. 29, 467 i Ann. Pkmm.

48, CG; /Vffin/i. CV«6'. 1843, G99.
Delalamje. iV. iH/i. Chim. /%«. 0. 346 ; Ann, Pfhamt. 15, 9^;

/V^/r?R. Cmti\ 184S, J 21,
Geriiaudt. A': Ann. Ckim. PhijB. 7* 217; Retf. $cimL 10.207; iiia

iV^arm. 45, 21; Phann. Cmtr, 184:5. 167-
CAHotfBa. Contpt reml. HI, B.'*3; 19, 423; .V. Jnn. C/»«#i, /*A^f. 10, 3IT|

13» SO and 1 13; Ann. I'kmm. b% iJ-JO; Pharm, CtfUi\ IS43, (Jgl,
Ettling. Ann, Pkamt, 53, 77; PAarn*. Cenir. 1845, 324.
SciiLiELi*KE. ^niL PAafm, 59^ 26*

Source. In the floweri of Sphwa itlmfina, (Loirlg Sc WeidiiiS»
Afl metbylsalievlic actd in Qmdtluria pi-oettmbeni.

Formation, h From salicyloua acid by ciidallan with m<|iieQiiB
(Ettlin^, p. 338), or^ by beating with ojride of coppo

of polf^ii (Pina):

diTomic ftcid (Ettlinir, p. 338), or by beating with ojride of io^pa
(EttUnnr, Pida.) — 2* By luekin^' salifvloug acid or ajiliciii wlib bvdial«

3. By brntiog indigo with bydrato of potaeb to 300\ Th»
Bot fclway* (uccccd j if Ibe beat be nut cflulitmcd long enough, ooW

P W M \m BALlCtLlO ACID. ^^^^"^ 24|

prodae*d; if too long, a hr&wn iabstance b formed. (Cahoufg*) ^ 4 . By heatiDg
hentoale of copper* (Ettling.) — S.^By the action of nitrous acid on
anthranilic acid (Gerland); " J

CWNH^O* 4- NO* = C"H«05 + 2N + HO,

G. Cumaric a<:id fused witli Uydrate of potasli yielda ealicylito and acetate
ofpotaJih. (Pelalaade);

C^H«0« + tKHO= - C"H«KO* + C<H*KO* + 2U. \

Pir^mratmi, — a, From tlid flowers of Sphwa uimaHa* — I, The
fltiweri are exhausted with ethor; the etiiereal solution difitillcd; the
residue treated with water, which dis.«iolves salicylic add and tannin;
and the aqueans solution is nontraliscd with carbonate of potash, evapo-
rated and distilled with hydrochloric acid. The watery distillate b!ow]j
avaporated yields colourless needles. {Lowig tk Weidmann.) — 2* The
water distilled from the flowers, with frequent cohohation, is ehaken up
witii etber; the decanted ethereiil solution agitated with potash; and the
alkaline solution distilled with sulphuric acid. At first salicylous acid
passes over, hut at last salicylic acid sublimes in long needles. (Ldwig
and Weidmann, ro^j^. 46, S3.)

6, From oil of (JfiuUhtria {Winttrgrem), — 1. The oil is heated with
strong potash-ley till no more wood- spirit is given off from it, and the
residue precipitated with liydrochlortc acid. The precipitate la washed
with cold water and crystallised from hot alcohol. (Cahours*)

e. Fmm Sallcyhiu acid, or fmm Salicln^ — L Hydrate of potash ii

heated in a silver basin ^ and as soon as it is melted, salicin is added by

I email portions, with contiiiually stirring, whereupon the mass turns

' brown, swells up and gives off a large quantity of hydrogen. It is the a

heated as long as hydrogen is given off in presence of excess of potash.

If the potsah is tiot iu eiLt'e^^^ onl^ n stnalJ qufintii:^ of salicylic acid ia ubtjiincrdi but iu^
stead of it, sulicylqui acid liiiiJ u brown rt-sifions i-ubst»uce whicb it U diflicult to convert
iut^^nlicylje ftcid, even by rcpfatcd fusion wUh hyilr«tt of pntwh. |f the process be
rightly conducted, the inae« becomes nearly colourless, exhihiting only a

Jllight yellowish tiut* Acconlini; in Mnrchnnd, the masu ^rat becomc§ i](?«p fellow,
then of n fine sotflct, tbcn giTrnihU yfllow, and «t lust nrftrly white. If the hp.it be too
itrong, the Jiiflss blackens fliidjgivcs olf citrhoUc a£id* The maas is dissolved in
water; the solution eupersatumted with hydrochloric acid, the vessel
being surrounded with cold water; and the resulting crystalline mass is
aeporated from the nrothcr-Hrpior (which contains oxalic acid), and
recryatalUged from hot water, f Piria, Gerhardt, Marchand.) — 2. Cupric
a&lJoylite is heated in a retort till nothing more escapes at 220", and the
^■lesiilue has assumed a uniform kcrmes-hrown tint. This residue, consists
^|p9g of cuprous saltcylite, is then introduced into a glass tuhe and snl-
pburetteil hydrogen passed over it, whereupon the mass becomes heated
and blackened, and salicylic acid sublimes; and in order that the enbli-
inate may not cover up the uti decomposed mass and so protect it from
further decomposition, it must be driven forward by the application of
a gentle heat. Or the cuprous salicylite is dissolved in warm acetic acid,
dr in hydrochloric acid diluted with an ecjual quantity of water; the
eolourles« liquid precipitated by sulphuretted hydrogen; and the liquid
iltored from the sulphide of copper is evaporated to the crystallising
point* Or, the solution of the copjper salt in acetic ac;d is sunereatu rated
^itb ammonia, and precipitated with neutral acftato of h^\ iVi^^xttlv

I

248

ike: OXtGEN-KUCLlUS 0*HKfi.

pitate Hu&peBded in hot water; eulphii retted hjdrogeD pfiss^ thmd
the liquidj ami the siilpblfle of lead removed by iiltration : the filtr
on cooling yields pure salicylic aciii (E tiling,)

rf, Frmii Indiffo (comp* p. 246),— If tlie required tfimpgratare IB cxtwedcfdi
aalicylic tctd decomposes and a brown itubfitan^ i» formed ? if th« heating ia uoC t
tinueJ long enough^ aothlug but ontliraniUc acid is produced,

FraperiieM. CrystalHsea by spontaneous eraporation of the alcoholic
eolation in large oblique four-aided prisms. From n hot aq^tieons sotnticti
it eeparates on cooling in slender needles often an incli long. PartietiUtly
largo and fine crystds are obtained by slow evaporation of the etbeM^l
salution, (Cabonrs.) Tbo crystals belong to tb© oKliqtie pricmalj'
(monociinotnetric) system. (Martgnac, Li^ig cf- Koppg J<iArf*h^
1855, 4840 — Melt&ab 158^ (Cabours), at 121" (Procter), at 125
(Ettling). Bubliraes at about 200"", without bt^iling, in slender needli
having a strong luatre, and when pure may be eotnpletely distilled
flarefttl heating. (Cabours, Ettliog.) Hua a sweetiab sour ta&tej an
produces irritation in the throat Reddens litmus rather strongly. Th$^
aqueous solution imparts an intenso Yiolet colour (blood-redj according to
Lgwig k Weidmann) to ferric salts. ■

Pirii*

Marching,

Dclaliinde-

GerbtHt,

14 C

6 H ...
6 0.

. 84 .
. 6 .

. 4% .

... 60^87 60-34

... 435 4-42

.,. 34-78 ........ 35^24

.... 60-44 ,
.... 4-64 .
„.. 34-52 -

... m4\ .
... 4-50 ,
,. 35*09 .

... 60 1^1
.« 4^5f
... 34-31

Ciai«0»„,

, 138 .

... 100-00 lOO'OO

.,.. 10000 ,

... 100*00 ,

... 100-OQ

}

0...

Cohouri.

a. L

...„ 60-76 ... 60S3 ,

..... 4-4 1 ,.., 4-37 .

..... 34-83 .... 34 -Sa -

EttUng.
... 60-80 ...
... 4-51 ,..
... 346d ..

Gerlniifi.
, 60-32
, 4-28
. 35-4a

1

loo'oo

lOO'OO

100-00

100-00

The add analf sed bj PiriA was prepired from EaltC]r1oua add ; that ^xamiMd 1
Mftrchand and bj Gcrhardt. from snlicin ; and ihat wmlfied by DelaUDdc, trm *
cumann by fmiao with hydrate of potash. Ettlin^ analysed the ecid obluiici bf
beaLmg cupric «aticylite. The acid B£«mitied by Cahoura mula pfiepared tt^m 0J3 d
wiijtergreen, a cryjtalliscd from alcohol, * obtained by lublimation ; Gcr[and*i vai
waa prepared from anthranlllc acid.

I>tfC(mposiiiom. 1 * Salicylic acid when quicTcly heated^ c^epedaDy i
it be impure, yields hydrate of phenyl, (Marchand, CahourB.) H< ^ *
iffith pounded glass or cpiick lime, it k resolved into hydrate of p]
and carbonic acid (Gcrhardt);

%. Th^ liydrate of pTienyl tbua prepared dilTeri Jti lomo respects from iliit «
[obtained by fractional distillation from coal-tar creosote. It crystallisea with
ftdlity and doei not deUqu^jtce act quit-kly on exposure to the air, Mor«of^r it .„„
diAertnl prodact^ with pentachloride of phoipbora^. Hydrate of phenyl froia'co^
tar creoaote ^leldi with pentachloride of pbosphonia, chloride of nheoTl a^
tripl*enylic phoaphate. P( C ^^ I l*)^0^a4 determined by Williarason & Scti IHlH

I pee also Chtm. Sav, Qw, J. ?» 240). But hydrate of phenyl from aiilit s ^^i^C^I

' whrn thus tinted, not i tn^ben^Uc biilft^\||Wii^^k i^V^%^WtA or tiphiugh^kg^Mmyf

SAlICTLtC ACID.

Udd P(C"H*)Mf,0"» contatnmg 1 At. of hydrogeo replaceable by mctaU, Tliti l3o<lj
re^coibles Scnagbam 'i pboapbate in distHlfng at a temperature much above tbft ronfl^e
of tbe merouriftl tbermo meter, but differs from it in rannj otber respects. It crystaltiaca
^Oeb more re<>*iily, aOLl nftei' ht\-n% freed from ndUeriTij^ oil by prpMure between paper,
may be kept in paper dnrini^ tbe warmest aud dampest weatlLei- withont altemtion. It
dissnkea m a weak solution of caustic soda to which a little ak'obol t* added, formuitj
the biphmylop/iosjjkaie of itofliftm P(C^-tH-NaO^, wbich cry«taIli3€S in well defined
pHsmntic crystsla containing 0 atoms of water. This salt is very eJUorescent and
dissolves readily botb lq water and in alcoboU 05 iniiin? tbe aqneous solution with
neutral acetate of lend, a nacreous cryfltalline predpkate h formed^ whicb iippeaia to
contain P(C^lF)-PbO^(lLWatt3: unpublished esperimeiits). If,

SaUc3rnc acid heatod to 250'* with ftisol oil in a sealed glasa tube, is
resolved into carbonic a<3id ami hjdrato n^pbenyl. while the fosel-oil
remftins unitUered. {ScLlieper.) — 2, By Uio action of hromifie or
chlorine, 1, 2 or 3 At livdro^ijcn in tbo acid are replaced* With a small
(jtiatUity of bromine, bromosallcylie acid, C'*BrH'*0^ is produced ;
with excesi^ of bromine, blbromoi^iilicylic acid C"flr^ll*0*; and if tbe
flctioD is aided by sanshiue, terbroraoaalicyUc acid, C"Br*l PO^ id formed
after aomo tinio, — When the qiiantity of chlorine ia Bucb that part of
the salicylio acid remains unalteredj chlorosalicyHo acid, C^*C1H'0' ia
formed; with excess of chlorine, the product is bichlorosalicylic aeid,
C**CFH*0*» No attempt was made to prepare tcrchloroaalicyliu acid with tlie mfi of
tun^igbt. (Cflboura.) AVhen chlorine la passed into ealicylate of potash, it
green body separates consiating of impure bichlorosalicylate of potash;
and when the brown liquid separated from tliis substance is ^aLumted
with chlorine, a yellowish-red substance is deposited containing bicbloro-
Bal i cy 1 ic an d terclilo rocarb u 1 ie ac i ds, ( Cah ours. ) — 3 , With; j^>i tachlonde
of phosphorite J the acid yields hydrochloric acid, the oily body which was
regarded by Chio^za as chloride of benzoyl and hydrogen, and by
Gerhardt as chloride of chlorobeuzoyl, and leaves a carbonaceous residue
(p. 116), — -4* The acid gently heated with dilut4^ mtric acid give-'^ off
but a small quantity of gas, and is converted in a few seconds into aitro-
Bal icy lie acid. ^Marchand.j Fumiwf nitric acid or a mixture of fuming
nitric acid and oil of ^'itriolj acts yiolontly in the cold and forma nitru-
salicylic acid, fGerhardtj Cahours.) When salicylic acid h heated with
fumintf nitric acid or with the mixture of nitric and oil of vitriol, a violent
aetion takes place, resulting in the formation of picric and carbonic
aoids, (Gerhardt, Cahours.) — 5, Salicylic actd heated with Aj/drochloric
acid ajid chlorate of potmK yield^^ chloniiiil (Hofmann, Ciihours,) —
6- With the vapour of an hydrous snlphurie acid, it forms a gum soluble
in water, which is sulpltosalic^lic acid, and combines with most bases,
forming salts which dissolve readily in water, (Cahours,) — 7* Boiled
with dilute sulphuric acid and peroxide of mangancsei it yields form to i
acid, (Cahours.) — 8. The acid is not altered by a day*fl contact with
fusel-oil ; distilled with amylo^ulphato of potash, it is resolved into I
carboaic acid and hydrate of phenyl. (Schlieper.)

Combinfttiom. The acid dissolves sparingly In celdj abundantly in
^oi water* It expels carbonic acid from its i^alts.

Salicylic acid is bibasic, formmg principally neutral salts =i
C**H*M'0* and acid salts — C^*H^MO^ It was formerly r<^arded as monobasic,
the 64ilU be re considered a» acid being tben regarded as neuti*^ y itidced the ejcistcuee of
■Alicyhites containing 2 At. metal in place of hydrogen was not known till 1855, when |
ceveraL of the in were prepared by Pi Ha. Moreover, the compound C^^NIFO*, formerly
fC"KH>' C"H»n'l

150 TOLUZXl : OXTGKX-XUGLSUS C¥Bra*.

liBslifidj VecaabTvxVj lig^^t to rrti^hrt rariaer ^ cbandcn of I
m,»brrbak»ai ^'^^"^S"^ t O", .tke ndkal C»HHI> bai« eaufdeafc to ff),

|«2t%wk »3ss ^b: faEs AsaAapes-^oif sftd iwioL Tlcextttoieeof acid eChcnof «E-
CT&c acai, f.c^ aM^jiattbeT^ aai fQz^ .H* ^ ^ *^ ^ Cnmv qf tUt vicv. Qi
tW £».->5s<b!C<:y ftS:cc<c ir li.'s ^uti^x-^ t^ fxsBla €f nBcylic add itgarded !••
bebttsv ac^ sbofL^ V C^R'.C, lai Br.r-odT^r, the add ifaoald take its place ia tki

T2^ a^c«c^ s::^:S:*f c-f tLe &Ik^:z3e salicjlates torn brown on expo-
su>^ to th^ air. a rr:v-^ s^lia^ce t<e:=^ fomiM wUch remminfl dissolTed
in tbe albal: M :<s; sali-cjlaietc^ vb«n subjected to dry distillation^ yiell

5«J«r^;/ ^ .twK.MEi^L — Wben tbe arid is ntnimtcd with i
i»d ili« r.ti^id KM.ec as i eTar*c<r&t<d, eryAailine acales aepante af it
cilViIs: br tf^^atar^^u era^caiica of ike dilated tolntioo, eilkj ncodlfi
ai>e <»UaiMd. ,CaLc«r^ Pivxser.) Mdts at li€^. (Pan^)

UC > f4 . U'l9 M-06

X U — r«S 8-M

f H # _ *-«i €-«a

*o 4^ _ »-9;

C^H\NK-N>» !5^ !<♦«»

Br err dU<.lla:k£ :lje sLt jie^ii vaier and aalicjlamie add.
(^CalK-a»*"

W^er* s.:V;^":<>i :.^ Irr ^.^•::':i:::r. :b:? «!: £r5l c:v« off ammonia, aad
U vvr,\^r:*\i ::,:o ir il-:i sj.".:. ar.ir wLIri iLe x«»:diie swelU op consi-
donViv aru y.cli* rvirfcri .: 3-:^tt* : p:;l^r '•-ith a sablimate of otf-
U>r.ale oi a^isi. ria. * ^ *-j- '•*-= • ^-^ -\" (rsriArdi.^

kV:.:/!'.*..:/ ,/."\;y6V — T*: ;* a:! I ;? aizrazed vitb m concestiatai
«\*u::x^:: ^a caTKr-ati- .: p.:i>: . ::; l.;-.i era|orated to drjnest; tk
nN^due c\K»*i>u>i *>.i >:r. r^ ':•: .:£ il.ribol: iL* crjstalllBe ibmi
oV:a,r,<>.: i:\:u :i:f a\^*: .".:.• >< ^:I:r *: v ->:'..i^ or eraporation, picfsed
K'likivr. t^Ajvr i: ,1 ,: j^.voi .- th:^:, ii.i :i.e snT^siiv^a left to erapoiate
it xac.:.v — 0, .. , :^ ^^ r ,\'-l ,>^ *: -^^ : j & j:.-.-^ * rtj '.r^Lrc; ihev rive off
o i .^ }\ c ^4 A: vTfc:er a« ".T,^ '^41:^::?.

0-; : ::*r£.

rab.*««.

kv^

* * :

ir *>

. - Si'lO

^4 V

>• '•

♦:- .:

. AhJt

f ':\

t f

.' -}

. -. J-S2

: v»

45?

i: «:

... 2<-16

i -U'kO* • X\ ;>4;t *.. ;jk'\4 .^. i#rM

^^"

SALICYLIC ACID.

--

" Or:

HO

,. 175-2 ,.,. 95^4

9*0 .... i-ee .-

Cahoim.
5^05

251

C»*H*KO«+Aq,.. 185-2

lOO^OQ

The aalt when drj ii not altered by exposure to tbe air, but if moists
it soon turns brown and aft^srwartla black. Resolved by dry distillation
into bydrjite of pbenyi and carbonate of potash, (Gab ours.) If the
product of the dry diatillation be mtumted with hydrochloric acid and

I then heated with potaah, an odour is produced rogenibUng that of aniline.

I (GerharJt) *

^_ The salt dissolves readily in alcohol and €fhei\

I SaitcJ/late nf Barf/ la. — a. Neutrfth — When etrong baryta-wator is

added to a boiling concentrated solution of 6^ the mixture deposits small
white crystalliue I am in in which may be rocryHtallised from a Jargo
quantity of water, apart from the air. — Snmif white opaque needles,
concentrically grouped and having a diatinct alkaline reaetion^ When
dissolved in water, it la decomposed by carbonic acid, yielding the acid
Bait h and carbonate of baryta. At 14 0*" in a current of dry air^ it gives
off 11 -SS p. c. (4 Atj calc/l 1-63) of water. (Piria.)

N

uo .

10 0 .

.,*.„.. ao .... 8 5$

.,...». 137*6 -M 14-44

80*0 .„. 2hm

Piria.
27*06
.2-60
44-51

25 S3

CHMln'O^ + 2Aq _. 309*5 lOOOO 10000

h. A cid. — Obtained by boiling salicylic acid with carbonate of barytR,
filtering at the boiling heat, and leaving the filtrate to evaporate in
vacao, — Short silky needled united in radiating groups. Contains I At,
waterj which is nut given off at I UO"^, but half escapea at 1^0^ and the
rest at ^SIS"". (Cab ours.)

BaO „„. 76-6

a*aW .,..«., 136*0

Cabours.

35-69 ....... 35-56

61-31

100-00

^^B C'H'BaO'^ -¥ Aq ........ 214-6

F ^At a high temperature, it decomposes, griving off hydrate of phenyl

jind leaving carbonate of baryta mixed with charcoul. (Cahours*) —
Bbsolves readily in water. (Ettling.)

SfiUe^liiit of Lime. — a> Ifeuiral. — A nearly boiling solution of limQ
!n sugar- water containing so much sugar that it does not become turbid
on boiling, is mixed with a nearly boiling solution of h iiho contain hig
sugar, and the mixture kept for half an hour over the water-bath. —
1! envy crystal Une powder consisting of shining granules^ Nearly insoluble
i n w ate r. A ft er d ry i ug at 1 00^, i t co n tai n a 2 At* wat er o f cry a tal I i sa tion
which slowly escape (^0 28 per cent.) in a atream of dry air at 180^
(Piria.)

S5t mXICKZ: QUU>-9DCLKCS

U C — ^ _ 45-» 43-12

t fl i _ ^<«f 3-is

iCx « -frt _ SWa 9»M

? O ~ U ^ S^-» »i>7

c^fi-Ci^of • iAt 1*4 ._ if*« itrtt

mjcr&£*;c =x Tkcu:. reujrfi:' nEC^cis-^fLS cftem of Tcrj largb mm

1^ aii: i;&f & :Li=dr u^I TtixTsz:: :wc&.

C*0 IS _ I« U-17

:«c — *4 «. 41 : 41-47

:h — r _ 4 4-n

ZO « ... » 3f-13

TV sus iissclxw Tisib^Ij Ezr ccLi sai fc2 bw

^'~ K-jCzTj r Z-r •• i" - — /. J" --tc •^' T»r. — A >:riix 5C»xtSo* oi cit mixed

:*c 5^-1 ^ :^» li-u

4 H 4-i _ i So - 4-^

iTi 5::-* ... ri« r44«

.* .-» •*i"l ... Hi? ii-*i

:*c - ^-J - i-*-^** — jt-x*

4 ■•: *-i .... : :: — i-i*

i 7*1 i»L* •> ... *l*W <9^4l

SO v> i . : ? -w . — !!-»»

SALICTLIC AC

ZS3

f* Add. — Salicylic acid m boiled with water and carbonate of load
(s voiding an excess of tlie latter, according to Pivla), the liquiil filtered
at the boiling beat and tlio filtrate loft to cool; or a conccn trotted so! ntioaj
of fiallcylnte of ammonia or potash is mixed witli a concentrated solntfen ^
of neutral acetate of load, the precipitate wft-sbed with cold water find
dissolved in boiling water, and tlio solution left to cool. — Reatitifttl
transparent cryatnla, wbich between 140° and 150' become opatjue nnd j
give off 1 At. waten {Cabonr^i.) Resolved by bulling with water into
the salt h and free salicylic acid. (Plria,)

Cr^staflised*

Ctibfiurt*

^ fhO

^^ 14 C

^V 6 H ....

f 6 O

urs ...

840 ...
. CO ...
. 48*0 ...

. 44-75 .-,..
. 33*63 ....
. 2-40 ..„.
. 19-22 .....

... 44*59
... 33 72

... 2-50
... 19*19

^^ Or:

1 am^pbo*

24y'8 ...
.... 240-S

- 100 00 ....

.... 90^40
... 3*60 ..

... lOO'OO
ColiOW*.

HO

.... y*o

3-C5

C^*H>PbO'^ + Aq....

.... 249*8

.... 10000

Salk^late qf Coppir* — a. A^etUraL — Produced by beating h with a
quanilty of water not sufficient to dissolve it. YeJ low-green ligbt
powder, wbfcb when heated gives off its water of crystilKimtion and
becomes brownidlt, and is completely decomposed at 1 80"*. It is sparingly
itoluble in boiling water^ insoluble in alcohol and ether. (Piria.)

14 C ..
C H .
2 Cu..
BO ,

84-0

CO

63-6

61*0

3e'63

2-76

29* IB

2d-43

?irk*

38*43

2-B7

28*36

30-34

Ci*H*Cu^O° -t- 2Aq.... 217^6 *... 100*00 10000

K Add. — When salicylate of baryta is decomposed ^by a Eolation of
iulphato of copper, tbo filtrate yields long blnibb preeu needles wbich
may be recryatallised from water at about 60''. — TW Fait gives off ita
water of crystal! iaation at a temperature raucb below 100^ assuming at
the same time a dark olive colourj and emitting vapours of salioylic aoid.
Above 100°, it melts and gives off copious fumes of salicylic acid. It
dissolves readily iu water, alcohol and ether, forming solutions of a fine
yellowish green colon r. When boiled with a quantity of water not
eufficient to dissolve it, it is resolved into free acid and tbo salt a^ being
at first converted into a dark green resinoug mass, which, when treated
*witb a fresh quantity of water, becomes pulverulent and yellowish green.
It is decomposed in the same manner by ether, even at ordinary tempera-p
lures. (Piria.)

14 C _

9 H

Cu

10 O .,.„„.

„.. 64*0 .
.... 9*0 .
.... 31*8 .
.... 80*0 ,

... 41-03 ..-
... 4*40 ...
... 15^50 _
... 3!J'07 ....

Piria.
..>., 41*25
..... 4*52
..... 15*57
38'CG

C^^H'CttO^ ^ 4Aq

..„ 204*8 .

... lOO'OJ ...

..... imm

S54

TOLUENE : WtCEN XtJCLCTS C^fM*.

SallciffaU nf Cfipptr and Fotaisittm, — ^ Cryatanised^ sdiejlic acid ii
added gradually aud with constant agitatiou, to n &c»latloti nf toli^lukt* <if
copper and tartaric acid la excess of caustic pota^U, or better to & dotation
of tartrate of c»)pper in niDderatcljr etrong potash ; the li»|'*id *I"ti
graduallv acquires a grt?en colour, ana ultimatelj forms a g^reea <
pulp, which must he dried oa porous eartherxware, and recrvri^*^-*^"^
from the etuallcst possihle quantity of lukewarm water. — Wien tlovlj
erystallised from tho aqueous Bolution, it forms small rhombic tables td »
beautiful emerald-green colour. It dissolves very readily in water. The
deep grecu solution when boiled, depofiits black oxiife of copper and
becomes colourless; a larg'e excess of potash t^rns it dark blue. It dort
not dbeolve in alcohol or ether. — In a dry itream of air, even below
100% it gives off UBi p. a {4 At.j calc* 14 82 p. c.) of water. (Piria.)

%ia«

14 C

B4 0 .

3t 2 .
31-8 ,

iao .

. 34-57
.. 3-29
.. 1613 _
,. 13*03 _
3292

,.. 16*11
.. 1320

8 H

K ....»

Cii..„„

lU Q ♦..♦ »«.*«.

CWH-KCuO* + 4Aq...

2430 .

.. 100-00

1

Salicylate af Coppm- and Barmm. — The solution of the pr^etdiiif
salt mixed with chloride of barium, formf after awhile a liyht |rre«a
crystalline precipitate. The salt is jusoluble in water. Bctwmj
35' and 100% it gives ofT 12 94 p. c. (4 At,; calc 13 21) of wi^Uj
(Piria.)

At 100\

14 c „. 84-a

4 H 4'«

Bm 68*8

Ca ...„ 31-8

6 0 .,., ...„...» 4a'a

a*tt^B»CttO*.... . 236 6

SWl 35-li

i"6i> ........ i-eo

29*01 .,„..„ «s*n

13-41 ....... 13 €4

20W ........ »r27

iooo<>

10000

^alkylate nf SilmK — Nitrate of silver Is procipttiiic*d by laUi
of amntonia, atid ttjc precipitate wa&hc^d witli cold and disaolvM to li
water (during which oj^erations it bliwrkeni dightlv i SUHn^}. A^lim
liquid coo 'a, the ^alt crvf'lullfKCR lu transparent nceJles bavijig a
lustre. {Calii»ur>=, Etlli^t^) To obtain the pure salt, Etlltng tai
iatu rates salicylic acid with lluie* water; passea carbon ic acid tlimi
liquid J heau it; (ilto i^j waruig tlie Ultrate and add» nitrate of
then vaahos the precipitate in the dark witli cold water, and
at 100^

AfO llfii

14 C ......... MO

A II i*0

t O ^„„ 400

riridi Dclalmride, Caboafi.

4r-3f 46-57 .-. 46'BO ... €0-80 .... IT*

.^4 '2 J ........ 34-.U .... 31-40 .... S4'24 34^

204 ...... 2m . ,, 2 23 .... 2-U _ 211

uva .>. um .... leas ..,. w^ ^ u<

\m^m ... . ., u^^^ ... \^'^^ .... \woa ^ iit#'

METHTLSALTCYLIC AOD.

as

Tlie aciJ digsolveB reaflily m wood- spirit ^ especial I j wlieti LeateJ,
rreaxlilj in alcohol^ and abundantly in ether^ especially when beated. It
is nearly insoluble in cold oil of tiu^^miine^ bat diesolvea in 5 pts. of that
.liqnid at tbe boiling Ueat^ and solidifies on cooling. (Cahours*)
For Salicylate of Methyl, see page 258,

MethylsalicyHc Acid*

^Cahoues. (1S43.) Compt. rend. U, 853; N. J. Pharm. 3, 364,—

If. Ann, Chitn. Pht/9. 10, 327; 27, 5. — Compt rend. 09^255;

PArtm. Centr. J 843,' 698; IBU, 434; 1854, (158.
Procter, N. /, Fharm. 3, 275; J» pn Chem. 29, 467; Ann. Pharm,

48, 66; FhiTim. Centr. 1843, 699*
Gerhardt, Compt. rend. 38, 32; Ann. Pharm. 89, 362^ J. pn Cftflrt-

61, 89; l^it^, 3/327; PAam. Cetiin 1854, 12JP.

Oavtikeriati^ttrtf Metht/bptr&j^UUnrt, H^drated M^thtfUmlhj^lf SaHe^l-
formttier.

^

Oceura iu tbe Kerb of Gmdtherla procumhem (New Jersey), fonning
^of tbevolfttile oil (wintergreen-oU) obtained tlierefrom by difltiHation
with water (Caboura.)

¥

Preparation, L Tlie volatile oil obtained by distilling tbe berb of
GanliAeria procumiien» with water, — or tbe commereial oil of wintergreen,
— is rectified, and tbe partion wblch distils over at 222^ collected apart
Tbe oil begins to boil at 200^ tbe boiling point quickly rising to 222°;
Tbe portion wbich first dietlls over contains a li^bt oil having the compo-
sition of oil of tnrjiontino. (Procter, Cahours.) — 2* Two nts. of crystal-
lised ialicylic aeid are distilkd with 2 pts, of anhydrous metbylia
alcobol and 1 pt. of oil of vitriol. (Cahonrs.) — 0. Absolute metbylie
alcobtd jes gradually added to cbloride of galicyl; and, as soon as tbe first
action, wbicb Is accompanied witb great riso of t em pe rat ore and evolulion
of bydrocbluric acid, bas ceased, tbe product is di«tille<l, and the portion
wbich goes over at 222 "", collected* (Oerbardt.)

ProptHm. Colourless oil, Commercifil wmter*rc?€tT*oil is redJiiii yellow,
but ttiay be rendered jetlowiah or cveu ooloarkss hj reetifiration* (Procter.) — ^ Has
ail agreeable, very penetrating odour, and a gweet, cooling, aromatio
taste. Sp. gr, MS at 10°, Boila conatantly at 222''. Vapoar-denejty
5-42. CCabonrf.)

Calioani

IGC 96 .... 63'15 63-13 .... 63*03

g 11 ....... 8 .... 5-26 & 43 ,,.. 5 37

GO 48 .... 3l'&9 31-44 .... 31-60

256

TOLUENE: OXYGEN- NUCLEUS CnW.

C vft|i(iiir IS ........... B'ftauO

H-£?as. ,,„ ._.«,.«,_ 8 -.« 0-1*51 1

O-gm ,.„„. 3 - 3'327a

2 ..„.. 10%^ ^^3

1 5 7191

Vapour of MetbyballcjUc acid ...
a wai prrpired bj (1) ; &, tif (2). — The compound is ifomrne w^

ntttfaf M^j«

D€c<ympo$iil(ms. Wheu tlte fteiJ is mixed with Btrcwg mtt-k
Tiolcut epirtmg takes placc^ if the mixtuio i.^ not cooled, biit when \X ti^
kept cool, TnetlivlnitroiSJil icy lie acid \& produced. (Cahour=E.) By fnmiaf
nitric fic'ni, it is converted into inetljylnitrosalicylic acid; by a wMxtun; of
fuming nitric acid and oil of vitriol, into methylbiuitrosalicylicacid^ or by
lunger actinu, into metbyl tern iiroi=al icy lie acid. (Cabonrs.) — t. BromUt
added by dmps Ui metbyl^licylic acid, causes considerable rije of l©mp>
mturo and evolution vt bydrobronjic acid; tbe inaag wbicb suHdiie^oli
cooling contains melbyllromo^allcylic and mcthyibibromosaUcylic tcidsj
tbe proportions yaryii>g accordiug to the quantity of brouime lucl
Clthnm forma ainiilar product?, tbe rjuaulity of hydrogeii replieed
r ever exceeding 2 At* even In minsljine. (Pr(»ctcr, tahonrs.) — 3, Ftnt^
chloride of phosphoi'tut acts violently on the acid, forming chloride cl
sal icy I, chloride uf methyl and chlorophoephorio acid*

CifH^O^ + PCI* - C**C1B'*0' H- C-ll*Cl + VQiHP.

GerUardt {Traitij 9, 343) supposes that phosphate of sdicyl is formed in
ibis reaction:

4C«H*0« + PCI* = 4C5H*C1 + Ci*ClH*0< + ^(C^msO*)S0^

thereby explaining why so email a quantity of chlorophosplioric mim
formed, and why, after treating the re^uUini* cblorido of sal icy 1 »itk
alcohol, and distilling off tlio ealicylale of ethyl tbert?by prrniuceti. t
considerable residue is left. ^ 4. CkhnJe of sncmipij chhritU of hfns^'i
and chlorklt of cumyl form with nietbylmhcyJic acid i methvlsniicjt- I
fiuccinate, — bcnzoate and — cuminato, together with hydrodiloN J
acid: €.g. : H

D*(Cm3)Il*0=^ + C*<H*C105 = C'^(C=H=)(O'11^0^H*0^ + l!Cl (G^rfwrfi).

5. By potash-kyj niethylsalicylio acid is resolved, after a few hoort it
or<linary tcmporatnrea, immtdiately when heated, into ealtcyUo addiKi
wood-spirit. (Procter, Cabours.) — Heated with anhydrous hoTTtA, i*
yiehla carbonate of baryta and an i sol. — 7. With a^jwtvni'i, cither gii««>6i
or alcoholic, it formj salicylaniide [salicylamic acid] and wood i^pml;

C'H^O^ + NIF - C^^MFO* + C=Tl^On

8, When pieces of potassium are dropped into metbyUalicylic acid Ik
to betwceo 50° and 60^, the temperature riseftj gas ia evolved, and »fi<f
the atlditioa of a considerable quantity of potaaiium, tho nifis^ solidifi«^
oven If kept at 105^. Soon afterwards it takes iiro aud leaves a bb«k
leitdtt^ la one experiment, saHcylons acid was pruduised* (CahooivL)

Comlinattcm. The acid di^eolvcs sparingly in water, tmpftrliiig W^
etor Ita imiQ and etnell; the solution Is coloured viokt by fento mi^

MiTlIYLSALICYLIC ACID*

257

It fllssdves tWme whlioiil decomposition, fonnmg' a brown solation.

Methyl Sill icy lie aciJ unites wltli lm('s, formiDg salts iti which 1 At.
liytlrogen is replaced by a metal. IJefure PirU huJ demonatrated tbe bibasic
eharacUrof MliL'ylif acid, Gerhardt supposed that ail icy late of methyl, iiiid the other
compound elhem of flalicylic acid, sbould be re;;ard?d us salicylic acid hx whlcli ] At.
hjdFosen is repJa^ed by an alcohoUradicul (C-H^ C*H* , , .)f l>«t tbnt the hydrogen^
atom thus replaced Tfas different from that which Id Ihe saUeybtcs i^ repUccd by a metal
(or in the compuund ethers of oth^p acida by an tied hoi -radical), and eonfcquent]/
that the pbcc of the lijtter might ttill be tukca by a metal (or hy an acid rudical), Thui,

k:

tbe formda of ialicyUc acid (supposed monobasic) being H ^*^^^ that of methyl-

.liclic.«id^ouldbe C-W(Cm')0^jo,_ «.dofiUpot«b.«ilt. ^""'(C'H'XJ-lo.

Mdhylmlkylaie of Fotaih, — With strong potaah-lej^ metliylialicylio
Bcid foriHij a mass wbicb solidifies in the crjBtalHne form. When potash-
ley of 45° Bm. free from carbonic acid and diluted with an equd bulk of
water, is ebaketi up with excess of metliylaalicylic acid, the potasb-salt
separates in pearly ecaleSj wUicli must be waiihed with the Bmallefit
possible quantity of cold water, pressed betweea bibulous paper, and
dissolved in absolute alcohol, a small quantity of carbonate of potash
then remaining undissolved; the solution Is left to evaporate in vacuo. —
Esttremoly delicate, white needles having a strong Instre and r^ieniLIing
asbestos, (Calioure.) Six-sided tables, (Procter.)

KG

16 C .„
7H ..
6 0 ..

Cahoarii
-l?'2 .... 24-32 ..»»., 24"&5
95-0 .... 50"4 7 ........ 49^07

7-0 ..,, 3-68 , 3*77

400 .... 2103 ........ 22*21

C'SH^KO" .„. 190-2 .... 10000

lOO'OO

¥

According to CahoarSt the compound still containi water^ which cannnt be G©pa*
ratftd, and appcora to be C^^H'KO" + | Aq. that formula reqniring 24*24 p. c, KO,
5-31 p» c. C and 3B5 p. a, H,

It dissolves abundantly In wijier.

When heated in the moist state, it m converted into salicylate of
potash. (Cahours^) The solution colours ferric salts purplo. (Proctor.)
It dissolves very easily in alcohol and etAer. (Procter.)

Methylmlk^jlate of Soc?^. ^- Hcsembles the potash-salt, hut is less
diible In water, alcohol and ether. (Calioure, Procter.)

Mdhyhaiicylate of Baryta. — When methyl salicylic acid Is added by
dro]^ to hot baryta- water, crystalliue flocks separate out, which increase
in quantity as tlie liquid cools, aUd at last, white crystalline scales ar©
formed. These are washed on the filter, first with wator^ then with
ftlcoholj and dried m vacuo*

Vol. XII*

BaO 76 6

16 C „ 96-0

8 H so

6 O ,.„....... *B*0

C^H^BiO* + Aq 228*6

Cahours*
33'5l ........ 34^47

41*99 41*98

3*50 3*45

21 00 ....,.,. 20*10

100*00 ....... 10000

299

TOLUENE! OXYGEN-NUCtEUS C'm«0»*

By dty distillation It l& completely resolved into earbonaie of 1^171%
anisolj iiud free carbonic aeid;

C'*H'B*0' + 2H0 ^ CWH^ + BaO.CO* + CO*, ^

Thtd decompositioa tends to snpport tlio fonnala. f^Wea by C&hoiir%
whcreaa the baryta-detorrtrmation seems to show tUat the salt is anhydroiaiM
(calculated (quantity of BaO=34*88 p. c). [ Per liapa the salt aualpeJJH
contained carbonate of baryta. L.]

The potash -salt fornia precipitatea with the salts of Lead, capp=**
eilTerand mercury, (Procter, Caboura.)

Compounds in which the Basic Hydrogen of Meth^lscdie^iic newf ill
replitced h^Mdhjl, Ethyl or Amijl^ are obttiined by beating metbylealicjliltj
0/ potaah with iodide of methyU etbyl or amyl in eealed tabea* ThM
methyl-compound (ialicylate of methyl, 2C'H*0,C*H*0*) boib at f IS^I^
the etbyl-compouod (=CH'0,C*H'O.G^*H*0*) at Ur, and the amy^
oonipotind at a temperatnro above 300°. They may be obtadned la m
crystalline form, (Cab ours, Compt. rend. 39, 250,)

Metbylsalicylic acid mixes in all proportions with alcohol^ etiier, flfl
of turpentine and oil of lemons.

Stimnftu of MethyhaVwyl O^H^^O" ^ 2C^*irOVC»EW = ,
C*H*(C**H"0*™«, -^ Prepared by gently beating chloride of a uoeinj!^
(x, 136) witn about t pts, of moth ylsalicy lie acid as long as bydrt^^l
rebloric acid continuoa to escape, digesting the resultin^j brown warn will
potafih-ley, and crystal I isinii; it from boiling alcoboL The eolation ofl
cooling deposits large rectangular laminiB composed of easily aeparttad
fihresi The compound is sparingly solublo in ether, (Gerhardt)
According to Gerbardt, it ia to be reg^arded as 2 At. salicjlio acid ia
which 2 At. hydrDgen are replaced by methyl and other 2 AX* hydrofm
by 1 At. sttccinyl: C»H»(C»H')\OH*0*}0«

Btmoaifof Methylmilleyl C*>H"0»= C^*H^O^C^*H*0^ acoordlnff l»
Gerbardt C^^(C^H^)(C^'H*O^)H*U^^0btaioed by heating mmX |iarlf of
aalicyiate of methyl and chloride of benzoyl, as long aa oydrocblom
acid continues to escape, washing the tetiacionsj gradually ctyttalliiir'
product with potash-ley, and cryfttalllaing from atcobol or ether.
Oblique rhombic prisms having a eplendid lustre. They remiMii iiaaJt«i«i
In warm water. U^hea heated with caustic potash, tlioy are slroo^f
attacked, and give off an aromatic odour; and on treating the aantoot
solution of the residue with hydrochloric acid, a precipitato of aac^lk
* ftoid is obtained. The compound is insoluble lu water, but dbtoiTvi
neadily iu alcohol and ether* ( Gerhard t)

ETHYLSALlCTtrC ACID.

I

Ethjlsalicylic Acid.

^CAHOFRa. (18440 -^^'' ^^'^^ Chim. Phfs. 10, 3G0.— CQmpt. m>^,
28, 58Gj J. pr. Cheni. 47, 417. — iV^. Ann. Chm. Ph^s. 27, 46^1^
Ann. Pharm. 74, 314; y^. pn CA^^k. 40^ 283; CompU rtntL
Z% 250.

O* Baly. CT(?m. Sot. Qu. J. 2, 28; Amu Fharm. 70, 269,— X pn Chem,^
47, 41 fi; Fkarm. Centr, 1849, 715.

Gebdardt* (7o?n.p/. re^cf. 33, 32; Ann. Pharm, 89, 362; J, pi\ Cliem,
61, 80; jPAam. C5r«f/-. 1854, i2Q,— rnn^^-, 3, 32$.

¥

Preparatwn* When 4 pts. of alcohol are distilled with 0 pte. of
erystallised eaJicylic acid and 2 pta. of oil of Titnol, alcohol abtjo passes
over first, then a inixturo of alcohol and salicylic ether, and hstly a
Bniall quantity of aJcolnd witli a large quantity of ialicylic ether. As
Boon aa Bulphurous acid hegins to escape, tlie distilktton is interrupted,
the distillate sltaken up with water containing a little ammonia, then
washed with water, dried over chloride of calcium, and rectified by two
distillations. {Caliours, Baly.) — 2, When absolute alcohol ia added by
drops to chloride of salioyl, the mixture becomea heated and giv^es off
large q nan titiea of hydrochlurie acld^ As soon ai tbo action ceases, the
Iiauid is distilled^ and the portion which goes over towards 22^"^ is
<K>llected. {Gerbardt.)

L IS c ...........

r 10 H

.... 108 .
10 *

„. 6S^06 ..
. C-03 ...
.. 28"9I ...

Cahaurs,
.,... 64-78
6^0

6 O. _......

..., 48 .

29-12

Qia|li«0« ,_

... 166 .

., 100*00 ,,

..... 10000

Propf'riUs. Colonrless oil heavier than water. (Cahonrs.) Sp. gr.
1-007 (Baly); l"1843ai 10" (l>elffa). Boik at 225" (Cahoura), at 22r
with the barometer at 28^ 1-3'" {DeltFa); at 229\5". (Baly.) It has an
agreeable odour, resembling that of salicylate of metbyl. (Cahoura.)

^ Demvipodiima. 1 . The compound is rapidly attacked by chUrim

f ftud brominej with formation of Bubfititution-products- (Cahonrs.) —
2. When fuming nitric acid Is added to it by drops, it becomes heated,
tnrns red and dissolves; on addition of water, ethylnitroaalicylic acid is
precipitated in the form of an oil, which after a while solidifies in a
yeliowts'h mass. When ethyl salicylic acid is heated with excess of

I nitric acid, picric acid is produced, (tahours.) — 3. Heated with aqueous
a ?jta/i'^, it is resolved into salicylic acid and alcohol, — 4. When brou^^ht
in contact with anhydrous baryta, it beoomea hot, and yielda phcnetol
by distillation. (Baly, Cahours.)— 5. Placed together with cauatic ammonia

! in a closed voasel, it disappears after a while, and a brown liquid is

% ^

260

TOLUEKEr 0XYGEK-NTCL1U5 C^H^O*.

Tide of plioEplioraa atid clilonde of benzoyl mi on etbylsaUcylic m ill

same luanuer els on tiietbjl salicylic acitL (Gerliai^lt,)

Comlnuattom. With bases, tlio acid forms conipouoJa similar to iho
of Tncthylsalicyiic acid, Tbo p<jtas^^iuTii and itxlium-compoiinda iro
crystaUisable, eoluble in water, and exactly siiuilar to the correspoodiii^
S3.1t8 of metliylsalicjlic acid* Baryta forms a cryaUUitie compoand
fipariDglj aolubSs in water. {Cab ours,)

By heatiog etbylsalicylic acid with iodide of metbyl, ethyl or aroyl
in a sealed tube, corapounda aro obtained in which tho bask atom af
hydrogca {that which might bo replaced by a metul) la replaced bj
TOetbyl, etbylj or amyl.

Bemoate of Ethyl-mUcfil C?^H"0«=C"IP0',D*H*O^ or,
to Gerhardt, C'*H*(C'H*}C^*H*U')0». Prepared bv heating ethjL_.„,
acid with chloride of benzoyl, as long aa hydrochloric acid continues
Cficapo. The mass which crystxillisos on cooling separates from tW
ethereal solution by spontaneous evaporation in the form of an ail, whieh
gradually eolidifiei^, by the separation of cry.^ta]line nodules conei^ting rf
email needles. Dissolves reaxlily in alcohol and ether, (Gerhardt.)

Amylsalicylic Acid,

Driok, Compi. raid, 38, 123; Afm. Ffharm. 92,513; /, pr. Chm^,
62, 480.

Formation. Only by the action of chloride of ml icy! OQ fuacl-oi
(Biion, a>mp, SchUeper, Amu Fhaim* 50j 26.) —

Prepamiion. By means of chloride of falicvl, m the same
aa methyl sal icy lie and ethylsalicylic acids. It Is neceesary to up«»i«
with small quantities only; otherwise the action beeomes too T]o]€at,iiid
a large (quantity of earbolic acid is produced, (Dnon.)

Propeiiki. Colourless, strongly refracting Hijuid^ heavier tLaa watir^
boiling at 270°, and Imvln^ an agreeable odour.

Boiled with potash, it yields amy lie alcohol, and salicylate of |>o4a^

It is insoluble in water. With cold potash-ley, it fornta amykalicyUte
of potash. (Drion,)

Heated with ehlortde of bcnzojfl, it gives off hydrocfilonc acid, umI
yields a body which crystallises in needles (benxoate of amyliiilgcyU)
(Gerhardt); a viacid mass which does not readily solidify. (Driou,)

ANISOL^

261

derivatives of (he Acid Salictflk Ethen, which tmy ht re^ai'ded m
hclonging to the Bemetie*8€ri€i*

Anisol.

CAnouRS. (1S4L) N, Amu Chim, Phi/$. 2, 20Q; Ann, Tlmvm, il, CO;

rJ. pr. Chan. 24, 353; Pltamu Cmb\ 1841, C82. — CompL rend*
15, 804,— i\^ Ann. Chim, Phys. 10, 354; 27, 440; Ann. Pharnu
74, 208; Phamu <JenU\ 1844, 43.'>, — Cojw/Ji* raid. 32, GO; Ant%.
Phaim. 78, 125.
AURENT. Pev. sclent. 11, 258 j Compt, rend. 15, 053,

Drt^ml^ Phenafe dt w«/Ay/r, Carholaie qfmtthyi ICartol/ormetitr]*

Poj-mfiiton and Preparation. 1 * Catbolate of potash and iodide of
methyl are heated together in a. sealed tube to a temperature between
100^ and 120^ Decomposition take<a place qiilckljj according to tke
following equation :

Or carbolate of polasb is distilled with methylosulpbate of potash, —
2. Melkysalicylate t*f baryta h subjected to dry distilUtiou (p, 258').
Or salicylate of methyl is elovvly dropfied upon a very large excess of
finely pulverised anhydrous baryta, whereupon considerable rise of tem-
perature takes place ; the mixture is distilled ; and the oil which pasaes
over, is repeatedly washed with water containing potash, then dried over
chloride of calcium and rectified* — 3* Anisic acid is distillod with
exceaei of baryta ;

PropmiitB. Colonrlees, transparent, very tliin liquid having an
agreeable axomatio ta«to. Sp. gn 0*991 at 15^ Boik at 152*,

14 C
8H
20 ,

d4
s

16

77t7

7-40

14-83

Cahonrfl,
, 77 bB

. 14-83

0*li^OK. 1118

Isomeric with benxjlic alcobol.

100*00 100*00

^M liomet

^» Decmnptmtiom. 1, Anisol is rapidly attacked by fuming nUric actcT,
and if the liquid be well cooled, nitranjsol is produced, but by boiling
for a little while, binitranisol is obtained. Treated with nitrosulphurio
add, it yields ternitrauiso!, (Cahours, Laurent.) Cbrysanisic acid is also
frequently obtained. (Cahours.) — 2. With hrominff anisol forms two
crystalline products, bromaniaol, C^*BrH'^0*, and bibromanisol, the former
of which is difficult to purify. Chhrine acts in a similar manner.^ —
3, With oil of vitriol^ anisol yrelds sulphanisolic acid. In fuming sul*
phuiio acid it dissolves with evolution of hcat| fotmli^^ ^ \ii\^\. ^»^

^

-2f2 TOULUkX:

mhiikm, from vkk^ wter t&iws

alffR, tl»e prodacU ftcsed an
Aaiiol k iMi mkeied br ~
It if iBMlnUe ia vatcr, bat

Cinms. (1S44.) if. Jm. CftoL Pif^ li^ «M; IT^iM; ii

Fkarwi. Ti, 31; J. /v^. Chem. 49, 280.

/'omolM. B J tlie actioii of aahjJnw

Freparaiicn. WhfB Tspoor of anhjJmi
•▼erMiBol wbieh is kepi eo(4, aad tbe
vatcr, nukered aaiiol Kpantoi avt^
aalpluiaiiolie acid diMolTei. Tbe i
eolleefted on a filter, washed, dried, aad diwulrrf
aolntion left to en^ionto.

Prcpertin, Delieato needki loivnig ft mltfmj
caiefnll J lieated aad edidifiet ai a MsW

14 C 84 „- €*-43

7 H 7—5-03 VW

S 16 ... 11 51

4 O 32 .... 23-C3

C"H'SO* 139 ._ 100-00

The compooDd dissolves id oil uf Titriol, forming anlphaniaolic add.

It is insolnble in water, hot disBolTas leadilj in nltokd and db|
separatigg therefrom in prisms as the solution eraporate^

Stilphiniiolic acid is soluble in water and crjatalliaes in 9e6dka-|-
Its salts are aUo soluble in water. The baiyta-ealt dystallisM ii
white scales having a strong lnstre» and has when diy, tlia <
C'*HH)',BaO,2SO'. (Cahours.)

Bromanisol.
C"BrH-0» = C»H»0,C^rHH).

CAiToims. (1844.) X.Ann. Chim. Phys. 10, 85G ; 14, 4M.~i
Fharm. 52, 330.

Anhoh monobrome^ Bromcarlotf or metier.

Formed by treating anisol with bromine, bnt eannot hj Ilu8
be obtained sufliciently pure. Passes over in the form of an oL ^
bromanii^tc of potash is distilled by itself or when hramaalrio tnl ■
iistilled with baryta.

KITRAfTTSOL*

2fla

U C _. 84

?H_„ .,. 7

Br. BO

2 0 16

c»*H7Bfm m

Cahoiirt.

4673 49-16

3 65 ., 3*69

39-59 ,. 39"15

e^l3 .,.,.„. 8^00

100-00 100*00

BibromanisoL

C**Br*H«0» == C»H»0,Ci*BrSH*0,

.CAHOtTBg, (1844.) JV: J?in, Ckim. Phy$. 10, 350^ v4?ifK Fkarm.
52, 330.

Anuole hibrom^^ Bibr&mcfirbolformetter,

Producedj fiimultaneoiael^ wHli bromanfsol, by the action of bromine
upon auisol, and crystal 1 tees on cooling from jte eohition in boiljn_g
alcohol in cryetalUne laminnc having a strong lustre. Melte at 54^
YdntiHees witbont reeicltie^ and la deposited on tho colder part of the
retort in well defined tables having a strong Instret

14 C 64

6 H „.. 6

2 Bf 160

2 O 16

Ci*Br^MW .... aOG

Cahomn.

ai-58 31-73

2*26 .,. 2'34

60 15 ...»,, 59*93
6*01 6*00

lOO-OO ^ lOO-OO

Nitranisal.

ICAHOURfl. (184a) Compt. rend. 28, 381,-3^. Ann. Chim. Ph^s.
27, 441 ; Anil. PfmnfK 74, 299; J, j>t\ Ch^m. 49, 263; Pharm.
Centr, 1840, 308,

AniiuU men&tti7riffMf| NUrQCBrHlformUitr.

Farvwtwn and ^^rparatton. When fnming aitrle acM la gradually
added to aniBol well and conetantlj cooled^ a thick, oi!y, blaok-bluo liquid
h produced; and on repeatedly wai^bing this liquid with alkaline water,
then tlebydratlng it with chloride of calcium and distilling, unaltered
mnisol p:tf0c^ ever at first, ai)d the receiver mw^t be changed as soon as
the boiling point reaches 2C0\

262^ and 204^
almonds,

Ainber*colonred oil, heavier than water. Boila between
Ha£ an aromatic odour somewhat like that of bitter

TOLUENE : OXTGEH-NUCLIUS C^tt'O*,

Cnhoura.

14 C ..........„„., 84 _ 54-91 5519

N 14 _. 9 15 .»»..* 9-29

7H r ,... 4*57 t.p»« 4-§4

6 O 48 ..,. 31'S7 ., 30-68

C**NH^O« ....... 153 »» lOO'OO *...„^ 100 OG

Hoftted witli fuming nitric acid, it la converted, first into biDilmiiK
and afterwards into ternitranisoL — It is quickly decomposed Ljalcoholi
hydros ulpLtite of ammouia, aulpbur Imng separated and antsidia
prod need ;

It ia not decomposed by alcoholic potasHj oren at high temperatures^

Dj^olve^ in oil of vitriol and is £epara.ted therefrom ta its oriftiny
fctate by water.

BinitranisoU

Cahoprs, (1844.) N, Ann, Chim. Ph^i. 10, 356. — Omfi,

27, 486; uV. Ann, Chim. Phys. 25, 21; J. pr, CAent. 4a, 3S8; Am
Pftarm. QO, 236. — Jf, Amu Ckim. Ph^B. 27, 441; Ann. Pharm.
74, 29J>; /. pn Chem. 49, 203; Pharm. Cf7dr. IBU, 43C i 1645,
165,308,

Anisoie Ifiniirifue^ BiniirocarbQlformeitier^

Formation. 1, By boiling an i sol for a abort time with fuming nitlil
acid»^ — 2. By boiling aaiaio acid for a longer time with f timing ~"'"^
acid :

C«H<0« + 2N0* - C^N^H'^O'" + 2C0= + 2HO.

Preparation. 1, When anisol b boiled for a few m inn tea witk
fuming nitric acid, and the liquid mixed with water, a heavy bil aepaimtai
out, wbicli solidifies in a buttery mass, forming with boiling alcoh^ ft
splendid cbrome-green solution, whicli, when perfectly coU, yields coIoiip*
le?s needles, — 2. When a solution of auiaic acid in nitroeulphurie arid t*
boiled for an hour, carbonic acid is evolved, and a mixture of picric leid
and binitranisol is obtained [^y predpit*tJoii with water? Gm-]^ mm whk^
the picric acid may he extracted by potash*

Pr<^eHies. Long pale yellow needles. Melt« at SS"* or $^\ wtd
Bublimes at a higher temperature in slender needles*

Calxoyrs.

14 C 84 ..., 4255 42-26 ,_ 42-10

2N p.... 28 .... 1414 1421 ,... 14*24

%n .....,„ 6 ..., 302 3-16 .M. a-nt

10 O ,...„. 80 ..,, 40 49 40 S7 ..,. U^h€

I"* * O*N^H«0^7,...„. 198 .... lOO-OO lOO^OO .... lOO'OO

' wii pref^aned from taWMi h froin wftms ik^4.

TEaNITRANISOL.

265

I

It is decomposed by strong potasUj bat only after continued boiling.
By alcobolic potash it in Quickly resolved into binitrocarbolio acid

aud wood-epirit.

With UydroauTphate of ammonia it yields nitranisidine.

It is insolnble in water, but dissofvoa in boiiing akoholt forming ^

eolution of a splendid chrome-green colour*

TernitranisoL

Cahourb. (1848.) CompL rend. 27, 488. — J^T, Ann. Ohim, J^hyi,
25,23, Ann. Fhavm, 69,238; /. pr. Chtm. 40, 336.— ^Y, Ann,
Vhim. Fhj9. 27, 441; Ann. Ffmrm. 74, 299; J. pr. Cltem, 40, 2G3i j
Fltann, Centr, 1849, 165, SOS.

h

Formation and Freparalion, 1. By treating anbol with fuming '
nitrosulphuric acid, — 2. When the colourless solution of 1 pt. ofant&io
acid in 15 pts. of a mixture of equal pts, of fuming nitric acid and
fuming oil of vitriol, is gently heated till it becomes turbid^ two layers
are formed, ono of which is oily and solidifies on cooling. The acid
Uaiiid diluted with a large quantity of water, immediately yields a heavy
oil which on cooling aolitlifies in a pale yellow mass* This mass is freed
from all acids by boiling, then dissolved in a mixture of ether and alcohol,
and the solution is left to evjiporate*

14 C

.... 84

.... 34-56 ...
M,, 17'2S ...
.... 2-05 ...
.... 4611 ..,

Cahoiirs*
..... 34-43

3 N „

5 H

.„, 5
... 112

17*29

2*29

14 0

,,... ib*9B

Ci*Nm*0**

.... 2G3

.... lOO'OO ...

..... lOO'OO

Frf^periies. Tabular crystals having ft very pale yellow colour and
strong lustre. From a solution in anhydrous ether, the compound crys-
tallises by very slow evaporation in rhomboidal tables having a scarcely
perceptible yellow colour. It melts between 58" and (JO"", When gnv

I dually heated, it sublimes undecomposed.
Deeomposii ions, Th e com pound i e no t al tered by bo i 1 ing w i th aqueo as
ammonia or dilute potash-ley. When boiled with moderately strong
potash- ley, it yields pier ate of potash and wood -spirit. When it is
treated with hydro sulphate of ammonia, sulphur is separated and blnl-*

t Irani si dine produced.
It does not dissolve in water, even at the boiling heat. It dissolves
without decomposition in oil of vitriol and hot nitrio acid.
It dissolves pretty readily in akohoi, whence it separates for th^
most part on cooling, more readily in a mixture of equal parts of alcohol
and ether, easily in eihtr.

— jr. Ann. €lUm
- 4^, 265.— J

•C ««ier, mi mtmi

SB

14 . 11-3

r^i*

m -. i<

m mti wkieli cmflaliki a
ojiiiBMyA «lla with ^^Mt$d

Mitmimdiiie.

CaO«nfi& (U^) €V»9rf. reii^ tS, :m.—N, Ann. Ckim. P^
tr, 445; Amu Plttrm 74, 301 1 /. ^. CAm, 49, S$6.— /lUi^

Prvpamf /(Ml. An alcoholic solution of Si-h^dros^lphate of i
^ded to an aleoWie sf^lotten of biDitraBi^ol; the ]i<{iitd pi-ajiomicd M ri^
AktfftI ftt a i-entlc beat, tben supersatarated with hjrifoclili ^ " Jp!

« Jjoiitufj point, filtered from the separated sulplitir» u..
mi of omiJioiua ; the r^Jish crystal line precipiiaee ib w^iihcd 9\^
dri«d, «iid dbedTed in koUing alcobol; and the aolitli^Ni '-^ ^

li WAiilPli will J

NITRAKTSrDIKl,

14 C

2 N ....™_.
8 H „.

... U .
.., 29 .
... § .
... iS .

.. 50-09 .-

., 16^67 ..

4-67 ..

.. ZH-h7 ..

C&boun.

... 49*99
..... I6'5fi
..... 4-85

6 O

... 28-60

Ci<Km«0«

... 168 .

.. 100-00 .

100*00

^1 PropeHxtn. Garnet- red needles having a strong liietr©. Melts when
^■leat«d and crystallises on cooling in n, mass eoni^iating of needles arranged
I in mdiated gronps. When csrefullj lieated above ibe melting point, it
1^ forms vapours which condeDse in jelJow needles.

^V Bromine acts violently on Bitranistdine, forming a rednoua

Twblch dues not exli (bit b:isic properties. — ^ With slightly beatod fuming
nitric acid, it evolves a largo quantity of red vapours, aud forms a
fummy mass insoluble ia acids and turning brown-red in contact with
Ikalics.

Nitraniaidin© is not altered by cliloride of benzoyl at ordinary
temperatures; but on ^raduully heating the mass^ a violent action takes
-plucej hydrochloric acid being evolved and ben zonitranisidide produced;

It 18 insoluble in eold water, hut diasolvea in bot tmttr bo abundantly
bat the solution solidifies on coolings

The i/dlu of nitranisidint are colourless when pure.

Bulplate of Nitranmdlnt, — When nitranieidine is dissolved in gently
beated oil of vitriol diluted with a treble quantity of water (the aolutioD of
lie crude baMsU black -bruwu, thai of tb« purified baae nearly colourless), thesoluttonj
^after evaporation over the watet-bath, yields on cooling a dark-brown
crystalline mae^^ which becomes nearly colourless when pressed between
pajier. It is recrystalliBed in vacno. — Blender, colourlessi silky needlea
united in radiated groups.

It dissolves readily in water^ especially if acidulated with sulphtuio
acid«

J4 C ......

2 N

0 H ,*......

....^. ,.«... J

. 84
. 28
. 9
. fii
. 40

.„ 1290 .
.... 4*14 ...

... urn

.,.. 1845

Calioiiit^

„... 38-77

12-63

4*26

7 a ..„,„.

so* ....

cl^^^*H«o*

,SO^H ,.

. 217

.... 100 00

Ili/drobrcmate of Nitmnmdine. — Obtained bj?' dissolving nitranisi*
diijo m the boiling aqueous acid. After purification it forms eolourlesa
needlea =C'*:S^H*OSHBn

Ilr^ilroclilornte of Nilranmdtnt, —The foludon of nitmnisidine in
bmlii^g hydrochloric acid yields on cooriuj^ brownish needles, which
lieconie colourks^ when pressed between p^iper and several times recrys-
talllacd. They dissolve with great facility in bolliug w^tat*

268 TOLUBNB ;. OXTGEf-MUCUUS CT^HKF.

14 C 84-0 ^ 41-07 40-89

2 N 28^ ... 13-69 13*56

9 H 9-0 _ 4-40 4-47

6 0 48-0 _ 23-48 23-52

a 35 5 _ 17-36 _ 17-56

C"X2H*0».CIH... 204-5 ... lOOHW 100-00

Xitrit^ of SitramisiJine, — Wben nitric acid of sp. gr. 1*36 dilated
with mn eqiul bulk of watery is satnimted wbile hoi with nitmiinduM^
the salt cnrstailises oat almost completelj on cooling in hiown needle^
which most be pressed between paper, diflsdred to sntnration in boOnf
water containing a few drops of nitric add, and the aolntion slowly
eraporated. — Large needles eanlj oolnble in hot wmler^ noarljiow-
laUe in cold water.

14 C . -.
3X

9H ..

12 O

84

42

9

96

. ., 36-37 _
-- 18-19 _
_ 3-89 -
.- 41-55 _

_ 36-43
-.. 18-05
^ 2^2
.-.. 42-70

C-'X^HW^CH .

231

^ 100-00 ^

_ 100-00

^A/on.\^^^7.'ix.rf<^ «/ SiirrrmisidiMf. — Obtained hy mixiDg the hot coi-
centrated ^^lutions of bichloride of platinnm and hjdrochloiate d
nitranisidine. Crrsuliises on ccoling in brownish orango-colomd
needles.

Cahooa.

14 C ... -. S4-0

_ 22-45

-. 22-34

2 S . 23J-0

- 7-48

9H . 9-0

.. 2-41

2-61

6 O ... „ - _ 4S-0

-» 12-86

Pi - 9?T

_ 26-34

26-25

SCI - .--, 106-5

... 2S-46

C'*y^HXV.uCi.P:CI- _,. . 374^

— lOOHW

NiiranUidice disisolTes abundantly in boiling a/boM^ the greater par
crv^talluicf oat a^ain on cooling.

It di^re^ r^viilv in ^fif r, especiallj whoi waim^ and crystalliM
thexvfrv^m in lone oranc^veliow needles.

Binitranisidine.
r*N»H'0« = C-*AdX'HH)»,ff.

CAUorRS. .V. AfHi. C\iM. Fkp. 27, 453: Jmm, Fkarwu 74, 906.

^' — ' — -" -'

BEKZONITRANISIDIDB.

&e^

^

Proration. When ternitraniaol is digested nt a gentlo heat with
aleolmHc Iiydrosulpljatc of ammoTiia, tbo liquid assames a ldood*rcd atid
ftflerwarda a dark-browo colour, and finally solidifies. As soon us the action
erases, tlie liqiiiU ia heated to the boiling point, and evaporated to one-
third, then eupersatarated with dilute hydrochloric acid and Hltered boiling
Iiot. The clear brownish filtrate nentralif^ed with ammooia becomes turbid
and depodita dark red flukes, which are washed with water and dried in
vacuo or over the water-bath.

Pro/5€rn>^, Crysttdlises from solution in hot alcohol or ether in dark
violet needles. When precipitated by ammonia from the bydrochloratc,
it forms a crystal line powder^ some times red, sometimes violet , according

I to the concentration of the liquid. Melts at a gentle heat, and solidifies
pn cooljDg in a hlackiah violet radiated mass resembling cinuaban
Pumfng nitric acid decomposes it rapidly, forming an orange-yellow
remnona mass 'which dissolves with deep browu colour in potash.

It dissolves very sparingly in cold water, somewhat more readily in
B Wiling water, forming an orange-yellow solution.

^L Treated with excess of sulphuric, hydrochloric or nitric acid, it forma
^Herystalli^ble salts which arc decompoeed by water^ with separation of
^■Ibe base,

^f It dissolves sparingly in coldj better in boiling alcohol; sparingly m
WUiDg ether.

14 C „„

3N

.. 84 .
., 42 .
» 7 .
„ 80 .

.. 39M3 .,.

,. 19- n ..,

.. 3-28 .„
., 37'Sg ...

C ah own*
.,... 33'34
19M3

7 H , ,,..

335

10 O ....,„

37-B8

C»N3H^0»« ..

., 2)3 .

. 100-00 ...

.,.., 100-00

Benzonitranisidide,

CaUqvub. iV". Ann. Clm. Fh^s. 27, 45^; Autl Fkarm, 74^ 305; J.pr.
Chem. At), 271.

Formatmi (p, 2(57),

Prfpamtion- Nitratiisidlne Is gradually heated with chloride of
eneoyl^ and the mass which solidifies after the action ceases, is repeatedly
treated with water, hydrochloric acid and alkaline water, to remove
nitranisidine and benzoic acid, and dissolved to saturation in boiling
alcohol. j\s the solutioa cools, tlie compound crystallises out almost
completely*

Light brown needier, which melt at a gentle heat, and volatilise at a
liigher tempcraturer

^

TOUJRKg : OXTCEK^KtJCIJIUS C**HKF-

iiC

fN

UH

^ 1€8
— It

-« I'll

. 61S4

4 57

C^-WH3^

_»2

^ i«ai»

IM*iO

IniolaUe la water.

DiaiolTes io g^silS/ tieateJ otl of ritrkil^ brmlDg m d^irk red*1
■olvtiiHi*

Kearij uaok%le in eold slooktil, liai ilkKilfM abmntUnUj m bl

BiiiolT«i bal ^atiaglj ia Wtliag etberi aad aepataltt ai a erfHaOiii

FhenetoL

CAHOfTBd. Oiispt rmd, 28, SS0; J: pr. CAm, 47, il7.--J^. jfaa. £l»a.
Pky$. 27. 4$3; .lim. PA^zim 71. 314; J. pn C»fm 4i, tsa—
Cl^i^ rvntl. r^ 60; Amm. Pkwm. IB, 2Ui i^om. Ctni^. ltl»,

Baiit. €3«, &c, C«. J. t, 3S; iita. P*»m 70, 2^$; J, pt. Ckm

47, 419.

iodi^ of el&jl ia a teakd laW to Wfcweea 100* aad 120^, Of hy 4^^
ling c^rbolite of polaah witk anJ^lMiTiBata of potaaL (Qilioafa}*

J

hVlaallefkle of Wrta

hj itadf or ethjlaalkjlw

2. Bj ^

add Willi barfW MihjU^ilicjlie acid is added hw drops to aa^jrdm
barrla, as bug as anj acttoa takes pla«»; ike ffodact dbitlled; aad lli
distillate w^h^d with alkaltaa walir le ftmo/we oarMlic aeid, Ikeii i^
orer cbkiide of c»lciam, aad rectified.

Froperti^t. Transpareat^ coioarkat^ TSiy tkia eil» Ugktar tWa
Boik ai 172' (Caboetej, U 175^ (B^j) Hae aa i«?B«aUe ar
odetir.

aronutW

U C .

lea

so

94 ^ 71-48
le _ $li
IS -.. IS-U

IS u ». i»-aii

Dmmpmiiomi, 1. Fbeaetol b viQleiitlj ftttackid b^ &f^Mi&Ml '
erolaiioa «f li;fdrockl0rie mtld and f<irmatioa of aa oH, wbick^ after a

Tbk sulwluice majbe oTTitaBiifediav
lofaaamberol ' '" * * ^

daji^iobdifiea in a erjitallijie
tm jotalioo and k f<&aad to

BUfTTROPffENlfoKT

271

honr^t Baly.) Similarly with chlorme. — 2. It dissolves in fuming
nitrk ueid^ formiDg a iiquid of a beauliful yiolet colour, wliidi is destroyed
by heating, biuitrophenetal being then produced. (Biily,) It is violently
attacked by fuming nitrto acid; with an equal Tolumo of the cold fuming
aeid, it forma a reddish liquid from wLich water throws down an oil,
probably cooiisting of nitrophonetol, but not oachibiting a constant boiling
poiut; when the liquid is boiled with a larger quantity of acid, binitro-
pbenetol h produced. (Cahours.)^ — 3, Phenetol is not decomposed by
boiling with potash-ley,

Phenetol dissolves pretty readily in water.

It dissolves in oil of vitriol, forming a conjugated acid which forma a
crystallisable salt with baryta.

Mixes readily with akoM and elh€r.

Bi&itrophenetoL

CABOUKa N. Ann. CIdni. Ph^s, 27, 405; Ann* Phatm. 74, 315; J. pr.
Ckem. 49, 284.

^^ALr. CAetTt. Soc. Qii, J, 2j 28; Amu Pharm 70, 26^; J. pr, CJitm*
■ 47|419.

BmiirophdniitAQl, Biniiroaa lit ho! ^ Biniiro ear&otvme*ter.

Phenetol is gradually ii]ix:ed wltb an equal volume of fuming nitriq
acid and heated for a while to the boiling point, whereupou the d«^rk
brown liquid gradually becomes lighter, and on addition of water
fields a yellow oil which sooe becomes buttery and at length solidifies
completely. The solid mass is repeatedly washed with water, pressed
between paper, dissolved in boiling alcohol, and the solution left to cool.
(Cab ours, Baly,)

Yellow needles very much like binitrauisol When cautiously heated
in small quantities^ it sublimes without decomposition, (Cahours, Baly.)

Calioari.

Baly.

16 0

... 96

... 45-28 ..

44-71 ....

43^40

IN

.... 28

.,.. 13'2l .

* 13^03

BK ,.„

.,., 8

..,. S77 .,

.,... 4*I1S ....

3*77

10 o ,

.... 80

.... 3?-74 .,

..... 38-23

C"NH*0« ..„

.... 212

... lOO-OO .

...... 100-00

The compound appears to contain an admixture of temitroplLonetol.
'y.) It appears to be converted into ternitrophenetol by boiling
excess of fuming nitric acid*
7Uh hjdroauiphate of ammonia, it jielda nitropbenetidine*

272

TOl.UKKK : oxtaiK-^tjCLStrs

Nitmpliezidtidme,

CAttovuM. Loc. cU,

WKeo iulplmrcttcJ hydrogen nnJ nmmmiui are piusoJ iimulUiioaa
Uironi^ti an ulcoboUo eolutioa of bliiitrop!ioi)otp1/iul|iUtir ii •apatmM i
Ditrt^phf^nitMitio remains (ll«doU*e4 in llio olculioL

Crytiailm^ iu Iruwii needles feiembliug uilniubidiiiff,

16 C. H ..

2N.. .,.._ 28 ...

10 H. ..» 10 ..

. 52?i ....

, 9*11 ...
. 26 3i

..„ §2'€0

6 0........ 48 ,„

C«N»tt»0« i.. m ...

. 100*00

Fonns crptftllimblo m]U with lulphurlCp lijclroclilonc iind nitrie ttnJ.1
Ac!U vitifciitly on dilorido of benzoyl when lioiited wltb it, and foow

a body whicli ii$ very e[mrinHy solnblo in alcahot, and cry»Ullisei Ui€»-

from In small n@edlc« on cooling.

Phenamylol.
18M, lea^

Obtalntnl by boatini^ cnrbokto of potoab witb Iodide of aiBjrt I
between 100' and 120^ in a ioaled tube,

Trnn^Iiurent, colonrlets oil, boiling botwceti iSl"^ and t25^, and liaTiif
an ngrooablo aromatic odour.

It h vbUatly attacked b^ nUrio acid find conrertod Into a lieaty J
which fitrms a eryataIUi<ablo bas^ with bydronulpUato uf ammi^nia.

It ^liasolves iJi oil of vitriol, ronning a red solution wbicb i^ not i^rt-
cipitatcd by water^ and forms a cfyst#Ui4»ble «alt with mMhomm d
barytAi

Ampclic Acid.

T» (1837.) CnmpL r^mi. 4, DIL— inn, C*Aiai. Ph^ JlJ
. icifJiL 0, TO; J\ tu\ Chcm. 11,418; Fh^rm. Cemr. 1837, f

Formntlmu By tbo action of nitric acid on tbo poHimi af i
which boiU botweca 80 and lOO^, or on the portion of coal^oil wUfklik
hetwcm 130 and 1G0\

OXrU^ZOW ACID.

27i

Prepfimtim. When tlirit portion cif roaloil wliicli loiU belwe^n
ISO"" aui) H;0' in 1i<?)itLHl wild fttmmf^trml nitric aeiiJ» !*lr*^(i^'^ efltirveaeLnjce
iakcH [jlaerj; arnJ if the aiMUion uf tiitritr iiciU W fuiiLimioil :ih Irmg a«
roil vajKMir** ti8capi% a hlightly oaloured «ulati<iij h (jbUiueJ together wjtli
«. ytrlliivfiaFi oil (tbe ^rejirtcr part of ihln oil it however curried forward
nth the vapour/*). The Mulutioii when evaporated p de[io»iti* cry^talii of
■icrio acid, aud yellijw flakes which are partially separated Uy one or two
rystalliflatioriM. Tho tnother-liqoor h neutraliflcil with amnion ia (potaab
would pcrhap.»j bo prefemhie) ; the solution evnporatcd u^arly to dryneas;
mud the residue treated with alcohol, whtuh dissolve*! the atnpelate,
lemrmg the greater part of tho picrate undlfliwdved. On cvaponUing the
foltttton, diifetting the roni^lue in eotd alcohol, a^^ain evaporatii^iTi dis^olv-
\g the residue in water, anil adding hydroehluricacidj a white floociileut
dpitato of ampelie ncifl 14 produced, while trarc^ of picric aoid
II n diMolred. The preeipitat^ ii washed itnd dried.

rropeitUi, White. Beparatea from »ulutIoii lu hot alcohol or ithefj
the form of a powiler wliich h:ifl scarcely aay cryitallino character;
'Odoroiu^ Molts lelow 20i}\ and distils undocompoied* — Roddens
itmof.

r

14 C ......

ell

eo .......

.... S4 .
0 .

in ,

.. S4'?8 ...

.... 4%l
35*6

0*^H*0« ...

133 .

... 100 (MJ ..

.. 100-0

Insoluble in cold, apanngl^ soluUo lu boiling tmUt\
jyifimlvm in wann oU 0/ vttriol, and U precipit:ited therefrom without
Ulteration by water.

I The amnion ifi-nalt prccipitiitoH the saltn of haryta, atroatia and niag-
uetia ; with rhlorido of caleiuni, it forms at ordinary temperatures a
wliito precipitate, wliieh U not produt?ed at hfgh«*r teUiperLilnfea ; on
cooling howiivor tho mixturo denosiu ery«tiils* With act tato of nickel
n greoninh preeipitjtta k formetj; with a^^orate of lead^ a white; with
lUpric ae«tate^ a L^reeni^h blue, and with nitriito of Rilver a white precipi-
le, 100 pts, of tho iilvor salt contain 4 40 pta. of wiivcn
The acid dissolves pretty readily in almhol and ether*

Oxybenzoic Acid.

}Ritr.4Kf]. (l«.53,) Ann. Phnnn. 80, 143; J)l, 18f>; Pharttu Cmtr.
lO.H, 829.

Formfttion, (p* 144).

Prepamtmi. NitroitJi acid Im pussed into a hot aqueoui Molatioti of
' 'oben^oie acid (p. 1 43) aA long aM bnbhlcN of nitrogen continue to eieape; ,
oling, osy ben 7.01 c a<^id cry.<itaLliM;!« out and may be purified by boiling i
ritb water and animal diareoal

Properim, Sepii rates from the hot aqneons or alcoholic solution in
%\ie form of a eolourleuw or yellowish cry stn (line powder, M«Ua ■siA. %

TOL, XII. t

L

^^ TOUTESLz OXTGCCKCCUra C^B^tK.

i':pae 'lan^ff-TLSE?* cbl £s3i vhkMt alteimtm; rohtiluKf eren wlien
liif iiuuKim hicczjic iff l*>3eil paMi^ orer vilb tke wstoty rapoiiiB,
Ti.irL o^nis: n :a 9-^I-k' oA^eete ia McdiM iMTug m stioiig lutro.—
I^iiusis liacss scn&f^r. Docs w4 coloar faiie Mlto.

Gcriand.

:«C 54 — €M7 M-99

i K € — 4-35 4-56

CO 4g — U's$ S4-4S

C -E -y US ^ IM-M ido-eo

Jt^rmrp^mTriiiTir^ 1. Wbm nddnlj bcated, it yields hjdfmte of
Tii^<? V! £11 s^.t:ji5e afii: swl tlits d«eompotiti<ni takes place eomplelei?
-1 j'fLiJir ili- ecnpDcrd vitk ezms of fajdrate of lime. — 2. Witt
z^jz l.:. .1 :z Fz>. it. l'^- it gires off nitrons acid eren at or^saiy
. %3}L ixms aitroxTbeBSMe acid.

C:mi:'ih:t'ir%^ Tke ^A dtsolres tifunnglj io eold, abondaatlj ii

I; «TT«;-'^ rtirrrcjc rci ^om its compoonds, and ueatfmlisM tke
bl 'fs. Tl-e iTktr-ge cxjbeantttcs are easilj solable and difficslt to
rfcxllifi!: ilie cxT^enxiL-alei of the alkaline earths are less soloble aid
rfciJ-ise ix sNHiT^iw Thciae of tlie hcafj metallic oxides are insolsUi

1 ■■^-ylr'ZZ'" '

■ ' h colourless.

Qcrland.

r-.O 111*3 _ 4C3« 46-99

C -H*0*. - 129-0 .... 53-62

C H»Fi<y.- 240-S ... 100-00
T': e i:!I I:si.:!T« fiaricgly in colJ, readily in hot alfnj^oi.

Sulphosalicol. C"H«0',S«.

OA!TorF>. (Vrr:s*. Tfr,^. 23, 458.

\\ lev: -:: r.\vl.c!ic s.-'lKiioa of salicylliriiMc is Ritaratcd with f*I}»li»-
ro::«^I ^\^!r^^:on. .i wV.ie nowtlor fepamtcs which may lie washed witfc
;.lv\ ?;, 1. - C\ Jours ferric «ilts violet. Dissolves in alkalis.

BOLPITOSAMCTLTC

275

I

ABOURS,

O. MENDirs.

f . Sulpliosalicylic Acid.

JV. Ann. Chim, Phi/^. 13, 93,

Ann. Fhamu 103, 39.

IHteovered bj Cthoorei more particulirlj eiamined by Mendius.

Format imi. By the tLC ti Qti o f Etnby dro ua a ii 1 pb uric tw id on m\ icy I ic acid*

Frepamiion. Perfectly dry aalJoylic acid U escposed to tlie vapour of
anhydrous sulphuric acid in n. capaoioua flaakj cooled externally by water
to prevent oxceesivo rise of Icmporature, The cryitalii then become
covered ipitli a yellowish, transparent^ viscid film, and by degrees tbo
gfeater part of tbe acid is converted into a brownish gnmniy umai wbich
envelopes tlio etill unaltered crystals and protects them, to a grent extent,
from further action, so that, to render the tmns formation complete, a very
large excess of anhydrous sulphuric acid is required. It is best ihore/ora
to stop tbe process when the action becomes very slow^ dissolve out 1I10
eaJphogal icy lie acid by a araall quantity of water, leave the liquid to coo),
ia that the remaining &ah'cy]ic acid may be rendered nearly insoluble,
Baturate tbe filtrate with carbonate of baryta, with tbe aid of beat, and
filter while sttU Lot to eepamte sulphate of baryta, Tbe solution on
cooling deposits tlie greater part of the eulphosaiicylate of baryta in
crystals, the remainder of which may be obtained from the mother-liquor
by repeated evaporation and crystalliiation, and the crystals nmy bo
further purified by recrystal ligation from hot water* — From the baryta-
salt the free acid may ho obtained by treating the solution, either with
the exact quantity of sulphuric acid required to precipitate the
baryta, — or by adding a slii^ht excess of sulphuric acid, afterwards
removing it by digestion with carbonate of leadj and precipitating the
dissolved lead with sulphuretted hydrogen, — Or, again 1 tho crude eolu-
tion of snlphosalicylio acid and sulphuric acid may be treated at once
with carbonate of lead^ and tbe lead precipitated by sulphuretted hydro-
geti, — The solution of sulphosalicylic acid obtained by either of theio
methods may he evaporated without decomposition, even over the open fire;
hut to obtain distinct crystals, the concentrated solution must be left to
evaporate over oil of vitriol; and to free the crystals from the red mother-
liqnor which adheres to them, they must be placed on a filter and left to
Atandover absolute alcohol, the %*apour of which condenses on the crystals
snd carrier the mother-liquor through the filter. (Mendius,)

Pmperiks. Long, thiuj silky needles radiatini^ with great regularity
from a centre; under the microscope, they present the apjjearance of
irregolaj sir-sided prisms, but without well-defined terminal faces*
Melta at ISO"", without decomposition and forms a radiated mass on cooling*
Mendius.)

D^tompQMiiom, L Tlie acid heated above 120"* turns brown and
decomposes, yielding hydrate of phenyl and a crystalline sublimate of
talicylic acid [and givitj^ off csirbanic aflid. ?]. — 2. \iU not decomposed by
heating with nitric or hydrocliloric acid; but wlicn it i^^ boiled with a
mixture of the two, the liquid becomes red and uii¥\A ai\^\ ^V^q&\\j& ^ts

rvf

9f*n m. -rSia^

$. - r»5*v* »'r# '«'*r7 s.-«rii:r"7 it fcioAii ssi ctWr, Tlw crrsuU sire

. li tta _ s-n

23-34

. k"^0 - *M ^«*'^*

^ . ' c i. ... .'.««*.. — 01«wn« Vt MizrJiaBs tW free acid wA

BUIPHOSALICYLIC ACID.

277

large 6]iliei-ical gton|>Sj conaisting for the iiio^t part of very slender needles,
I Tbe crystiila when collected form u vcjy liglit inuss Imving a *ftfoiJg silky
lustre. The crystaU give ofl' 12"14 p, c. la tlie raoi^t atate tliey eiuiily
turn red in contact w'aU tlio air< They Jidsolve very readily iu watei*
but are insoluble in alcoLuK

CitjMiQiiUeiL
0mt.^.QM_ 2170 ,

K ...._.„.. , Z%% .

„ H-21
». 13^1 »

... 12-32 .

*.... 13-43

4 HO 36'0

♦ ♦ 12'U

CWH^KS^O*^ + 4Aq . 292*2 .

.. 1 00-00

5''P*g'«t^^/^»^ Crystallises from a mixtnre <if the neiitriil suit with a
quantity of the free acid .-ginjiller than that already contiiiuerl iu it, in
yety llilu, lights ra^diiiting crystiila having :i strong silky luatre. They
live off from 3-3 to 3^4 p. a (2 At. water) at 200",

Ciyttailitt^,

Mcndiui.

168^0 ,.

.. 29-52

9Q ..

!*a8

117*6 „

.. 20 O ,„.

... 2055

64 0 ..

.. 1124 _

... lb 6

192-0 ..

.. 33*69

190 ..

. 3*34 ....

... 3- 3

20*64

3' 4

C'ni^K'S'0'-,C^nMCS"0** + 2Aq ..„ 5fi9'6 ,... 10000

Sulp/tmailc^Iaie of Sotltt. — rt, XfutraL — Prepared like the jjola^li-
Bait* Bmail, well defined^ transparent and colourless erystak, having a
strong glassy luatre, and the form of irregular six-sided prisms, some times
tvitU one oblique tennina! face, sometimeii with two, eet at ditftircut angles.
They are permanent in the air at ordinary tempemtures: give off from
IG to IT |i. c. water (C At.) at 200*^; and when heated on platinum-foil,
take fire and leave a carbonaceons re&idue. The salt is very soluble in
water uml fornt:i a neutral solution; it in insoluble m alcuhol and in
ether, both of which liquids precipitate it after a while from the aqueous
fiul utlon in erystalliue flakea*

^ Ci*HiSJOJ^ ...* ..,».... 216*0 ..,. 68-35

14 C

4 H „...
2 N*„„.

%n

12 o

Ai 200'-
.... 840
.... 4 0

46-4

32^0

sa'O

Meadiui.

3200 .. 32-13

1-33 * 1*93

17-50 ..,....* 17*59

12'21 „. 12'C0

36-64 3575

C'*H*NVS?0'i' „-. ZC2M

100^00 100*00

Mondiuft

2 N*

6 no

... 46*4 .
.. 54*0 .

... 11*56 ....
... 17-09 ...

> li*S9
.... 1599 .,

*
.. 17 05 ...

. ,.. ^

... 31G"1 ,

... 19000

M

iSn-'THCUZS C*SX>.

T«rr lifkiy tliifl
=x Vft Air. Gire

IT ^r Zicilj juixikiJB a va;£r, sfana^j

-.1 -.- f:*l _ f;2

^ -.:-iii-s«: T- :i ii* :ii-- e .- -:. iriin. l xs-r cccctiliatcd but

:.— : r-^L*l_-rrr : .1::^ n suul rv:*uarxJLr }»3i£ bevelled

-T- *. =il- =--1::-^^^ i*-*=-. :;i.L i.; ^ air * S2-.«sr s-Sjiwuv. Soluble

:: Z¥ .... II :5

^ ^.- ...f-T^--:. ;;z-> .' :r-^?u^. l1 .if viidi Lft^e loirevcr tie

«.:-.- ■:•-:: . >.- ?^-':- s'.'j^ Ti!»-:'iLia. *>a«r rriie-i :n concec-
■' :- ■" ." . - — ^•^. >:-.. - : r-^i-^ r. j^rrirriri-lie .irfbraTi-iike
:■:•>. " . - TT"^ ..,. ;>— . : m '.c -.M irs ciT' :€ crysnie fn>m iLe
: . -• -- < . :. — •. >i-j.. i.LTL r7«ril* n/z-iilj ia cr-cctniiic

: ■ : •- :* :.i'i^ -:•: r :-:« ::L-r^^.-i>» kri3L:xis<»i witili Kcirftcn. fct
. 1 •»*. '.: . ..-^ :- : .:•: :-• -iiin-^ zi-rts ic u. zi^'^z^ |ri*in. Tbese

.» : ~'»^r<^ ^r« « ;:-: i: '^ i*r^ da^v^ri u ^u m i ~i" r fcttfa'.jwe c'lUOtiXTcl

. .:^ -u' >K •k'J*.^ *%iL:=ir iB£S. 1 r.a&KU'.^-uus tVEZiTZT ctf :^ i^Ic w ivu-l'.ftl

.^ ^ -^vj ■.- ;.. ; v- . .^'^^ hi%i. -i: ^xi3Ki-r: jl i JiSTer ^u-tstr of mac-.r i«*

•":><..-:-: -v. Lie -u-.^-t zie uci r7>ieu j-ut * sMnciooe^ -

> .4. s . - ..: ^ >i : ^ L ;- T ;.:i zji Jsr :>»• z3r»»icope appeared w

V ," : a<*i .. sK^ r i.-^iirrL-u^j jr-j-iTt*! r^wlle*- These were

:;jL ■ >- ^. :; :jf. 11 ^I'iC :; .^ i.T::r r^seAii*; en^onxion. All lb ;.•■-•

■ >. L T^ .^ ~u.X3«i»i i.i-.L. ..' :ur r^i'. : JL- '•"tisr, cf wliicL 3 At. Tri«

... >. i : . : :•.' r; -T :_ ; i • r > : t :-: :. I rO' itd f c«J . The sal:
. v.,i .1 .«-i: I — ■! Ti.TTVTifcrL-; "* ■. : .: ii*r:=ifc^s: ;:•:::. but wL-.a
. V > : , « : x ■- : ;...i> l:- ^ •-- .1 rrlriSe .:i j.:ioetI. 1:
^^ .> ^ ^ ■ - .- - :•;■*: -J : : ^t: -. ..; :?|^Tfcc;lv IL^^-Iulltf

■ i .\ . ;. .. « . . ■

=■■10

SULPH03ALICYLIC ACID,

in

C"H^S^Oi^.,„„.,^ 21G^0

2 Ba ,. _„_, 137-2

e HO _._.. „.,..„.... 54-0

Cryttaliiied,

tit

MendiuA,

p.

7-

J _ 6S-0S

! .... 3S*Cff .,.,

.... 30-6

.... 33-8 ...

33$

3 .... 13-20 ....

.... 13 1

... 12 9 ...

13*1

u

C"H*B^SSO*2 + 6Aii..,. 407-2 .... lOO'OO

Sulphcisalj(!7Hc acid de»es t)Ot nppemr to be capable ot taking up more than
S atom A of i\ basq. H<}t eoni^eiitrated a<>lutionR of tliti ptc ceding salt and diiualia
barjU mix«d togedier, did not ^teld any crystaJs oti cooling ^ and on adding: alooHol to ^
tUe dear soluiion left after all the csccsi of barjta bad been renaqved bj carbonuU by
cxpoflure to the air, a fine ligbt powder wm tlirown dawii| itOl cxbibidng the eompo-
sitiou of the bibaBie salt (Metidlui).

h. Acid* — Obtained by precipitating the baryta from a portion of
tlio salt a witli eiilpburlc acid^ and niixm;^ t!ic filtrate with an equal
portion of tlie same ealt. Crystallieea m well defined, oblique^ irrc^^ular
»ix-fiidcd prisms, p<jrfectly tmusparDnt, having a atroiig glassy luatre,
and permanent in the air< At 200^, tbcy give olF ll 17 p. e. (4 At.)
water* TLey dissolve readily in water^ but are insoluble in alcohol
or ctbsr.

CrtfifialiiHd,

C'*H'S20»^ ., 2170

Ba 68^6

4 HO 32'0

Meudtuif

67-50

21*31 , 21^32

1119 1M7

C'*H^BaS=0^5 + 4Aq ... :il7*6

ioo*oe

SulphoialicyhtQ of Lime. — Tlio liot aqueous tiolutitm of the ncid,
eatu rated with carbonate cf Itme^ jiclds very small, light, silky ncedleaj
united in hemispherical groiijis, Tticy give off €*43 p. c, (2 At.) 'ivatcr
ftt 200^, They are fioluble iu water^ but ins'dublo in filcohol and ether^
wLteh Indeed precipitate the salt from its aqueous solution.

2 Ca

2ie ..

40 ..

.. 7a*6i

.. 14 SO ..
. 657 ...

Mendla«,
..... 14'5l

2 HO

,. 13 .,

... 6-43

C»lPCa'S-W3 + 2Aq.... 274 .... lUO-OO

Sttlphosalicplfrtt ff Maf^nmtt. — Prepared like the lime-salt. Crys-
llisea iu rather long rectangular prism § irregularly crossing each othefj
they have hut little lustre, which tliey lose when expotjcd to tbo air.
At 200% they give off ]8'24p. e. (G At.) wat«r. The salt ia so very
eoluhle in water that it can bo crystallised only by evaporation of a
concentrated eolution over oil of vitriol; it is iusoluble iu akohoL Tfjo

fiolutiou forniAs with phofiphate of soda an ini mediate precipitate, l)Ut if
ammonia and sal-ammoniac be previously added, tho precipitate forma
only on loiliug, and partially rcdiseolvca on cooling.

Cr^niatiiited^ MonditiSi

CUH'S^Qi^, ,.. il3 .... 73*44

2Mg..., „„ 24 .... 8-16 «, lid

6 110 .** 54 .... 13"40 18'24

C'^H'Mg"S^^O'^ + 6A<j„.. 294 ... 10000

^^

la ... iM-i ...

— . 47-y

u s-i

. - 35 ii-r
Si . »*i -

_ 3S-3

:ft«

xft M pcecifiUtcd bj

c*s»:* == '^T^sv^.

4^0*i«.s»^cr

«7,l«i

K*

mdiyalicTlitei'

Itoilt

■ Tfiy

rater k

rr^^^

jks* «;ii*^ •># ^'^«^'»

>«t>.H •v^tt^ ^ »^^

JLPHOSALlCnATE OF ETMYt.

Su!ph{mtHct/hit€ fi/SUvei^ — Obtained hy acliJmg recently precipitatcHi
oxide of gilrer m excea^s to a Lot eolutioii of i^ulphoaalieylic ncid, whicli
quickly disaolvos it. Tlie hot concentrated solution Bolidifioa on cooling',
id to i\ stltt' jelly, whioli disappears after soni« timo, the ssalt falliiin; to
the bottom in the ii^vm of a heavy pow*lei\ eouiposctl of perfectly
rounded spherules, which when eriishcd^ exhibit uniler tho iiiicroscopo
|an appearaiico of crystaliisation. The salt gives off 3-iip. c- (2 At,}
water at 150'^, melts at a higher temperature, and decomposes with
etrong intumescence. It dissolves sparingly in cold, readily in hot
water, hut is in^oltihle in aleoliol The solution boiled for some time
deposits metallic silver.

^
^

2Ae.... 2ia .... 4% ill .... IB I

2 110 ....,......... IB ..., 4 ■■...■■. 3-9

c'Ui'Ag-s-o^*.,.;.. 45(1 .... lao

Stilphosalicylic add dissolves in all proiJor lions in alcuho! nml In dhrt'^
(Mendius.)

IT. Sulphosalicylate of EthyL

Mesdws, Ann. Fhann, lO0j G2,

Pz-rparaiion, Perfectly dry snlphosalieylate of silver is agitated
itli an eqnivalent quantity of iodide of ethyl, either in a sealed tuba
or ill an open Hask; and after the action, which la attended with moderate
cvoluti(m of heat, has extended throughout tho entire mas?, the product
j3 exhausted with ctlier and the ethereal sol nt ton left to evaporate at m
gentle hcatj any excess of iodide of ethyl then e-scapei* together with tho
etber^ and su!phosalicylate of ethyl remains in the form of crystaHiiiQ
crusts, which romain moist and gummy even after standing for e^ome
time; it may be purified by re crystal 11 sat ion from a small quantity of '
warm alcohol. The formation of this compound i^ represented hy the
equation :

cnrAg-^S^'O'^ + 2C'Hn - 2AgI + C»^H*CC"H*)^r<^«.

1 1 IS not produced by pacing 1i jdrochlortc actd gai into on alcoLolic lolutioii of ibe
ftcid.

PrftpeHUi*. Small, da^zlmg white, silky cry&tals^ which under the
'inicroseojie, look very much like the ordinary crystals of sulphate of
lime* They arc soft to the lou^cli and become soft and kneadablo like
wax J even by pressure between the finger^*. The compound melts with-
out decomposition at .jG\ and remainB aoft and pasty oven after cooling
considerably below that temperature. It melts unilcr water at the sama
tempertiture, and may bo di^tillctl over unaltered with the water. It is
perfectly neutnil, both to litmus and to ciirbouate of egda.

L^perleci

282

TOLUENE: OXYGBN-KUCLKUS C"U»0».

82 C .«...„..„».

„.,. 132

... 481 ..

.... 5^1 .,

...... 47-7

14 H ..,,.,.,

2S

12 0

u

32

9S

..... irs

35-3

Cs^Hsso^

...» 274

.... 100 0 ».

..... 100-0

WlieQ an dcoliolic Aolattozi of the eompound wm beated for two or thn
in a Aealtd tube with alcoholic ammoQis, audi the alcohol s^rwmnls distilled off, mt
tjrup remaioed, which was soluble in water, insoluble in tthtr, liad aa
odour atid neutral reaction,

SulpLosalicyUto of ethyl is insoluble in water, bnt ilm&lYm readily
in alcohol and in ttker; from tlio alcoholic eolution it is precijpiUted by

water; (Mendlus.) ^,

Anhydroiis Salicylic Acid,

Gehoahbt, 2f. Ann. Chlm, Php. 37j 022; Ann. Ptiarm, 87, IS^j^
*f. pr. Chem, 01, 300.

Salicylic Anhydride , S^lit^yUc SaUcyhte, Salicylate qfSaUcyL

Produced by the action of chloropliosphorio acid on diy mlicylat^ rf
Bodji. The action is alwajs attended with cTolutioa of hydrochloric aqidp ev«i«lMB
the Iwo bodJea B,Tt mixed in eqniralent proportiouK (1 AL ch]orophos|ihoric add td 4 AL
taljqrlati: of sodti)^ salkylide being formed at the Eunie time. The product if VOT
I lard and adherea closely to tho vessel, lut when heated with water. K
becomes Gi>ft and teaaeious and soLidiJies after €ome time only. Bollis^
alcohol extracts anhydroua jsalicyHc acid from it, and tho oolulton o&
cooling yields a thick ail which solidtfies after some time. Th© aolation
in boiling ether yields the acid on cooling, iu the form of a flexiMfs i
With boiling Tvater it yields salicylic acid; with alkalig, a ailicylatc,

I

Acetic Salicylate-

^

Chloride
turea on

ing after a short time. The product
cnrbonate of soda^ fi otbe up and yields ^ieylat^ tmd itcetalo of <
h(Qerhardt.)

ride of acetyl (C*H'0*C1), aett violently at ordiiiftiy teupn*

salicylate of soda, the mixture first becoming llc^aifl \mi •Nidify-

r a short time. The product treated with » dilute ^olalioa •f

lODOSALICYLOUS ACID.

283

Benzoic Salicylate.
C*H"0» = C'*H»OSC'»H*0'.

Benzosaiiciflic Anh^drkhi Anhydrous Benio-^aUcyHc acid.

Produced by the actbn of chlorida of benzoyl on ealicjlat© of soda.
Flexible mass diffioult to purify, Boiliug water cooverta it into

Lydrated benzoic and salicylic acids. When heated, it yields benzoatc of

pheayl and bodies soluble in potash. (Gerbardt.)

SaUcyUde, C^*H*OV

[G^RtiAnDT & SocoLOFP. (IS52,) N, Ann. Ohm. Fhy$. 07, 323;
Ann, Fhuntu 87, 150; J\ pr. Chan. 61, 300.

Produced by the action of chlorophofi|>horic acid on aallcylate of soda,
and coDtaiDed in the residue wtiich i^ iti^oluble in boiling alcohol.

»4C^^H^\aO^ + PO=CP = 2C'*H*0* t 0^WQ^ + NaCl + 3NjiO,PO* + 2HCL
White amorphous powder, not attacked by botJing water, Eparingly
^lubie ia boiling alcohol, insoluble in ether. Molts to a transparent liquid
ifrhen heated^ and remains transparent after solidification, — With potash-
^ }U* it rather quickly forms salicylate of potaah. It is slowly altered by
bmliog with caustic ammonia, but remains unaltered when boiled with
carbonate of goda<

Thiotoliiol or Sulphotoluol.

EviLLE. N. Am, Ckim. PAg^. 3, 172,

Produced iu very a mall quantity by the action of fummg sulphuric
acid on toluol^ and rcmamii in shmiug crystals wheu the aulpUotolmc acid
is dissolved out of the resulting crystalline mass (p» 230),

Hlowio. (1835.) ro^<^. 36, 403 ; rharm. C^iUr, 1836> 62.
^H Iodide ^Spit'oyi, ladiJe qfSaticyL

lodosalicylans Acid.

I

When bronifpispirnylous or chlorospil-oyloua acid is heated with iodide
€»f fiotfvs^iutUy iodo^aticylQus acid sublimes.

284

TOllEXE; OXYBROAnNE-KLCLELS C'^Brll^.

SuIkI, daik bfowo, eiMjily rusibie m^is^ wliicli with water, »1co!jci
€tl>cr, and i!!«jilifiable basesj exbibiti reaclicm iimikr to tlio&e of brom^
ifaJieylgu j or cbloroflal icy Ions aeitf.

Bromosalicylous Acid.
C'*BrH'0* = C^*BrH''0',0'.

pAGENSTEciiER, (1S?14,) Jif/jerL 49, aj:*,

PmiA, ^n/** Fhartn, 30, 171 1 -ilim. C'Atm. Ph^&. G&j 281 ; J^Auii

Cmti\ 183ft, 375.
LiJwio & Weidmann. P^y^jg. 4fi, 57; Phoim. C^ntv. 1830, 101,
HcERLEiN. J. pr. C/tfni. 3if Gj; PhantL Cmtv. 1844, 5S>S*
Behtaoniki. Jh», Mtfrw. 85j 198,

Bromifie &/ Salic^if Bromi'fc of ^aVojy/p BromGapifQ^hut 9cid^

FonnalioH. By tbc actbn of bromine on mticylous acid At ordln

tempera turesr (i^i.338).

Prfjiavatmu L WLcn bromine is brought in contact witU ^a^lieyluii
acid, tbo niixtnrc becomes very bot, bvilrobroniic acid ia evolved, aod o«
tooling, tbc wbole solidifies iu a crystalline ma?s, wbicb may be pnrified bf
tryet alii sat ion fro'n alcohol. (L^wif^-, Piria ) Lawig k \Veidinanii alloU
the it^pour of bromine to act upon the acid at ordinary temperatuv
ft bottle filled with bromino-vapowr, for example. ^2. Atjneoua
long acid is shaken wiib broajine- water, and the flakes whtdi scp
are purified by kecpiiig ibem in the melteil state over the water-batb i
long as hydrcbromic acid coiititiuea to escajKr. (Lowig.)' — 3. Bromine it
added; not in cxccf^, to the alcoholic solution of £alicylo(i€ acid; and tU
mixture immcdialcly diluted witb a large qanntity of cold ivati^fi'
a refiinons body is then prteipitated wbicb inetantly solidifies, wInJf
flaketj continue to float in the liquid. The rednout^ body i:^ dis^olvi^d ii
alcoholj and on leaving the solution to evaporate Bpeutaneou^ly, broinirj
salicylous acid crystallises on t first, (H eerie in.) "

ProptiileR. Hmall colourless needles. (Piria, Lthvig %k Weidma
Yellowish crystals which look like square prisms when examined bytlil
microscope^ but bavo a woolly aj^pect when teen in mass, (HoerlduJ
Melts at the lieat of tbc watcr-Lath, forming a colon riess 1 liquid whidi
solidifles in the crystalline fnnn. May be ir^ublimed without de«iitta{M^
ittion. Volatilisscs nndecnmposed wdien boiled witb winter. (Lftirijj^j
SnielU like benzutn. 1'he alcoholic solution deci^lorin's littiHjamnd indif
(Heerlein.)

14 C .

ft II ...

Br...

4 0 ...

41 75
2-41*

nn

37-Bfl
4OA0

Piria.

2-53
30 J S
16*10

^€*'BrU*Ot 201

100 00 .....,M IWQO

wmo

IdCNM

BROMOSALICYLIC ACID.

S8S

Tiie alcolmUc sftlntion mtumtp^l at tlje bmlin*^ lif*at with eiiulphiireUeil
liydrox*?!** a.^snnif^s n r^nldiali colour ami precipitator milpliur. The
fifjfiorptiiiu i.^ accelerated hy aJditlou of QniniQuta* WiUer thea precipl-
lalc-s sulphide of liromosalicciie, (Hccrlciiu)

With ammonia aiid aaliBablo bases, the ae'id bchav*^s Ukos chloromU-
cylaus acid*

The wlkalino broTnfjHiiIicvlite.H arc less soluble in vsrater [timri tlie clilnro-
antii'ybtcrs?]. Tjie haryta-ealt coutaiiiit 28-4(1 p. c* (1 At) of baryta,
(Lowii,' x^ Weidnmnn,)

With bis II I pb I to of ptrtu>-h, the acid forms a compound wbicb crystal-
Iti6e3 in needles, and with hisiilpbite of ^oda, f*m:ill agtjrogaled lieodlcs.
Both compounds diis^olve readily iii water and are dcooiuposed by heat or
by the action of acid^^.

In&uluble in water, Pi.ssolvos readily in (timltof and ftltrr.

Bromosalicylic Acid*
C»*BrH«0« = C"BrH*0%0*.

G run A RUT. (1842*) N. Ann. Cfttm. Phyt. 7, 217; Meu. icmd. 10, 210;

Ann. r/tatm, 4.1, 21; Phavm, C^nlr. 1843, 169.
Cahours. X Jnn, Chim. Ph/4. 13, DO; Amu Fkann. 52, 342; J^pr.

Chm, 35, 90; Pharm, Centr. 1845, S84.

Acide Mouo&fomQi&ltcffliquef BrmHi&tie^hUure,

Formalmi, By the action of bromine on e:£CC3^ of galicyllc acid,

Pri^pm^athiu Pulverised salicylic acid h gradually triturated witli a

c^aantity of bromine, such that part of the acid remains unaltered ; the

brown gummy n^a-is is wni^hed wltli amull quantities of cob] aleohcd, which

extracts the unaltered acid; the roaldue dissolved In boiling alcohol; and

I the soiutiun left to evaporate.

Colourless pnsma having a stronn^ lustre^ and tome what like aallcylie
icid; they melt when slightly heated.

14 C .

5 H .

Br,

SO .

S4

5

SO

4$

2-30

36B6
2214

GerliariJt,
.. 2-3 ,..

C*!iOurt*

33-;h

2'62

3G^02

21*5S

c'm*BrO»... 21 r .... 100 oa

lOO'OO

Decompoied hy dry distillation. When distilled witli fine sand and
imall quantity of barytSj it yields thick vaponr^f condensing into a
reddttih liquid, which, by repeated distlUatiou with sand and baryta,
yieldi bromocarbolie acid;

B C'*BrH»0« = C^Brll^O + 200^,

Broniosalicylle acid dissolves but very sparingly in wat^r, even at the
boiling heat. With ammonia, pota:^b and soda, it forma crystallfftable
saltv, which are less soluble in wjiLer than t!ie salicylates* — It colour*

i ferric salts red. Like stilloylic acid.
It disjiolvea pretty readily in nlcohil and tihtf^ especially when

rarm.

286

TOLUEME : OXYBRO^^^fE-NUCUUS C**BrHH>'.

Methylbromosalicylic Acid.

CAnotma. (1844>) N. Ann, Chlm, Ph^M. 10, 330; PAiu»j»,
1844,437.

When bromine is slowly dropped into rnetliylaiilicjlic acid kept as eofd
as possible, and tlio nia^s which solid jfios on cooling' is freed from hytlro
bromfcacid by washing with weak alcohol, and dissolved m boiling alcobo
iifSQ^ the liquid as it coole deposiU ghining cryMatline lamiiifo of melhjt^
bihroinosalicylic acid, an additional quantity of which i^ obtained fromtbl
motherdiqaor on cooling", after eraponition to one-half. The remaiaifli
motlicr-liqiior however yields by further evaporation, crjetala of methyf
bromosalicylic acid, which may be purified by three orygtallisatlona froa
alcohol or by eubliraation.

Silky ueeJlea having a pecullnr odour aad melting at 55^. Subliini
withont decompositioii,

16 C „

Br.,
6 0 ..

m ,... 41*56 41-6^

7 .., .V03 .., »«17

80 .... 34 63 34"30

48 .,.. 20^78 fM4

CinrBrO** ..* 231 M» 100*00 .^»... 100 00

\ acid dissolves la hot potash -ley, forming bi-omostilicylato ofpotaiiliAl
taet with aninionia, it ilitappeara after somo time only. Mmenll

The
In contaet witU ammonia, it ditappeara alter somo time oniy.
acida nihled to the solution throw ilt>wu m hite flakes, which crjitalliit
from hot alcohol. The ammouiacal solution^ ovapfiratcd and bubjeel^d
to dry distillation, yi*.4Js, fir^t ammonia and then eaihydrninid©. l>iitiUa|
with cyanide of mercury, it forms a compound in which the bromitit
replaced by cyanogen.

With cold strong pota^hdey, it forms a compound similar to tint^
which is formed by niptliylsallcylic acid^ and very soluble In aoetic wMf
the fiolution mixed with water, eithihits a milky turbidity, and afbri
while deposits tho unaltered substance in ncedleit having a stlky liuitre,

Disi^olves in akokoi and readily in Hher.

I

Ethylbromosalicylic Add*

C"BrH»0' = C*lPO,C^*BrH*0^

Cahours. (1844.) X Ann. Chim. Ph/i. 10, S4K

Produced by the aetion of bromine on ethyUalicylie arid, the
being in oice«». Dissolves very easily in alcohol, and ery«iialliji«>«

from in Mleinht needles, very \\md\ Uke iiiethylhronioaalicylic ari-l

BIBROMOSALICYLOUS ACTD.

tSf

Sulphide of Bromofialicenei

-HEEnLErN, (isaa.) /. pt\ Chtnu 32, 08; Fhatm* Caiir, 1844, 50l>.

^ Sal plin retted hyrlrogen is pasi?ed to saturation throtigli a boiling
solatifin of bromosal icy lone acid, (tho absorpiiou in somewhat accelernted
by addition of ammonia), tLo Hf)uid mixed wHb water, and tbe resultinij
brown rewnous precipitate purified by rt^peatod solutiou in alcohol and
precrpitatiou by water; it is then dried over tho water*batb, whereupon
the nms3 wbicU was tenacioua at firstj becomes ijorfeelly brittle,
Aniorphoua, Melts eoniewhat below 100\ Not volatile.

14 C .,

Br,

5 H .

%0 „

2S .

84

BO

32

7-37
U7»

.. 40-10

. 6*74

., 15*28

C'^BrtPSW...,. 217

100^00 100*00

^L AniorpE

p Btsolved by dry distillation into enipyreumatic snbstancoa eentaining

I sDlphnr.

Dissolves in potash and is precipitated therefrom by acltls, with
evolution of a amall quantity of sulpbnretted hydrogen.

Eibroraosalicylous Acidt
C**Br'H*0* ^ C"I3r*H*OnO«,

Hehhlein. J. pr. Chm* 32, B5; Pharm, Ctntf. Ifi44, SOS*

\ Pr^araimu When bromine-watar is added to an aq neons solution
iftf fialioylous acid till the colour becomes pemjonent, a white cmtHllo*
tioceulent precipitate is formed, while lighter fleet s romaiii suspended in
the liqaiiK Tho preeipkato melts togttber when heated in the w^ater-
batb, and 8ol I Jiliea on cooling ; the aleoludic eolution left to cvaporaie
spontaneously, firat yield a crystals of blhromoenlicylous aeicl, but after-
wardii bromosalicylous acid likewise separates from it. — When bromine
I is added to an alcohoHc selntion of Falicjloua acid till tbe colour becomes
permanent, or when tbo teeinons mass obtained in the preparation of
broraoaalieyloufi acid (p. 284) ia dissolved in alcohol, and broniine added
in excess, the mixture becomes beated, and yields on cooling crystald of
bibremoflalieylonB acid* Lijwig & Woidmann obtained in tho sanio
manner, or by treating the oily acid with bromine at tho beat of the
water- bath^ mixtures of bronioealicvlou^ and bibromosalicyloua acid,
(/-o^/?, 4C,57,)

k

98§

TOLUENE ! OXY BROMINE-NUCLEUS C^*Bi^H*0^,

Propiriif/i. Yellow isb, very 1

hUcs cr>n.^Utinsr of

square pn«ms.
citlDur like til at
ramus aaU inJi^o*

Melts at the

iieedl
liPnTt of ibo w.ifnr4r:itll.

Htie a peril liar

of gam bonzoYu. Tlio alo^jLolic solatiou decolorti

uc .

4 II..
2 Br.
4 0..

84 .... 30^00 20 52

4 ... 1-43 \B7

160 .*., 67*13 sti-rs

32 .,.. H-44 ....... 11 SI

C^^Brni'O^

2S0

loo'fto imm

tlie dd of

(Liiwi^ k

Treated with bromine for some time in sutishme nw\ with
beat, it yields a body containing 67 12 per Cfiit. of broiiun^*
Weidnmiin^ com pure p. 238), — When sulpharetteJ bydrogcti is jini^^for
some hours tb rough a srarm alcoholic solution of Ibe acid mixed with ft
little ammouia^ a brown resinous mass aeparatea eoasuUug of su1|diide of
bromoialicene. (Hecrlein.)

Bibromoiisilievloua acid unitea with ^abfiaUo bnsos. Wh^ti iu salati^
in potflsb-lcy \& evaporated and be^itcd, the residue becouica rod-faot
Booner than the vessel. (Heerlein.)

Tnaolahle iu water^ but soluble in alcoJiol and ether.

Bibromosalicylic Acid.

C'^Br'H'O^ = C'*Br^H*0^0^

C^noun!*- (\BirK) N". Ann. Ckim. Phji. 13, 102; Ann.
52, mZi J. pt\ Chm. 35, 82; Fharm. Gmtr. 1845, 8S4.

Formation. By the action of bromine in excise od fialicjlio aciil.

Prcparnttoti. L Pulverised ealieylio acid la gnidually triturat<*d with
e%€eas of bromine aa long as any action takes place, and tbe mixture i^ W
to itand for dome hours ; tbo excess of bromine ts then wiisbcHi out '
cold water, and the iviiidue dissolved in boiling ammonia. As the sohiti*
cooU, the ammonia-^alt is deposited in dcnder shining neeille^. TUe(
crystals arc dissolved in vvnt^^r; the acid precipitated by hydrocldt)
arid; tbe white precipitate waj^hed and dii$^olved in boiling ;tfcolxi>l;
tbo solution left to evaporate. — 2. Wlien bromine Is dissolvrd iu a w«-"
ccntrated solution of salicylate of potash, tbe liquid becoitica hcatc4i9J
ioon deposits crystals of bibrouio^at icy late of potnah; this ^jvU i^ deeooh
posed by hydrochloric acid, and the sepatated acid washod and crp
talliijed from aleohoL

Short oolourloss or slightly reddish needles which molt at :il>otil 1^^

UC...

i 11

2 Itr
GO

04
4

IGQ
4tf

28'3«
1 35

54*05

iG2a

(10

l*G2
f}| 20

(J«bo«rSt

C**ll"ttr*0« TJ&

\m*m loo'oa

MeTUrLBIliROMOSALlCYUC ACJID.

2H9

Distilled witt Kind and a a mall quantity of baryta, it yields bibromo-
tmrbolic acid* — It dissolves readily ia boiling nitric acid of 36^, giving
DJf nitroEis vapours and bromiac-vapoufa, and yielding cryataLa of picric
acid as it coob.

Dissolves sparingly in water Dissolves in gently beated oil of vitriol
and is precipitated therefrom by water*

The bibroniosalicyLatea of ammonia, potaah and soda are even less
polnble than the bromoaalicylates. The potash-sait crystallises from
;^Jcoho] in shining colourless prisms.

The aoid diasolves pretty readily in acetic acid, itiU mor? readily m
ether.

Methylbibromosalicylic Acid,

Cahoues. (1844.) A-. Ann. Chim, Fkps. W, Bih
BidromMalin^iformeifier,

The first oTjatiilB which separate from the alcoholic solution of tha

I obtained by treating raethylsilicylio acid with bromine^ are crystal-
from hot alcohol The compound is also formed when methylbro-
mo^licylic acid is brought in contact with bromMiej the mixture beooming
hot and giving off hydrobromic acid.

Shining pri&ms, which melt at 145^ and volatilise at a higher tetn-
peraturc.

^V The solution of the acid in very strong potasli-ley assumes a yellow
colour when heated, and acids separate white flakes from it, which no
longer exhibit the properties of metiiylbibronioFalicylic acid. It dissolves
sparin^^ly in bromine, remaining uijultered and in large lamtnee wlien
the sulvent evaporates. With cyanide of mercury it behaves in a similar
maimer to methyl bromosal icy lie acid (p, 286),

It dltisolves in cold potash or soda- ley, forming crystal]! sable com-
pounds, and is separated again by acidei in its original state.

It is insoluhlo in water, but dissolves readily in alcohol and ether
©specially when heated.

16 C ,.„„

6 H ._.

.. 6 .
». 160 .

.. 30-97 ..
.. 1-94 ,.
.. SI 61 ..
.. 1548 „

Culiourj,

31-29

204

9 Br

eo

... 5143
15"24

C»H«Br=0*

.. 810

. lOO'OO ...

,.. 100 00

\UL. XII.

CULOROTOLUOL.

2di

Oxybtvndm-nmkiu C**BrIl'0',
Terbromoaallcylic Acid.

'^Cahoprs, (1845.) Amu €him. Fh/g. 13, 104; Ann. Fharm, 52, 33^;

J. pr. Cham. 35, 84; Fharm, Cenir. 1845, 8S5.

ForinMion and Fr€pamtwn. A raixtur© of finely pulverised blbm-
uoaalicylic acid with excess of bromine is exposed to fiuusliiDe for 25 or
BO daysj and the res d ting yellQwiali cryst^la waaliad witb water and
t«crystallised from atrong alcob<*l.

Fivperties^ Small jollowiah prbms, very hard and friable.

H C 84

3 Br £41]

3 H 3

6 0 , 48

22*40 24-05

64-00 63-72

0-BO 133

12-80 .„ noo

CWBr'H^O* ..» 375

] 00-00

10000

JfceompoMtion^. Wben distilled with sand and a email quatitUy of
bary ta^ it yields terbromocarboltc acid contaminated with a small quantity
of oily matter,

Wbeu boiled witb nitrtc acid, it yields bromine- rapours and yellow
ciystab.

It ia insoJuble in water, — Ita compounds witb ammonia, potash and
eoJa are crystal livable, but very sparingly soluble in water. Tbe ammonia-
^aalt forms with silver-salts a precipitate of a deep orange-yellow colour.

It dissolTea with tolerable facility in akoholj ?ery readily in e«/i<rr.

Ohhrine-nuclem C**CiH\

Chlorotoluoi

O^CIO^

I>E¥ILLE. #< Ann, Chim, Fh^s. S, 178. — X pK Chan, 25, 336; abetr.
X Fharm, 27, 640*

Benzo^M nt^jufckiorit ChhrGh€moins*§*

Toluol IB saturated in the dark with chlorine gaa (p, 229); the excess
of chlorine expelled from tbe liquid by a stream of carbonic acid gm at
a temperature between 50^ and 60 ; and the liquid distilled till hydro-
chloric acid begins to escape. Tbe di^itiliate is purified by repeated
distillation^

Colourless, very tbUi oiL Bolls without decomposition at ITO"*.

iirl _ a-lS «V-it

•i >l _ 1^5* #-0

bjmi

^': *»-* --- JS-3» 3&>4S

Ad i4l-t _ «-!•

BilijdraAIanle ef QwntiiJiloroffaJadL

Detiux. loc. dL

Wbeii dJoTine gu is p&sseid for m ooaadermble time by dajligtit
tbrcviL^ toluol, m tluckish liquid is produced in which erjstmb sepante.
The liqaid is dejAnted from the ciTstala, still farther treated by ehloriM
with the ftid of beat^ aod purified bj m stremm of earbonio add. Whea
distilled it giTes of hydrochloric mcid.

DeriUe.

14 C 84-0 ._ 24-W 24-74

: Cl 247 8 73-57

b H - - 5-0 ... 1-49 .„ 1-63

a*CFH» 336 8 ... 1(MW)0

I I>eTi11e'i memoir, the formula assigned to this oonipoviKi is C'H^PiF (proM7
rnit), whence Gerhsrdt dedacvs the fonnuU CWH*Cl,2Cn (7V«/4 3, 56€). L:

16 compound \s aoVuVAe xu e(A<r.

CnLOROSALICBmN,

Terhydrochlorate of QuiBtichlorotoluoL

Produced by the action of chlorine on toluol in dayllgbtf and with

peculiar rapidity in sunabine, together with bihydrocblorate of quinti-

chloratoluol, from which it eeparates in cryataJs, Theso are purified by

recrygtallisation from ethor, bat are difficult to free completely from

ithe adbering oil.

Colourlesa transparent crystals.

14 C ........

8 CI ...

... 84^0 .
283'2 .

.. 22-50

. 75^88 ..
.. 1*62 ..

Dcyillc.

... 22-6S
.. 75*53

6 H . ,.

6*0 .

1"82

CMC18H^.

. . 373*2 .

.. 10000 ,..

100^00

It is soluble in etherj especially when heated or under somewhat
increased pressure.

Sexichloro toluol.

DEVTLtte. lo^ cU.

When the mixture of bihydrocbl orate and terhydrochlorate of qutnti^
ebjorutoluol is distilled in a stream of chlorine gag, and cohobztted 10 or 12
ijmeSj a small quantity of a substance baving a silky lustre conden^s id
the receiver at the end of each distillation, and at length the entire
liquid is converted into this substance. A large quantity of hydrochlorio
acid is evolved at the same time* By pressure between paper and
recrystallisation from ether, the silky substance ia obtained quite pure.
It may be volatilised without decomposition.

liC

6 CI

... 84*0 .
... 212-4 .

... 2815 .

... 7 MB ..

0-67 „.

DeviUc.

, 27-6

..... 71 7
.... 0-7

2 H

2'0

c^h;i«h» ....

.... 2&8'4 .

.. lOO'OO ..

.... 1000

CUorosaligenin.
C^CIH^O* =^ C^*CIH»0\2H0.

PiBiA- N. Ann, Chim. Phyt, U, 284.— ^/m. Fhxrm. 56, m.

Cblorosalicin is treated with emulsin in the same manner as salicin
ID the |>reparation of saligenin (p. 233),

254 TCIX151: OrrCHU>SI!CK-9k I'CLBUS C**C9BKI*.

Crj?cirJa» frrm h:r^ virer ia >teantiliBl oalonrlcflB ribomlne tibl«
w^jsL =L i^izana^ apye^naeg ai» gmdl^tiMg^iriimbla from aUigeniii.

Firift.

14 C f4-# __ i3-16 52-75

r H _ _ :-• _ 4-4» 4*64

a _ »-4 _ tM5 S2-M

4 O - SS-# _ »^ «0-27

Wha :£l :c rrzrul h UEzsas m brigiit graen eolonr. It ooloon fenie
ScC-xxe rz v^s^. k^^ia sad ^£4^.

Chloride of SaHcyL

Gexrakt?. Cnpc. -r^i. S$. ^: ^m Fharwu 89, 363. — TVm^ya.SII

/^'kr-v:A>«. Tm prv>ds<t c£ tke actioii of pentaebloride of pki-
phoni:^ oa ru^-i'ciTLs&lxT-l^c acid, forms, mfter m small 4|iiantitj of dikit*
ph^^$^h;^A'' ic:i r:k? ^^s «xf^flle«i bj beatiiif to ab.>ot 160**, a fisBiii;,
«itUr>-«iV \v';'::r>^i 1:^1. viiirii a^zv:4 be dbtiUed witboot deooaiKMitioii,
but s;oiv>6:::& a Jkrp? v;^ir:::T «:: cbAzrcud, gires off bydrocbloric uA
and v'seUb a hc3>i vb.ch apf^fan to be tbe oompomd i«gM^ hj
Ckkvn^ as C^HVa^'.HC: h^ ll^V and bj Gerbardt as ohlori£ of My
n^S^Bsoyl ^C-nTIHHy.Cl . )s prvbablj alio coataias f^oepbate of mhctl
^|v :^;^f$V. Wi;h v:ft:^r. i: KKv^meii beated and yields bydrocbkrie wii
mUovlK* aokU. Wha Vvvd-spirlt or alcohol, it fonu metbylsalicjFtie «
fHbvWai:cviic a<xi and bwirvvbloric acid.

Chlorosalicylons Add.

IS KNsmuKK. /? :vr*. 4?. 541; Jaa. Ckun. Pkyg. 69, 334.

l.o\>u;. /\^v ;*^. Cx^S.

l>iMAS ,('■ •^•« :' ># 6^. o^6: Amu. Pkarm, 29, 306; Fkam.

riHiA Ak^ r\ v-'m t^iX l^•^>: Pharm. Cfntr. 1839, 375.
|.o\%uj \ W KU^MiNN. r.v' 4'?, eS; Pharm. CfHtr. 1839, 130.

Km iN»j .1 •«•*. .'*'t" ■'•* ^y -♦'^

rWi>rM;tt>«\ ('*;.»n(jrtr«^;. ekhrtyirofUft Sdmrt, cAtenjpirt^ fiisra

i'lN^iii/MfioM. Whon dry cblorine gas is passed at ordinaiy ti«f«-
urt0 into dry 9alicy\ou« vrU, ^^ liquid bocomei hot, ananMS a jtUtf*

CHLOROSAIJCTLOUS ACID.

295

Bo!otir« gives off hydrochloric acid, and soliilifiea on cooling into a crys-
talline mass, which may be reorystiilHsed from hot akolioL (Duraas,
Pjrift, Ettling), or Biiblimed at a gentle heat (Lowig.)

Propertm. Beautiful crysLalliue laminoe of a dazzling whiteness.
(Liiwig.) Colourless rectangular tables having a pearly In it re. Melts
below 100*^, forming a coloiirlcss liquid, and then evaporates, eubliming in
Jon^ needles. BoiIb at a temperature not much below 100°, andanblimes
without decomposition together with the watery vapours. (Lowig.) Flas
a peculiar aromatic odour, somewhat like that of dilute hydrocyanic acid
(Lowig); has a peculiar disagreeable odour and n peppery taate. (Pirn,)

Damns, PHt. - ^Z^«

i4 C 84*0 .... 63^6t , 53 48 _ 53-01 527?

5 H 5*0 „.. 3*19 3*28 .... 3 30 _ 3-60

CI 35-4 .... 22'tl:i 22*32 24-10

4 O 32-0 ... 20 jy 20M7 19^47

C**CIHW .... 156*4 .... lOO'OO lOOOQ 1 00*00

J}eeompo^Uiom. 1. The vapour may be set on fire and btims with a
green-edged flame. (Piria, Lowig.) — 2, By the action of chorint it m
converted into bichlorosalicylous acid. {Lowig & Weidumnn.) — 3. It
absorbs ammQumcal ^as, acquiring a yellow colour, and fonniug a resinous
mass of chloroialicylimide, while water eecapes. {Plria.) — 4. After
hoiliog with excess of potasU-ley, it is precipitated in its original state by
acids* (Piria, Lowig.) — 5. When fused at a gentle heat with potassium
it exhibits vivid combustion, pari of the acid being decomposed and
charcoal separated, while the rest combines with potash produced in the
reaction. On dissolving the residue in water and adding nitric acid,
chlorosalicylous acid is precipitated, and the li^^uid retains a large <juan<
titj of hydrochloric acid, (l-owig,)

Combinationi. 1. The acid is ineioluble in water, — 2. It diasolveB in
cold oil of vitriol and U precipitated without alteration by water. —
3, With bases it forms yellow ealta. The chlorosal icy 11 tea of the alkalis
are less soluble in water [ibno tbe fiaUcyliteu ?] j the solutions impart a
black-bine colour to ferric salts. (Pagenstecber, Lowig.)

C^lcrosalic^liU of Potash. — When hot aqueous potash of 45** Bm,
is saturated with chloro^licjlous acid^ the deep yellow solution deposits
the aalt in red scales united iu radiated groups. (Piria.) — Insoluble in
alcohol. When heated, it exhibits incandescence long before the contain-
log vessel attains a red heat. (Lb wig.)

Chlot'osnlicplite of Baryta. — Obtained by decomposing chlofosali-
cylite of potash or ammonia with chloride of baiimn* Yellow crystal-
lioe powder, (Piria, Lowig.)

L^fslg U WeidtDUia.

B«0 .„ 76*6 .... 3419 .. .„ 33 01

CWCIH*0* .. 147 4 .... 65*91

C»*Gm*B«0* 2240 .... lODOO

Piri* found 31-92 p. c. baryta and 14-98 cUlonrm;, n^redpt; nearly with thoformab
:;>*ClH*BaO< + 2Aq wbicb requires 3l^G3 bao'ta and H*63 chlorine.

^^1

207

Methylchlorosalicylic Acid.

^^ABOCFRS. (1844.) .V. Ann. Chim. Pki/s. 10, 343; Pkarm. Cmtr,
V 1844, 438,

Saiicglaie de mtikyleit^ mtfn&chlt>ri, UhioranlicylfQrmfJtie*'^

Wlien niethylsalioylic u^id is exposed to the action of a iraall

ItiaMity of chlorine, methylclilorosalicylic acid is formed, with rise of

mperature and eyolution of hydroehlorie add^ but is difficult to purify.

Bichlorosaligeam.

C**CPH'0* = C"C1»H*0S2H0.

R1A. jr, Ann. Chim, Ph^$, 14, 285j Ann, Pharm. 50, 60.

Fioduced in very small quantity, when bichlorosalicin is treated with
imlain in the aanae manner as ealicin for the preparation of saligenm
233).

Bichlorosalioylous Acid,

C"ClH-0* = C^*C1H»0',01

& Wetdmann. Po^^. 46, 60; Pharm. Cmtr. IBSB, IBO.

Sal icy long or chloroBalicylous acid treated with eaccese of chlorine-
water first turns yellow, then red, and ultimately black, the water also

I acquiring a reddiali colour. As soou q& the action is finished, the excels
of chlorine is removed by adding a few drops of ammonia; the whole is
shaken up with ether; antt the ethereal solution is left to ev^aporate.
Crystals of cliloroaal icy louB acid arc then deposited, and the mother-liquor
yields bichlorosalicylous acid, which when freed as completely as possible
from chlorosalicylous acid by repeated solution in ether and alcohol, forms
ft red, thick, oily liquid, becoming perfectly fluid at 25^; it has a pungent

^ odour and excites tears.

I Sparingly fiolublc in water. Dissolves with deep red colour in potash*
J, Wiib baryta it forms a ruby-coloured compound sparini^'ly soluble
m water-

The acid disaolves readily iu aicokol andrfAtfr. {Lowig & Weidmanti.\

14 C

4 H

, 40 .

. 70'B ..
. 32^0 ..

., 44*02 ..„_ 39-84
.. 2*09 .- 2"S9

2 CI

4 O

.. 3711 .._ 3706
.. Ifi78 -,,,.. 20'7l

cucimw,.,

. 190-8 ..

... 100 00 100*00

L

296

TODUENK T OXTCHLORII^-NUCLEUS CWC1H*0»-

When chlomsaltcyloua aclil is boiled with excess of bmrvtA-'
the excci?8 nf baryta removed by carbonic acid, the liqnid depoaita _

silvery lamitiBB consist ing of a eompc^and of 3 At bicarbonate &( hmjim
with 1 At. acid chlorosalisalicjJite of baryta. (Lowig 6: WeklmAniL)
[Inateid of ihid imprdbable t?c}iupoaition» we may mbatitnte tbe forrouU (B«O.CO'4'

2 BaO .....,„ 1S3'2 ,.„,... n*^

16 C ^..„ „........, H^ 26*17

6H ._, „ .„ ^..,.. eni res

CI „,..«,». .„ ..„_... ^. 351 g-70

& o „ ,„:„ , ..„.._.»..... 72*0 ». It's?

(B«0,CO= ^ HO.CO*) + C«*ClH*BaO* + Aq 362*6 I

4 BaO

34 t ....
12 H „,.
2 CI ...
22 f>

& Wcidmuift.

3064 .. 39*83 41-66

204'a ,„. m&t .:»,„ 2S-I1
12-0 .... !*&§ ,_^. K5
70S .^ 9-20 ... Hft

ne^o .. 22-09 _ 2i*a«

3(tijsO,HO,2C03) + C^^CIH^BaO* + C»Cm*0* ... 7692

laooo .„,.. io<Mw

Chi crosjil icy Ions acid dissolTe^ readily in atjueons bisnipbite d
ATTimonia or potash; the solution formed with tbe aid of heat, deposit!
tbe resulting compound in the crystalline form on cooling. (Bert^^iur)

The alcoholic solution of tbe acid forme a yellow precipitAt4^ with
Imd-mlU, aod greenisb yellow with acetate of copper* (P^gensVclicr,
Ltiwig,)

The acid dissolves readily in alcohol and tth^, ~

Chlorosalicylic Acid.

c^^ciH'O" = c"H«clo^o^

Caiiou^s. (1845.) N, Ann. Chim. FIi^s. 13, 106.

Formation and PreparaUon. L By the action of cblorine on eieiM
of eal icy lie acid, a portion of tbe acid therefore remaining und^compoMil^
it is dimcntt however to purify from bichloroaalicyliu itcid . ~ 2. CbJuiw
}S^ is very slowly passed into a concentrated solution of salicylate d
poiaah, till the liquid, whkh beoomes brown, begin § to depoail a ibt%
groen substance; the solution is then decomposed by &ii aeidt anil tbt
resnlting white precipitate washed with water. By cryfit&Uiaa.tioii fivai
alcohol, slender needlea are obtained, consiatitig of cMonieftlicylic add a^
(|uite pure.

BICHLOROSALlCTfLOUS ACID.

f»7

I

OABoirs«. (1S44.)
18H 438.

Methylchlorosalicylic Acid.

C"ClfrO* ^ C*H»0,C^*C1H*0'.
JV^ Ann. Cfdm, Ph^. 10, 343; Pharm, Cmtr,

k

Wbeu njetliylaalicylie acid ia exposed to tbe action of a small
quantity of chlorine, methylchloroaalicylio acid is formed, with rise of
temperature and ovoiution of hydrochlorio acid, but is difficult to purify.

Oxi^chiorme-nudem C»CPH*0»

BicWorosaligenin.

PiRiA. ir, Ann, Chim, Fky$. 14, 285; Ann.Fhaim, 5% €0.

Pjodueed in very email quantity, when bichloro sal rein ig treated with
em Q Is in ID the same manner as jsaUcin for the preparEitioD of saligenin
(p. 233),

U

Bichlorosalicylous Acid.

N

L<5wio & WeidmakNp Po^<j^ 46, 63 j Pharm, Cmtr, 1839, 130.

Salicylons or chlorosalicylous aeid treated with excess of chlorine-
water first turns yellow, then red, and ultimatfsly black, the water alao
ftcquiring a reddish colonr. As soon as the action is finished, the excesa
of chlorine is removed by adding a few drops of ammonm; the whole is
shaken up with ether; and the ethereal solution is loft to evaporate.
Crystals of chtorosalicylous acid are then deposited, and the niother-liquor
yields bichlnrosalicylous acid, which when freed as completely as pussihle
from chloroaalicylous acid by repeated soludou inetber and alcohol, forma
a red, thick, oily liquid, becoming perfectly fluid at 25"*; it has a pnngent
odour and excites tears.

Ltfwis St Weidmann

uc

. 64 0 .

.. 44*02

,. 39'fl4

4 H .......

. 40 .

,. 2 09

289

2 CI

. ?0'8 .

„ 3711

37-06

4 0 ..

. 32K» .

.. 16* ?8

20*71

ci+cr-'H^o*...

. 190-8 .

.. lOO'OO

... 100*00

sparingly soluble in water Dissolves with deep red colour In potash-
iley* With baryta it forms a ruby-coloured compound epartn|jly soluble
in water.

The aeid diseolvee readily in alcohol and ftker^ (Lowig & Weidix»Ava.\

»s

TOLUENE: OXYCHLORINE-NUCLEUS a*a*mO*-

CAnoufts. {1845.)
1845,885,

BicbloroBallcylic Aci4

N.Ann. Chmu Php$, 13, I0«; i%arm CsOr.

Prodttced by tbe &GtIon of excess of etlorine on salicylic Acld.

Cblorioe gns is passed through a concentrated solutioo of ^icjtaU
©f potiish, till the liquid wliieh hm become brown ceases to depostl s
dark green bodj; ibis itibetance 16 washed on a filter with water till ikt
wat^T runs away coJourlass, theo dissoWed tn boiling wfttar wbieb b
mixed with J of its volume of alcohol of 36^ Bni.; and the Deedles of
the potaeh-aalt which separate ou cooling, are repeatedly cryslalltsed frvm
very weak spirit till they become colourless. Tbc^ crystals are tbeo
dissolved in water; tbe uolation mixed with hydrochloric acid; and tlm
resnlting white precipitate dissolved in boiltng alcohol of 82 per oent:
the solution on cooling yields the acid in needles or in acmlad^ or by
spontaneous evuporationj in hard^ well formed oetobedrons.

14 C

2 CI

4 H

6 0 ,..

. 70*8
. 40

. 48-0

... 40-62 ,..
,.» 34*24 .^
„,. 1-93 ,*,
-.., 2321 ..,

Cahourm.
.. 40T<

.... ai2g

2 09

22 93

C"CFH^O«„.

. £06 8

.. 10000 „,

,.... iOOOO

The acid distilled two or three times with ivid and a small quatitiiy
of baryta or lime^ is completely resolved into carbonic find bicblorocv-
1>olie acids. It dlssoKes gr:idually in boiUng Eitric acid and depotjli
beautifnl yellow lamins^ on cooling. ^"

Chmhinaiions, The acid dissolves sparingly iu boiling w&kr
crystallises in slender needles on cooling. It didsolvee in gently biftldi
qU of vitriol J and Bepuraiea partially as the liquid cools,

BkhhrondUplaie o/Ammoniu, is sparingly soluble in wst«r.

Acid Bichhrosalicyate ^ Totwii. — Greyish white oet^dles very mttch
resembling methylbichlorofialicylic oeid.

KO„„......._.... 47*2 ... 19*27 IM4

14 C .„,..^.^ 140 ..., 34-29

2 CI . ......_ ^. W% .... 2890 ........ 28*39

3E .„.,......., 3-0 .... 121

5 0 ..,,,.. 40*0 ... lfi'33

C»*Cra*KO» 245*0 ... 100 00

The acid forms reddish precipitates with lead and siiver sall«.
U dissolves very t^adily in akohol, still mote in dAer.

ETnYT.mCHLOROSATJCYLlC ACfD,

299

Methylbichlorosalicylic Acid*
C»«CPH«0« ^ C^H'0,C»*C1'H*0*.

Procter. (1843,) #. J\ Pkarm. 3, 2T5] J. pr. Chm. 29, 467; Ann,

Fkat-m. 48, G6.
Caqours. N, Ann. Chim. Ph^, 10, 340.

clilonDe gas ie passed into methybalicjlic acid till the aetion

^_F* yellowish crYHtalline ma^s is formedj coBHistitig of mothylbiehlo-

Tosalioylic acid mixed with a small ^jiiantity of liquid m othy I ch I orosal icy-
lie acid. By cnra tall i sat ion from boiling alcohol, the bichloriiiated acid is
obtained in cofourlesi rhombic tables (Procter), in needles (Cahours)*
Melts at 104^ (Procter), at aliotit lOO"" (Cahours), and crystallises on
cooling. Volatilises without decomposition at a stronger licat (Cahoiirs)*
and sublimes a little above its melting point in rhambic crystals.

2 CI
6 H
60

Calioam.

96^0 «„ 43-48 43-41

70-8 „. aaoe aais

fi-O .». 272 2m

4$0 .... 21-74 21 «

D«CmW,...». 220-8 ... 100-00 100 00

H Tbe acid burns with a yellowish flame.

H It dissolves slowly in ammonia, forming a cliloFtnatcd amide.

^ (Caholirs.) When ammoniacal gas is passed over the acid for several
liours, it turns grey. The product wasbed with water, — which then
becomes yellowish and preci pita tea a solution of silver,— and afterwards
dried and dissolved in hot alcohol, crystallises on cooling in yellow

Ilamiuie which dissolve in potash without evolution of ammonia. Acids
jirecipitate from the solution a white substance which appears to be
ehloFosoeal icy 1 i m ide . ( Procter, )
The acid is not altered by chlorine in sunshine When di«til!od with
cyanide of mercury^ it yields a compound in which the chlorine is replaced
by cyanogen.

It is insoluble in water. It dissolves without decomposition in edld
potaih'Uy, and may be reprecipitated by acids.
It disaolvee in aicohol and ether*

Ethylbiclilorosalicylic Acid.

'cIhoues. (1840,) I^. Ann. Ckm^Phgi. 27^^01; Ann. PAarm.7i,B^Bl
J. pr, Chem. 49, 231,

Bickl&mali^lvimiKtfr.

SCO

TOLUENE: NITRO-NUCLELS C^XU*.

Kthylaalicylic weld heated m the watet-balh ia emtu rated wtlti
chlorine gas, the product ultimate) j solidifying, and tlie solid mxm k
pressed between paper and twice crystalHaed from alcohol.

Colourless platee having a strong lustre.

Cmhonn*

18 C ,..

...».,».. 108*0 »» 45-95

. l&-7t

2 CI

„ 70-g „,. 30-21 _..

.. 30*4 J

B H „

,„.,„... B-0 „„ 3'4l MMt^

.. 3*44

6 0 .......

48*0 .... 20-4$ ....„

.. 20'4S

C^]2lPQ6

234-8 _ XOO'OO

Nitrotoluol.

100*00

DEvrtLE- (1841,) ir. Ann. €him. Ph^s. 3, 170; J* pr, Chem. S5, 341;

PhaJVt. Centf\ 1842, 198.
GLKJfARD & BoODAULT, N. /. Fkavm. 6, 250; Compt, t-end. 19, 505;

y, pr. CAfOT. 33, 459; Fhm-ni. Ctntr. 1844, 156.
MrspHATT & HoPMANN. j^wn. Phai^m. 53, 221 and 224,

Niiroioh,

PronitrG&eHJO^et Nifrobeniotnastj Niir&draejfit NiirQiohiSdi^

Proration. Toluol li ponred by drops into fuming nitric MJ
which ifl kept cool^ the addition of the toluol being continued as loiif ti
-it dissolves immediately (Devllle), or fuming nitric acid is poured mto
lioluol till the latter ia completely dissolved (Olenard <& Boadanlt), and
tthe clear red liquid is mixed with a Jarge quantity of water, whlok
f!«eparates the nitrotoluol in the form of a red liquid; it may be deooloriied
by washing with water and repeated distillation*

Fropi^iks. Kcarly colourless liquid (Deville) ; amber-colomef^
(Gl^nurd & Boudault.) Sp. gr. M80 at 16^5^\ (Deville.) Smelb Uki
bitter almonds (Deville) and benzol (016nard & Doudautt.) Its Ia«l9
is very sweet, with a some what pungent aftertaste* Boila at fl$*
I (Deville); at 230^ (E, Kopp, Compt. chim. 1849, 143); at 220'' to J25* |
(Wilson, Ann. P^iarm, 77 f 216), Vapour-density ^ 4-93,

I
I

Derllli.

11 c

§4 .

... 61*31 „.

_ £118

7 H ...,..„

... 7 .

... 6 11 ...

... 52$

N .,.„..

.. 14 .

,.. 10*22 ...

... 10*75

4 0 .,

.... 32 .

.. 2S'36 ,...

22*81

CWNH^D*

.... 137 ,

... 10000 ...

..... 100-00 .

Itomrnc vith b«tiftmic, inthnniUc, and MUeylfimte ACidi*

Ptmmptmtirmi L Each time it is diatillrd, it left ret a rt^^^idueil
yields a diatillate containing more carbon and leas nitrugen than ili« I
ceding; Uence it must only be distil led with water and dried ©f*
Monde of calcium* (Ql^natd & Ec^^<kult) The rapours |a«fd

mNITROTOLUOL.

SOL

Uirougb a red-Lot tuHe filled with pieces of glussj remaiti nndeoompo^ed
St a modemt^ Leat^ but a stronger beat deconiposea thern^ producbg a
deposit of black aoot {Mn3pratt & Hofniann.) — 2. Tiae c^mpoaml
bums with a sooty flame, emitting the odour of gum benzoin. ^ — 3. It
dissolved with decomposition in aqueous poimk, forming a red solution
(Deville), more quickly in alcoholic pota*hj forming & bUck liquid,
(Ritthausen, J, pr. Oliem. 91, 111,) Hydrochloric acid added to the
potash-solution throws down a brown powder. When the solution in
alcoholic potash is distilled, there passes over, after the alcohol, a reddish
01 L probably analogous to azobenzide (Deville), contauiing aniline and
*2obenzoene. (Mugpratt ife Hofmann,) — 4, The vapour passed over
red-hot barpta is resolved into aniline and carbonic acid. (Muapratt &
Hofmann) :

5. With fuming eulpburie acid it forms nitrosulphotoli.io acid
C^*XH'SW (Church, FhU. Mag. [4], 9, 250.) — 6. By boiling with
an alcoholic solution of sulphite of ammonia, it is converted into the
animonia-ialt of thiotolnic acid, C**NH*S*0*, {Hilkenkamp, Ann. Pkarm.
,05, 86.) — 7. With hydrosulphat© of ammonia it yields toluidino.
It dissolves with great facility in alcohol and ether.

I I

I

mtro-nud€U4 C"X'H*.
BmitrotoluoL

BErihLE. N, Ann. Chim. Ph^s, 3, 175; J. pr, Ohem. 25, 341 j Pkarm*

Oenh\ 1842, 109.
Cahours, Comjii rend, 24. 555.

Biniirohtufnet Biniit'obtnzoene, NUrobenzomU^.

Produced by boiling toluol for a cousidemble time with fuming nitric
acid (Deville)or by treating it with oitrosulphuric acid* (Cahoura.)

Crystallises from alcohol in long needles having a strong lusire, and
iu prisms belonging to the nght prismatic syatem. Melts at 71*, and
solidifies in a radiated mass on cooling. Very hard and brittle. When
strongly heated, it gives off vapours which form a sublimate on the
neighbouring part of the vessel. Bails at 300^^ becoming coloured and
leaving a considerable residue.

^p Its solntion in potash yields a red-brown powder on the addition of
^liydrochloric acid/ (Doville.)

j With bydrosulphate of ammonia it forms nit rotoluidtne. (Cabours.)

It dissrdvea bat sparingly in water, even when acoidulated with
nitric acid.

liC ,

2 N

6 H ,... .

.... U .

. UH ...

.. 16 39 ...
.. 3-30 ...

... 35-15 ...

Devill«.

..... 40-1

..... 15-5

3*6

8 O

. 64 .

34-9

CMNSH<0« . .

.... 182 .

.. 100*00 ...

1000

302

TOLUENE; NITRO-NUCLEUS C^^Xm*.

Glirysanisic Acid.

CAHorma. (1849,) Compt rmni, 28, 385; N. Ann. Ckim^Fhy^. 27, -
/* pn CAm* 49, 274; /"A^rw** CiWffn 184^, 309,

Fc^rffi^fiotL By the actfon of fumitig nitrie acid on anido ftcic^
l^lnitraDisol and temitraui^ul beiog formed at the same timOp

9 its Uitlk
to m solfii^l

s md is^

Preparalian. Wbeu 1 pk of perfectly dry anisio acid la reiy g^oily
boiledj for half or tlipee-qii;irters of an lioor, with 2^ J>ts. m fummg
uitric stcid, and the somewhat tJiick Itquid iamlxad with 20 iimee^ iu hitlk
of VI ater, a yeilovv uil separates out, whicU ^uou coagulates into m solii^'
mass conei^tiDfr of cbrjeanidc acid uilicod with hi* and ter-nitruai&gL Thl
misttnre, in the form of fine powder, is washed on a filter with aiamoi '
diluted with two or three times its bulk of water, whereby the add
extracted ; the ammoniacal liquid^ after btnug evaporated to one-thir^
yields on cooling brown ueedlea of the ammonia-salt. These cryatals &r»
dissoWed in water; the soluttou mixed with dilute hydrochloric acid; the
separated yellow flakea are collected on a filter^ repeatedly waished wiili
cold water, dried between bibulous paper, and dissolved in hot al^obol;
and the dcales which crystallise from the solution on cooUng, are dneii

Smal! gel den -yellow rhombic tables. The acid melte when <matiiHtily^
heated and solidifies in the cryetalliuo form on cooling; at a etronier
heat, it emits a yellow vapour which condenses in small cryEtalliae Bcdei
liaving a strong lu^itre.

14 C

r 3 N ....

} S H

^ UO

84 .

4S .

5 ,

112 .

.. 34'&7 ...
.. 17*2S ...
... 2-06 ».

„. 46-09 ...

..... W-54
.... n-48
tm

45-98

I»amerk irith iernitnniaoL

24S «

.. \mm ...

.,.,. lOO^OO

Jkcompmtiom. 1. When boiled with strong nitric aeld, it is eon
Into picric acid. — 2. Distilled with aqueous chloride of lime, it ytfllfb
chloropicrin- — ^3. By boiling with potash^ it Is converted Into a browft
fiubstsJ^ce*

ChmbinaiumM. Ji is not perceptibly soluble iQ oold wmtar^ wxA
dissolves hut sparingly in hot water j crystallising aa it odok.

Ohr^Manimic of Ammonia. — The solution of the aeid in dilili

ammonia, evaporated over the water-bath, yields on coiding^ imall biti«a

I needleei haviug a strong lustre. Finer crystals are obtained by ipvCt*

\im/tia evaporation of the solution*

4

i

CHllYSAJilSATE OP ETHYL.

'303

14 C ,. 84 ....

4 N -„..,., ^™ .... &fi ^.

8 H ,. ........ 8 »..

14 O ., 112 ....

32-32 H 32 72

21-54 ai-2y

3-08 3'U

4306 „. 42-85

lOO-OO lOO'OO

ChrifsanixUe of Pfylash. — Obtainetl by exactly saturating th© acid
with potaab. Very easily soluble.

TKe aTumon]a-sa,lt produces iu soluiions of sine-salts a paJa yellow
precipitate; witU nitrate of C(^U^ a greenish yellow gel ati none precipi-
tate; with nitrate of leadt a copious deposit of chrorae-yellow flakes;
with/^ric ^Its a pale yellow, with &uprk salts a greenish yellow, gela-
tinous precipitate ; and with merctirie chloride, yellowish red flakes,
which itt dilute solutions appear after a time only,

H Ohri/mnimte of Silver. — The ammonia-salt fonns with nitrate of
eilver, beautiful yellow flakes, whieh must be washed with water and dried
in racuo.

14 C 84 ..*. 24*10 23 97

IN,.. ^ 42 .... 1200

4 «•...„«... 4 ..,, 114 ........ 1-20

Af,..^ , .,..».. 108 ,.- 30*85 ........ 3090

14 Q 1J2 .^. 31*&l

CWNSH^AfQi^ ...... 350 .... 1OOO0

Chrysanisle acid dissolves hut very sparingly in coM alcohol, but so

abundantly in hot alcohol that the llcjuid soliaifiee on cooling* It di&-
soItds in eiher especially if bot^ and crystallises In shiuing laminee when
the solution evaporates.

Ghrysanisate of Ethyl.

iholio ei>lytiou of tlie acid is eatarated with dry hydrochlorio
ntly boiled for some time and then mixed with water; the

The alooholi<
add gas, gent _

resulting precipitate is washed^ flrsb with arumoniaeal^ afterwartli with purv
water, then dissolved in boiling alcohol; aud the solution is left to oooK

Transparent orystslline laminiB of a splendid golden yellow colour*
Melts at about lOQ".

IB C 108

3N 42

9 H .... .....««„ 9

14 O 112

C»«N"H*Oi* .... 271
Solubb in warm eifier.

39-85 3965

15-49 ........ J 5-27

ZZ2 ^^„^ 3-33

41-34 _..... 41*75

lOO'OO lOO'OO

TOLUKNE; OXYNITRO-NUCLBUS t»XH*0».

NitroBalicylous Acid*

Pageksthcher. (1834,) ^i?prri. 49, 337; Ann. Chun. rh^t. 00,'

Fkarm. ChdK 1835, 137.
Lowio. /'o;?^. 36, 304; Pharm. Cmtr. 1836, 6K ^h

Lowm & Weidmaj^n. jPc*^'^. 46, 57; Phami, Cmtr. lSS9j 131. ^H

Heerliiin. J, ;jr, Ch€m. 32, TO; Pharm. Cmtr. 1844, 600. ^^^H

BBRTAGlflilL Jnn. Pharm, 85, 196. ^^^^

Nitr&taticide^ Niimapiroytic o6id^ Nitroipiroihatin, Spirda9tdpti*T*£mt,

Fotmaitmt ami Pnparaiiotu Salioylooa acid is heated wltk mod^
mtelj strong nitric acid not in exceaSj and the crjstaUiue mnm wild
aepaiutea ocl cooling h re crystallised from alcohoL

Propertia, (iolden yellow transparent needles. Kearlj inotLoroOi
taates but eliglitly at first, but after wjirds produces irritation in the tl
and cotigbing, Mek^ when UeateJ »nd solidities in the cryatatline
on cooling ; at a high temperature it sublinies partly iindecomii
leftYing aBiimll quantity of charcoal. Colours litmus paper deep yellow,
nut tm. The solutions produce a permanent yellow stain on the > ^
and nails,

u c . . „ .„ 84 .... 50 7a ..,..». a-05 ..,...,. 4yn>

N 14 ,... 8^30 &i3

6H 6 .... 2*96 ...... 3*46 „_ 3'42

3 0 64 .. 37 92 ^99

C**NH*Oa 167 100*00 100 00

iMnierb witli nitrobenxoic idd,

Demmpmiiim. L Heated for some time with nitric acid, it

picric acid. *— 2. Pota^sinm very slightly heated with the acid m%
mercorj, decomposes it with the moat vivid cotubustion, attendiHl witll
def^truction of the vessel, the product being a mixture of ctirbouat« uid
^icylite [? L.] of potash, (Lowig.J — 3. The alcoholic solniion i»tO'
raiea with ammonia and sulphurettea hydrogen, acquires a dark bnntn*
red oolottr; water precipitates from it only a few flakes; but bydrocltlanc
acid throws down a copious red-brown, resinous precipitate, wfatch, whei
being several times dissolved in alcohol and ether, and then dried Qrm
the water-hatbj con tains 33 or 34 per oenL of sulphur. (Hetrleiii«)

CmnbimUiont. The acid absorbs moisture from the air, acqurtai
ltie7«by a deep yellow colour. It dieealvea but sparingly in water.

It dissolves abunrlHtitly, with the aid of lieat, in aqueous brsulpJiiti
of am moil ill, potash or «otfa. The compound with bisnlpliito of aniBiaabl
4om not aj>ptmr to crysialllee \ the compouud with hisulpbit« of i

NITROSAUCyLIC ACID.

305

Sparatea on cooling from a warm solution, m ag-gregate*! gold en -ye! I oat
needles, wbicliare soluble in water, but insoluble in alcohoL The potash-
compound appears to be more solubla. (Berta^ini,)

Tbe nitrosalkgUfei are yellow or yellow isb red. They detonate
Tiolently wUen heated, leaving a residue of oxide or carbonate.

NkrosfiUcylite of Ammonio. — The acid disaolvea abundantly in
ammoniav The dark blood- red solution leaves when evapomted a dark
yellow reaidue, which immediately gives off ammonia when treated with
potash (Pageostecher, Lei wig), and wbon heated in close vcssel#> yielda a
amall qnantity of ammonia and an oily distillate. (Lowig,)

y\i% fixed alkalU combine readily with the acid, forming dark yellow
Boluttona, which, when eraporated, leave small crystals soluble in alcohol
bat insoluble in ether. (Lowig,) The soda-snU yields by evaporation^
delicate saffron -coloured needlea having a silky lustre*

A^tirosaiicj/lite of Bdrifia, — By dissolving the acid in baryta- water,
precipitating the excesj of baryta, by carbonic acid, and evaporating the
reddish yellow filtrate, this ^It is obtained in reddish yellow crystalline
Jaminoe, soluble in water.

At \m\

B«0. 76^6 ..

O*NH*0' 168-0 ,

. 31 aa

I^ri^ & Weidmaun

C"NH*BaO» > 244 e ,

. 100-00

■ - -

NitrmalkyUu of Lead, — T^eutral acetate of lead mixed with thf»
baryta-salt forms a dark yellow precipitate; the fiUiate has an acid
reaction.

Ai 100".
9 PbO 100€'2

cl^N^*o^___... 168-0

LSwig Sl Weidtnann.

B5'60 .- 84*73

14-31

a*NB^O^»PbO 1174-2

100*00

The solution of the soda-salt forms a light green precipitate with
pper-salta and colours ferric salts cherry-red, {Pagenstecher, Lowig.)
Tii# acid dissolves readily in alcahol and Hkcr*

I

Nitrosalicylic Acid.

FouRCROY & Vauquelin, (1800.) Ann, Ohim, 45, BOB-^^N^^Gehl

2, 2:36.
Chetaectl. Ann. Chim. 72, 13L
BdPP. SchuK 51, m; 54, 163.

DtJMAS. Ann, Chim. Fh^s. 63, 270; Ann, PAarm. 0, T**i Pog^, 29, 90,
^ — A\ Auft, Chim. 2, 224 ; Ann. FJmrm, 39, 350; */, cr. (7A^w».
I 24, 21L

Haechand, J. pr. Chem^ 26, n%h\ Fharm. Centr. \M2, 883.
Procter, N. J. Fharm. 3, 285; Pharvu Cenir. 1843, 700.

CA»:*rsfc. -T jttai Ti-iit Jti.-^ ". S: : -«*•- /^Wth. 48, 61, J. pt.

Srt*i'.T*a. --^ -. jf£/ / *:?- i?: -***- Pfctinii. TO, tSSiJ. pr.Chm,

45. M S' t*r.-n '.^r- l-**. fir
EL. K^~.3 X'^ lifcSBL I p7'i#-iDir-«ii e-r- Ti/t- CirtilnwM. 1854» & W.

Cfe'ii <u''i TntiriK arri _' tm SuS'tn. wr
iubijncK ami. _& "ifi.mi, ^uAanrc wefiu
•MTV. Vf -w^ruf'ijr ami. Auf/usr artL.

i^.f-ibrr^.-A. 1. 3 J iirf itni'id ic i»:< ft3»i — Aerately ^ilait Bitne
a«i£ :a zi«£ur:*:iirf- rzixrrrjj i Y*»^T»firm. CWirtBl.) — 2. Br the

»?:.'': a :c r.i'i £Zi:-> x-irii: itiv/i :ii alci^. -w.-sh, sMiIaneotti IbmuUiooof

P ''^pzr'ir r.n^ L. P.-^^wr-'i .Z'i'^7 ii j^n-is^j mdded to » boiling
ailinrf :c 1 pc riaL^or iiiric *,"!■£ la-i 10 :^> 15 pu. of water, u loo^
&ff ITT -t: t::..i •:£ ri* » :afrerr roinceii (wrih a stronger acid, u
€1l-»t7"'x> x;<-i ::. lir-p* ;ia2rii*» :: p^rrie ac»i aai &rtifi«l tannic mcidwe
f r:ixiir««i : iIl< L ;t: i s :^*ia ^Lil^d :':r a vkik. tlie water being renewed
a« ifi CT^pcra&». aa>i i ZfeT9*i k-:c : c&# bcow«>retl rendoe containiiig
■HiifwmmKti mlir:. & 'i^iwji-T^d inhiFvtce analkr in ^aaatitrta tbe
bi'iisTi i* Li-nT 1= i =::r:."ial '."tI:.: io:L U r«pea:edlr boiled with pore
▼iKr \zL ~J.'s =.i:::.j ▼::■: ti:-;? •r^i-iziiziz^ iiiiri-: acid to extract the
n:".r:'=al.':7l.«: i*:i.i. izi :!:•? :z.:-i t-?1".«- ilcrates are left to cooL The
fl.ak-w :f :E:par«* -::r t?al.i:T'..c I^::•i which separate on cooling are pressed
ac'i ■! "j.-H.!v.i«i !- t;; wiwr; :b«* y.lj irpts wbioh rise to the surface ire
r»cioT**i br n:*an* •:? r-raljos rai^r: :h.» warm eolation is decanted from
the :inpf:ri::« wzi^zz iu-re -ii^k :■: :he b«:c:oni f^m which, however, ft
cocrLierahle '^^azititT :f n :r eai'ii.'jlii: ici»i maj still be extracted by hot
water >, and tfa'^c lefc &} c«:rl: the cicprealicjUc acid which kis crTfltaili«d
in ne»*iil<4 u dijt<oiTe*i in :& lar*^ '{oacctr of hot water; and carbonate of
Iea<i '.3 sn^ia3.i.y %*id-id to uhe solation till carbonic acid is no lon^
eTolre^i frjm it. aai :he Ii>ji:<i remaia:* turbid after the brown film wluch
fonn.9 OQ each aii'iicioa ha^ be<a remoT^I ;^if an excess of carbonate of
lea<l U a«id•^l. a baei'.* :ea«i «ait i;$ precipluted together with a lead-
eompoan>l of the resin with which the acid is contaminated. ) The warn
filtrate '.e«!omes tart- id, and after a few minutes depoeits red drops ol
liquiil. and the solution d*? can :e«l therefrom deposits, after 12 hoon, ft
rather large quantity of n:tro<?aIicjL&te of lead, which mar be reerjitftl-
lised: the mother-! iqa<.'r <t:II yields a ci:'nstderable qnantitjr of salt Ob
decomp«^»io.r the warm aque^aj «oLu::on of the loail-salt with fnlphsris
aciii. n'npj-s.ili'.-vllc aci i csy?:a!l:i».s froni the I'qaid in needles harin^ i
fa-nt yvll-iwi.-ili tint. PerVeciIy col-uriejs liee^llcs are obtained bj decoBh
po-in^ the tiirb;<i M^lution uf the lead-^it with nitric acid. (CheTreal,
Buff, Man:hand.)

2. FiH^in^ nitric acid is poared, with constant stirrin^f upon nlicTlic
acid c<»ntaineii in a ves;<el surrounded by cold water, till frnli additJoM
of acid produce no further action, and the reddish yellow i

Nmi084fc!CtLIC ACID.

p.

tfina produced is washed with cold water^ dissolved in boiliujir water, and
left to crJ.*^taHise by coaliujE'* (Gerhrtrdt, Marcliiind,)

3. Methylnitroanljeyiic acid is decomposed by boiUn;; with potaah,
the brown-red Ifqufd supersaturated with weak hydrocbloric acid, and
the separated flakea of the acid crystallised* (Ciihours.)

4. Wheij one pt. of pulverjtjed salicin ie fihaken up with 10 pie. of
nitric acid of SO"" Bm. till the whole is dissolved, and the solution is left
to stanil iu a stoppered bottle at a temperature of 10*' to 15°, it deposits
crystaia after a while, the quantity continuing to iflcrease for more than
a week; they dissolve for the most part in ether, leaving a residue of
helicin. The ethereal eohtion yields, by evaporation, cryetab of nitro-
salicylic actd having a faint yellowish colour, (H, iLijor), Piria, by
treating salldu in the same mantii^r tn op«a ^esselfl obtaiaedt (agether with helicin, qatf
tmces of tiitroftalicjrtic CaaiJutiuj acidp

Properties, Colourless needles having a bitter, rough, somewhat
acid taste, a slightly sour, pungent odour and feeble acid reaction.
(Che V real. Buff.) Melts when gently heated and crystallises in six-sided
tables ou cooling* Sublimes even at a gentle heat, and if the heat be
carefally applied, mvky be completely volatilised without docompositioiii

Buir.

Damii.

Oerhardt.

€aliOQr«>

14 C .....„*

84 .

14 ,

,. 46-27 ...
.» 7^48 ...

45-73 .
. 778

.. 45-32 ..

.. 45-55

N „....

...,

7*55

* H _...

i.»

5 .

., 273 ,

,.. 2-11 ^

276 .

„ 2*83 ..

.. 2*98

10 0

..,.

60 .

., 4372 .

... 44-14 .,.

. 4373

43-92

L

-'

183 .,

.. 10000

. lOO-OO ..
M ■ r € h

100 00

and.

lOO'OO

W

d.

b.

r*

d.

B

0

■^*.,,ii»»

..„ 45-49

,. 45*27 ..

.. 4S-8S

.., 45*fl8

■

n

**f .«.•*..

¥•«

7-67 .

.. 7-69

. . 7 70

■

.>itt».«*

2-75

... 2n .

.. 276

... 2 81

W

0

■■-

4112 .

., 43-67

.., 43*61

^
w

100-00 _ 100-00 ..., 100 00

The add »aa] jsed by Bujf and by Dumaa wna prepared from indigo. Marehand
dried bit add a at tbe temperature of tbe »ir ; Aal 150° and e at 230^ i d wag prrpare^d
frvtn saUcjrlic add; ao likewiiv waa tb»t which Gerhardt &iialj»edi Cabouri prepared
bia acid from oil q{ wuitergr^en.

Dactyntposiiionit, 1. The acid snffera partial decomposition when

i|uickly heated^ giving off carbonic acid and nitrogen, and leaving a ,
large quautity of charcoal^ which quickly burns away in contact with the '
air (Chevreyl.) — 2, Heated in the air, it takes fire very readily and
buma with a rtry sooty flame- (Buff) — 3: The dry acid is not decom-
poaed by chlorine gm. (Buff.) — Chlorine gas parsed into the hot
aqneous solotion converts it in a few duys into cfiloraniL (Stenhoiise.) -^
\Am Boiled with cMortUe of potash ana h-^drfjchlnric acid, it imrnecttateljf
yields chloranil and carbonic acid* (Stenhonse, Hofmann.) Boiled with. '
chloride of limej it yields in a few minutes chloropicrin {but not nnder
J 00^). (Stenhouse, Jnn. P/uirm. 78, 5.) — 5. Stnmg nitric acid decoui-
po&es nitrosatieylic acid by boilings into oxalic and |ricrio acids. (BnC)
— 6. Hot oil iff tnlriol forms a brown solution from which water throws
down brown flakes. — 7. In contact with na^cait hydrogen, the acid dis-
edvea in water, forming a blood-red soltrtion, which ufet ^ ^\^^*

308 TOLUENE; OXYNITRO-NUCLEUS Ci*XH»0>.

deposits purple- rod flakea. (BufT.) — B. When boiled with hjditmiA^
pliate of ammonia, it h rapid Jy deoompnsetl in a Bimilar manDer to nitto-
n ap h th at 1 n , (Pirio, )

Comhinailons. a. With Waiti^.

Bydrated NiiroBalkplic mid. — Colourless neodlea (CheTreDK Btdf);

if the hjdmte hus a jdlowbh tint Mhile mobt. it b contaiDifiaCcd with picHe «ci4
(Dumas.) By exposure for some time to dry air, it loses 2 At, water; la
vacuo at 100^, it gives off 10"72 p. c. and at 150°^ lt*§ p, c, a portiOQ of
tbe acid eyapurating at the same time, (Marchand.) (Ciktikluiii gitalor
2 At. wate^r gf erjataJUfration, & losa of 8*95 p. c.)

{hf^mUtd. Marelxand

14 0 ..»». 84 .... 41-79 ,. 4274 ,„. <143

N , ,., 14 .... ^m

TH ,«... 7 ..., 3-48 3t57 ..,. 3'iT

12 O,, m ... 4777

C"NHW^ + 2Aq .,.. 201 ,,.. lOO^OO
M was prepared from ladigOp h from sallcytic aetd.

AqumuB NiiromlicyU^ acid. — The acid dissolvea in 1000 pts. of wH^
water, and in all proportiouB of hot water. The Bolation %& eolomteiL
(Buff-) J

h. With BaMs. — 1\i^ neutral uitrosallcj^latea are C'*XH*M*0*; t^«lfl
are mostly yellow, take ^re when heated^ without actual detonatiotij m^|
bnrn Like giiopowder. They redden ferric salts strongly. ^H

Nitrmoticifhie of Amvmnia. ^^ The aeid is saturated with amrooitia
and the hot saturated solution abandoned to spontaneoas evapomtiaiL.
Beautiful golden -yd law or orange-yellow uoedles. Anhydrous, gtYii flf
ammotila when heated, but afterwards the free acid sublimea. ^^

14 C B4 ... 42

aN .,..„_._» 28 ... 14

SH 9 »„ 4

10 O 80 40

Domu.
. 42 1
. 13*7
41

. 40^1

MardiAQd.

„ 41 §0

. 4 06

200

100

lOOO

loaoa

NUroicdic^hU of PoktMh. — When the aeid ia d!«solri»d in »qQ«»if^

Cberreul
lieedle«.

tbe salt in red crystals;

Buff^ io orang»jp<HKf

KO, ._„,. 47-3

C**NH*0' .., 1740

21-34

mm

Mareiutidi
.. 2132

9"KH*£0* * t%vz .„, }oa 00

UlTROSALtCTLIC ACIdT*

309

SUromHq/laU of Soda. — Yellow ciyatala soluble in water.

Ni^romlhylftt€ of Bartfta. — a, Neutral. — 1 . Obtained hj continuous
heating of the salt b. (Marcband.) 2. By boiling b with baryta- water,
(Marchand.) -- 3. By boilbg the hat aqueous aolutiou of 5 'with
ammonia. (DufT.) — Yellow powder resembling cbromate of lead.
Dissolves sparingly in cold, somewhat more readily in hot water,
(Bu£)

2BaO „ 153*2

C^NH^QS ..._..„ 165 0

6 HO „_. 54*0

BuJf,

M^rctifltid.

4115 ,.„

.... 41-04

.». 41-26

4432

1453

C"XB*B«*0* + GAq ,.„ 372-2

lOO-OD

h. Add. — The aqueous acid is boiled with carbonate of baryta, and
the hot-filtered Bolutlon left to cool, if the add U «ut quite pure, a yeUow
powder peroainfl miied with the iniolublc carhoniite of bjy7U. (MurchanJ,)^
Beautiful shining needles united in tufts, (Buff, Marc hand,) Contain a
5 At. water, four of which are gi?en off at 200"^, the remainder only
when the salt begins to decompose^ At a strong red heat, the salt
decomposes, with strong intumescence but without detonation, throwing
out carbonaceous pyrophorio masses, which immediately burn away wbea
exposed to the air and leave carbonate of baryta* (Marchaud,)

Ai 200'.

BaO _.... 76^6

CHNH*0* 1740

HO ,.,„., ,. „ S'O

Marchftod,
from indigo. /rom taUcylieacid,

2&-51 3034 30-56

67-02
3-4?

C^*NH*BiO«' + Aq..„ 25t'6 . ,. lOO'OO

Ory*taJiiMid. Mtrcband.

BaO..».., 76-6 .„. 25^02 „. 25-57

C^^NH'O* „...._ 1740 .... 58*87

HO... 9^0 ,.., 3-04

4 HO 360 ... 1M7 ........ 12-67

C'^NH^BsQi" + 5Aq 295*6 100*00

The nitrosalicylates of strontia^ lime, and ma^iiOi are yellow and
diseolvo readily in water, (Buff.)

NitroMtlicylate of Lead* — a. Neutral* — Obtained by treating the
Bait c with hot ammonia. Dark yellow, very fine powder, perfectly
insoluble. {hu% Dumas.)

2 PbO ., „.

... 223'6 .
.., 174*0 .

.,. 56'a4 „,
... 43^76

Bttff,
.... 56-14

.,. 55-3

C**NH*0«

C'*NH«PiTO»« -h Aq .

. 397 6 .

.. 100-00

h, Se^uiba9ic. — When nitrate of lead is added to a hot solution of
-" of nitroBalicylate of potash, the liquid deposits delicate needles of

SIO

LUBNKs OXINtTRCHNUCLKllS t^fXIIMl*

tit froo nitniPialicylic ncitJ. Tho mk i« olitniiird in ft It»*ii i»arf iUii4
jfittffl)

... U$*fi .... &a*93

I PbO ......

SPbOjC»*NH*0« ., etl3'4

soomi

f. ^fwl, »- 1, Obtniii('(1 by grn4luii)1y adding fiilfosR^ic^yleitfi tt
to nn ^]icr*ii af liot mjiioouip nitmte of lo'id, — ?J* Wli»*n ra *
Imul ii mlUetl lo n licit iu|umiiiN solution of nitrasalirvlio »oi4 tiU tli
t^tforveNei^nro Uf^coiiirii nlow itnci n few yotlow flnkot cofiftriWi llio ]i<|«U, tf
ill te rod hot, ilopo^iu tlin iidtl nail in ory«tnl« im it i^>ol»* — Bjr iKt im
^ j^roeoM; tMil*i yollow Imlky pri>n|»ituto» \v\iw\u •ft*^' wmihlnf witb «M
' w«t«r &n<l i!rjm|2', proMMiUi tl»e aiiiM^iirnneii ivf n pule yi*Ht)V cnpvtelLiai
■najta. — Thr M^emnl imiooim yi^ld* yi^llow ill d^flned efy«lftlik-^Tli#nU
ia •omiswiuit inon^ hoIuIiIh in'wiitof ili5>i ilit^ fr^# ftdd. 90 ibui 01
nitric acid in lU aoluli#n» uitTomkioylie ncid la fftotptlAUid. (Ball)

>t)«|«(.<Ui[^* 1

110

174 ft
9*0

(I) (t>

31 «iti . ua

D*«XH*PtiO» 4. Aq ,. 304 H 100 00

^w^ttmi witit rrrir iixido mid ri'ddt^np ff^rrlc iinltm <CUrvreul«) Ji«ii
flilroaRliryliitif c^ry^lallini'fi in iltirk tvd, nhnojit Mnek r«^d no«ill«, whk
dia«olyo Kjiariuj^ly in cold wmor. fHrmtti|( n Muud rml notutiaii. (B«f)

Vuprk yifmmliryitfff, — 1*kct iii|tti^nni •eld diMnlvea cnipric cixido tinf
kfiftdily ; l^it tlio unit k mUMa outy in hot wMor, mud aqmrntf** %^in ^
f^^uthikm un fooling (BufT.)

ry<i

Mftrtffitm Nih'ottffiei^ffte, — Tlio iioliimb-niilt fontia wiiH merem
idtmic II p(%l^ Tollnw pt^oipitAtfv ytU'wh li not c*!iMi|y dc<N>iiiimafd k^
bydroddona nnd. It in irmolnUlc in cM, ntul HpAtlitgly wdntdfi in b«t
water, (Biift*)

flf^ =.. tm

c'^Niiw 4. loiio m

Bur

e^'XH«lt|«(l' 4 IOAh . 47i ... 100 00

nt tha boil in jf brut, but tlvc« ttdtiiim

eonthiut^l (Cb<i¥rmd ) Ntsitbor niirtiKunevLiciuTMi nur niiriMmli
|iotAal» }*n<ci|dtiiitri nttrnU uf iiKi^r, Nitfo«Alicyl«to ttf munM
«iioM with nitmli^ of lilvcir ft Jigbt yollaw jm^oipiiAtt uliicb

Hio auuooui ]if!id dintolvf^a oxldt of »lvvr
aiimi (diflkon* if tbo boilttig Imi %tm t^H

' niifumUvyWc VkeUi nt*T nilitMmltevkli «

METBYtNITltOSAUCYLiC ACID.

811

pretty re&dilj in boiling water; t!ie Aalution elfloregcoa eH^rhtly wlieft
cyapor&tecl. (Dumaa, Marc-hnnd.) Small light red tieedk*!^, htjluUe witI|T
difficulty in cold water. (Buff.) Straw-cnS<>ured needles united io fik^llatfj
eronfyn. (Marcliand); they become durKer in colour by expogur^ i*^ lightJ
(MBJor.) 3

3fi-C6
29-22

151

Mardiond.
.. 3&"80 .
. 25 00 .

». I 54 ,
2§2I

Miijor.
3? 05
2920

l&O

100*00

100*00

The aalt dot** not detotintc? when heated, but throws out shoots of
earbur<*t of njlinr, which humi! and leave** jiare silver. (Marchand,)

The acid dliiolvea in akohalj id alt proportiotii at the boiling heut.

MethylnitrosaliGylic Acid«

€4^017110. (IB41.) #. Ann, Chimt. /%«. 10, 345; PAarm. Ctnir.
1844, 438.

WhcTi fuming nitric acid is added to methyl saUcylic a^d, cooled
that nti «t|>irting m;iy tako place, ttio lit^uicl boou BoLidiiies in a cryAtalliuo
' tna^ from wliicb Oie free nitfio acid m\iy b^ exiracted by boiling water:
the f^rodiictniay be purified by two or tbre« crystallinatieua fritm dcaboL
(Caboiire.)

Very delicate yollowisb needles which melt between 88^ and 90"^, and
may fcir tJie nioet part he volutilii^d without decompofiitiun.

feCthot]F•.
lie U »« 4i'73 ,...,„, 48*53
K ,♦-, U - .. M0 ...... 7*27
7 H ,„ „„... 7 .- a*5& ...... 5*fi5
lOO... .10 .... 40e2 40-6&
c«NH'ow Iff imm 100 00
npotiiiam. h When fuming nitrio acid in eligUt exoesa ii
r added to metbyluitroBJiltcylio acid, a bri^k action takee
liiiwt;, ufid tt dark red i*oiiitiou i« 'formed. If the mixture be not
cooled bnt gently heated at the last, tho It4uid become* turbid and
iltpCMtt* dropJi of oil, whitd), if tbt? heal be dit^contitiued a« «oon a« they
fifiBM lu incrtane* forrn ^ yellow reiiiuous imi^ii; and this ibubatanoft^
when diwolved in hot alctdvof, separatwi* almobt eouiplctcly on coulittg in
pale yellow iieedlcH wbieb molt at 1>.^ , and fnriu on cooling a yellow
wmA'yMd ma«a, wb id*, if 0*irt?f*diy raiwjd loa higher tefupemlurt'j tubUmea i
m pale yellow iilendcr ncedlca; it dii^HoWcd lijiaringly and with idiglilj

it^ntt^3Rirr

:i^ r ^«* Sjnm. F^m. r*. ;

Himri niiw miiiuiK^ iumii. iic j«««snfc ttj%. '^

?4I

5:-:!

»ik«

0*>iV-

:w-K»

t.'vvf 3 tnui iMifi «r 4

BINITROSALICYLIC ACID.

3ia

Appendix to NiinymUc^lvc A dd,

Nitroxybenzoic Acid.

Iebland. Ann, Fharm. 91, 192; Pha}^fi. Cenlr. 1854, 829.

O^jben^oic acid is treated with nitric acid of ap. gr. 1 '36, and tlie

excess of nitric acid evaporated over the water-WtL The aolution of

the yellow residue in hot water yieldji beautiful yellow rhombic crystala

bfivttig an un pleasant bitter tastej thej may bo purided by repeated

, crjstdliaatioD from hot water*

^^b Geflatid.

^B 14 C .., »4 .... 45-90 45-95

^B N U .... 7^05

^H 5 H 5 . . 2-73 317

^m 10 O _. BO ... 43*?2

C»<NHW.. .... 183

100-00

When acted upon by strong nitric acid, it yields 6!ib8titut(on-|>roducts
in which 2 or 3 At. H are replaced by NO*, and which detonate with
great violence wbeu heated.

The acid dissotvea readily in hot water. The eolation has a strong
yellow colour even when dilute.

The acid expels carbonic acid from its compounds and forme crystal'^
livable salts.

^Uro.T^hmssoa(e of FijtUMh, — Crystallises readilj in b^iantiful yellow
shining prisms or needles, very much like picrate of potaah. It dissolves
very sparingly in coldj readily in boiling water. Gives off Jta water of
erystailisatioa at 100^

Gerland.

KO... 47*2 .... 21*34 ,.. 21-62

C**NH<0» .... 174-0 ... 78"e6

CHNH*KCy,.. 121'2 ,„. iOOOO
Decomposes with slight detonation when heated.

Binitrosalicjlic Acid.

Cabours. (1 849.) N. Ann. €him, Fhys. 25, 11; Ann^ Pharm, 60, 2S2j
J.pr, Chem. 4^^325] abstr. CfmpL rend. 27, 485; Fharm. Cmir,

1849, lea,

SxENiiOLisK. PhiL Tram. 1851, 143; Ann. Phami, 78^ 1 ; Pharm. Ctntr.
1851, 434*

N\if^9j^w^urM^ Acidt mirotmlicgHqut Amitn*

311

TOLUENES OXTKITRO-NUCLEUS C^*Xm*aK

J^rmation , 1 , By tb e ac It on of n 1 trosu 1 ph a nc ac id on uiethy l«i 1 iejl 5e
acid. (Cahours.) — 2* By beating the aqiieooe extimct of the braochei ol
J^npului baliamifera or Popuius ni^ra witL dilute nitric aeid, (Stenho ^~

Prrpa ration. 1 . Frovi Metht/IMnitros^jlic^Ite add. — WBeu meth
binitrosalicylic acid is boiled for a few mitiutdS with strong cauGtic pol
a brown-red solntion la formed, wbicb on cooling deposits red binit
Balicylate of potaab. This salt, or the yellow eiilt obtained hrtm it
boiling with dilute nitric acid, m treated wttb fumin/; oil of vitriol at
temperature below 50^, whi?reby sulphate of potash is produced* T]
binttrosalieylic acid ie precipitated from the solatiyn by eold wal
(Cahours.)

2, From Nitropapulla acid, — The chopped branches of Pt
hafmmi/era OT Populus nigra b,tq exhausted with boiling water, the
bro^vn bitter liquid evaporated to an extract, and this extract heated f^jf
24 hours with dilute nitric acid, whereupon large quantities of nltrooi
vapours are erolved with a pleasant aromatic odour. At the boilin
beat not lung hut jiicric acid would he formed. The liquid ia evap
to dryness over ihe water- bath, the residue dissolved in a large qi
of hot water, and the liquid filtered through a cloth after cajoling— w1
Tipon it deposits a large quantity of resin, which wlien treiited wii
nitric acid, etiii jrields a lar^e quantity of binitrosalicylic aeid. — Tbi*
dear liquid is then concentrated over the water-haih, and after cofilinf,
exactly neutralised with carkinnte of potash, wberenpon it grmdoJilij
d^io«it« pierate and binitro&alicylate of potash in epy£t»l«, wbik eitiUl*
and nitrate of potash remain dissolved. The cryelal^ are waah«d with
cold water, pressed and triturated with a email quantity of eold dibte
carbonate of potash, which disaoKxs the bin itro^aticy late of potash; tb*
solution ifi filtered from tlie picrate of potash and sHglitly su|>^r aturmte4
with hydrochloric acid; the binitrosaHeylate of potasli, which is pTe«|iK
tatedin the form of a crystalline powder, is waalied with a small qaantMy
of water, and redit<sn]ved in a very ©mall quantity of carhonaU* of puta*^,
which again leaves picrate of potash nndlssohed; the binitrosancyliie
of potash precipitated with hydrochloric acid, and repeat**dly cryst^-
lised from hot water with addition of anima) charcoal; and the now light
yellow suit, is boiled with a large quantity of liydrochlorie acid, Btnili^
sa 1 i cy 1 i c a € id 1 1 1 en c ryti tal I i ses o u t^ a t i 1 1 con tarn itkated w 1 1 h a y c^H o w en h>ata»<t
which adiierea to it closely* but may he removed hv crv^allisatioo, fint
from hot hydrochloric acid^ then from hot water, witli addition of aniiaal
charcoah The crystals are quickly freed from the m oth er- liquor ^prevad
between paper, and dried in vacuo.

Properties. By shtw erystallisation it forms small, hard, e4>1oafl««
priems; by quick cool in c;, needles having a silky In^tro. &lptti ml >
^ntle beat and sublimes nndecomposed whenearefully heated. (Cahoorip
StenhouseJ The air-dried erysti* Is ^ive oil' io vacuo t'21 per ci?aL of
water (2 At. calc. 7*31 p. c.) (Stenhouse.)

VI G ...

m N (wiMM
4 H .„.»..

14 O

US

se§4

12*30

17S

49 J I

Cihoori.

. aeet

. 11-25

. 4509

3wl .. ^il

1-75 l^

...... -19-31

c'WH*o**,... 2a8 ,_ iwm ,... im oo 100*00

BINITROSALICYLIC ACID.

315

DttompoikionM, 1. In contact with tlie air, it burne witli a bright

Same. {Stenbouse.} — 2, Expoae^J to the air in tlie in olst state, itqiiicklj
turns yellow. (StCDliouse.) — 3. By Wling with strong nkrk a-cidf it li

quickly coiiT«rtcd into picric atiU. (Cftliours, Stenbonse.) 4, Boiled

witli hydrocUloric ucid and cblorate of potash, it fornis cUtoranil. (Sian-
liouae ) — 5. It h not decomposed by cbWido of limo at ordiniiry tern-
j>erature3, but if the liquid he boiled^ violent elTervescencf* takes place
and cbloropicrin is given off in abundance. (Stenliousi?.) — 6, The solu-
tion in oil of vitriol decomposes at lOO"^, giving off salpharoua acid and
I leaving a carhonaceoue masa, (Cab ours,)

^.

C^ymhinatmu. The acid is Tiearfy insoluble in cold water i*ut dissolves
abundantly in hot water. (Call ours.) It dissolves readily in water,
fornung a yellow solution. (Stenhonse,)

It dissolves without decomposition in sli^^htly heated oil of vitriob
and is prmpitated by water. (Ciihonrs.) In dilute sulphuric and hydro-
chloric acidj it is less soluble than in water, forming pale yellow solutions
which become deeper in colour when farther diluted, (Stenloiuse.)

Tbe htnitroaalicylates are mostly yellow and sparingly sojuhle in
water. They detonate violently when heated. The formula of the
neutral salts is C^*X^H^MW.

BmitrmaUc^late of Ammtmia, — The aoid dissolves readily in ammo-
nia, and the solution when evaporated forms beautiful small yellow
needles. (C ah ours,) It is somewhat more soluble in water than the
potash -salt. (Sten house. )

U C .„ .,,... 84 .... 34-28

H N At .... 17'H

1 14 7 .... 2*85

14 O 112 ,. 45 73

C**X^H'CNH*)0* .., 245 .... 100 00,

. 34M6
. 17-3B
. 2*78

100*00

Mifiitnysaliriflaie of Potash. ^^ a. Kmtral. — Produced when nietbyl-
nitrosalicylic aeid is decouipoticd by holjing with excess of strong potash-
ley* Beautiful needles having a splendid yellowish red colour undsuiny
luitre, and united in stellate eroups. Appears to be completely decom-
posed by continued boiling with poiaak JJetonates violently on glowiuy j
I coals or on a hot plate, (Cahours.) ^

Citbourt,

2K0 „ %iA ... 30 05

14 C 84-0 .... 26*B3 ........ UO'IS

2 N 28 0 .... %-m .„..,.. 9*05

3H_„_ ..„,.._ 3 0 ... 0 95 ...,,.,. 1-Ofi

13 Q 304 0 ... 33*22

C'^Xni'K^ + Aq 313-4 .. 10000

h. Monohmk, — Produced by nen trail?' ing the aqueous acid with
car bon ate of pota eh . { S ten b o use ) . or by ^ hea ting a with dilute nitric
acid ; it then separates on cooliug. (Cahours.) Small Icmon-yelJow
prisms, (Stenhouse.) — Tbe salt dissolves very sparingly in cold water^

316

TOLUENE: OXYNrTRO-HUCLEUS CWX'H^O'-

and not at all in alcohol or ether. (Cabours.) It disssolTei rery readil'
in alkali ae li<juida and i^ precipitated therefrom hy acids. ( StenbousaJ
It depuisitt^ the free aeid when hoited with strong bydrochlorie acldb
(Btenbouse.) It dissolves in slightly heated oil of rUno], and tbi
iolution^ on being mixed with water» deposits the acid in crystalliat
I&tniA». (Cahoars.) It detonates on glowing coabj but not so etronglj
ma a.

KO

14 C „......».

2 N »..

.... 47^2 .
.... 84-0 .
.... 2fi'0 .

„. 17-66 ...
... 31-58 ...
... 10*63 ..,
., 1-13 ...

... 39-10 ,,.

Caboun.

17-46 ..

31-32 ..

10 33

I 17 ..

39-72

17-49

..... 31-4 J

3 H

.... 3-0 .

1-17

13 0 , ,

... 104 0 .

c**xm»Ko* ....

.,. 266-2 .

., 100-UO ...

lOO-OO

BmilromlkyhU of Soda^ — Obtained by neutralising the aqoeoa
acid with carbonate of soda, (Stenhouse.) Small i»picular cryitala^i
(Stenhuuse.) Yellow shiniDg needlea (Cahonr^,) Hare soluble iif
tvater than the potash^ salt.

NaO ,. ..... 31

C^Nm»0*« .... 219

12-40
§7-60

Stfitiboaae,
... 1234

C"X*H»iraO« ... 250

lOO^OO

Miniirmalicylat€ of Baryta, — a^ ^tfttfra/, -*— Boiling hsryt^-water i
19 added to the boiling aqueous solution of the acid as long as » precipi-
tate is foi-med; thii precipitate is then quickly washed with hot w&tcf
and dried In vacuo. Very sntali cryetab.

2 B»0 „.. l&3*2

C"N5H*OJ* , 210-0

41-16

5S-g4

Stfulioiiae.

... 4M2

C**Xm^B»=0» + Aq ... 372 2

lOO'OO

h* Acid. — Baryta- water Is added to the hot aqueous acid ^ l^yn^^
the resulting precipitate rediseolves on agitation. The aolutJon on oooU
ing yields cryjitaliiae grains which are dried, first io vacuo, aflarwarfi
r ©v©r the water- bath.

B*0 ............. 76*6

C**N»H"B»OM 2190

2hn
74*09

Stenbooie,
.. 2^-84

C"X^li*BiO»... .... 2956

100*00

The aqueous acid ccbnrs/«'rfioii« salts j el loWj/^rmc salts dark red.
The piitn^h-Hiilt precipitates neutral and basic ftcetate of i^mt with
Ihe aid of heat. (BteuhoUfie.)

BinUro»niUiflate ©/ 5ilwr. -- Separates in ttnall crystalHtie frmjfii
from the solutiou of carbonate of silver in tbe ftqueous acid. (CabonTtft
Btfubou^e.)

METHYLBINITROSALICyLiC ACID. 317

Cahouri, Stenhotifle.

Ag 109 .,.. 32*24 .... 32*00 .,. 3^-28

HC_„ „,, 64 ,.„ 2V07 .... 24 69 ........ 24*84

2 N „ 28 .... B^m

3H 3 ,. OSS ... I'U .„ 0*94

14 O 112 ..„ 33-44

CMX»H»AgO« .,.. 33& ... 10000

The acid digsolFea in alcohol whether weak or strong-, m'^rercadUj
than in water. (Stao house.) It ie very sparingly soluble In alcohol and
etlier. (Cahours.)

Methylbinitro salicylic Acid.

^Cahouei, (1849.) Compt, vend. 27, 485. — N'. Ann. Ohim, Phya.
25, 6; Ann. Phmm. 69, 230; J. pr. Chem. 46, 321; Fkarm. Omtr.
^ 184D, I6K

^P Formalion and Preparaiim, When methylsaltcylic acid is dropped
^^t)to a mixture of fuming nitric acid and fuming oil of vitriol kept cool
by cold water, a clear dark orange-coloured liquid ia produced. As eoon
fte the drops of methylsjilicylic ncid cease to dissolve, a small quantity
more of nitroaulpliuric acitl is added^ the mixture shaken till the iolution
i« complete, and the liquid after some minutes diluted with eight times
the quantity of water, whereupon the methyl hinitrosalicy lie acid sepa-
rates out and maybe crystallised from solution in boiling alcohol. The
aq^ueoua mother-liquor contains methylternitrosalicylic acid,

" Pjnpirties. Yellowish white crystalline scales which benjome nearly
colourless after two crystallisations, Heavier than water. Melts
between 12i° and 125°, forming a pale yellowish liquid which solidifies
in a fibrous mass on cooling. Volatilises completely when carefully
^eated in a retort, and sublimes in very delicate shining laminee.

CahouTBi

16 C - 96 .... 35^66 39-42

2N 28 ..„ n-&7 ........ 1P61

6 H 6 .... 248 2-54

14 P.. 132 .... 46-29 4643

C«X^H*0^.,.. .„ 242 .... 100-00 ....... 100*00

DecomposUions. 1. When suddenly heated, it detonates, and dceom-
poses completely, emitting a black smoke and leaving a copious carbona-
ceous residue* — 2* By continued boiling, either with fuming or with
commercial nitric acid, it is completely decomposed, with formation of
picric acid. By the continued action of nitrosulphuric acid, it is con-
yertod into methylternitrosalicyUc acid. — 3. Its solution in oil of vitriol

318

TOLUENI: 03CTNlTRO-NUCL£i;S C?«X»HK3»-

girea oft carbotiic acid between 75^ and SQ^; jf it be gmdoaUy hmX^
and too great a rise of tempemtiire prevented hy frequent Immersion m
cold water, a <?oloarIesa lL|t]td is formed, which h rendered turbid hy
addition of a lar^'^a quantity of water, and on cooling yieldsstuaUflbiiiJo;^
needles, wliicb diasolre readily in boiling water or alcohol, and ci^dtat*
liao on coolinj^. — If the aolation in oil of vitriol be heated somewbat
more quickly or above 100 » the liqiiid tarns red and ultimately black,
giving oiF carbonic aud sulphuron^ acid^, and deposiLa brown fiakes vbeii
mixed with water. ^4, Boiled with strong potoab^lcj, it forma biniiro-
salicyUte of potash and me thy lie alcohol,

ComhinaimM. The acid ia insoluble in waierj evea at ibe boiling
beat.

It di^olves in gently heated oil of vitriol, and m precipitated ther«-
from by water in nearly colourless sealea having a strong lustre. i

It does not disioUe in nitric acid either dilate or eoneentra.ted. — II
dissolves without decorupo^itlon in fuming nitric acid at temperalurvi
between 30° arsd 40", and m repreci pita ted by water in it9 original
The solution in gently heated nitrobydrocblorio acid deposits on e
needles of the unaltered Bub^tance,

With talifiahle base^, the acid forma the nhHh^lhimirmolu
ifi€tulihirai€9 binilriques.)

Mttkylhmitnmilicjflale of Ammaaia. — The acid dissolves in
nmmonia, and the solution on cooflrig depoii is yellow transparent needles,
which diidolve sparingly in cold, readily in hot water* AcldB precipital*
the methylbinttroaalicylic acid tn its original state.

M

itsc ,_.....,...

3 H „....

Stt

u o _._.

.. It .

.. 112 .

... 37-07 ..
. lG-21
... 317 ...
.,* 4323

... 36-97
.... 5-47

C«xmHNH<)0* .

259 .

... 100*00

Methylbinitrosalicylic aeld dissolves without decomposition In di]at«
pQiath or $oda-\ey^ forming salts wbiob crystal tii<e by evaporation.

Mfthfflbinkmmtlieylaie of SUvfr. — Nitrate of «ilver added toadib
aqueous eolation of the amnion ia-imltj forrn^ a beautiful yellow puJve
precipitate, which may be washed with water and dried in vacuo,

CaSkoura,

le C _ 96 .... 27-50 , , . J7 15

2 N ..,. , sa .... a 02

&H... & .... 1-13 — ** 137

A$. 108 ..„ 30-94 ,«...,. 31-24

Ij Q 112 .... 3211

C»X*11*A|0« ... .... 349 ... 10000

MethylbitiitroF^licylic acid is nearly insoluble in cold aleobot,
diaaolvea readily in that liquid at the boiling hmt.

MlTHVLTErtNirROSAUCtllC ACID. 31fl

Ethylbinitrosalicylic Acid«

C^^N'HW = C-H*0,C^*X'HW.

Cahocks (KS49.) y. Ann. Chim. Pk^t. 25, IB; 2T, 4^3; Ann. Pharm,
eo, 235; 7i, ;S13; /, pn Cliem, m, 332 j 49,232; Ann, Pharm.
1849, 164,

Biftilrotaiic^hmeaier, Eihtr mUc^liqtte biniir^,

Fofifn/itton and Prrparfttion,. — 1. Wheta bmilrtMalieylio add is dis-
eolved in absolute alcohol, tlry hydrochloric nM ga^ passed into the
boiling solution, the W^md evaporated to ixie-half, and water added, a
heavy oil is thrown down whtch soon solidifies; and if this oil he washed
several times with water and then dissolved in boilinfr alcohol, the aolution
on cooling yields crystals of ethyibinitrosiilif^licacid. — 2, Ethyl^licjlio
acid is treated with nitrosulplniric acid in tho same manner as methyl^
£&lkyUo acid for the preparation of methylbtuitrosalicyliDftcid.

Properim. Beautiful yellowish white scales and pktes. The com-
pound melts at a gentle heat and Bolldides again in the crystalline form
on cooling. After being heated for some time, it remains liquid for a
eorisiderable time on cooling and then eolidifies in the form of a resin.

^F Boiled with potash- ley, it yields alcohol and binitroaalicylatd uf
potnsh.

With alkalis It forms aoluhle crystalli^ahle salts.

O^piitro-nmlem C'^X^H'O*.
Methyltemitrosalicylic Acid.

Caiiours. (1849.) C(mpt rend. 24, 553; ^^. Arrn. Chim. Phjs. 25, 20;
i /. pr, Ckem, 46,321; 49, 282 ; Ann. Phann, 09, 230 ; 74, 313;

^ Pftarm. CentK 1849, 165.

I 81

CHhoari.

(I) (2)

IS c. ,,.

IS ..

.. 4rii ,.

.... 42 21 ... 42 31

2 N.

28 „

» 10»4 ..,

.... 1076 „. 1070

d H ......

% .

. 3-12 ...

..... 3'30 ... 319

14 0.„.

112 .

.. 43 75 ..

.... i3'83 .., 43-80

C»X»H'W.

2i4 .

. 100 00 ..

..... lOOOO ... ItJO 00

k

Formed by the continued action of nitrosulphurie add on methyl-
salicylic acid/ and is contained in the motherdiquor from which the
methylbinitrosaUcylie acid htia ciystalltsed out (p. 31?); it separates In
%h& crystalline form when the muthar-liquor is evaporated. After sola-

S20

TOLUEMl: OXT-AMIDOOEN NUCLEUS C»*Ada*0*>

tioi] Tfi cold fiilcohol, in which tlio meth
eoluble, the tern it rated acid is obtam&
ifi difficult to purify from plciic acid*

bylbinitrosalicylic acid i« mucfb !
ill b yellow t ran spa rent tables.

16 C ..,._

3 N

... 96 .
-» 42 ,
... S .
... 144 .

» 33*45 »
«. 14*63 ..
., 1-74 ..
-. 5018 ,

CAboan.
....„ 3295
..,.« 15-19

5 H

18 O

1-61

5025

CiWH^OiB .

,. 287 .

.. lOO'OO .,

100 OO

SalicylamiG Acid.
C^NH^O* = C^AdHX>%0'.

fROCTTfiR. (1843.) N: J, Phnrm. 3, 278; Ann, Pfrnf-m. 4^~^

X pr. Chem. 29, 470; Pharm. Ckntr, 1843, 699.
Cahocbs. j\\ Ann. Ckitrt. Fh^s. 10, 350; Fitarm. Cmtr, 1854,55, m.
LiAcpRiCHT. Ann, Fharm. $B, 25S,

Formation. By heatiug aalieyUte of ammonia^ or by thm
ammonia on methylsalicylic or etbjlfialicylie acid.

Preparation. When methylaalicylic acid is ahak^n np with amii
it gmdually disappears; and the brown solution when evaporated^
crystals which may be recrystalliaed from boiiing alcohol, (Pn>cttr.) —
The compotitid is not fornifd by the action of ammnniificAl g&s on oil of wiotM|m»
(UropricM.) — 2. On© measure of methvlaalicylic acid placed for mmm
daya in a closed vesael together witL 5 or 6 mea^^ures of utaistel
al cob olio ammonia, gradually disappeare and forms a browD -yellow Bdili
which} when evaporated to oDe-half at a gentle heat, depusiti Imf
needles. On evaporating the lic^uiil to dryness and distil ting the reMi%
ammonia is given off at first, and after warda a liquid coUecta in the tipfier
part of the retort, which soliditiea in the crystalline form on cooling;
thia liquid is dissolved in ether and the aolntion left to eTaponlft
(Cahonra^)

Froptrtiet, Yellowish white laminae having a strong lustre. Mdti
when gently heated and volatilises iindeeomposed when carefully mmi
to a higher temperature. Has an aromatic odotir like that of aiikiel
and reddena Htmtis rather strongly, (Cahours.) Four-aided primii vrtti
di|iedral summits which melt at 118°, and at a tempemtufe a hm
degrees higher, sublime without decomposition in amal! sealea. loodor-
ona^ or having an aromatic odour only after cryatalliaatlon from akuhoL
(Procter.) — Crystallises from boiling water or alcohol lu long laniiDS
having a yellowish colour not removable by treatment with atiitnal ch»^
coaU Has an acid reaction. Melts at 102^, and gublimc^ undeeonpiii'
at thia and a somewhat higher temperature, in lari^ eoloarlen * - --^
(Limpncht)

SAL1CYLAMIC ACID.

321

uc

N _

84 .

14 .

.,. 61-31 .,

... 10*22 ,.
». 5 11 „
.. 2S36 ..

Cuhotirs.

6106

1002

...... 5-29

23-63

LimpHcbt,
»... ] 0^3

7 H »»..

7 .

6-5

4 O

32 .

.... 22-7

C"NH?0* .... .

., .. 137 .

. 100*00 ..

100-00

.... 100^0

Tbift com pound U tiomeric with btitiiamic [amidobemote] and anthraniHe icidi.^
It has uittallj been regarded u saJtcjl amide, that is to «i^, a» the neutral amide

K( H fOf mdnohaaic aalicytic add (pp. 249, 250J. Bat Liinpricht has ahown that

1 H
It forma definite ialta with batea and maj be regarded as an amidogen-add fanned from

the tjpe ^*^ lo^by the aubBtitution qf the bUtooaio radical C"H*0"» for 3 At.
H in NHS itf rEtiosal formula being therefont ^*'*(^^*2^*^^)lo».

r Decompositions. L Wlien beated considerably aboTe ita tnoUing
point, it bcjgins to boH at 270% giving off water and small quantities of
secondary products {carbolic acid and carbonate of ammonia), and if tbe
operation be stopped when one fourth of tbe subatance is V'^latilised, tUo
residue conmste of salicylimide, C^*NH^O* = C^*.\HW - 2H0. (Litn^
pricht.) IT — 2. Ita vapour pasj^ed throagb a red-bot tnbe containing
quick'limo, yields a very small quantity of anilinej together with large
quantities of ammonia and carbolic acid. (Muspratt St Hofraann, Ann.
rhftrm. 53, 222.) — 3. Treated with fuming nitric acifif it yields a
beautifully crystallised fiubatitntion*product. (C'jihours.) — 4. ft h de-
composed hj Morine and brojniiie. — ^4. Treated with etrong bases and
acids in eiceesa, it is resolved into salicylic acid and ammonia. (Cahoura )

[Thia at Jitement reqiiirea modification {i?. ti/.)] — Dissolves Without decomposi-
tion in hot hydrochloric and nitric add, and is precipitated from Uie
solutions by water. (Procter) — f>. With cblonde of benzoyl, it f^irraa
l>enrofiaiicylamide [benEoaalicylamic acid] and bydrocLlorio acid. (Ger-
hardt ^ Cbiozza.)

ComhiimtHtns. Tbe acid dissolves sparingly in cold, more abundantly
in boiling *f*''^€'", and crystallises in long neetUes on cooling. {Procter,
C fill on rs ) T t d i^so I v ea read I ly i n potush - hp an d i n a mvioti ia . ( Procter. )
— % \i diasolvea in aqueous solutions of the alkaline carbonates without
elimination of c^irbonic acid, and cry stall i^ea out unaltered when the
Aolutions are concentrated. It dissolves reudily in warm aqueous ammonia
and crystallises out nualtererl as tbe ammonia evaporates. (Limpricht.)

Tbe SaiiC^hnnntfs of Poia^i arid ^SWa are obtained by decomposing
tbe baryta-salt with an exactly equivalent quantity of sulphate of potash
or flodaj tbe liquid filtered from the sulpbate of baryta and evaporated
to a syrup, solidifies in a radiated crystal line moss difficult to purify.
(Limpricbt.)

Salletjamaie of Bartfta. — The acid dissolves readily In strong
baryta- water and the solution yields by evaporation concentrically
groufjcd needles of the baryta-salt, easily soluble in water,

Salieu^amaU of Struntift. — Prepnred like the barytansalt, whicli it
mucb resembles.

Tot. XIL ^

I

322 TOtUENE: OXY-AMIDOGEN HUCL1C8 CMAdH»0».

At 100*. limpHdht.

8r 14 ..,, 24*4 24*4

C»NH«0* ,. 136 .... 7h*% „ 75 6

C"NH«SrO* „ 180 lOO'O - . . . 100 0

Saltq/lamale of Limt, — Obtained by treating tbe ftcid vitli nitk
lime. — Vcrj aolubte crystals uiuted iu warty grau|i8«

M 1(K>^ Limpnclit.

14 C .,.,...,..__,„ 84 .... 53*8

N .*...... 14 ..« 9 0 ... .,.. «-»

6 H .,„ .„»..« 6 ..^ 3 9

Cft... 20 .... 12*S 12*4

4 O -*. 32 .,. 20-5

0*NH*CaCH_.,., 156 ..„ 100 l>

SitUcylaTnate of Magneiia* — Obtained in warty, easily adal
cryataU by dige«titig salicybimic aeid witb water and m agnosia.

Tbe aulutions of tbe salicybtnabes of tbe alkaline eartbs a|»|ie^ ia
bo Ueeotn posed during evaponktioa by tbe carbonio acid of iht Ms*

(fJmprlcbt.)

Saflei/lamaU of Ctrpp^r, — Soluble salicylaniates form with
of copper a greeu precipitate conslatiug uf microsoopie crystalau

At 100'. Limprickt.

UC ..«.»... 84 0 .... mi

N « UO .... B3 ., 8-3

6H 6 0 .... se

Cii..... „.„ 31-S .... 18^9 «. 1§'?

4 O 320 ..-. 191

C'^NHHTuO*.... 167-6 .... 100*0

SftUci/lmmU qf Silver. — Kitrate of eilvar added to tlie BolytifflT
j%n alkaline an 1 icy lam ate, tbrowg dowD grey auiorpboud llakt^ wkiek
blacken wbeu the liquid is boiled. ^

Dried over oil qfvitri&L Umprit^hl*

14 C _.,. 84 .... 34^4

N ..._ 14 «.. &'7 &4

6H.» 6 ... 2 5

Af 108 .... 44-3 44-3

4 O ...„ 32 .... 13 1

C*<NH«AgO< ...^.. 244 ,„, 1000 f ,

Sttllcylamic acid di8SGlre« abundantly in uic^d and in €tJ^.

ETflTlSAl

883

T[. Salicylimide. c^^NHW

LmPRlcax* Ann. Pfmrm. D8, 261,

Produced by the action of heat on ealiojrUmic aoid fp- 321)* The
residue obtained by heating the acid to 270^ is washed with cold a-lc^dio),
to renioT^e undecompoaeil aalicylamjc acid; it thco coueiita of a yellow
powder, which under the microscope appears to cooeist of cry^t^illtne
needles* Does not melt at 200 ^ It la coloured purple by se84uicbloride
of iron.

14 C ,

5 H
2 0.

84

14

5

16

C"NI1*0* 119

Liiiipncht.

70-6 .

70-3

U-8 .

117

4*2 .

4^4

IS'4

13'e -

1000 .

100-0

^^ May be regnrded at N-f |, Ihnt ii to sa^ ai untnonia in which 2 H are

replaced by the bUtomia radical C^*H*0^. The formation of thia compouiid aiforda
dccifliire proof of the bibasic aatnre of saticylic acid.

Saltcylimide ia insoluble in water and in aqueous ammonia, but k
dissolved by alcoholic ammonia, forming a yellow aolution, which when
evaporated leaves the compound apparently unaltered. Acids decoloriae
the solution; acetate of lead forma in it a white precipitate, nitrate of
silver a yellovridi precipitate, and sulphate of copper a slight green ieh
precipitate.

It ie nearly insoluble in boiling alcohol and ether.

P

IT. Ethylsalicylamic Acid.

LiMFRicHT. Ann> Fharm^ 98, 262<

Obtained by thB action of ammonia on methyl sal icy late of ethyl
p. 258).

Bj tk« further Action of amnnoaia, neutral sdicjiamide appears to be formed :

Crystallisea from the liot at^uenu!? solution m small cnlourlesi! needles;
from alcohol or ether in i^omowhat thicker crystals. When immoreed in
» quantity of hoilini? water not sufficient to dissolve it, it melts into an
oil; but when heated alone it melts only at 110% and solidifies again in
the crystalline form on cooling. Snblimea at a very moderate heat*
Ha^ a slight acid reaction*

324

TOLUENE: OXT-AMIDOCBK NUCLEUS a*AdH*CF,

Limpricht.

ir, &. t.

IBC...,.,... 108 ,,., 65-4 65-i .... B^4 ... 6&-3

N „ «. 14 .... 8"5 B-5 .... e-5

U H ...„ 11 ..„ ti 6 , 0 6 .... S'8 _. 6-9

4 O ,-......».» 32 .... 19-5 19-5 .... IS 3

C^H"0*__._ }U .... 100-0 _ 100-0 ,.., lOO'O

a wfli prepared from methylaalicylate of ethyl obtaiiipd % beatJnf metfayljaUqrlftt^
of barytJi with sulphovinftte of potub to 100^ in fealed tubea ; the oi\j nentiml ether
thus obtain <rd was heaM vitb aqitcous ammonia to 100' in sealed tube* for a fev
boiirs; A and c were obtained by leaving aqaeous ammoiiia in contact for some diya at
ordinary temperaturefl mth mt^tbylanlitryliite of ethyl prepared by heating inethylRali^—
cylate of potash with Iodide of ethyl. ^H

EthylaalicjlaTnic acid is fiearly inaoloble in cold wat«r, but dissolvit
pretty n?adily in boiling water. The solution is colon tvd purple by S69<j<i'
cbloiide of iron, green by sulphate of copper, and yields & precipit
Willi neutral acetate of lead after addition of ammonia.

It dissolves at a gentle heat in h]/drochl0tiCtnUric and etrotig stilphun
acidf and is precipitated from the two fortner on coolings from the !■
on addition of water.

It diijsolves in warm poimh-ky and separates ont on cooling.

In alcohol and fther it dissolves very readily at tbe boiling be
mneb less at ordinary temperatures. ^

Benzoylsallcylamic Acid.

Geriiartit «St Qnmz7.h. CompL rend. 37, 86.
LiMPRicnr. Ann. Pharm. 99, 249.

Formation. By the action of cbloride of benzoyl on salicylamb

arid : "

C"N11*0* ^ C»«ClH*f>3 - C»NH»0« + HCK

Preptimfton. Chloride of l^onxoyl and ealicylamic acid in
numborf* of atoms are beated together to 120'" — 145^ as long as hi
ebloric acid continues to escape; and the retidtie — wbicb remains li
and viscid for a lon^ time after cooling, but becomes crystalline on
addition of a few drop^ of jilcobol or ether — is washed witb a in
quuotily of ethoT and dissolved in boiling alcobol^ whenoe it crystalt^
on cooling.

Very alender needles united in Bocks.

Tho arid when heated gives off water and is conTcrtod iuto Ijeni
mlieyliioide (Limpricht):

C»NH"0« - 2liO - C»NU»0*.

DKNZOYLSALICYLIMIDE.

325

Ter fuamu it rem aba far a long time remnuus and gummy, and is no
loader completely soluble in liot nmmonia. Tht* yellow residue diaaalvcs
easily in alcohol j nnd the yeliowr solutiou depoBiis after evaporation small
nee^dlca wlncb dissidve very readily in alcohol, foroiing a yellow solution
which is decolorised by Lydrochloric atjid; they appear to consist of an
ammonia-salt — It is attacked by chloride of bcDEoylj and the crystal-
line product appears to be reconverted into beuioylsalicylamic acid by
the action of water or alcohol (Gcrhardt & ChioazaO

The acid dissolves very easily in ammonia, but ia deposited in its
original state when the ammonia evaporates (GDrhardt & Chiossm,
Limprieht), or when the solution is mixed with an acid. (Llnipncht.)
The acid dissolves in the fixed alkaJiSj forming deep yellow solutions,
but is generally resolved at the same time into benzoic and sal icy lam ic
acids. (Linipncbt.) — It dissolves in warm carbonate of soda without
evolution of carbonic acid; and the solution when treated with acids,
depoi^its very soluble crystals, probably consisting of benzoic and
ealicylamic acids. (Limpricht.) — Its eolntion in etrontia-water fir^t
deposits crystals of benzoate and afterwards of salicylamate of strontia.
Tbe first crop of crjstoJi contamed 26 '6 p* c^ etroaCium, nnd the aeconil 24''! p. c. ; tjbe
foromlA of the betuoato requires 25*4 p, c*, aaJ that of the salicylamate 23*3 p. c
Strontium. (Limpricht.)

The ammoniacal solution forms a light lemon-ysllow precipitate with
ueutriil acetate of lead, and light blue with sulphate of copper, (Gerhardt
&r Ghio^a.)

Silvtr-mlL — The ammoniacal solution of the acid forms with nitrate
of silver a yellow precipitate which becomes strongly heated with chloride
of benmyli forming chloride of silver. (Gerbardt & Chio^m*)

A« ..^ .-^

240

108

69

Liinpridit.

30

C^NH^^AgO* .348 .... 100

Tho acid diifiolves very sparingly in boiling alehohol,

H BenzoylsaUcyUmide,

Ljui^EicuT. Ann, Pfiarm. 09, 250,

Benzoylsalicylamio acid heated to 210° in a small retort till about
*€»nc-tbird has volatilised, yields a diitillate containing water, benssojc
acid and oily products, and a residue consisting of benzoylsaliuylimido
and undecomposed benKoylsalicylamic acid, which latter may be removed
by boiling with small 4uaiitities of alcohol. The remaining pulverulent
benzoylsaiicyliTuide didsolvcd in a larger quantity of boiliog alcohol,
separates on cooling in small yellowish needles^ which when dry form a
Blightly interlaced mass.

ms

TOLtmN£: OTt'JkMWQOm

in wy^A f At, H m

The coBtp9U0ii dii«olr«B in

Autbraiiilic Acid*

J'JkirwL

FftiTZScntu (1841.) */. j>r. Chem.
Pkatm. Cemr. IS4L3^7<

J 84% 032
Gerla^td. Ann, Pharm, SO, 140; ftbslr. X pr. CA^m. 57, t5S; il^ M0«
CA^iw 6?a3. 1^52. 237; FLrr^ Cmtr. 1853, gOL

FotDiaivm. t. By be&lmg mdigo with poUsh Te^. (Fritxitlit,}^
2, By beating chry^nilic add witli dilute acide. (FnUvdid,) — Z.
the acrtioo a/ potatili on aniline- urea, (CbanceL)

C»N'H»0* + KO,HO = C^*NH«KO* + NH".

Preparation^ I. Indigo from tLe rat is added id small poctkoi ll
boiling potash^ey of sncb a Ftrengtb as to boil at 150"', till dbTjWBbH

of potasb begins to separate; tbe nia^it wbich eolidifies on aooliaf ii
diisolTed in idcobol and ditered; tbe filtmte is exposed to tb«f air tmlu
green eolour changes to brown; tbe caustic pc^tasb oonverietl itiio tv-
Donate by pacing carbonic acid into it; and tbe liquid decajsied frt^i"
ibis salt is freed from alcobol by distillation : as tbe eohitioii beoott^ c^«9-
centmted, anthranilate of potash separate.^ out. Tbe gaJinc nm» tfvA
from the mother- liquor by tneana of bibulons paper ii; dissolve^l in tk
eroallest pofisibte quantity of water; and the filtered ^otutiun is mixed villi
ace tie add, wbleh at Sri^t pniduees turbidity and afterwards an abandaal
crystalline precipitate of antbranilic acid. Tin: Acid firsi MiMmm in mti^
drop* whicli nftrrwardsi UiiUc into crystals. (Frttlscbe,) — 2.. W bi^O ebfjnsifiB

acid is boiled for some time with dilute sulphuric acid, the solution no
cooling deposits black-Muc needles; and the liquid se|*amtcd thenefTOra
containing anthrauilic add and another acid, Is saturated with snl|fbilf
ot zlnOf II ud carefully neutralised with dilute potash, wbcn?bv aut!ir«i»di«»
of zinc is precipitated in iho form of a fine yellowish powiler dtffietiUt*
wash- 1^ *^ irjiull bri^wnith floccuLcjit priM^i^itnte forms «t the brE;tti(ilnf of tW f«iif»>
liAAiioii, the liquvd mutt be filtered ffiim tKi« prect pitfite htfore^ the ifne-^ult t* fnrtM
iMwir»Ui«!d with potoJi. The xino ea!t is heated wilb alcohol tii ibi* Udm
point; ffulphuric acid diluted with alcohol is added by dro|iii| atoidiiif it

ANTHRANILIC ACID.

327

excw; and the liquid b filtereci : iiutbraDLlie acid then separates frum it
either on cooling or after partial evapriration. {FritztscKe.) — 3. One pt.
of finely pulverised indigo boiled in ft flilver diah wlili 10 pts. of potash-
ley of ep* gr, 1*35, is quickly attacked, without ev*>iutif>n uf gas. The
solution, which becomes red and thick iishjs repeatedly diluti^d with water
and then concentrated by boiling; and befi>re all the indigo is dii^solvedi
f>eroicide of manganese ia added in eticcessive etuall portionif till a sample
diluted with water no longer tuniB blue oa exposure to the air. The
thick mase, which now contains nothing but anthninikte of potai^h anil a
little free potash, ;g diluted with hot water, and euper&iturattdwiihrli lute
enlphuric acid; the reaultiug grey-brown precipitate separated by liltra-
tioa; the filtrate neutralised with potash and evaporated to dryness; and
the aathranilate of potash extracterl from the residue by cold water or
alcohol. The aqueoua solution (obtained by treating with water the
reeidne of the alcoholic solution, if alcohol has been used as the solvcut)
mixed with acetic acid, yields after 24 lioors an abundant crysUillisation
of anthranilic acid. These crystals are washed with warm water^ dia-
aolved in 10 to 15 pts. of boiling water, and milk of lime then added
sufficient to produce aa alkallae reaction; the liquid filtered from the
ejicess of lime yields on cooling colourless crystals of anthranilate of
lime« If coloured, they must be dt^coluri^d by Aolution in hot water and boUing with
aiiima] charcoftL The hot aqueous aolution of the lime-salt mixed with
acetic acid, deposits the acid in yellowish crystals as it cools. If the
crjatailiaatioti is preceded by a milky turbidity, there is au impurity
preaeut which must be removed by boiling with blood-chiircoaL {Liebig.)
4, Aniline-urea is boiled with strong potash ley a,H long as ammonia
continnes to escape, and the liquid is supersaturated with acetic acid. If
the solution has not been too niach concentrated, no precipitate appears,
but the authranilic acid separates on cooling in crystals which may be
purified by recrystallisation, {Chancel.)

Fto^^ertiei. Transparentj very lustrous laminai with dihedral sum-
mite. — The nearly cooled solution of the linie-aalt yields, after addition of
ftcetio acid, slender white four and six-eided needles. (Liebig.) The acid
obtained by the first process (p. 32(j) is a sandy powder; if the acetic acid
forms a layer above the other liquidj colourles?* crystalline scales are
obtained, resembling those of benzoic acitl; the alcoholic sohition yields
large crystalline laminaj, (Fritzsche,) The acid melts at about 135^
(Fritst.sc he.) It sahlimes at a gentle heat in shining laminm resembling
those of sublimed benzoic acid (Liebig); as a fine crystalline powder.
(Fritscsche.) Has a sweetish taste. (Fritzsche.)

^m C**NH?0* 137 ItW'OO ....... lUO'OO

^H Isciisfric with amtdobeaKotc and salicjrlattiic acidp.

^H Decompoiiiion^. 1. Boils when heated above 155^ and is resolved
^iBto carbon io acid and aniline. (Fritzsche.)

C**NH70* = C«NIF + 2C09.

Fritzgche.

Liebif,

14 C„

..„. S4 ..

„ Gl-23 ..

61^08 ..

.. U'U

N „.. „.,

14 ..

., 10 22 ..

I0*9r>

fU

,...,.» 7 ..

.. &'U ..

.... 4i*7 ..

.. 5 16

4 O...

....... 32 .

.. 23-44

,.. 230O

328

TOLUENE: OXY-AMIDOGBN NUCLEUS C*^AiiH*0>.

Tlie decriui position is most eomplete when the acid U mixed wiUi
its bulk of powdereJ glasa and diatilled in a gh^m tube o^cr m
lamp; th^ die^tiltate yields iamlniB of antlimuilic acid which disappml
rectification. (Liebig,) — 2. Heated with ordiiiaiy nitri<: acid^ it does i
evolve any nitrous viipoura, ancl the \h\iik\ on cooling deposits erystaJlin
lamina? wliich dissolve readily in water, do not precipitate tmrjUi-Wi
oolotir ferrio salts blood-red^ and give off amDionta when IreatadJ
potaah: they are therefore nitrosal icy late of ammoDia, (Qerliardt^ JfA
Chim. Phifs. If 227.) — 3, When ultrona acid m pQAaecl mU> the
acjueoue solution of anthranilic aeid^ as long as bubbles of tttt
evolved^ it is resolved Into ^Iieyltc acid, nltrogeu and wBter. (Gerb^nlt)

C^^NH'O* + N03 - OmK^ + 2N + Ha

4, The acid treated with chlorate of potash and hydrocUorio 1
yields chloraail (Hofmannj Ann* i^fturm. 52, H5) i

C"NH70* + SCI + 40 - C^Cl^O* + 2C03 + 40+ NH».

Combhiatiom. The acid di^solyes with some difficnlty in euld

pretty easily in boiling w^Uer*

^, Sulphate of JnihraniUc Acid. — C^*NH'0*jSHO* — Obtained
precipitating the bydrochlorate with Bulphate of silver* Generally form*
ijeedlee united In concentric gtoupa. (Kubel)

Ci^NlFO* ...„,... IS? .^ 73*66

SHO* ^ 49 ,... -2^24

Kubci.
26-26

C"NHW,SHO* .. 186

100 00

IlydrvcAl&raUy C^*NirO*,HCL — Dry aothranilic acid prepAied fro«
indigo absorb! hydrochloric acid gaMj bnt does not in this manner r^a^lil/
form a definite compound. But when anthramlic acid i^ dissolvid m
warm concentrated hydrochloric acid, the new conapound ery9t§Ukm h
eleuder needles on oeoimg. (Knbeh)

Jiried over oU 0/ t?ittioL tkuWI ,

C'^NU^O* ,... „. 137 0 .». 79-46

HO :,., 3&-4 ... 20-54 20 96

a^NH^a*,HCl.... 172*4

100-00

NUmU. C"NH'0\NHO'. — Obtained by precipitating the hydrecW*^

mte with 1 At. nitrate of silver. The lirjuid filtered from th** ehliirUt
of silver yields by evaporation large prismatic crystals ea«ilv t^olubleii
boiling alcohoL — When 1 At. of fajdrcK^bloraie of aothfuiilic acid ti Qiixfd vi^
2 4t. oiLrstc of &\Uet^ the filtered liquid after concentp*tion jteJd» a coiup * *^"^
eon tains fiiUerr liut Rppurcntly nut in sufficient ([uantiljr to fona tbt vam
C>4KH^OSNH(l<^i< NAgO«— KUriite of baryta does aot appear X& oombbt viih
of witbraaiUc acid, (KuheJ.)

OxaUitf. — Prepared by trt«itfng the hydri>ehlomte witli eidblt d
0Uf0r, Of/tttaUisca in im&U eilky eealca. (KubcK)

aiRYSANILlC ACID.

329

P Ai 100*.

i 2 C»*NH7CM _ ,., 274 .

C-*Hao«........_...„ SO

... 75-27
.. 24-73 -

Kubel.
... 26-25

(C^*NH70*)^,C*HW . . 364 .

,. lOO'OO

T.

Tlie compaunda of aDtbratiilie apid wHh bases yield aolline bj dry
distillation, liko lUt? free acid, but a coosiderable LjuEutity of citarcoal i^
separated at the same time. Tbe decomposition is less simple than that
of the free acid» because in the salts, one atom of hydrogen in replaced by
a metal, (Fritjsche.)

The anthmnilateH of the alhalis are crystalli sable, dissolve readily in
water aud alcohol, have a sweetisb taste, and do not deliqueice when
exposed to the air. (Frltzsche.)

Anthrmtii^U of Lhne crystallises from the hot aq neons solution Id
colourless tranaparent rhonibohedrons; it dissolves sparingly iacold^ but
with tolerable facility in hot water. (Liebig.)

AnUtramlaU of Siiver. — The solution of the lime^ealt, or the aqneooa
acid neutralised with ammonia, yields, when misted at the boiling beat
with nitrate of Bilver, a precipitate composed of white lamina', which
diseolvee completely in boiling water and crystallises with silvery lustre
on cooling, (Liebig.)

14 C ....

84-0 .... 34-41

14'0 „.. 5'73

60 ,.,. 246

108 1 ,... 44^28 ...»
32-0 .... i:i-12

Liebig,
.. 34-19

^^^ N ,^,

^^P € H ....

2 '45

|~ As...
■ 4 O .»,

.. 43-90

m ' " ■ ■'

*""**'"'

( C"NB»AfO*

The acid dis^lves readily

244*1 .... 10000

in atcohol and eiha**

Apptndix to AnthranUk Amd,

Chry&anilic Acid,

pRiTZ&CHB, (I841-) J. pr. Chtm, 23, 67; Ann. Pharm, 39^ 78. —

J. pi\ Cii^m. 28> 199j Phu/^m. C^iUr. 1841, 323,
Okkuaedt, Eev. Bckntif. 10, 371.

I Frep^iralion^ Finely divided indigo is added by succoHiive portions
to pota^h-Iey boiling at L^0\ till chrysanilate of potash begins to sepa-
rate ^ the mixture is then left to cool, and water added to the aoiidified masa-
The liquid is either mixed with a tjuautity of dilute acid sufficient only to
saturate the greater part of the potash; the bluish green precipitate
separated by filtration; and the chryeanilio acid precipitated from tlio
golden yellow liquid by addition of excess of acid;— or the eolation of
cbrysanilate of potash is immediately aupereatu rated with very dilute
acid; the precipitate of impure chrysanilic acid thrown into a large
quantity of water; potash-solution then added bv drops aa long as the
aoltttioD retains its pure gold-yellow colour; and the iit^uid immediutelf

330

TOLUENE: OXT-AMmOGEN NUCLEUS C"AdIi»0«-

fi)tore<l into ao excess of dilate acid. (If too tducU potasb-flolutJOQ til
iiseil, the liquid immtMiiately acquir*?8 a greenish liot) a portion of tb«|
impurities being then redissolveii, and a decompositioD takes pkee m thm\
liquid, a tbin film of indlgo-bltie forQiinj^^ on the surface; bot hj cardttl
jiieHtrali&atioti with dilute acidj the pure goU-jeHow crdour maj be
I ties to red. After the precipitate bus been thrown on the filter, tbe llil
I portions of liquid must be allowed to drain off before the precipitate ii
[washed with water, because the residue is partially dissolved bj pore
[water, and consequently the wasli- water does not yield a perfe^tljf pQft
'acid by pieeipitatlon*) — The cbrysanilic acid obtained by preelpitatm
is purified by solution tn a boiling mixture of equal parta of alcoW and
water, which depoBits it in the crystalline form on cooling.

Pmperties, Hicroecopio needles united in dense stellate gronpi; by
precipitation, rod -brown flakes resembling kermes are obtained^ Ughter in
colour the greater the excess uf acid added, but becoming danger by
washing with wator^ and dark brown-red or sometimes dark greeii vbat
dry.

According to Frittsche, tha acid contains in 100 ptfl.:

a. . 4-34

66^03
4-23

4*46

§862 „., 68 74
4 27 .... 4 38

a, b and e were obtained by precipiUtian ; cf^ e ftod/ were punficd bj iohHieil k
■IcohoL Aocordicf to Gerhardt, chr^rsamUc flcid h a mtituri} of IM^ MiduriMii
with more ar leu reduocd indigo {Retf. tt^imU 10, ^71 )« J

Deeompmition^. Boiled with dilute mineral acids, it forms a br^wn
red eolutJon conlinualiy becoming deeper in colour, and is completcij
resolved into anthranilic acid and an indifferent substance, whteb Oi
cooling separates almost completely in t^lender blue- black needles, Tlftefi
crystals when recently formed dissolve in alcohol, forming a d«0p wd-
purple solution with a tinge of blue; but alter drying, tbey fom witli
cold alcohol, a red solution, leaving on the filter an indigo-coloured sib-
itance which forms a violet solution with cold alcohol or ether, diMolfii
I aomewhat more abundantly in boiling alcohol^ and crystalliM^s on oooliof
in black blue scales not exhibiting any coppery lustre. After dmnib
the black- blue needles dissolve less easily and wilh red brow q coloor;
both solutions appear to be altered by exposure to the air. In Ibe fiM
and still moist state, tbey are qui^ly decomposed by alksUu^ vhk
separattun of indigo j after dryings they decompose slowlj* Tbtf
contain in 100 parts

6G*S$

72*56
357

a wiu prepared from rhr^runilic i^id obininiM bj prmpitatioQ ; $ itKi e tt^mi^
B4:id jiuriJied by solutioa in hot nlcolioL — When chrysanillc acid Is boii<
! mlcohol to which a few drops of sulphuric or hydrochlorie acid mitt ^ ^
;m red-browu solution is furmed, which by coobng or by eYmpontioa st i
gentie heat, depi/iits a red-bruwn crystalline product, A liol alwhoiiQ
solution uf chrysanilate uf ajumouia supersaturated witJj hydrodiloisi
ftcid deposits on cooling long very slender »eedlea. (Fritsaolie.)

SAIJCYLtJRIC ACID*

83f

U>e

% Recently precipitated clirysaniUc acid forms witli excess of con-
•eiitrated ammnnlFi, a green isb yellow cryuLalline prtniiict, wbicb doea
mot evolve ammonta wben treated with eobi solution of potash. Tb©
aqueous or alcoboHc solution of thia subsUiace miated with bydrochlorio
acidj and left to evaporate, deposits yellow green needles; freriuenily
however — #,;/. after beating or continued coo tact with the alr^ — ^blue flakea
are deposited, either inatead of these needles or together witb them.
With nitrate of silver^ the solution fnnne a precipitate ooDsiaytin^ of
interlaced microscopic needles, it separation of metaHic silver occasionally
taking place at the same time. (Fritzscbe.)

3. 7*be eolation of an alkaline cbrysEinilate exposed to the airbeconiaa
covered wjtb a light-green film which appears crystalline under the
microscope, and yields arnall crystals wben dissolved tn ether.

4. A solution of cbrysanilic acid mixed with nitrate of silver forms
at first an orange-yellow precipitate (probably cbrysanilate of ailver)t
which however eoon aasiimes a dark-brown red colour, and after addition
of a little nitric acid, changes into a heavy gvQj precipitate containing a
la' ge quant' tv of metallic silver, whilst the liquid retains in solution a
silver salt which separates in Reib-coloured flakes wben the liquirl is
neutralised with aninionia. From the heavy grey precipitale alcolnd
ertrttcta the substance obtained in the preceding reaction (3); it has more
or lees of a dark green colon r, arising merely from inipurities, since

hen heated witb nitrie acid, it assumes a lemon -yellow colour^ without
ing much attacked.

CmtbinaUffm. Cbrysanilic acid dissolves very sparingly in water,
forming a yellowish solntiou. It dismal vea with gold-yelloW colour in
alkalis^ but is readily decompo&ed by excess of alkali.

ChrysaniltiU of Ammonia is obtained pure only when alcofaolic
solutions are employed,

Chymniiate o/Fofash forms small yellow crystals easily soluble iu
water * With m e tal I i c ea I ta , i t fo rni s p reci p » tates of vario u s colon rs,

ChrymnilaU of Zinc. — Obtained by adding a solution of the potash
or ammonia-saU| as nearly neutral as possible, to a boiling solution of
acetate of zinc mixed with acetic acid. Pow^der of a fine brick^ted
eolouri which settles down quickly, and appears crystalline under tbe
microscope. By analysis it is found to contain sometimes 14 At*,
sometimes 42 At carbon to I At, seinc-oxtde,

CkrymnUaU of Lt^jd. — Obtaine<l like the ssinc-salt and exhibits
siniilar properties- Its composilion agrees nearly with the formula
C-*H ^^N'O^PbO,

Cbrysanilic acid dissolves readily in tdcokoi, forming a reddish yellow
floluiion.

Salioylimc Acid.

J, B&RTAGffiNi. (1855.) Nuovo VtPimto. I, 363.

Occurs iu the urine after salicylic acid has been swallowed-

SB3 TOLUBi^B; OSI-AiimOGEN NUCLEUS C»*AdH»Oi.

Prepamiion. The acid urine voided after tskiiig a&lii^lk acid at

levaporaiediiQwn to 12'' Bm., acidiikted wiih hydrochlorteaddielii'

with ether and the etlier distilled from I be etlaereal eoluttaii. Tb« i

» jieldj by spontaneoua evaporatioOj large crystaUioe noduIeSj which, i

freed froiD the niother-Uquor by pre^ure^^ dis^oWed in boOiDg water, wai

treated with animal charcoal^ yield a crystalline mass con^lsliog far tit

most part of slender needles, mixed with larger needles of ^Uleylic wdL

On beating this mixture in a current of air to betweeo 140" mud 150^, lit

Ltallcylio aeid volatilises, and the residue crystaUised from bot wiKr

'containing animal charcoal yields pure aalicyluric acid,

Ptvpertiea, Slender, shining, ctystallin© needles, whicli wbea obtabie^
from the aqueous solution are grouped coucentricallj. Has & aomewlil
bitter taste and a strong acid reaction* Melts at aoout 16(P, and tdliiO-
BeB in the cmtaltinc^ form. The solutions colour ferric sal Li v^iolet likt
salieyiic acid,

18C,,,. ,108 ,„. w-38 .,„ 55 er

N 14 .... y*l8 ,„_. 7-44

9H 9 «» 4e2 ....... 4-81

e O 64 .... 32'82 , 32-08

C^NH«0^.»... 195 .... lOO-OO ....-..* 10000

Btlated to salicylic add in the 9»mt manner u blpponc to benzoic acid.

De€ompositimis. 1, Between 160" and 170°jtheaeid turns brown
begins to decompose, yield iug a sublimate of salicylic acid* At *
kitrongcr heat, it swella iip and gives off ammonia, leaving a retidttt ^
charcoal. — 2. When boiled with oxcesi of baryta-wateT^ it do6l not
form any salicylate of baryta; a small quantity of ammonia is howoT4f
given off. — 3. Heated for a short time with fuming hydrocblonc itH
tt dissolves and crystallises out again an altered; but if tlie bot ling k
continued for two or three hours, the acid is resolved into salicyiie idd
and glycocol.

4. When it is boiled with water and peroitide of lead, the latttf il
decolorised, and on boiling the aglutloBi small shining needlei
out.

CombinaiumM. The acid diiaolvee readily in boiling wmier, km m
cold water.

The ^alkphimits crystalliso with facility. The i^id expeli mi^
homo acid from its compounds ,

SalicyluraU of Baryta, — Obtained by dissolving c^rboaate of h^sj^
In the warm acid. As the solution cools, the salt crysUlUaet in bigl
hard prisms^ which become opaque and give off water when hcatad, tbil
melt and decompose^ g>^ing off ammonia and an oil which smeBt ll^
hydrate of pbeuyt, and leaving a residue of carbonate of baryta, Tbt
salt is sparingly sol uble in cold water.

SaihyluraU of Lime. — a. When carbonate of lime is ditKilTtd h<
the aqueous acid, the solution on couling yields aggregattd I
u hich are ssparingiy tioiuble in cold water and iiisoluble in aieuhol.

TOLUrOINl*

33S

L When milk of lime is ad<led bj successire small quantities tf> tli©
warm aqueiius ncid, a solutioa is at first obtained wliich euddeiilj
eolidifies lU a crystalline mass insoluble in boilings water.

The acid diseolves readily in idcohol and witb tolerable facility in

I

Nitrosalicylamic Acid.

CAUoiTEfl iV', Ann. Chim, Phys, 10, 352; PAa»m CffUn 18i4, 400.
NitromUct^iamidet Anitamide^

Methylnitrosalicylic aoid left for three weeks ia a warm place in
contact with jstrong nmmonia, gradually disnppeara and yields a yel-
Jowrsb red liquid^ whicL, when evaporated at a j^entle heat| depoatta a
bright red luasa easily goluhle in water eepeciaUy if it contains anmiouia,
and ]>Tec]pitated therefrom by acid in yellow nakes; and on dia^olving
these in alcohol after they have been washed with water, and evaporating
the solution, the acid separates in yellow shining crystals* — May be
[>aHialty rolatilised without decompoeitton.

U C 84

t^S ................ 2B

6 H 6

8 O ............... U

Cahonra.
46-15 ........ 45-90

I53a 1531

329 ........ %U

35^18 35'3&

Ci^N=HH>»

1S2

100^00

100*00

Boiled with potash -ley. It gives ofl* ammonia, and forms uitro^l Icy late
of potash.

It IS nearly insoluble in cold wnt€9\ but colonra it nevertheless. In
boiling water it is much more soluble.

It diBsolves readily iu cold ammonuifpota^ of soda, and is precipitated
therefrom by acids in its original state*

It dissolvei* readily in alcohol and elher.

Toluidiiie,

K II dissf

BMuspratt ^ Hot^MAKN. (1845,) Ann. Pharm^ 54, Ij Phnrm, Cenir,

1848,-513.
NoAD. Ann. Pfiann. 63, 305; Phat^. Ctntr. 1848, 182,
A, W. HoFMAKN. Ann Pharm. 6(1, 144; Pharm. Centr. IS 48, 582.
Wilson. Ann. Phmmt. 7?, 216; Chtm. Sm, Qu. J* S, 154; PhnmL

Oenfr. J851, 110,
CnAtTTAno. N. J, Pkarm.. 24, IGG; J. pr. C^m. 60, 240.

BU

TOLUISE : AlO^smCLEtlS CMKW:

Formsitim. T, Wben nkfotaliiol li
tiydrogen in [>reseiioe of simtooQia or |Miaik. (IfHipntfi iL \
Wilson,) — 2, By tiie ael ion of potash on the jMttw mlmUam df nmrn^
obUmed by treat inf^ oil of iiLq>eiitiiie wiib nltrie «ei4, (CliMitBrd}

Prepartitlon, Nitrotolnol Is dtsH^lvied in ileohol e&t&rated villi
ftminonia, attd euLph a retted bydnj^^eil parsed into the HqciiJ till itt inloflf
no longer dfsaf spears even after loiig standing; fiuipJiar tlien ec[iar&t«i n
fine Grj9Ull& To Bccrleraie tbe iIrcompo!«iC]c»Ti. the tiqvid M>«nirJl witib tvlpkvNttil
hydr'-f^eii ii Imted in a rekirl to the boiilnf poiiit, vhcnApoa • \mr^ ^^mat^ tt ml-
yixt^rttvtd. bjdrofcn it erohed ; th« diatilkie u Chen potireil bacl(« U»r l^qfiil m^fum mfm^
riiti?il with aalpbDretted fajdrof^n, And thes« DpemtionB np^trd fite or tts tl«itA,r Tllf
liquid b now mixed wttb water and exceM« of hydrochlorie add an*! fliaktt
np Willi ether (whlcli etill takes op a certain qaantitT tif imteroiiipoiid
nitrotoluol* even after long treatment with «ti1pburett<Hl bydrcj^a); wxA
the !ilc**Uolic liquid is evaporated down to one-tbiril to expel tke mkoM,
and distil I lhI with potash^ whereupon amntimia anil t4ilijidine pm'm ftrer
with the water, the tidnidine oollectioi: at the bottom in tJM brm of •
bt*a.vy ml whkh cryatallie?eis after a while. The etitiie dtstilbto tij
BnfH:*r«ntiirutL'd with oxn.lic artd and evaporateil to diynen otrer
watcr4r:ith^ the residual mixture of oxalate of ammonti^ uiii oxalate ofj
toluidtne bmled with ahaolute alcohol, which dis9<dre0 cjuly tiie oxabl«
of tolniitine and dep^isitfi it in slender white needles on eoolitij^, Th^m
crystals are dia-solved in bt^ water, and the f^ohttion is mixed with filri^
potaah-loy; the toliijdine tlien ^parates uninodiately in *>ily (Imp wbiHi
ride to the aarfiice, and <;ollect into a film of liqnid which crystalltsvs
with a ntdiating structure on cooling. The cr3mta]lin« crn^t is wmM
with cold water till it no longer imparts to the water an alkaline rcaftiut;
then preasei] between paper, and rectified by one di&tillatiun (Muspfait
h llofinann)^ or it is diij^lved in etber and the H^otution liift to era|x»r»t«
slo w 1 y . ( N oad 0 — *r b e com p I e te con v e rsi on o f n i t rt>tol u ol i n t« tol a idin«
by hydni.siLlphate of aminouia is difficult. With bydttisitlfihttit si-
potash only half the time is required and no ee|mjation of aiDioaam
The oxalate merely requires to h% several times reerystallbeil ill
distilled wiib baryta. (Wilson.)

*2. Potash -solution is gradually added to the yellow r^^inoits loixlait
produced by the action of nitric acid on oil of turpentine (if theaii^
tity is large, it is bej^t to make the mixture in a retort prqridci] with la
S-uhaped funnel-tube). The mixture then ai^^umes a dark red-browtt
colour^ becomes very hot, swells up, and yields an alkaline distilbti
smelling like ammouia and phoj^phuretted hydrogen. As noon m tk«
spontaneous ebullition has ceased, the mixture is heated till it no hsM
smells distinctly of ammouia. The disrillate is superaatnralod with hw©*
dxloric aeidf whereby rei«inoua matter^f are sepa rated, then evapfiratW ia
dryness over the water- bath, and treated with absolute alcohol whick
leaves nl-ammoniacand dissolves hydrochlomteof toiuidiue* (ChaaUnl)

PropertirM. Crystallises from solution in hydrated alcohol iatsnial

k«whiL' bott in large hroad colourlesa laminie. Melts at 40'^ into a iwlonr^

I leaf ^ strongly refracting 'oiL Evaporatea at ordinary tC!m}ierature« **»!

formi white clouds with hydrochloric acid held over it (leas with oitrt

acid). Forms on paper a grease-a}>ot which soon disappears. Boil* st

108"* Has a vinous aromatic odonr (just like that of aniline), sdJ *

. l^iiming taste. Bines litmus ettghtly, changes the colouring matter of

i
i

TOLUIDI!^E.

335

daliliat to green, but does not redden turmeric* Colours fir- wood deep
yellow, Doea pot produce a violet-blue colour witb chloride of lime.

U C

N
9 H

64
14

C*^NH» 107

rR'51

13-OS

100*00

MuspnitC Bi. Hr^fiAllUll.
., 78'&3

..... 8-61

^V DecompQsiimm, 1. Tolnidbe oq wlticb bromine is poured becomes?
strongly heated and eTolres copious fumc^a of lijdrobromic acid; when
the resnliing mosa is lieateJ, white shiutijg needles sublime, coiiMJ^ting of
a bromrne-ctJinpound which is no longer ba^ic, very nmch resembles ter-
bronmniline, and is jnstdable io water, but soluble in alcohol and ether.

— 2. With aqueous chloride of lime it acfjuires only u, fmnt reddi«b
tint — 3. Nitric acid colours it deep red. When boiled with atron^
nitric acid, it is decomposed, with violcDt evolution of nitrous acid; water
addt^'d to the solutiim throws down sulphuryeliow flakes, which dissolve
in alkalis with brown -red colour, and are re precipitated therefrom by
licidst (Muspratt & Hofmunn.) — 4. Toluidiuo m not set on fire by
chromic acid. With a<|ueoua chromic acid, it form^ a rod -brown preci-
pitate which appears to be chromate of totuidiue. ^ — 5, Vapour of
toluidiue passed over melting pnLiSsium forms cyanide of potasdnm with

Hpivid comhuBtion,

^f 6, An alcoholic solution of toluidiue through which cyanogen gas la
pasied behavcfllike that of auiline (xi, 253; vid. VyftnQttfivifUMe.) (Hofmann.)

— 7. Toluiiline over which the vapour of volatile chloride of cyanogen
isi passed^ is converted into hydrochl orate of mctoluidine. (Wilson.)

h

2C''Nn^ + C^NQ = C^WH? + HCL

8, Heated with bromide or iodide of ethyl, it forms ethyl toluidiue.
(Hofmann.)

9. With anilocyanic aeld it forma a solid cryj^talHne massj correspond-
ing with carbamide and carbanilide. (Hofmann.)

K

Combififttions. Toluidiue diasolvea sparingly in cold, more readily in
arm water, whence it is j^^radually depositcil in iridescent hiinime ou
eooling* It dissolves readily in bisulphide of carbon. (Mu.^pratt ^
Hofmann.)

Toluidiue precipitates ferric salt*. The mlu of Toluidine are deconi-
poaod by ammonia, potash and soda and their carbonates, toluidiue being
^fepamted In the form of a crystalline curd- They have a great teudeucy
to orystalltse; an alcoholic solution of toluidiue solidifies w^ith most acids
in cryetxilline masaes which yield beautiful crystals when recrystallised
from water or alcoliol Tliey are inodoroue and colourli;*ss (excejiting the
gold, platinum and palladium double salts) but quickly become rose-
coloured on exposure to the air. Their acid solutions impart a deep
ellow colour to fir-wood and elder-pith.

The Pho»piiat€ and iitdphiu of Toluidine are ciystallisable.

SidphiU of Toluidinf. — An ethereal solutifin of tolnicliiie to which
few drops of sulphuric acid arc ad«led, immediately forma a suow-white
ystalline precipitate, which may be washed with ether. — Easily soluble

water, sparingly in alcohol (Muspratt *& Hofmann.)

33fl tOLUET^Ej AZO-NUCLEUS O^NW. ^^^^^M

Maspritt & llofminii* I

C"NH» 107 .... 68-59 1

HO .., 9 _ ^77 1

SO* 40 .... 25-64 25-22 J

' C«NH«,H0,SO- .... 156 ... 100 00 ^M

Hytlrothtoratt of ToluuHne. — The salutiao of toltiitliiie in b|flH
chlonc ai:kl yjeMa when evaporated and coolefl, white crystftlliue smMB
^bicfi quickly assume a yellow colour in contact with the air^ and snV
lime like sal-ammoniac. It dissolves readily In water and alcohol,
sparingly in ether. The solution haa an aetd reaction. (Muspratt &j
Hofmanti.)

Miupratt & H of maun.
Ci*NH» ...,«. 10r»0 .... 74*62

OH .„ S6'4 .... 2V3a ..,>.... 25-29

C^^NH^CIH ...,.., H3'4 ... 100^00

Nitra t f. of Tolu idint is c r y stal 1 i sat i i e .

Tc»kidine forma with c^it-omk acid a red-hrown precipitate., wliicskl
appears to be chromate of loluidine.

Toluidine forms with trw/?rtV6ulphate or chloride, a green tab, BomewhstJ
crystalline precipitate, and with nifrafe of silv^t a white precipitati
which soon black eosj and must be a double aalt^ (Muspratl ife HofmanQ.}]

0doro-aw*ate of Toluidine, — Hydmcbl orate of tolujUine forms wilkl
chloride of gold a thick preeipitate, which ftoon aggre^te« into lij
interlaced ory^talline mass. Melts in water between 50 and 60^ an4]
dissolves in rather hot water, separating In splendid yelbw needles i
the liquid cools. (Chan lard.)

14 C U'ti _ 18-82 ........ IS71

^m 10 H 10 0 ,„. 2 24 ....... 2-3&

^H Au. 196-6 .... 44-06 ........ 43-26

^^^ 4 CI I4P6 .... 31-74 ,-...>. 31-87

CJ*NB"^a,AuCt' 446-2 .... 100-00 ........ 100-6)

Cfkhroplatinaii of Ttfluidlne. ^^HydTochlomle of toluidine mti6
Willi bichloride of platinnm solidifie^i into an orange^yellow pulp (
csryetalline spangles, wUiub may bp washed with a mixture of other »a
alcohol and dried in the water 4>ath. (Muipratt k Hofinann.) CootAin
31*36 p»o, of platinum (MusprattSt Hofmann); 31'4p.c* (Noad), aniLi
therefore C"NH^'^Cl,PtCP.

CMoropaHadiaU (f Tniuidine. — Orattge-yellow precipitoie . ^

bling the platinum-salt, hut aoniewhat paler, (Muspmtt k lUfniann^

Ox<d<iU of Tfiluidme. — An alcoholic sol nt ion of toluidine mix
with oxalic acid forms delicate silky needles, which dissolve spartngll
cold, more readily in boiling water or ak-ohol. and are iniioluble iti r
The solution has a i^trong acid reaction and a saline tdsti!, with unplj
burning aftertaffte. Contains 34*33 p. c. hypoth. anhydrotifl eicalio i
(Muspmtt k Hofniann.)

LUTIDINE,, 337

Mnspratt & Hofmann.

18 C 108 .... 52-43 51*99

N 14 .... 6-79

12 H 12 .... 5-83 5-90

9 0 72 .... 34-95

C"NH»,Cm«08 + Aq... 206 .... 100-00

Toluidine dissolves in tcood-spirit, alcohol^ and ether; ether abstracts
it from the aqueous solution. It dissolves in acetonf, and in oils both
fxed and vohtile. (Muspratt & Hofmann.)

Lutidine.
C*NH» = C"AdH»,H». ?

Anderson. (1851.) Phil. Mag, J, [4], 2, 457; Ann, Pharm, 80, 44;

J. pr, Chan. 54, 36; Fharm. Centr, 1851, 914.
C. Gbeville Williams. Cl\>em, Soc, Qu, J. 7, 97. — Phil, Mag, J, [4],

8, 209.— J^(/in6. Phil, Tram. 21, Pt. ii.; N.Ann, Chim. Phys.

45, 488.

Formation, Bvthe dry distillation of bones (Anderson); also of the
bituminons shale of Dorsetshire, and of coal (Williams); and bj distilling
cinchonine with caustic potash. (Williams.)

Preparation. 1. From Bone-oil, — The oily mixture of volatile alka-
loids obtained from bone-oil in the preparation of petinine (x, 150) and
dehydrated by hydrate of potash, yields by fractional distillation: at
65% propylamine, C«x\H»; at 120° pyridine, C^^\H»; between 132' and
137**, picoliue, C"NH^; and between 152° and 155°, principally lutidine.
This latter portion saturated with hydrochloric acid, deposits, after addi-
tion of bichloride of platinum, a pure salt of picoline, and afterwards a
mixture of picoline and lutidine salts; the mother-liquor treated with
alcohol and ether yields a pure salt of lutidine. (Anderson.)

^ . From Shale naphtha and Coal-tar naphtha. — The thick and treacly
matter produced by agitating crude shale naphtha with oil of vitriol for
the purpose of purification, was repeatedly boiled with water to resinise
and separate the tar, during which process a large quantity of Bunge*8
pyrrol was evolved, as shown by the purple colour which the vapour
imparted to slips of wood moistened with hydrochloric acid. The liquid
was then evaporated to a small bulk, saturated with lime or potash,
distilled, and the product supersaturated with hydrochloric acid to sepa-
rate the non-basic oil. The solution was distilled with an alkali to
separate the oily bases, which were then freed from a small quantity
of ammonia by washing with strong potash-ley, and dehydrated by
means of sticks of potash. The anhydrous oily bases were then sub-
jected to repeated fractional distillation, whereby they were divided into
two groups, the first boiling below 160°, and being soluble in water, while
the rest, which boiled at higher temperatures, were perfectly insoluble.
After about six rectifications, tbe portion boiling below 160°, which was
at first very small, amounted to more than all the rest united. — The
portion of this latter distillate which passed oyeT b^lNvt^u ^^"^ ^ti^^^^

TOI*. XU. J^

— - Azr-Kucixrs chxh?,

~-'— ^^ "^'- ::n;diDc. "wLich were separated bj 'i*
■ - '-^^ lii^itinimt-saJii (x, 407): the pcWa

— -iz^iin-rc t\z iLtidJDe mlicd wisli a nail!
~" ~ -^-^^ '^' i:\-L r.L5«*d over between 15")' lad

'■■"~~ ~- -.: . " ^^ . fonsiisted of pcre htwiaf.

— - '"71"^^ -^'' "^^ -.5", was chiefjlfldihi*

-^ " -1-..- ii^iiTTT lia^e alio piss« *u:

— j?:~ ii:-^err smuU jionion vkicb diftiiied

:_:-..:- zLLiiy w ohiiiDeJ froia ccal-ur: tb

-^ -" -" - ." ;;:". 2. 524; '..V.."';ii

— T-.:-.:!.::;^ r:.. ci^iilit-J with brhaie fJ

~- **■ ~ ~"^ ^":"'~w:^riii L'.': aula ted ir-l :"':.fi

^^^ - :;: :::.>i-r V -re I Lea set free M:t*

' *—■-'" — ■ ' —-•■ -"^-.1^- :-r flick* of pt'taih'aN

■- :'-.-: j:— ^.--t — ^i-, :.. w: crebv fractions »:s

— • — - ^-^i- :»- -"I". Tbc more roliiil?

■ -- ■ ^-i---- X :: ?n:all yortions of piA'iiy

''- - - '^- ^'^~"'. -=^^ rj n-re reciifieatioB*. !K

— - ■ ' > Is *'---•"" -'"d apart. — Tfccroi

^ ■' : ^ i: . :y?-. cr-riained colIHine. aai

.. — - OhT tDd iepidine C».VJi'.-

- - — =*^- :i: ^***rT-;£. ( Williiin*..- '

-•_; • • ..: ■ .:- ■vnr is It^ss p^DiP^Dl a«
3 -r a .• I- 1:=. . Sri. CT. abuuil)*?5.

i. i. r-

■■ :- i :* r^l?se'i over rt^i-hot !'t^ ■

: :•; i;::ifr :«i?^ cal;^ h 7 'n •

"* : :: ri? r:: jc: b^ea xsrertiir*-^

f-^ ■■•- i:i rvirvxhlonc ac:«l. i:-

IL l^r'.- .^»f > fTn.-T^-T >:."-:;* i^ orlJ water. amJ s^
. •iii{iw»i::»??.7 ftfCiin-*? VI :i-» rVrro cf an oiiv larer

METHILLUTIDINB. 339

ChhromereurdU of Lutidine. — C"NH",2HgCl. — The alcoholic solo-
ticBt of corroaiTe sublimate and bydrochlorate of Intidine jield a white
jErranalar precipitate, which diesolves in boilin;^ water, with partial
decomposition, and separates unaltered on cooling from solution in boiling
tilcohol. (Anderson.)

Chioroplatinaie of Lutidine. — Fonr-sid?d tables often confused and
irregularlj formed. (Anderson.) Pale yellow ensiform crystals, nearly
half an inch long, or ruby-coloured flat four-sided prisms. (Williams.)
DiMolyes readily in cold, and still more in hot water, and is likewiijo
soluble in excess of hydrochloric acid. (Anderson.)

... 84-0..
... 14-0..
... 100..
... 98-7..
...lOG-Si.

Anderson.

.. 26-81....26-35..
.. 4-49

. 319,... 3-23...
.. 31-51....31-40...
.. 3400

C. Greville Villiams.

14 C

r "
a.

..2694..

. 3-36..
.31-14..

b. c. d.
..2614

.. 3-16

..31-76. .31-66. .31^ •31-7..

>

N

10 H

Pt

3 CI

..31-8

C"NH»«Cl,PtCl« .

..313-2...

.100-00

%. Anderson's salt was prepared with lutidine, obtained from bone-oil ; Williams's
salt a with lutidine, obtained from cinchouine (B.Fi 160** — 165**) ; b^ e^ d and e with
loHdine from shale-naphtha : b from the fraction of the distillate (p. 338), boiling
b6tireen 132* and 135^ ; the mother-liquor of these crystals yielded the platinum- salt
of picoUne ; e from the fraction distilling between 150** and 153^ (the same as analysis
c, page 338) d and e were obtained from the portion of the distillate which, in the iir^t
rectification, bpiled below 98°, not by first separating the several based contained in that
]fortion by fractional distillation, and then converting them into platinum- salts, but by
treating the whole of the liquid boiling below 98** with hydrochloric acid and chloride
of platinam, and separating the Several platinum -salts by fractional crystallisation
(z. 407). The solution evaporated over oil of vitriol yielded : first the crystaU d which
were pale yellow, uniform and nearly half an inch long, together with thick flat four-
ilded roby-coloured prisms; secondly the crystals e, which were thick prisms; thirdly,
long, thin, square prisms of chloroplatinate of picoline containing 32*29 p. c. platinum
(calc. 32*94) ; fourthly, short, hard, dark red prisms, also of picoline-salt containing
32*69 p. c. platinum ; and fifthly, radiating needles of deep orange-yellow colour con-
taining 34*71 p.c. platinum, which agrees nearly with the platinum-salt of pyridine
(calc. 34*6 p. c). This method of separating volatile oily bases by the crystallisation
of the platinum- salts is recommended both by Anderson and by Greville Williams as
greatly to be preferred to fractional distillation, because it entails much less waste ; it
has however the disadvantage of requiring a very large amount of platinum. To obtain
correct results in the analysis of these platinum -salts, they should be pulverised,
washed with a mixture of alcohol and ether to separate a peculiar resinous matter, and
dried over oil of vitriol, as they decompose at 100^. ^,

Conjugated Compounds containing C"NH' or similar jS'^uclfi.

IF. Methyllutidine.

C^«NH" = C"AdHXC»H»),H».

C. Grbtillb Williams. Ed. Phil. Trans. 21. Pt. ii, p. 317.

Lntidine mixed with twice its bulk of iodide of methyl becomes
heated, hoUa, and almost immediately solidifies into a mass of crystaU

2 2

«riodUe«rcd9iati»

whh iodid6«rcA)laa
-vwW fcrtw «»»;: MtfNc *. At ^•wwiiA fcr two vt time 4g% 4»

>wn<«» >*iwnm jg^WB^aiWHiii odour. Boibatir.

■Bii- -jw _ «Mi — 7r«e

^^^A uuiiiiiiiniii anwNt oImmI s MiH, wweh m ■■•■■■*

TRIBTHTLTOLUIDINE. 34 1

crashed with ether. Pale yellow, becoming dark-coloured at 100^ ;
dissolyes easily in water and alcohol. Contains 29*11 p. c. platinnm and
is therefore C^NH^,HCl,PtCi'. (Calculation requires 28*93 p. c.
pUtinam.)

Biethyltoluidine.

MoRLBT & Abel. Chem. Soc, Qu. J. 7, 72.

When ethyltolnidine is heated in the water-bath with iodide of ethyl
and the liqnld gently agitated after two or three days, beautiful crystals
form in it, which redissolve at the heat of the water-bath. The excess
of iodide of ethyl is removed by distillation; the residue distilled with
potash-ley; and the base which passes over in the form of a light oil, is
recti Bed over caustic potash.

Colonrless oil having the odour of ethyl-toluidine. Boils at 299 •
Sp. gr. = 0-924.

22 C

N

17 H

132 .

14 .

17 .

... 80-98
... 8-59
... 10-43

Morlej & AbeL
80-90

10-47

C«NH»'

163 .,

... 10000

HydriodcUe of Blelhyltoluidlne, — Separates when its solution is
evaporated over the water-bath, in oily drops which crystallise when
toached with a glass rod. Decomposes in contact with the air, when
heated over the water-bath, and by contact with alcohol. Contains
43' 45 'per cent, of iodine, and is therefore C^NH",HI. (Calculation,
43-66 p. c.)

Triethyltoluidine.
C««NH" = C"(C*H»)NH*,H«.

HoBLET &f Abel. Cheni. Soc. Qu. J. 7, 73.

If it be sappoted to contain 1 H more, it becomes IHeihylhluylammonium s
CMH»(C*H»)»N (compirc xi, 308).

Known only as a hydrate and in combination with acids.

Biethyltoluidine is heated with iodide of ethyl, till crystals form in
the liquid. After the excess of iodide of ethyl has been distilled oflT, the
bydriodate of triethyltoluidine remains in the form of a heavy oil, which,
when heated with oxide of silver, forms an aqueous solution of hydrate of
triethyltoluidine. This compound has a very bitter taste, a strong alka-
line reaction, and precipitates the salts of baryta, strontia, lime, magnesia,
alnmiius chromic oxide and the heavy metallic oxides; the precipitates
formed with the salts of alumina, lead-oxide, antimonic, stannous and

342 CONJUGATED COMPOUNDS CON. C^^NH' OR SIMILAR NUCLBI.

staunic oxide, are soluble in excess; the precipitate formed ia caprie nlti
blackens on boiling. Mercnric salts are precipitated white.

Chloroplatinate, — Beautiful crystalline precipitate, insolaUe in co^
but soluble in hot water, whence it crystallises in fine needles. Loses
platinum when recry stall Ised.

l^rorlej & Abrl

26 C 15C-0 .... 39-27 3911

N 14-0 .... 3-52

22 H 22-0 .... 5-54 &-44

Ft 990 .... 24-85 24-71

3 01 106-2 .... 26-82

C»NH=2Cl,PtC13 397-2 .... ICOOO

Metoluidine.
C*»N»H" = C7«CyNAdH",H«.

Wilson. (1850.) Chem. Soc, Qu. J, 3, 1.5; Ann. PAirrm. 77,21«;
riiann. Centr, 18j1, 110.

Fojtnation. In the decomposition of toluidine by chloride of

cyanogen (p. 335).

l^refaralion. Toluidino is sproad, by the application of » gentle Leit,
over a glass tube somewhat bent, and vapour of chloride of cyanogen ii
drawn over it by means of an aspirator; the heat evolved by the reictioi
is then sufficient to keep the substance in a state of fusion. The result-
ing resinous mass, consisting of hydrochlorate of metoluidine, is diaiolfti
in water containing hydrochloric acid; the liquid filtered and precipiutf^
by potash; and the precipitate is boiled for a while with the liquid contli^
ing potash, in order to drive offany undecomposed toluidine together widk
the watery-vapours, then washed with water, and rccrystallised froo
alcohol.

Crystilllne lamina". The best crystals are obtained from a mixtm
of water and alcohol.

Wilwn

30 C

.... 180 .

.. 75-31 ..

74-54

3 N

. 42 .

.. 17oS

17 II

17 .

711 .

7-34

C*NMl''

.... 231) .

.. 100-00

Pi><.>lvos sparingly in cold, somewhat more readily in boiling water.
I>:^- In OS readily in hydrochloric acid.

Chloyopltt'iiiatc (f Metoluidine. — The hydrochloric acid sol«ti« ^
'ctoluidino furins with bichloride of platinum, a deep yellow pndpio^
licli U insoluble iu water and alcohol, and may be dried at lOO'-

THIOTOLAMIC ACID.

843

30 C »».. 180

3 N ,_.. ._ 42

UH « ..«.. 18

Pt. .»»„. 59

3 CI ,.., , , 106-2

C*>PH>^HCl + PtCl^... 445 -2

40-43 40-40

9-43

4*04 „ 4*24

22*17 22-15

23*93

10000

I

L

I

Cyanotoluidine.

W. HoPMANK. (1848.) Ann. Phamt. 6e, 144; Ck^im. So<r. Qu. J,
1, \5B; y. Ann. Chivu Fkys. 24, 67 ; V. pr. Ckm. 5\, 216^
Fharm. Centr. l%m, m%

Formation (p, 335),

Freparaiimi. 'When eblofide of cyanogen is passed tUrongb an alco-
IjoHc iolutiou of toloidine, the rcd-browri liquid deposits after a few hoars
a erysiilliDe rai:tlure of soveral substances, from wbicb Ujdrocljloric acid
extracts cyaDofeoluidino, Tbia compound resembles cyan i line in every
respect, excepting' tUat it is leas soluble in alcohol and ether »

Thiotolamic Acid.
L HiLEENKAMF, (1855.) Afiu. PhaiHi, 95, 0G-

Format i(tn. By the action of snlpliite of ammonia on nltrotofnoK
Known only in combination with bases*

Frepuration of the Ammonm-ialL A miituro of BO grm, nitrololuol,
400 firm, of a col d-sato rated aqueous solution of sulphite of ammonia,
a small quantity of ammouia, and a litre of ahsolute alcoliol, is placed
in a flusk provided with a condensing apparatus, and heated to
the boiling point in the water-bath, the distillate being from time to time
poured back into the flaek, till a, sum pie of the liquid is no longer clouded
by water, ^^^ nddltion of carbonate of ammotiia |>retetit9 the liquid from turiiing
ucu\ and the ransequent de com position of the tblotolaaitc acid produced. The
cooled liquid is decanted from the crystallised sulphite of ammonia and
craporated, with addition of a small quantity of carbonate of ammonia i
on cooling, it deposits nidiating groups of delicate laniin^e. which are >
filtered otf and treated with ether, in which, after stirring, the adhering)
motber-liquor sinks, so that the lamina? may he poured off together with
the ether; they are then quickly heated to between 50° and Gif and
placed iu vacuo. By a repetition of this process, they are obtained in a
it&te of purity. From the mother-liquor, small nodules separate, which
jtinrecfystallifled from alcohol, yield thigtolamate of amuionia in IaminaB>^

344 CONJUGATED COMPOUNDS CON. 0*^H* OR SIMILAR NCCUI.

TkiotiJarmtt of Ammonia formg delicate laminip baring a silky li
and tiEictuous to the toaciL It b t^ery soluble iti water, €o lliat It cai
be crystallised thcr-cfrom; it also dissoh'^es readily in alcobol, but vT
insoluble in etlier* The aqueous solution baj a fiint yellow caloag, h
peculmr sweet odoor, and a slight acid reaction.

14 C _

2N.

..*. 84 .

.., 28 ,

., 4M8 .

... is-ra .

... 5^89 ,

... li-SS .

2353 .

BUketikiunp.

4084

...... 14 08

12 f! ,..

t S „.

„» 12 .
.... 32 ,
... 48 .

6*35

....... 1511

liO...,,...

23:i2

C^^NH^fNt

IO,2SO^

... ao4 „

,„ ItlO^OO .

100-00

Tills tcid heart the umt reUtbn %q tolaol tbit ihiQnapbthuiiic »cii ban ts
tinplithiilit] ,

In damp atr^ the salt gradually acquires a roEe-red tint, He&tdfl «q
platinum foil, it melts and chars. Sulphuric, hydrochloric and nitric
neids do not produce any alteration in the aqueous solntionj even at tlic
boiling Lcat, The acid aolutloua assume a rose-colour when exposed t"
tha air* Nitrate of silver ia decomposed by the aqueous solution of tl»»
salt after a while, and more quitikly by the akoboHc soluliau with pr^
ctpitation of nietaUic silver. Aqueous sesquiehlorido of iron aec|uife< i
purple-red colour when mixed with it^ and after a wbile a black prrc^-
pitate is deposiled. The dilute sulutions of sulphate and chloriJ« of
copper arc coloured green by it, the former becoming turbid when heilr^l
In a solution of corrosive sablimate, calomel i^ precipitated* A «oliiii*«
of protocyanide of iron is rendered turbid by it and gives otFa faiwl odi*ir
of bydrocyanic acid; similarly with ferri cyanide of potass* uni. only tV

turbidity does not show itself so quickly. By the Action of ohlor

heavy yellowish oil is produced gnioHiug like chlomnih

Thiotoiaimtie o/Fotmh. — When tbiotolatnate of amiiionift is added 1*^
aqueous carbonate of potash and heated as lon^ as ammonia contiuaee to
escape, the liquid evaporated to dryness over the water-bath, the rt&^w
exhausted with boiling absolute alcohol, and the solution filtered hol«d
deposits f^niall nodules, which when dry form a powder having a lufli
leddigh tint. This salt Is less soluble in water and alcohol than dit
ammoD la-salt.

C»*NH«SW „„,... 18$
K 39-2

82\\9
17-41

. l?-22

C"NH*K8?^0* .... 225*2

100-0<»

Tklfdolamate of Soda, — Prepared like the potash-salt
cryfitalline nodules wbjcb form a white powder when dry. Eauly iofuUi
in water, spariiigly in alcohol, insoluble in ether.

Thiatolamtite of Baryitt, — The ammonia-salt ii added in
water and the liitULd kept at the boiling heat as long tu$ amtiKmia(«^
iJnueB to eacape; th^ exccii of baryta precipitated hy c&rbome acid, i

SALHYDRAM1D£.

Bitered liqaid erapomtedr whereupon it depoaits wbit© cry^talllao
its. The salt disaolvos reaJily in hyilrated alcobol, but U insoiabte
absolute alcohol And b ether.

Salhydramide. C"N»H"Ol

rKxTLTNO. (1839.) Ann, Fhann. 29, 309; 05, 201; Pharnu Cfnir;

I 1S40, 836.

[LAUflENT. MfV, icient 10, 393,

Formatioiu By the action ef ammonia (or hydrosulphate of ammo-

r'l) on ealieylous acid:
3CIW0* + 2NB1 = C4JN«Hi«£y" + GHO.
rreipondi Co hydroben^tunide (p, 19]).

W

> All

Prtparatmu 1, When dry ammeniacal g'as is passed over sail cylo us

Bcid» a sljn^ht heat b evolved, the acid incrcaaea io weight and solidifies to
yellowish crystalline mass, wh-ich melts between 30"^ and 40"^ and yitslds
a scanty .lubliniate. (Ettling,) 100 parts of dry salicyloua acid take
up, according to Ettling, O'GQ pta. of ammonia; acconling to the above
nquatiori, the quantity should be 929 pts, — 2, One measure of flu 1 icy lo us
lid is dissolved in 3 or 4 measures of alcohol, ^^d L measure of aqueous
Ammonia Is added. Yelluwish white needles of salicylate of ammonia
are then formed, which ultimately reduce the liquid to a nearly solid
mass; but on applying a gentle heat, the whole dissolves, and the solution
on cooling deposits heavy, deep yellow crystals of saHiydramide (p, 338).
If only a small quantity of alcohol U uJscd, or if the liquid aftpr It has
become clear, is mixed with water, a brownish ycKow oil Ecparates
which gradually changes into crystalline salhydramide. (Ettling,)

PropftriitM. Deep yellow, shining, transparent, hard, four-sided
prisms belonging to the double oblique prisnmtic system. JY^, 121
(oo'P . 00 P' . op), uiv ^MV 30'; y i u = 93' Wj y \V— 103' 30\
(Laurent.) The alcoholic solutlou has an alkaline reaction.

Ettlitig*

42 C .......

... 252

.... ?283

2 N ....„

.. 28

.... 8-09 ....,

,.. 8-92

18 H

. 16

... 520

..* 5*30

eo.

. 48

... I3'fl8

C«N^H"0« .

.. 346

.... 100*00

DecompoiUioni. 1. Melts at 300^ into a brownish yellow mass and
yields a very light white sublimate. The residue solidifies on cooling
and forms a tranipareut mass^ which chars when strongly heated. —
2. It is not altered by dilute acids at ordinary temperatures, but when
heated it is converted into salicylons acid and the ammonia salt of the
aoict employed. — 3, When boiled with potash leyi it gives ofi* a large

346 CONJUGATED COMPOUNDS COK. C"NH^ OR SmiL4ft KTCLK.

quantity of ammonis and tearaa aalicjlite of poteBk. TIm
sc^lutioQ loay be mixetl wUti weak potmsh without dit^trnfmrnp-^

4. When ammonia ia poured upon it and l%h to evapor^lo in toe Uf, ik0
rompound b gmduaLlj coaYertecL into a din^j jelJoir-gT^e>eii pciv4ir
The alcoholic st^Iulion mised with ammonia qatckly tarns brown <n
exposure to the air and absorbs a volume of oxjgen eqaal t^ lU own, —

5. An aloohotic solution of salbjdramide tbroogb wtLieb fiiiIplin£ttt«J
bydrogen is pa^cdj yields tliioi^nlicol.

C&mhinetitom. — Salhydramide appears to be mooluble in wslmr*

Lmd-mmpourtd. — a. Wbeu an aqueous solatiou of oeutml
of lead ia mixed witb 10 times its^ bulk of alcohol, ibe mixture tkfi
heated, and, after addition of a little ammonia^ Tnixed wttb a solutiao d
inlbydmniide and a small quantity of ammonia, ai long zm ihm fiiMjpilile
at first produced redissolves in the bot ti<]^nid, this liquid dcpoAtl li
cooling, a deep yellow, beavy^ granular powder, wbieb, after being wuM
witb water and dried, resembles cbrorae-yellow,

h. Neutral acetate of lead added to » solution of Balhydmntide wttti
witb ammonia and water^ prod ueei» Iigbt yellow fiake^^ which wheo^
become etrongly electrical by friction.

Iron*€nm^und , ^^ \\\i{^^ ferric bydrocblorat© is mix^ widi a miE
cieut quantity of tartaric acid to prevent precipitatioti by ei:oesi of
ammonia and a solution of ealbydramidc in animunincal alcohol prtpAml
hot} and containing so much ammonia that it is not reuder^d t4irbld If
40 times its volume of cold water, is added to it, the mixture iauMli*
atcly assumes a dark blood-red colour and deposits, after tk few ieoottk
yellowish rt.'d flakes, which soon acquire a deeper atid more fiety eol«sf
and a granular te:xture« The product is washed witb water xna driei
— If the iron solution is f finicnhat ixi eiDe^jit tbe precipitate quickly £<tlJf^ to lltf W-
torn* The mother- Ikjuor is clear, aitd in ihe counse nl a few montlift depoiiUtvf^ ^^
dark violet crystnU which have a strong luitTe and yield a rcd-browa pawder* — ^Sdicf*
I QUA acid may aliia be used instead of salhf dramide, bat |q thai ea*e tlK eonpottod bla*
some time to aeparate.

Dark fiery-radj j^-ranular, like ee^quioxide of iron Toltrably I%K

Fe^O*

42 0 ».,,..

3 N

18 H .»

8 0 ....

Eltlini.

SO ,.,. 19-23 19-46

i5i *.. 6057 ..,.,.« iO-Sf

42 .... 10*09 S'Sr

18 .... 4'a3 4*30

24 &78 , ..„. I-ia

C«N3H**CP.Fr^0*_ 416 ... 100 00 ..... 10000

Alponling to Gerhrtrtlt, lhi« eompound it C«N^fe*(KfeH*;Hi*0*, t^t *• ia «♦
"^ lliid« in wMcb 1 At, H air r«plKeed by 2 At. fe, and 1 At . H ^ ftvmm^f'^
Fei ferammqtiium = KfrH^ thai [s la *aj aannoniiini In 'm%\dk I AL M *

(ft .

replaced Uj k\. — The formitipn of the coia pound from free fftUeyiona i
lu « matrntT similar la tliat of silhf draiiitde» hf the eqtiatioti :

3C^»H*0»,Fe*0»,NH> + SNH' = C*^K»H**0*,WO» ■¥ 6HO [U>

Whoii beat«d above lOO^ it niettSr giret olF wbitt vipourv^ tad hi^
oarhiiret of iron. ^ When bujled witb water, it r^taiiu its tof^nJ
oolourp hut tb« amount of irou riii^ to 20^ p^ eatiL mad thi^

i

SALHTDRAMIDE.

347

^_ CO

■fe

^

acquires ft yelloMT colour, leaves a slight residue when evaporate d* ami
lorms with acetate of eoppar, a (ew spangles of the copper-corn pound of
aalhjdramido. — It is not altered by cold very dilute nitric acid; hut
when heated with the strong i,^r acid, it dissoivea and forms a yellow
eolation which deposits salicylous acid on hoilinir. It ia dissolved by
hydrochloric aeid diluted with alcohfd, even in the cold; the solution
niiaced with bichloride of platinum, yields after a while a deposit of
cbloroplalinato of ammonium,^— The solution in aqueous hydrochloric
acid, forms with ^ulpharetted hydrogonj a precipitate of »?ulphur; with
ferrocjranide of potassium, a precipitate of prussiau blue after a while;
with seaquicyanide of iron, it immediately acf|uires an emeraM-greeu
colour, and after a few hours deposits pruisiau blue.

It dissolves in alcohol, forming a dark blood-red eoluliotij from which

ater throws down a lighter-coloured compound containing 29 a p, e.

ferric oxide; the supernatant liquid mixed with ammouio-cuprio acetate

does not form the copper-compound of salLydramide, but only a dingy

greyish green precipitate.

^

C&p}ier-Gompound, — When a very dilute solntion of ealhydramide ts
mixed with ammonlo-cupric acetiite, an omerald-green liquid is produced,
which loses its colour in ten minutes and deposits emerald-^rcen, shining,
interlncingi crystalline lamina^; these are washed with alcohol, till that
liquid runs through colourleas, and then dried. If ia the preparatjon nf sali-
cylitc of copper (p. 243). tUc frea acetic add is DeiitE-uUsed wStli anunoniH^ tUii eora-
pound is prepipitutod together with oxide of copper.

Very light crystalline krainaj, of a dark -green colour and strong
satiny lustre. From n solution in water niixed wiih a litlle ammonia ^nd alcohol, tt
ii precipitated of a pde blue-grefn colour on the addiiion of tcetate of copper.

a Co ...,.„.,..„, W-4 ».. 20*95 ........ 25 53

42 C ,... ....,„.,.. Zai'd .... 65 34

3N ..., 42^0 .... 9*22 8-97

18 H „..., 18-0 .... 3*95 4-04

6 O ,. „ 480 ,.,. 10 54

C»^*tt»9Cu30* .... 435-4 .... 100 00

According to Gerhard t, it ia Balhydramide jo i^hkb 2 At, H are replaced by 2 Ca,
and I At. 11 hy NCaH^ (cuprnmTiionium), so that itsforraukb C«N^Cu"(NH5Cu)U«0=.
— ^Tbft (brnaalioii of the compouad ia represeoted bj Ibe equation :

2Cwcu!i*o* + a<ciiHW,NH' + 2Nn3 = v-wcmv^^o" + mo [1-0-

Wben lieated, it melts into n blood-red mass, und gives ofl*a greeui»li
vapour wliicli condenses into oily dro]).% crystalliiiingas tbey cool, peifectly
volatile, and emtfUiug like guui benzoni. At a lifj^dier temprraturCj tlie
residue solidifies and slowly burnai leaving oxide of copper. It dissohea
in cold dilute bydrocliloric acid, forming a green solution, and on neutra-
lisint^ the acid wtth notash, or even adding a ratber large excesi, iLe com-
pound iaprecipitatrd in its origmal etate* Wben heated with strong' acid?* ,
it yields the ammonia-salt and tbe cu|>ric snlt of the acid, and gives off 1
salicylous acid. It is not attacked by wetik jtotasb-solution in tlje cold, and
but&lowly attaeked at the boiling heat. After boiling for some time, tbe
lion id sudd en! V neq aires a light copper colour^ and deposits a red pitchy
Babatance on the eides of tb^ vessel^ the rest of the liquid still retaining

Mi

C«S»lli»JH"^0».
TaOA. (IBM.) AmM.Fiarm.M,l7X

Tndmotd hj tht aedus of amsMOtt on WoaMMlicjloM mai; id
are exact! J naular to tkoae of dloRMaUijdnBuda.

42 C »2 _ 43-tt 42-«

tS 28 _ 4-80 5-07

15 H 15 _ 2-57 2-67

2 Br 248 _ 41-17 4#-78

6 0 48 .... 8-23 8-63

C«N»Bi*H"0* 583 .... 108HI8 188-00

Chlorosalhydramide. C«N'a>H»o«.

PiRU. (1835.) Ann. Pharm, 30, 172.

Chlarotamide.

Foftnation. By the action of ammoniacal gas on cblorosalicjloof icU :
ZO*C\HH>* + 2NH' « C«2WPH»0« + 6HO.

Preparation. Dry ammoniacal gas \b passed over dilorosaliejlou
flcid ; the resultinff resinous mass pnlyerised ; ammoniaod gas agaia
passed over it; and these operations repeated as long as any action takei
place, that is to sajr, as long as water continues to form; the yellow masi
IS then dissolved in anhydrous alcohol or hot anhydrous etaer, wheace
the chlorosalhydramide crystallises on cooling.

Properties, Yellow iridescent crystalline scales.

Piris.

42 C 2520 .... 5610 55-39

2 N 28-0 .... 6-23 6-45

15 II 15-0 .... 3-34 3-43

3 CI 106-2 .... 23-64 21*46

6() 48'0 .... 10-69 13'27

C^^'N- WH ' O^ „« U^-2 „,. 100-00 100*00

PYKOGUAIACIN* " 349

Heatefi with acide^ it yieMa aimnonia and cliloroeaJtoyloiia acid.
With hot hydra ted alcohol it gires off aronionia.

It is insoluble in water, hut colours that lifiuid yellow wbe« left in
U contact with it for some time.
^L It distfolves in hot anliydroaB nlcohol and dhei\

^^^^K % Salicylosanillde.

L. ScKiecHKOFF. (hrnpL rmid^ 45, 272; Ann. Pkann, 104, 373,

^P W h en eq u al vol q m es o f sa I i c jl on e achl an d an i 1 i n e a re heated together
"under the ordinary preeenre, water separate?, and the fluid mixture

Eyn cooling:
iful light yellow crystals which melt below 100\
SchischkoflT.
26 C 156 ,... 79^0 ?8*65
N.,„. „. U .... 5-50 7'Ofi
HH .» 11 .... 7-10 ....... 6'f»0
2 0 16 ... 830 ....... n2B
C^NH"(P. 1!^7 .... lOO^OO 100*00

l^ N.(C^m5),(Ci^H*0'),H, aaQiDtp in whicli I At. H Is replaced by wlkylMyi

Ilaomeric with bcnzauiUde).
When heated with acids or alkalis, it yields aniline nnd salicylous
icid. Its alcoholic eolutioo is not decomposed by Eulphuretted
hydrogen.

Insoluble in water^ easily eoluMe in akohot. T.

Unknown Fnmarf/ NucUm C"H**,

Pyroguaiacm. C«*H^on ?

^Pelletier It Deville. (1843,) Com}ft^ rtnd, 17^ 1143; Phmm. Centn

1844,03*
Edermaier. /. pr, Chenu 02, 291) Phatm, CmU\ 1854, 2S0.

Formation and Preparation. Obtained together wtth guaiacene and
the " "

I

pyroguaiacic acid in the dry distillation of guaiac resia; not perhap*
from all varieties, inasmuch as it is not mentioned by Will {^iyin. Ph^rm,
$a, 345) among the producta of distillation of that resin..

350

TRIMARY NUCLELS C»<H^<^: OXTORN- NUCLEUS C^ni"0*.

Pmpertks. Nticreous lain ma?, voktilo without dccoin|Ktiiticiiul
( Pell e tier & Deviile.) AVhcn aublimed in a Motir's af»pamttit, it fonail
kmiiieoTloiigneetJlea. (Ebermaier,) McltsaLl80% (Petlctier^ Derillo,)!

u c

8 H. „

20

... U

..... 8

**♦♦ 77*78 .*.
... P4f> ...
.... 14'32 ...

... 746 ,..

... 13-59 ...

. .. 78*46

6*97

... Ha 7

C'^BSQ^ ._

im

.... im-m ....

..„ io«>-oo ...

.. 100*00

I

At-cordiuj to Ebtfrm&ier, It i^ C^nPO^ {wUi.*li reqyirfs 78*30 p. c, C ind 6*54 II H
and fticcordiu^ to Kiit>]> [Phttrm. Crnir. 1844, u90) it U pcrUnps taltiAt« of phenyl, J
C**H^-U* = CJ-"H^O.Lini'U\ which view howiver does iiol ngrec with the decomiJOti- I
tion by BulphaKc jidd, Tlii^, rni wrll ns the reatrtioii vrKh c:h1t^rine„ teetna to iRfljr lliiA I
the subsUuco i^^aiiiineJ li^ ELermaier w^ j:iot pure. [L.]

Decomposition I. 1. Witb ntfric ac/fZ it forms a purple-red aoloti on . j
Shnilarly witli aqueous ceramic acid. — 2. When oil of vitriol ifl^H
dropped lii to water in which pyroguaiiidn is suspended aod the liquitl ^B
heated, the giibsttiiice firat turns yellow and iheti yields & roee-coloufr^d
ett>lutioii, wliich afterwards turns green, and ultijiiatdy deposlU a black-
blue substance which colours the Vu}\i\d violet. Oil of vitriol in contaci
with pyroguabein becomes very hot, and a.6sumes first a brown, then a
dingy green, and ultimately a cfark blue colour, 31 black- biue subataaes
then separating which contains t^ulphur, but not in tht^ form of sulphuric
acid. —3, Pyroguaiacin suspended in water into which chlorine gas i
passed, tnrns yellow, cakes together and thou assumes a d&rk brown
ttduur; the still n mist product aud the wash - water have a strong odour
uf musk which disappears on dryin|^. — 4. Caustic ammonia coloun
pyroguaiacin 3^el1ow; the alcoholic solution saturated with ammonia yields
nearly unaltered p^Toguaiacin when evajiorated. — 5* The &l cob olio
solution of pjrogaajacm reduces nitrate of silver.

Fyroguaiacin is insoluble in water.

Pyroguafacin immersed in cold potash awelk up considerably, aud
when the liquid is boated, forms a solution which solidifies 011 coobag
into a solid nuiss, from whicli, after saturation with carbonic aeid, aloobol
extracts unaltered pyroguaiacin.

Pyroguaiacic Acid.
C»H"0* ^ C^m"0',OV ?

UNYEaDOitDEN. (1826,) Fof;g. B, 402,

Felletier Sc DeviLL^. CmnpL rerut 17, 1143.— -.V. Ann. Chim^ Phy^

12,228; N,J.Fhaim. 6, 118; J, pn Choft. 33, 318; rharm.

Centr, 1844» 45,
SoBBBRo, N, J, Fharm. 4, 3$!;; €kmiy(. rmuL 17, S77; Pharm. CMr,

1844, 19.
VliLCKEL. Ann. Fhirm* 89, 345; Pharm. Ctntr, 1854, 434,

Pjfr&jakMMHrf, GHaj/tkffrandfdure (Untifrdorheti), Fyrfft^ui^ukttlare (ViJlekd),

Prtpitfati^n. 1. The oil obtained by the i\ty distillation of |viiM
re^ln h distilled with 0 pts, of water and | pt. hydrate of p<>t4»li »»
hag as th& diirtiilate tibiolta any u^out; l\i%i^kluttX lii^uid li de^Mied

PTROGUAUCIC ACID.

351

the tar, diluted with 2 pts. of water, and exposed to the atr, after
wbkh it Ja evaporated, wiih frequent renewal of the water, till it no
longer smells. On subsequently distilling tlie liquid jnixed with sul-
phuric ncid, a yellowiJ&h grei^ti oil coUecta in the receiver below the
water. (Unverdorben.)

2- The heavy oil which paaaes over in the diatillntion of gimiac ra^in
IS dissolved u\ pwtasb; the solution diluted with water and hoi led in the
retort as long as any yellow light oil passes over; the residue Tnixed
with a quantity of Bulphuric acid not quite eufficient to convert the
whole of the potash into ewlphate; the sepanit^'d oil dissolved in
potash; the solution boiled in the retort till the milky water which hau
pa.^sed over becomes perfectly clear on the addition of a* small quantity
of potash I and the oil again separated {3 ]ht. of resin thus treated
yielded J 60 grnis. of oil). This oil is dried in vat-tio over oil of vitriol
(because chloride of calcium is sonie^vhat soluble in it and gives off
wator in distillation) and rectified. It he;Lri«» to boil slightly at 100%
and h in conjplote ebullition at 200*; only a, small qoautity however
I>as.^es over from 200^ to 203% about ^ of the oil from 2VS" to 210",
half from 210'' to 220'', and the miiall coloured resiilue between 220" and
230% By repeated fractional distillation, it is freed from an admixcil
ensily decomposible oil, and pure pyroguaiacic acid h ultiimttely
obtained. (ViikkoL)

3, When the mixture of guaiacene (x, 411,) and pyroguaiacic acid
obtained by the dry dii^tillatiou of gnaiao resin is washed with water and
tuicfuUy distilled, all the guaiaceao posses over ^tf^U the pyroguaiacic
ikciil distilling at a higher temJ^eratu^LJ only; tho uiubllo portion of the
difltillato obtained at about SIO"" cctutsiins iho pure acid^ which is ob-
tained colourless by repeated recti ti cation in an atmosphere of carl>onio
acid. — Another method is to deeompose the lead-salt by sulphuric acid,
shake up the liquid with etUer» wusK the ethereal solution with water,
and rectify in a stream of cnrbouic acid* (Sobrero,)- — The acid Is very
difficult to obtain pure ; the pupification is conducted like that of
creosote, (Bcville & Polletier.)

Fi-operlies. Colourless oil; sp.gr. = 11 10 at 220^ (Sobrero); 1*125
at IG"* (Volckel). Has a faint peculiar odour resembling that of creosote,
and a pungent peppery taste like that of cloves. Boils at 210'^
(Sobrero), at 205^ (Volckel), Vapour-density =^ 4^4Q (Deville ^
Pelletier); = i'SQB (Sobrero.) Does not redden litmus.

14 C ...„. 84 .... 67-74

8H 8 ..„ 6 45

4 0 . 32 .... 25 -SI

*.|j*4l

Sobrero. Volckel.

, $878 ... m^n

. 684 .». a-38
. 24-38 .... 24-70

C"H«0^ 124 .... 100^00

^^B C^vapour „.*«,^.«,.«M

14

8
2

, 100*00 .... iOO'OO

....„™. 5*8240
0'5544

^^^ O.&JLS ..... ,,,.,.,

2*2186

T^ ^UO .... ....44^.^.,. .-..--

Vapour of Pyro^uaiicic acid..,.

2

1

....« 8-5970

_, 4-2985

According H> Sobrero, it la Ci^'O* ; according to Vmckel C'^H^D^.— The acid
cKftTnined by Sobrero was not pore ; m the pure stHtt it h C^^H*0* (DcTille)i Tlie
formula C^^irO* wsuld recjuire 70 '5 per cent, of csrbaa. £L.]

352 PRlUABf KCCLEUt €^U^l OX^GSS-mJCLEtn C^'BW*

Bf^GmpomiimA. U Ihm add haum irti^ & wlitte mdy
(Solum*) ^ i. li U v«t7 ▼ioliotlj atljc^ked bj uttne aey« «rM vWi
verj fliliie^ and in the cold, wilh fonaiioii of oxmllc waA aail s mA^
Wown rrsin. (Scibrero, VoIekcL) Ia tJieitiae of aqocoas Mlvtioo, it b
couTCJt^4 into »red*1ir0ini w^o b j liqaidt vlileli rt^iljelf-e upoi: ;
eiieliaAblcbrc^mateofpotafi^fOTiciiiJplisi^Acu (TilekeL) Tbc^c
[(ilaljon ftdneefi gold ahiI illT^viAltt U> fhm meialWc ttaie^ atiil feiru- : r
crnpric ^ts to fen^iis and mpfoiis oilto rospeetkelj. (Sobrem.)*- ^ W i .
diknine of Ironiine It fonnt ft cfjst&Uin^le ftdd, in vlyeh lialf tbir
bjdniiFeii i« replaced bj cbkrine or broi&iiie. (Pelletier h Derilk)
WitH chlorine, it forms a crrstalli Sibley ea^ilj fusible urns?, icBidi wfcm
^nlly heated eublimes in long white needles; iodine arad bmmtot ad ii
Tike maoner* (Sobrero.) The cir^talline rnb^lftiiee diiappeaT* wph
when acted upon bj a larger quantity of cblonne. (Valekel.) — 4, El-
poeed to the air in contact wltb squeooe pota^b^ ligtrndnaily tamt tfA
and uUioiatelj dark ^reen. (Ptdletier k Devjile, Sobre^rti.) When pw*,
it does not ei^hibil this colouring, ereo ait«r two tnoiitba* eJcpQi«i«^
(VmckeKJ

C<mhimtions, Pjfrog:natacic acid m qnriogly Bolqbie im water.

It dissoirea in oil of vitriol^ and b precipitated hj w^ter In it>
origitiml «iaU. {V5lckel.)

With baaea it foima er^sta^Uis^ible flalte which turn hlmeik in tbt ami
ttate; it does oot deeompoae cafbooates. {Pelletier & Deirille^) Itdit-
eolree readily in aqycoua potash but does not decompooe alkaline cwbo-
Datee. ( Pellet ier i Devil le,) It is m£oliibte in ammoola, (Sobreru/i

With potash and ammonia^ it fortnB wbita cry«tllllisabl(^ ma«t<&

(Vfdrkel)

The jiotajsh'^t aftFumes a bine coloar when fosed in coQiiet with tk
air; it is but ipanngly soluble in aheolute alcohol, itUl Icm ta flier.
(UnverJorben,)

The Gaits of the alkaline earths and heavy tnetallie oxides at« tfa*
ringl J soluble in water. (Unrerdorben)

The alcoholic solution of the acid forms with baaie aeetate of 1ei4 «
precipitate which is insolnblo in water^ eolnble in strong a)eohol, mA
melts at TOO', (Sobrero.) The same compound is obta.in<Kl wbca ii
alcoholic solution of the acid containing ammonia is mixed with an unot-
niaciJ solution of acetate of lead, (VolckeK)

UC....,.,». «„.. lift

4 o»., 3»*a

2PbO ,„ ._ 223*6

Sobwrp. TaickeL

2i'ifi ,...,.„ Z5s^ a^^ea
2H p .... 2-30 a-ai

ft'U ........ S-45 _ H'Sl

fi4'35 $S*?0 ,.,. iS^l

C»*H»0<,2PbO,. 347-6 .... 100 00 ,. 100*00 .*.. tWtm

Pyrognaiacic acid diss<ilre« readily in nico^o/ and in efAer,

OBCIN,

353

^^^^^^^^^^^^ Orcin. j

BoBKXUBT. (1920*) J?in. OArm, Ph}j$, 42, f3G; i?n J;vA. 36, 315, —
Ann. Ckim. Phyn. 5%, 320; .V. Br. Arck 5, 174.—/, Phann. 2 1, 26[>| j
J. pp. Chem, 0;i3O; Jiiw, Plyarm. 15, 280; PAanji* Oeytir. 1805, 438; i
1838, 690.

LiEBiG k Will, -inn, Fharm, 27, 147,

Dpmas, ^n/n Fkarm. 27, 140; J. ;yn C/*e/». IC, 422* — Fhann.. Chn'r^
1838,091.

ScHUKCK. Ann. Pharm. 41, 15D; 54, 260; i'^rw*. (7wj£r. 1845, 727*

Geabardt, CompL chim. 1845, 287*

Stenhoube, PUiL Tram. 1 848, B5 ; i?iji. Pharm. 68, 93, 99; J^, pr, Okm»
45, 1 80,— iVt^m. G^ntr. 1848, 3)8. J

Streceer. Atm, Pkat^i^ 68, 108. ^

I*AURENT & Gerhardt. N. Ann. Chim. Ph^. 24, 315; N, J, Phrtrm.
14,304; J,pf\ Chem. 45,304,

Sources. Orciu appears to exist, partly t&tAy farmed, in the licliena
"^'! for tlte preparatioti ol archil and litmua.

Forffiatkn. 1, Bjr boiling orsellic acid with water and thenefora
I also by boiling lecanoric (alplia-orsellic) acid, erythric acid, picroerythrin
^ or evetuic acid with alkalies, llieso latter euhstances heiti^ first converted
"-Tito oi^llic acid, — 2. By ihe dry diatillatioE of lecaaofio acid, erytbrio
* 'f ereroic acid and picrocrythrin.

Preparation^ Dry Yaruilaria dtalhfttais ^^n>ii^i%^ by boiling alcohol |

Itbe solution freed by evaporation and cooling from the a coii resinous body

l^hich soparatea; the remaining liquid evaporated to an extract; and tliis

I extract exhausted with water. The at|ucous solution evaporated to a

kfyrup deposits after a few dayi crystals of orcio, which may be purified

Iby rccrystallisation from water, with addition of animal charcoal, durto^

i^hich operation however tho ebarcoal absorbs a considerable quantity of

\ mtm, (Robiquet.) — 2, A roci?ella or a lecanora is macerated with milk

. of lime; the strained liquid boiled for a few liours in an open ve8scl, and

evaporated to ono-fonrtn; carbonic acid ^aa passed through it as long as

precipitate of carbonate of time coiitinoes to form; ^nd tho Ultra te

[evaporated to dryness over the water- bath. The residue is boiled with threo

F or four times its bulk of strong alcohol; and the solution is [iltercd and set i

Aside to crystallise; after three or four days, the dark coloured crystals \

are dried between paper and dissolved in three or four times their volinno

of anhydroug ether; and the filtered solution is left to evaporate in

vacno. The large six-sided cryatahj thna obtained beenm© still paler by

recjystallisation. (Stenhouse*)

3. Perfectly colourless orcin iB obtained as follows : OrseUic or erythrio
acid is boiled with water for half an hour or an hour, whereupon a larg©

?[uantity of carbonic acid is givea off, and the evaporated fiolution
mixed perhaps with animfil charcoal) deposits on cooling a large
I quantity of colourless cryitaU of orcin* — 4. Or, pure lecanoric acid, or
I its green motherdiquor {nid* preparation of lecanoric acid from Ltcanont ^f3r^Ua\

% K I

35 » piuiAKT isccurs om»z oxtgen-iiuclbus gnbw.

15 botleii vhii £tzonz l»iTts-water; tke buyta pieeqiiteied after tkp
Jei»aiCh:<&:u<:a i^ complete, bj a stream of cuboDie aoid gas; and the
Lv^si'l L^;U£d »o tbe Uyiliiiff' poiBt» iltered, eoneentrated, aod kft to
erJ.rl•^7:&:e. To varJr the cfjilal^ ibej are diaeolred in hoi vater, aal
K: UW vlih kriritip ci alomiiia or feme hjdrate, till Che liqoid ia BMiiy
c^f<^'l j^ri^r'L a;:i- : ike aUntioB is filtered and Mil to ciyetmlliae. TW Ifdrali rf
ili,M..i^ -c f.^Tv ijl-i:^ uJcet sptaep^^Kot with vlark the iapwe oraiaiieBlnnl;
As.i -TO. a.?scl raz u» a^x.:.iiA or u^de oiF boh m hjiroddorie aeM, tbe pHseBlrmiiv
r« tie vcv Y a itauMw^ Kui iankWe ia viter. cmOt Boldble Id aiomi eed ilter.
If :': e on::c still recains coloczcd. it is distilled from a reCortylhedirtini-
t'oa W:az :2:errzpec^i JL« soon as the orcin Ti^MNira begin to ^i^nj toUm
isr m liter orer vktb tlicm. Tbe aqaeoos eolation of the dietiUate cvt*
p:r:L:<:\i is. v^coj vz ^ver ell of vitrioL yields nearly eolouleBi cijitik
b^vic^ 03 It £ $i-^!i: Tello«i«b or Uaish red tint.

T.^ :::.-.::! :izlLj':r =» orrin from tbe bjdnted cfyatalKeed eOMponJ;
tl:e lizziT :s dried ir. ncno or oxer oil of Titriol, or repeatedly ajM
V.<^1 ZT.zi --■ viro-ii e:i:er Scbanek), or, after drying at lOCf, its
tl:?:..lT:^I ::: -l i:iL^\\ T-.z.r: h^^:eJ 0:1 all sides; a email qnaatity ef wite
iben vu^.-<i Vera: £^^;: bat as soon as tbe mase arriTee at a stele sf
c>>=.:l::? ec::'.! !::.:!. a iru^parens coloarless snhstaaee dietile oreTi wbiel
after 5c=Lie Lv^^r^ tecx.>cies crjstallice and opaque.

Pr:, if. t\:o(ir:e:?«. emtalliBe. When freed frmn valsr If
jTv\:y-< cbilli-.Lc, i; l-.lU between 2S7 and 280'. (Dnmas.) Wfctt
^aicklv dissiJel i; pokfte^ oTer ancbattged. Vaponr-denaity s5^.

Tue a-i^c-. 2^ sv&stzoa bas a t<tt svcet bat naaeeating taete. It im

m^X cv^oar i ism as.

A lit: .tj. Robii^iKC Domas.

uc J >* . 6::* «di ^- 6;-5e ._ es-ei

<H .. < 6-45 6-82 ._ 6 50 ^^ 6W

40 >^i 23yl 26-37 .... 2&-92 .... iS-gJ

C-.irvsiT .. . 14 5*8240

ll-i« ... ? . . 0-5544

jV^ . .^ 2 2^186

0!:da.-n{>:«r ... . | .^ 8*5970

1 - . 57314

/--» :..\<-,.'i:'i$. I. With nitr'o aciJ. orciu forms a eolation MA
ii\:\\< rvvl^b^ra ht;it<\!, tlen ? •iJonlj pve* off large qaaatiticfl rf
!ii:rvi;> VL!^-I^^: a.::i Jcjv^itj ne%i r^inots flakes, wbi^ are ligtitic'
af:.r !rv •\-, dsskl^o :r i'.vbcl wl:!i yellow, and in alkalis witb hro«
Art' v rtv }■ i c i:c\i ikc n: : rv m I y aci J$. A fter boiling for «■<
■<^'v.ou> ^dkke^ r\.diNs.^ive. tbe liquid acquiring a deepTcOov

.: :i:':t.rvirvl? foar.J to coatain notking bnt oxalic acid —

1'. i>r\'i:: tvils-i w::-. bio: r n;a:e of p ta^^b beo^iues dark browa afters
\\\iW .1! i v;c!iU a tisrk br-^vs ^edicient: tbe decomposition is bw^
:»-.i-s'K'r.ito I f\v a.i.iiticn of sulpkario aciJ. — 3, Wh«i inmme

I'r.v

contact wjtb solid orein or with tbe eonceutrated aqaeoii8 8oltitioii| bjdro-
Lromic ncjJ is given off, with iim of tomperature, and a brown crystal-
lino mass b formed, cousiatiD^ of torbromorcin coloured by a brown resin.
(Biiman^ Liinrent & Gerhardt.) — In a current of chlorine ^cf/, orcin meltrf
with cfiusjderablo rise of temperature and ©volution of hydrochloric! acid
gas; tbe product solidiiies into a crystalline mass of cblororcin* (Schunck,
Stcnhouse.) Orel a does not undergo any alteration when melted with
iodine. (Schunck,)— 4. Orcin moistened with a few drops of a solution of
chloride of lime^ first assumes a purple-red colour, like orsellic acid, but
soon after becomaa deep yellow. (Steuhouae*) — 5, By the fiimultaneoud
action of ammonia and oi£:ygeu in presence of water, orcin i^ eoaverted
into oreein;

C"H«0* + NH* + (SO = C"NH70« + 4H0.

Dry oroin remains unaltered in dry air mixed with ammoniacal gaej
but mOLBtened urcia in a inixturo of air and ammoniaeal gas absorbs
oxygen from the air and a large riuantity of ammonia, forming orcein;
with ammoniacal gas and pure oxygen, the absorption Is more abundant,
but instead of orcein a brown euhstance m produced, — If the air be
estcluded, tbe orcin is not coloured by ammonia.^ The aqueous solution
of orcin^ mixed with a few drops of ammonia, gradually assumea a
brownish yellow colour, and after two days* exposure to the air becomes
dark brown-red. — Orcin placed under a bell-jar over atjueous ammonia,
gratlually assumes a darker brown colour; on tbe ft^llowrng day, it forma
with water, a brown-red solution; but if it be exposed to tbe air for some
time in ibe dry state, the brown colour changes to deep violet, and water
forms witb it a beautiful red -violet eolutiim, es[)coialIy on addition of a
little moil? ammonia. (Robiquel) — 6. The precipitate which aqueous
orcin forms with ammonia and nitrate of silver, is reduced by boiling,
^'ith formation of a silver speculym, tbe liquid at the same time turning
red. Tercbloride of gold h reduced by aqueous orcin, slowly in tba cold,
immediately when heated, a dark browtt powder separating at the same
^tioie. (Sehunck.)

^^ C<mhiimlw7m. With water, -—«. llf/drnted Orcin, — Anhydrous
r orcin rapidly absorbs moisture from the air and is converted into hydrated
' orcin. — Colourless needle-shaped crystals, consisting of oblique six-sided
Itrismi generally with an oblique terminal face, a P. ooPoe.-— Pas
and soniotimes oP. (Miller, Ann. Pkirm, m, 103); Fit;. } 03, without
m^faces (Laurent & Gerhardt); ao P ; «P=10r 30' (Laurent), 102" 24'
(Miller); ^ P« : oP=83^ 57' (Miller); ooPcc : t^: P= 1 20M5' (Laurent
*fc Gerhardt); oo Poo :-p3c =136' 30' (Laurent); 136'' IG (Miller) ;
the crystals cleave very easily in the direction of oe Poo . Hydrated
orcin melts at a gentle heat, and boils at a stronger h^^l^ all the water
eecaping at first and anhydrous orcin volatilisine afterwards. It gives
in vacuo over oil of vitriol at 100 nnd when distilled.

W

oit 2 At. water

14 C B4 .... 59*15

10 H ...♦...^.........„ 10 .„. 7 04

60. 48 .». 33'Bl

DiuniLS.

Wilh

Sk^huuek,

Stenhouie.

5722 .

, 5793

... 58*0B

.... 58*90

BB7 ,

,. 6^75

.... 7n

.... 0-1^2

3591 .

.. S5'32

.... S4-fi8

.... 34^28

C»H»0* + 2M-" 1*2 -* 100-00 .... IDO^OO .... lOO-OO „.. KW-OO ... lOO'OO

2 a 2

OXTGEK*3fllCLEOS C**H*0=.

vmier.

precipitated hf hmdc

' aeelAle, and wmil

whiali b white at int

tarns red b ooeiad

.)— Draw

^^Mfid Ipj mlkali^ inA BepsumtMrn of «i«Aric iri4

it miitei hf ■■■■iiciii ■! rmpotirs aad ifiinlfw

Hi ifiyBiTw to hm ^imiit frooi orctn. (BeitlMH

4Lp 45t} — k Am ai|«ed«> ailittloii of oretn eonlamini

~ ¥f mfs wkk Htnte U Ic^ till dboot lialf ^ ii ti

'in tfa# H^aid, mud wmsfaad viti

41M

to

« — l^« -, I 14 _ lit __ M«
i« ^ t-it . 5 li _ s« _ s -10

5M _1

it-S3p.c. leaiL (Sfe
iii]p3i«jte of copper,
of aiw; m. wUi^cm of sBU&onia, %
m ^ eald wit^ mmXm of aSw.

Teilimiiordii.

IiAmwtAQnaAWV. X .dM. CkmL Pk^ Si, at7; alMlr. C^uoL
ft»lr. I Sl«, 717.

iid JVepofiilMii. fif^Mftm la eontsci wtlb fMa, pm
«ff m litft MMlitT of fcydto^MMk »od, ives at ordiiiarf ImMmtam;
Ai MiCw&k ii lk|«MM iiH, 1«t Mdidifies after tli« exoe» dFbfMMt
^u t»6«Q cqcpdlcd^ tft jTiiiplttid la aleolMiU ««ter added daring tb^ twLlia^
aad lli# 8iip0n»laBl lifaid deeaatcd fraa t^ impare crrvtalA a4idb M
itpafUto fti tli« liQ«^d ««els. n^ liquid solidif a« on eooltnif , tmik^km
of ^kwisb a««^ ^^^ * »1^J lattfie. (Laartat & GtrlAidt}-
Broniae tt add«d to a cxMuvntnled aqof^ovi doktmi of oma «i bif t*
19/ iietjoa lafcei ibAe^iaA iV^ ^t^^tM«d Imiia-cod eijalaUiBC mm i*

CHLORORCIN,

U7

fiepamtetl fronj the liquifl, washed with col J water, and purified from an
admixture of Wown odoriferous reaiD by digeetion with weak alcohol and
ji £ii2all qtmtititj of animal diarcoaL (Stett house.)

Properiifs. Long white coherent needles. InodorouSj tutitelese,
jWcIts yery easily, even in hot water, into an oil which cijstallisefi on
[«oding.

14 C .

3 Br.

4 0 ..

Si

5

210

32

23-2?

]-30

66-47

B*S7

St^ w ^«^^

2S-62
6gOO

23-1
J -7

660
92

C"Br"H O* ,., 301

10000

100-0

Dn{trtipQj^iimi9. 1. When heated, it pivce off hydiobronut^ at id and
[on oil which crystallises on cooling and leaves a large qnanlity of char-
coslL (Laurent & Gerhanlt.) — 2. With potash-ley^ it usfeumes a dark
TioIet'Orown colour, and forms with a large quantity of water a hrowa-
red fiolution wliich i^ decoloris^ed by acids. Ammonia does not produce
tbia colour. (Laurent 6^ Gerbardt.) — With alkalis it forms a brown
iiolution, in which hydrochloric acid praduces a yellow re«inoua preci-
pitate. (Stenhonse.)

It is insoluble in ipahr^ but diEaolves rtry easily in alcoM and ether.

CadororciH. C»C1"HW

STE^HOlTSE. TML Trans. 1848, Sg; Marm. Centr, 1848, 318.
f E, SciiCKCK. Amu Pftaim, 54, 271,

ChiorGre^ti*

Fo^-mutimi and Prefi^aliom, Dry chlorine gas is parsed over orcin
til the mnss which is fus i < it first, cools and erys tall tees, after which the
product is crystallised from hot water and alcohol. (Schunck.) When
dry orcin or its aqueous or alcoholic Eolution is treated with chlorine
gai*, only a small quantity of crystalline chlororcin is ohtained^ buta large
quantity of closely adhering dark brown resin which is ditHcult to sepa-
Ltate. (Stenhonse.)

Properlieft. Chlororcin crystalliEcs from its aqueous or alcoholic solution
in white needles. Melts at about 5S'd°j and becou^es cryistallinc ngain on
cooling; Heated iti a glass tube, it volatilises partly nndecom posed,
leavin*f a brown reaidne; the vapour condenses into an oil wbich eoon
cryt^talliscs.*— Tastes sharp :tud cooling after continued mRstication.
The solution reddens litmus strongly, (Schnnck.)

" Dfa^mpontioiis. 1. Heated on plalinum foil, it volatilises, emitting
an irritating, BufTocatin^j vajjour, which burns slowly with a red, smoky,
ti edged flame, and leaves a considerablo residue. It i^ ^Ui^'tg

^r^

S58 pinciKT xrcuus C«V»: octgin-nuclxus cmrw.

attacked bj nitric acid: bj coBtinocd boOin^ with tbat sdd, a aolitiM
b foraed coatafniitr free ddorioe. — The aqneoos aolation is not pn-
eipitared b j !iisnte of silrer; bizt a large quant itj of chloride of diver
5s formed ca boiliu. Clilonde of gold is instant! j redoced. (Sefannek.)

CUororcin diaEolres im boiIin|^ water; in a quantity of water Bot
mficicBt to diasolTe :t« it Hehs into a brown oiL

It EssoiTvs La alkolii an*i is precipitated therefrom in its original itatt
br jci*i£<w e^en after looz boiling. It forma an inaolnblo compoand vitk
barr^a. (SckoBck.)

It Baohres in sJc.'wL?/.

OrceiiL
c'^xira" = c^AdH«o»,o*. i

Rc»K^rrr. n>»> Jn». Ckim. PAjw. 42, 845; Br. Arek. 16, 315-
jLi-i. rim. Fryf. 5S. 9*»: J. FUrm. 21, 269; J. pr. Ckfm. 6, ISO;
JT Br J-=i. i. 174: al«r. Amm. Pkarm. 15, M9; Fkarm. CaUr.
15C3. 43?>. — /. /*icm«. 21, 337.

PCVJL5. ^«.i. Fverm. 27. 143: J. pr. Cftm. 16, 492; PharwL Oiitr.

!Lk>Y. Sl*\ r-m*. 1>4l\ 2>o: 3'. Atuu Ckim. PkpL 2, 21 and U7j

Jtvt. F^rrm. ^. S^: FlkMrm. Ctmir, 1S39, 662; 1841, 565.
LAraK>T «K GssAJLBL^r. -V. Axm> Chim. PAft. 24, 315.

r. ^urr;-'/!. Jr:ci .'r*::^ '"J ^'J action of ammonia and oxjgen
x\ Js.V . !• 5? ti-ere^-'W wntaiwd in aithiL

.. 'c < '. y ■ -n >•"!'. — Tlie brown mass (p. 355) formeJ
♦v.. J .;.,. - >Y ;r\T« >;-*: • : ^4 "i-dr? :■• air o ciainlng- ammonia, is gently
hv\i,,"vl ii a^< '- - ' * "-'" •- exwl :he -^hole of the ammonia, then
iotf^ ^\v; :: * -i^" "- ' > -* - ^ = \:d whh acetrc acid, and the brown
w"%v I :A\/wTb=^*<vi ^^- .- i w:i:er Rvb^:ict ) Heeren, hj digcstmf
Jr\,Vrv *cil ^• ^'.n! v.;-- ▼':"': a j=:a11 laintitj of ammonia at 40",
V^''I--t •*-•»■':::-*'. -*:ci:irf'i /v!i-:!i-Ted. wbich does not diier earah

:- ;*.,, -.;: •" ^VvT. J*-7C '"■*"- 5. • c..t<i and A^er^krim fnm

' „V, .,j . . tA-:ri T^ :• Xi- : — C.amercial archil is ali^btlj

:.-: ?«:'.-::on eraporated to compile

.>; r:> ■^*? ^\Vi-:?"';*i '^ •- iL-%^bo1. till that liqoid is b-t
],.,; >^ •:. T:!^ i\"»b"-.r «o*.i::oa i* then eTaporatp.! t<*

V^ ■ ^ y..' , . ^t:,.- :^:** i? : :: : :trk •r.-^wn-rv.Hi residue is warfcnl

*'*^ \^^ .' ■.^. ^ — -Tir?' Si.: > >-'r!fulj extracted, then ilmi,

' ^ , . >• - .': j::-^?. 15 ". ;-r -* i* i'"paru anv perc»*p:.'»ie

7-.> :>-« ..r. ir.er Srinr kept at 100' fort»"'

"' . \ X ■ .* *•>'* -^" * ^'"^ AziSfr-re-i colour and consi>t« -f

\j\\\' ' ^^^ ■***■- ■■*^'^*^^^ :itri*:iw of tW aleoholie axtnrt d

ORCEIN. 369

remains a semiflaid oil, whicli becomes perfectly liquid when heated,
makes grease-spots on paper, and after a few days still deposits a small
quantity of orcein. To separate that substance completely, the oil is
dissolved in the smallest possible quantity of ether ; the liquid decanted
from the undissolved orcein-powder; and evaporated at a very gentle
heat; and the residue kept for some time at 100°, to expel the ether
completely. — The erythroUic acid thus obtained is semifluid at ordinary
temperatures and of a purple- red colour.

Erythroleic acid. Kane.

26 C 64-84 64-70

22 H 900 y 33

8 0 26-16 25-97

CasH^C^ 100-00 ICOOO

Exposed to the air for a few weeks, it gradually solidifies and is then
no longer soluble in ether.

It is nearly insoluble in water, which is however coloured by it.

It dissolves in alkalis, and forms purple precipitates with metallic
oxides. The lead-compound has a purple-crimson colour.

At 120°. Kane.

PbO 31-33 31-64

26 C 44-36 43-41

22 H 6-18 6-24

8 O 18-13 18-71

C»H«08,PbO 100-00 10000

Sometimes the analyses yield less oxygen.

Erythroleic acid is soluble in alcohol and ether, not in oil of turpen-
tine (Kane, Fhil. Trans', 1840, 295; N, Ann. Chim. Phys. 2, 34; Ann,
fharm. 39, 47.

When the portion of archil which is insoluble in alcohol is repeatedly
boiled with water, the first water acquires a rose-red colour, the second, a
yellow. When the dark-red residue insoluble in water is boiled with
potash-ley, woody fibre remains undissolved; and ou mixing the potash-
solution with an acid, evaporating to dryness, an<i exhausting the
potash-salt with water, a small quantity of azerytlirin remains behind;
it is difficult however to obtain this substance free from azolitmin.

Dark red powder.

Azerythr'm
22 C

39'69

Kane.
SS-bO

N

4-11

5-33

51-29

19 H

5-70

22 O

C^NHi'^O-"-

100-00

Azerythrin yields by combastion, 1 vol. nitrogen to between 20 and
21*8 oxygen. . . ^

TBia

»t ^ SMI ^ »1 ^ SHI

Jjssirmif a Gkcaiacuni H. ±k

C*>tfV, vaidk. itia aoc ipv » wil

/>«sMip«i(K«j. I. Orrn sK^ectcd to irj fsdUitioB jkl •
s«iia£ml rsjc^iTs. — 2. Bc-C<ii vkk /uTbij fqr, it giTes off aaKoui ;
tk« fcIxEtLoo. eTV5 af:«r cc&crcoed bulmf . jieMi whli acetic acid, a eta*
t»ienb{« qcaadtT cf asaltered oiccia. wkxk IwveTcr becoaws ramoii

wbes Arj aad exhibits a ccscbcidal fractarc: — 3. Orcein aomeadcd n
va:er and dlarelred m alcoltol, if eoBTerted bj tbe action of duprhu iili
brova cLlcrorceio, while cnlj traces of hrdnicblonc acid are jpniwotL
(Kane.; — 4. Orcein is decoloraed bj ndpharetted bjdrogen. Wbei
the lca«I-ci!>mpoacl of oiceio is decomposed bj snlphnretted hjdr^gci»
the precipiute doe« cot impart anj coloar to boiling alcobol, bat after
addition of ammonia it immediatelj acquires a Tioiet aJonr. (Kue.)
An ammoDiaca] eolation of orcein acidulated with bTdroehlorie acid if
decolori^d bj zinc, bat becomes red again when exposed to the sir;
rmnionia throws down a white precipitate of the eomponnd of lencoieeut
with oxide of zinc, which on exposure to the air acqnirea a Tkdet vti
*timatelj a parple coloar. (Kane.)

ibinatioM. Orcein dissolres 8paringl;r in water, hm% oc^MUS i<^ u
Bipitated from Iba eotetMVL by metaUic si^ts.

OKCEIN.

361

2. It dissolves readily in potash or atnnionia, formmg a solution of a
fiplendid purple -rod colaur from which tlio colouring matter la prccipi-
tatt d h J excoBs of common sa.lt. — 1 00 pte. of dry orcein ahgorb, with
evolution of hejit, 806 pts. of amnmniacal gas (—1 At* atcording to
Kane); the compound has a deep riolet colour and gives off all i£a
ammonia at 100^

Ptfpai'ation of OrseUUQY Archil, — There nre two varieties, y'u,^ orseilh
ih mfi\ which is obtained from varloue lichens of llic genua ^t*t^C(f//rt grow in ^^^
on the rocky coasts of the Azores, the Canary and Cape tie Void islea,
also of the Cape of Good Hope, Madeira, Coraica, Sardiniiij &c.| — and
oriseilh de Urre^ for tLe preparation of which, Variola via oreinrj. (Ach.)
from Auverjrne, Varioltiriu dfalktia (D, C) from the Pyrenees, Lfcaaof^a
tavfarea and others from Sweden arc employed. The largeet amount of
colouring' matter 16 obtained from Jioceelia Montagmi from Angola^ viz.,
12 percent; Lecano?^ iartoira coutaina only from l\ to 2 per cent*
The cleanBed and crushed lichens are rubbed up to a thin paste with water
fint! putrefied nrine or carbonate of ammnnia, and left to ferment, with
additioD of quick lime, a small quantity of a!nm or arseniuus acid being
BO meti m ee ad dc d p e rl i a ps to eh cck pu t re fac t i o n . I n a w e ek a v io I e t c o 1 on r
is obtained, which becomes brighter iu a fortnight; sometimes also an
©dour of violets is evolved. Orseiile m kept in the moist state* — Tlie
rolonrin^ mutter of orseiile consists mainly of orcein; its decoction is
flark~red, but becomes lighter when treated with [acids, and violet with
alkalis.

Femo^ Cudbear^ Archil is prepared in England from Swedish Lecanora
iajimra, or from the rock-lichens of Wales or the Orkneys, in the same
manner as French orseiile* It ia eent into the market in the form of a
jTurple or violet powder-
s' The alkaline solution of orcein forms with metallic ealts purple-
red lakes of several shades, which lose much of their beauty in drying.

£inc-cempQvnd of Ormn, — Violet.

I-

aZnO 121^5 34*37

18 C lOS'O 30-55

N , 14 0 3-96

14 U .».. 11-0 3-56

12 O 960 27-16

XL

2 ZtiO ..»..,.».„,„ HI

14 C 84

N „. H

10 H .,.„... 10

9 O 72

3111

32" IB

5-36

3-83
2752

Kaae«
33*71
30*86

4-10

C"'NH'^0%3ZtiO + 4A<i 353^5 100^00 a^NH^0V2ZnO+ 2Aq 261 lOOOO

Lead-compoufid: — The solution of orcein in ammonia is neutmltsed
with acetic acid and precipitated with neutnil acetate of lead- Purple
precipitate which gives off 13 94 p. c. water at 100^ but is not completely
dehydrated even at 12r. (Kane*)

^KfeK) 335*4 61*05

IL At 121".

5 PbO ...-,.„.,....., 559 62*05..

28 C 16R 18-64..

Katie.
,62*76
.Ja'66

N «. 14-0 2-55

2N 28 3*11

12 H ,.. 12*0 2*18

JOO ,.., 800 14*56

IB 11 .„..., _ 18 2'00..

.. 2*27

10 O ..... 128 14*20

ti-^H»«0»,aPbO + 2Aq &43 4 100*00

2Ci^NHW,5PbO-*.4Aq 901 lOO-flO

A20LITMIN. ' 363

Cfaloreroein disiolyes in aqneons ammonia and potash. The solution
oontains sal-aramoniao and chloride of potassium. Acids added to this
solution, precipitate chlororcein more or less decomposed.

Leucorcein. C"NH"0*. 1

Kanb, N. Ann. Chim. Phys. 2, 147; Pharm. Centr. 1841, 522.

Kpown only in combination with oxide of zinc. — The zinc-oxide is
added to an ammoniacal solution of orcein slightly acidulated with
hydrochloric acid ; the decolorised liquid precipitated by ammonia;
and the white precipitate is collected on a filter in an atmosphere of car-
bonic acid, washed with boiling water, and dried in vacuo over oil of
YitrioL Daring these operations, in spite of every precaution, the preci«
piiate acquires a pale violet colour arising from incipient oxidation. —
After drying over oil of vitriol in vacuo, it is C"NH'*0®,3ZnO -f 2Aq
and gives off 2 At. water when heated to HO"" in a stream of carbonic
aeid«

In vacuo. Kane.

3ZnO 121-5 .... 36-00 35-22

18 C 108-0 .... 32-00 31-31

N 14-0 .... 4-15 4-65

14 H 140 .... 4-15

10 O 80-0 .... 23-70

CWNH»0»,3ZnO + 2Aq.... 337 '5 .... 10000

II. At 140^ Kane.

3 ZnO 121-5 ... 3803 37*33

18 C 108-0 .... 33-80

N 14-0 .... 4-38

12 H 12-0 .... 3-76

8 O 64-0 .... 20-03

C»NHl20^2ZnO 3195 .... 100-00

The compound absorbs oxygen very quickly from the air, and is
converted iuto the violet compound of orcein and zinc-oxide.

Azolitmin.

Kane. iV. Ann. CJiim. Phys. 2, 129, 137; Ann. Pharm. 39, 57; Phm'm.
Centr. 1841, 569.

Preparation of Azolitmin and of the other colouring matters contained
in Litmus. (Kane, Phil. Trans. 1840, 298; N. Ann. Chim. Phys.
2, 129; compare Gelis, J. Pharm. 27, 477.) a. Commercial litmus ia
the state of powder is boiled with water as long as the water acquires
any colour from it. The decoction, which contains but littlo colouring
matter in proportion to the depth of its tint, is precipitated by neutnil
ae«tat0 of lead; the pnqile precipitate is decomposed by sulphuretted

PKIMAEY NUCLEUS C>m^ : OITGEK-mTCUrS VWf.

k^fi^gen; tbe resuiiittg mixture Is w^sLed witlipsre wilcr,iDdt&ciit
Willi w^ter conUinlng ammonia; the dark hm>wn Unmitamitxm^^
sm^Uim if lea'l is OYaporated to dryness; snci t]i« imin§ m mmai
mii\ EjLlivijliloric acid smd washed Vith b<i4 alectJidl td extnel tl« ^
■ kc> The residue llien consists of pmn da>(ttmm : Eooetei
thk sobetauce 1$ mixed with Spanioiiimm} ortfaiibUci bn
• fOMlattite tije entire residije,
TW file blQo powder wliieh re mains after Utmu* i- '-'
" rhoBid with water, is mude tip tttto m thin pask ^
lUnfe ftcid b added till cflerresoeace oeasts atuS
tmf^f alkaline reactioih The mmm h thm thrown
I iiiiliie^ after heio^ freed from excess of aci4 hj wvbrns ry
» ii w^ igmA aod repeatedly boiled trith aloohot* u]mgulM
'■-' rxUmm Mythiog from it. The alcoholic mhiim h eripviM
rtcif wfftr ^ wmter-baib, and the reeSdne liK-ei-t^Hi wiili «v
rr n:tii«IP«illc€tker is coloured hy it. The ethereal - y

* " " tctiOTO Ibe ttlier, lea res Erytht-ol \m

I o«L TIjg portion of the aIc4>hoIie ^xinrA v,^%
\ of £t^thmiitmitK
I>owdt?r which remains after tbe btiiliaj^ii
«s if impure AtoUimim Thl« suhturoih
vmler, aod pare nzoHlmiu obtmin«d Ij etiM^
f^MlstJcnj —or tiie residue itisoltiUf in tiali
water, and the blue sol tition erapnatelfc
^ ifvaljon the greater part of the mam
wm muated by moi&tenlDg Uie mum wilJi if**-
^^ tis resulting mi-!inmi<iiiiac with fllfolJi-
^fi|pi ohtatced by boiling litmutf wid iiW
Bilale of lead; the precipitate h w^iJitt
« with tdphtiretted hydrf^|?t»D, ami ms^itM
^ihitofcbUic liquid is evapo»t«4 l» 1^
, ijiiicUoHQ acid ; and the ad-aisanniev
«ff mmm mk«lMil.^The residue l* but of i«l
Imp robur of the folnii^u; it eoneoia
i« xwF^j of spaniditmin^ a fttb^tlMi i^

Pfc^liKWn-red amarphoiti powder.

& stiir. m

lie u -. ^f-M ^ irti ^ *

X U _ fi-3t

AZOLITMIN. 365

Mgrtm beit with the analyses of azolitmro and its compounds, azolitmia contains 1 At.
oxygeo more than according to Kane's formula C^^H^<^0^°, and 3 At. oxygen more
than orcdn, according to Kane's formula for that substance.

Azolitmin suspended in water through which chlorine gas is passed
yields yellow chlorazolitmin.

It is sparingly soluble in water.

It dissolves readily in aqueous ammonia and po^^i, forming the blue
of litmus. When the ammoniacal solution is left to evaporate, the
greater part of the ammonia escapes; the residue does not exhibit a
constant composition. Neither does the absorption of ammoniacal gas
by azolitmin obey any regular law.

Utmm is obtained from the same lichens that yield archil^ by treating
them with carbonate of potash in addition to ammonia. — 30 grms. of
RocceUa tinctoria : (a) mixed with 5 grms. of carbonate of potash;

ib) with 2 grms. of slaked lime; (c) unmixed, — were moistened during
burteen days with urine which was saturated with carbonate of ammonia
and the mixture stirred several times every day; a yielded beautiful
litmus; b and e yielded archil. — When 2 pts. of RocceUa tinctoria and
1 pt of carbonate of potash are repeatedly moistened with urine which
ia saturated with carbonate of ammonia (pure carbonate of ammonia
exerts the same action), the mass acquires in 3 days a brown or dirty red
oolonr; in 20 or 25 days, a purple-red; in 30 days a blue colour; and
in 40 days yields litmus of the best quality. (Gelis, J, Pharm, 24, 277.)
— Litmus {toumeaol en pains) is prepared in Holknd from Lecanor a
iartarea and Roccella tinctoria of the Canary Isles, the coloured mass
obtained as above being thickened with chalk or gypsum. The colouring
matter contained in it consists chiefly of azolitmin.

The ammoniacal solution of azolitmin forms with the salts of the
heavy metallic oxides, precipitates which are red or blue, according to
the quantity of oxide contained in them.

Lead-Compound. — The recently precipitated compound has a beauti-
ful violet colour but turns blue after drying at 170''.

3 PbO 335-4 .... 60-39 2 PbO 222*8

18 C 108-0 .... 19-44 14 C 84-0

N 140 .... 2-52 N 14-0

10 H 10-0 .... 1-80 6 H 6-0

n O 880 .... 15-85 7 O 56*0

C»NH>«0",3PbO.. 555-4 ....100-00 C»NPb08,PbO 3828 ....10000

Sulphuretted hydrogen converts the compound into a black powder,
which appears to be a compound of azolitmin with sulphide of lead,
inasmuch as the azolitmin can be extracted from it by water only after
long boiling, but is immediately dissolved out by potash or ammonia,
whereas azolitmin is more soluble in water containing sulphuretted
hydrogen than in pure water.

Stannous compound, — a. Prepared in the cold, — [The method is not
giyen. L.] Has a fine violet colour. It is partially decomposed when
dried by heat. It is decolorised by boiling with water, the protoxide of

Kane.

58-29 ..

.. 59-38

21-90 ..

.. 19-08

3-65

1-56 ..

.. 2-00

14-60

366 PRIMARY NUCLEUS C"H»": OXYGEN- NUCLEUS a*BPG0.

tin being converted iQt6 ijiiioxLiI^. The greeniali wliite eotntioitmd tliu£
fonn^d quickly al)sur(»3 oxygen horn the air, and forms & red Qompuniid
of regenerated azolitmiti witli etauolc oxide.

18 C »., lOS .... 21-3i ..... 20-85

N ..,....„ ., 14 ,.„ 2^77

JtH. !2 .... 2-8/ ,.,,.... 2-84

4 8q....».... ...» 236 ***. 46*e4 .....,„ 45'0»

17 0 136 ..« 26-88

Ci»NB«^0",4SnO.. . 506 .... 100-00

h. Protocbloritle of tin forme with an animoniacal sohition of axnlit-
mhi, a beautiful violet precipitate^ wliich moat be wjished and then dri»L
at 100",

By boiling with water slightly acidulated with hydrocbloric aeid, It j
converted into a white compound of leucazolitmin with stannic oxidn

K«ne.
18 C M,»..».... 108 ..„ 29 03 , 29-45

N . ™„.. 14 ♦... 376

12 H. .,._... .„... .,..„...„. It *... 3'22 3'5S

2 9ii Il§ .... iM-n

15 O ■ 120 .. 32 yT ... 3.^*22

C»«NH'W,2SiiO + 2Aq .,.. 3/2 ... 100*00

Stannic cuth pound, — The com pound of Icncazolitmin with
oxide is exposed to the air in th^ moi^t st^te, till it acquirer % tmdi
colour . Tbia «earlet compound givee otl' 2 AU water (4 5 per cttit|
h% 140°,

18C...„, .»,„..««,n.t.*»** lOi .,„ 3J-83 ....*... 2;*43

N 14 .... 3-61

12 H „... 12 .. 309 3-65

2 Sn ^. US .... 30-41 31*43

17 O .... ..,„_ 136 „.. 33-06

C^''Nli^"0»MSuO^ + 2Aq ..,. 38$ .... 100*00
[ Vr^iftk (•erliiirdtV formula for Azolitmin, it h Im^osAihU to dodttM any IbnntillM

Azolitmin is iudolublo in alcoboK

Chlora^oUtmin.

Ka«e. N. Ann. CAim. Fk^i, 2, 155) PAam. Cmlr. ia4l| 5? 4

When oblorine ia pasaed into water in wbicb azolltmiD is inpendel *
yellow eub«Unce is formed, wliich t^i iasolublo in water, but djaaolvii ^
alcohol^ etber and alkalia^ and is precipitated from the Utter in itiorigia*^ |
atate by acida.

SPANlOLlTMTNp

367

IS c ..« loeo

N IfO

s H ,». 9 a

Cl 35-4

1 1 Q 8&-0 .

IT. Kane.

42H5 14 C S4'0 ,... 41 30 ... 42 94

5*50 N .,. ,„.... 14 "0 .... e*88

3-54 6 H , ...,, 60 .... 2B^ .... 4-64

15 92 Cl ^ 35^4.... 17-40 .„. 14-32

34 59 BO. 64 0.... 3147

lOO^OO C"NCm«0« .... 203-4 .... 100-00

Leucazolitmin,

[pOLMAi^y. Ann. CMm, Phyn. 54, 2ai ; Phatm* Venlr. 1834, G4C*
kAJfB. ^V. Ann. Chim. Phy^, 2, 150; Phann, Cmtr. 1841, 572.
FoGKL. J. pr. C/ttnt. 16, 311,

Produced from ft^olitmin by naiL-ent bydrogen, but cannot bo prepared
tbe pure atute, because it immediately becomea coloured by takiug up
bxj^^en fn>iii the air.

The com pound of kumiolUmin with Uanme <m%de h produced by boil-
ag the compound of auolitnijn and stannous oxide with water slightly
joidulated witb hydrochloric acid. Wlnte or slightly yellowi^jh powder,
rliich by exposure to the air, is i mined lately converted into the scarlet,
oiDpound c^f azolittnin with staDnic oxide. (Kiiue.)

When tincture of litmna ia mixed in a bottle completely full, 'with & few
irops of sulphuretted hydrogen water, it is decolorised, but on expoanro
o the ajr, the liquid regains itjblue colour. ^^ogeL) Tincture of litmua
rhkh had been kept for several »i out ha in a closed bottle, acc|uired a
addisb yellowish colour, and yielded sulphuretted hydrogen (perhaps
rising from decomposition of sulphates), but resumed its blue colour on
cposure to the air (compare Malagnti, -^^. Ann. Chim. Pht/a. 37, 200),

a i^imilar manner, tincture of litmus ia decolor i^aed by hydrosnlphato

nmmonia or by protoxide of Iron. (Kublniann.)

Spaniolitmln.

[ANE. N. Ann. Chim. Phys. 2, 140; Ann. Pharm. SB, GO; Fhtmiu
Crtifr, 1841, 370.

From 0-frai'iof, nre«

Sometimes obtained in the preparation of aitolitmm. As tbere is no
IcnowD method of j^eparating' tbeac two bodies, an adniixturo of npanio-
iitniin in azolitmin is recognised by the combuation yielding moro than
18 vol carbonic acid to 1 vol. nitrogen; if the substance is free from
Ditrogen, it consists of spaniolitmin^

Ligbt i^^.

Ai 100-. Kao*.

18 C 108 .... 44-44 .., 43'93

7H......... 7 .... 2^88 3 11

16 O 128 ... 52-68 ...... 52*96

eifl|]70» .,^,,^,, 243 „.< 100^00 lOO'OO

368 PlIiaiT NUCLEUS C»H^: OXTOBK-NUCLKUS OVm.

Tlw analjas likevije agreet with the formola G^H*Hy« mooBK&ag to
ipa»inlinnin ih<wld be formed from crythrcaitmin byddiliott of 11 O; b^ttUifa
doct wit ai^ree with the anelytit of the leed-compooiid. SpeaioUtefai it pnbd^
iwmed from Molitmin bj ahitrectkm of ■mmonia end addidoa of oiJiCB (Kiee):

cxH-o" - NH» + 50 - anpa».

SpanioliUnin dissolres in water with light red coloar.
iLlkalie tarn it blue; the mmmonia-compoand ia deoompotedi thoigk
not completelj, at a Tcry gentle heat.

Lfthl-^ompoHnd </ ^niolUmin. — a. Of a fine riolet eotoar; tte
diying* it gtres off 3-3 percent of water at 121\

SFbO

Ai I2r.
U9-8 »«

69-70

13-47

0-87

15-96

Kene.

M^.*. 70-00

18 C . -.
711

.... 108-0 _

12-63

....... 1-^

16 O -.

lW-0 ....

16-28

C*ffO*.5PVO^ 802-8 ^ 10000 100-00

k la an ammoniacal aolntion of apanioUtmin, baaie aeeiate of UU
fbrta* an anrt^oloared preeijntate woieh is not altered by ezeaaof
aMMoaia. Dried at 82% it contains 5 per cent (9 At) of water, vkU
<«i»pe«at 121 \

JU 121\

12 no 1341-6 ^ 84-67 84-31

ISC 103-0 ^ 6-82 6-45

TH 7-0 .... 014 ^ 0-43

16 O . . 123-0 .^ 8-07 8-81

C^irO^a^PbO 1584-6 ... lOOiW 100-00

5^tvir>«>\atjv^vx7. — Of a fine purple colonr. Oradnallj UadECV
wh^ o\po«d to H^ht.

Ai 100*. Keoe.

3 JU 324 _ 54-82 53-92

l5i C' lOS _ 18-27 18-66

7 H , 7 _ 1-18 1-61

1* O Ii2 ._ 25-73 25-81

C»^H\V*,3AsO ... 591 .... lOOHIO 100-00

S|^ai<ilitiiutt »$ in^glnUe in aJcvAol and in ttker.

Alpha-orceiiL

K KNr .V .lv>i. ri/K. rXi^, 2, 27: Amn. Pkarm. 39, 42; PharwuCtdr.

IS4K :orv

Oixviu |^!\ v.wsl fi\M« awksl (p 3.'»S) is reiy often mixed with slph"
Hi \^f wh.ch hx^w<\er the azdiil contains^ less ia proportion u it if

ERTTHROLEIN. 369

older. Alphft-oroein agrees iu all respects with orcein and cannot be
distiognialied from it excepting by the results of analysis. [Hoir is it to be
•ejpftrated? L.]

18 C

N

... 108
.... 14

.... 62-79 ....
.... 8-22
.... 5-81 ....
.... 2318

Kane.
.... 62-45

10 H

5 O

... 10
... 40

.... 600

CWNH»0»

... 172

.... 10000

Mphororcein with Leadroxide. — An ammoniacal solution of alpha*
orcein mixed with nentral acetate of lead and neutralised with acetic
acid, yields a pnrple precipitate.

At 200*. Kane.

3PbO 335-4 .... 6611 66-13

18 C 108-0 .... 21-28 21-29

N 14-0 .... 2-7C

10 H ^ 10-0 .... 1-97 2 21

5 O 40-0 .... 7-88

Ci«XHW»0»,3PbO 507-4 .... 10000

Erythrolein.

Kanb. Phil. Trans. 1840, 299; N'. Ann. Chim. PhyB. % 131 ; Am.
Pharm. 39, 32; Pharm. CerUr. 1841, 568.

Preparaium (p. 364). — To pnrif^ the product, it is dissolved in ether,
and after a few hours, the solntion is decanted and the ether driven off by
the heat of the water-bath.

Properties. Semifluid at ordinary temperatures, perfectly fluid

Kane.

26 C 156 ..* 74-28 73-24

22 H 22 .... 10-47 10-68

4 O 32 .... 15-25 16-08

C»HaO* 210 .... 10000 10000

The qnantitj of oxygen varies in different analyies, but the ratio of the carbon to
the hydrogen it constant.

When heated it decomposes without volatilising.

It is nearly insoluble in water, but imparts to that liquid the red
^onr of onions.

It dissolves in ammonical water with a splendid pnrple colour with-
t>Qt a trace of blue.

With metallic oxides it forms b^ double decomposition bciutifal
Yiolet lakes; in the lead-compound dried at 1 00'', the organic matter has
mlways the same composition; but there is no simple stoichiometric
xriation between the erythrolein and the lead-oxide.

Srythrolein dissolves in alcohol and in ether, forming solutions of a
flue red colonr.

Tor^. XII. 2 B

L

STG primary NICLKUS O*^: OXYGEN-NUCLEUS Ci*ITOi.

ErTthrolitmin.

Kane. FkiL Trans. 1840, 301 ; J^. Jim. CJtim. Pky$. 2, U^; J«l
Pharm. 30, 5Z] PhmTn. Cfntr, ISU, 56S.

Prfparatton (p. 364). It mtiHt he heate<3 for an lioiir or Iw© t<» 110', ib
order to expel the ether com plot el jr. ^dl

Ptoperties. Of a liiio and pure red colour. Separatea od eoolinf
from tlie boilm^^ alcoholic aolotion io email, dark red, ciyttalltst grtiiu
dettitute of lastre. Givea off 1 At. water at 100*,

^ae.

26C..« „. 156 .

23 H „_.. 23 .

ISO... „.»,. «.,»» 104 .

., 55^12 ..-
... S13 ..
. 36?5 .

a.
.. 5501 .
.. S « -
. 36*30 ,

.„ M§4

... 37'3«

C»H*^Oi' + no „. 293 .

., imm

... 100*00

100*00

i

^vyi\ii\t\kmm mi^peuded ia water b concerted by chlortue g:ii btAi
yelliiwiwl* Bubstiinee, which ra insoluble in water, and when drieJ tx
'W\}\ ct^ntfilus .'iG^5J p.c. C, 8U8 H, ttnd C'8^ 0, corres^iondjn^ Co tk
runTuilaC^-Cill"0*»

Krytlirulitmiii dissolved very sparitigly in water, foimftig i iri

With ammoohi it funus a bluo compound insolnble In v«l«r, wU
Bopamtes when the afjueons solution is mixed with a umaJt fjnaiitflf «tf
ammonia; when dried, it gives off ammonia and aa^umeis a purfit^M
colour. — ErythroHtmiu ahaorbs dry animoniacal ^s^ wilb ri«« of l#*-
pemture and loss of the second atom of water; ibe restiluiijt bli^ osb^
pound contains 1 _\t. ammonia, Iialf of which goes off nt 130^ ItftHif a
red-violet-bhick substance v^hieh is insolabla in alcohol, iuimedia^t
tuni!^ red, like erylbrolitniin, when treated with a dilute acid, aj]dc«>aii^
of C^H^0" + 4^^* L'A.ccording to this, t ho atomic weight of Cfjll*^
litmin eliould be doubled. L.]

ErvthrolitNiin dissolves with blue colour in strong potajli*lf!y.

with metallic oxides it forms kke* of a fine purpl.-red colotir*

Etyt h ^iitm in tv ith L end- oj* kU . — Ery th ro 1 j tm i n i^ Imki
alctibol, basic acetate of loud added, the liquid boiled fvr m wbij#^i
dark red precipttato washed and dried at 10Q\

2 PbO ... 223-6 , 44^3

UC 151-0 .«* 31*35

22 H ,-...... M'O .... 4-42

12 O .,.. WO ,,. 19-30

41 13

aO-011

in

c»H"o»,2Fbo.. isre

100 00

itomt

Erythrolitmin disaolvct abundantly in ttlt^M^mnil m aoSntion HHOii^
at the boiling heat deposiiits pari of it in tht' eryatnllino form «iffiU>|
If ilm^hci very gpaTu\g\^ \u tihttu

ORSBLLIC ACID.

•71

Conjuguted Compounds tf Orein,

W

Orsellic Acid.

Stekhoube, FhiL Tram. 1MB, 66; Ann. Fharm. 68, 61, m.^PhU.
Mag. 32, 300; J. pr. Chem. 45, IfiO; Fharm, Cmlr. 1848, 316.

mtid, Acide orMtliq^e^

Formation. Froduced from lecanorio acM b^ boiling witb wAter,
Jcobol, or alkalia:

from erytliric a^ltl, sinmltaneuuslj with picroerytbrin, when the bar/U
or iime 8alt of tbat acid is boiled with water:

C^n^O^ + 2110 ^ C5*H'«0» + C>*H'0*!

om eirdFDic acid, mmultaneously with eTeminic add, by boilitag with
tryta-water:

C»*U«0** - C^m^O^ + CWH*0*;

toni ^orsellic acid, simultaoeotialy with TOccelHn, Hv boiling witb water
|r alcohol :

1 th^M reacUonA, Ibe ortellic acid is ofUn reiolred into oroin and carbonic add.

Ftv^amtion. When recently precipitated gelatinous lecanorio acid
exactly tieutralised wl^th tmryta or lime water, mid boiled till the whole
I clearly disaolvedj the lecanoric acid is found lobe completely converted
fltn orsellic ncid l if tte baryta of lime u not in excess, no it^nmntbu of carbonate
_^iikci|tWe, The cooled aolulion i& decomposed by hydrochloric acid; and
"the resultiTig gelatinous pnecipitnte u waabed with water, dried, and eryf-
I tallUedfrom weak alcohol. — In like manner, oraelHcacid may be obtained
^Hrom erytbfic, evemic or bcta-oraellic acid.

^m PropeHies. Crystal Uses from water or alcohol in long, wblte needles
P^minged in stellate groups. Tastei slightly »our and bitter. Reddeni

litmuiS distinctly.

Stenhotit^.

15 C

,. 96 .

57*15 ,.

57*95

8H....

..., 8 .

.. 4*76 ,.

5^7

80- . ...

.. 64 .

.. 3a-&9 .

S5S8

C"H«0»

. .. im

. loo'oa

- 100-00

^m\

372 PRIMAEY NUCLEUS C»*H^: OXTGEN-NUCLEUS C"U«0*,

I>^:compos it iotu. 1 . Boi 1 e<l w 1 1 h w ater, i i gl v*c9 o ff carbon] c ac id i and U
fjoickly converted into orcln, which is deposited from the concentiated
soft] ti on in colourlcsa cryetale;

Ci«H«0' = C^*H»0* + 2C0%

2. Baryta or Hinc-i^ater in escce^^s acts in a eimilar manner, with
ration of carbonate; the orcin thns obtained is coniiminated with
reddish colonring matter difficult to separate* — 3, Chloride of li
imparts to it a transient blue colour. — 4. The ammoniacal solntion yiel
on cipoaure to the air^ a colouring matter resembling orcein,

' "i n

1

(hmhlTtatiom. Orsellic aoid dissolves in hot water more reoidity than
lecanoric acid (p. 377).

Onrllatt of Buftftff. — The warm alcohoUe solntion of the aeid if

carefully mired with sm:in quantities of biryta-cryatal^^, the acid beiag
left slightly in excos^j and the solution not neutralised completely till tC
has been evaporated. The synip thvi^ obtained crystallises on cooling m
thin prisms, which disaulve very readily in water and weak: alcohol; m
that to obtain crystals^ the aquoous solutic^n must be evaporated lis
vacuo to a syrup : from weak alcoliol, long four-sided prisms are obtaiadi
which give off between 7 and 1 1 per cent of water in vacnoj accordiof
to the strength of the alcohol. The salt decomposes at 100%

B*0 . ..

lac .........

., 766
... 960
.. 7*0 ,
.„ &6-0 .

.., 32-45 .
... 40-78 ..
... 297 ,,
... 23-80 „

St*iih0Ti8e.

31^87

...... 41*29

7 H

7 0

3*63

23-21

a^WBBip.

.. 235 e

. . 100 00 ,.

100 00

The acid dlsaolres very readily in oimhoi whether hot or cold*

Or&ellate of Methyl

C. ScHtmcK. (isr45.) Ann. Pfiarnu 54, 268; Phmm, CtfUr, 18l3,T17tJ
Stekhocse. Ann. Phartn, (JS, 75,
Streceeh. Ann. Phatm. 08, 111.

Lmanerste ^Mefkfl^ EffiArate qfMiihtfL

Prep^rratiofu Lecsnoric or erythric actd is boiled for several l«ail
with strong wood-spirit; the liquid evaporated to dryncsifl, and the rtmh^
boiled with water; the filtrate on cooling becomes filled with netdlf*
having a silky lustre.

Pn^ertm. Crystiillises from wood-spirit in shining erystaH fr"*"!!
water in silky needles. (Schnnck.) The crystals are geaerttl? ^ '
pointed or united in laimiu^. (^tenhouBe.) Volatile without dM
pomiiQu.

ORSELLATE OF ETHYL*

373

lie

10 H..,

8C

103
lU
64

Scliuuck t
from lecanor, at^
b^^b , 57 -92 ....

5*49 ^n

3&-10 ., 30-67

StenhouBC,
/rttm trifthrin,

59-44

.,.., &'61
... 31*05

C"*Hi«0«,.. 182

100-00

100^00 ., lOO'OO

TLg com pound dissolves id alkalis and ii precipitated from Ibe
Ljlutjoii in the fonn of ii cryBtiUIiiio iiia*.'^.

When the jilkidlue solutiou h boi!ed, wood-bpirit is given off aud a
irbonate of tlio alkali b produced, (Schunck,) Exhibits with reagents
1© eaiiie cbaracters as orsellatcof ethjl (Schnnckj Stenkouse.)

It ditsolvea in water more readily than orsellate of ethyl j the excess
»f the orsellate of methyl meltT^ in boiling water, forming oily drops,
tecUniick.)

Orsellate of Ethyl

EEREN* (1830.) Schw. 5%%U.

lEBiG. rogg, 21,32.

ANE. Phil. Tmm. 1840, 237, 279] N, Amu Chutu Ph^s. 2,514;

Ann. Pltanti. 30, 32, 76j Pharm. Cmti\ 1841, 563.
:CBUNCK. A7in, Fhatm. 41, 160; 54, 265. — P/tiL Mag, */. 29.261;

Ann. Pharm. 61, 72; X pr. Chem, 3S| 456; Fharm, Ctmir. 1845,725,
ociiLEDEn & Helivf. Ann. Phann. 48, 5.
iTENnocsE. Ann, Phamu M, 74.
Strecker, Ann. Phat^nt, ^S^ 1 1 L

Pittudtr^iktm (Heeren), Et^lhrin (Kfine), Z,«e#K«ri« #lA'r (Eockkdtr 4 Hddt],
^r^ihit ether (Schunck, SCenhoiaic), Ortellhmmuter,

I

^B ^ Fonnation. By boiling orsellic, lecanoric, crythric or ^-orsellic acid

^^Vith alcohol. By treattn^ an alcoholic sottition of kranorfc add nitb hydrorWoric
[ or Aulphurk acid. (Ro<:hk*l€r h Htliit;)

k

PtTptimthn, 1. a. /iocc^l/n £r/icio/-ia is repeatedly boiled with alcohol;
lie filtered extract Is mixed with twice its rolnme of cold water, whereby
a mixture of roccelliu and chlorophyll is precipitated; the liquid la then
heated to the boiling point; powdered chalk k added till the precipitate
aggregates in white fliikos eaty to separate hy filtnition; and the liquid
la filtered as cjuitkly asi posyihle. The filtrate does not become turhid ou
cooling; neither cloes it dejH>£iil any spongy aediraent till after sonic days.
If the liquid decanted therefrom, and the residue contaiaing the tedirnent,
be heated to the boilinn point at.d quickly filtered, the liquid, on cooling,
Jirat becomes turhid, and aftertvards deposits cry^taliine laniinm of orsellate
uf ethyif the turbidity then diJ^appearing. The crystals arc purified by
recrystalli^tion from alcohol, with addition of animal charcoal. (U^ren,)
— b. The finely chopped lichens are repeatedly exhanstedwith Hlcohol al a
tenipcratur© just below its boiling point, the mixture beiu^.cach time
heated in a retort for pereral hours. The nnited liquids e^t© lW\ ^\U^!\\W'^

k.

S74 PRIMARY NUCLEUS C^m^t OXTGBN*lfUCLEUfi C^-HW.

to drynesi over tbe water-batL; tbe yellowish residue is boiled for sf
minutefi wilh w&ter, tlie hot Hqiud dllered bm qriickly as isomhle, vail
res id 06 boiled a few times more witli water. — The ftqueotiss<jliiticm,r'^

ing-, deposlU orsellate of ethyl ni lamintE resembling borne: ic acid,

if the liquid has been boiled atid filtered quick ly, often cskuav it to soliif
completely; the hrown in other- liquor evnporated OFer the water-lji
yields mwtiytkrin, in the form uf a semi-fluid ei:Cract» (Kane*) — c, T
powder of various kinds of Lecanora or Variobiria is boUf?d wilh *!ct'l
the liquid evaporated to dryness, and the residue ex^haustcd wkh Wdii
water^ which on cooling depo^^its shining lamina or neeiUea. ' ^^-S "i- V4
— 2, Lecanoric acid, e, g,^ the crude acid precipitated by [1
acid and dried, is boiled for fi or 8 hours with strong abohril; 4.1
ovaporated over the water- bath till nearly all the alcohol is expclfpdi
the residue boiled with water; and the liquid filtere^L On cooUo| r
deposits crystals, which are coloured yellow by an adhering fotii, Pit
may be decolorised by repeated solution and boiling with auitnal rhir-
coil, fSchunck, Sten house.) Schunck evapomtes the alcoholic fiquiJ t''
eomplete dryness; Stcnhouio, on the other hand, finds that the eiri|n>n
tion causes Ueconi posit ion of the ether, a resinous substance being' fonurd
h\ the motlier- liquor, Schunck found a lar^^e quautity of orcin; ^t
puritication, he boils the coloured crj^stals with a quantity of wat^r m'.
sufficient to dissolve them ; the undigsolved portion then meU" m*'
drops which retain the impurity. — 3. Erythrlc or ft-QTw\\\^ a' -
boiled with alcohol, the process being conducted as in 2. {Stejifj"-'
The alcoholic solution of erythric acid is boiled for some time ani ^n'
added; orsellate of ethyl then separates gradually in needles. — ^4, ll\ r-
chloric acid gas is passed to s^ituration into an aleobQlic solul:' r.
lecanoric acid saturated at the boiling boat; the liquid healed in :
water-bath till the greater part of the liydtochloric acid Is ejipelk^, li-
the residue washed with water, which precipitates a bUck-green tt**w*«>
sabatancc* This precipitate is hoilcil with water as long a^s any lli'^;
dissolves, and the liquid is filtered at tlie boiling heat Thc'filmif
deposits yellowish crystals which must be retry stallised from a!«o^iL
(Rochledcr& Heldt,)

Fropeiiks. Snow-whitei very thin luniina> or ]ongne«<U«i* (H««ib.)
Flat needle-shaped or laminar crystals. {Stenhoiise.} LamiirA oriif^Ai.

The ether prt'pared by (2) crystaLliied in }irmna wtieu iU alcoholic M^lntltm wi Wt^
evaporate* (Schtinck.) Shiuing crystalline lanuua?. (Rochleder *i Heldti —
Melts at a temperature a tittle above 120'', forming a ooburleflt oil whkh a
cooling forms a laminar crystalline mass. (Heeren.) Melt«at 104'. (K*fti
When boiled with a quantity of water not suflicient to dissolve it, il i»c>^
into a hea%'y oil which eolidifies in the crystairtne form 0m 0m6t§*
(Heeren, Sclmuek,) Tbe ether (p«psr«d by 2,) melts when bested i« •
glass tube, auil distils almost complet<?iy in the form of & liqaJd »l»ui
soon crystallises, (gchuock) It is tasteless at Brst^ but pr^ucet » Ua*
ing sensation on the tongue when chewed for some tiniiL Ita mAuMf |
araneatrah (Schunck, preparation 2,)

21 C

nm ...»

8 P ^".

....„„, 120 .
12 .

-' «4 '

. 61*31 ,
. 6 13 ,.

.. 60 00 .

:::: iM :

. 50*M
. ffft

CWPV ,

...„..; 11%

.W^ .

100-00 .

. lirti

pRSKLLATK OF KTIIYU

Z7$

tn c

12 H
BO

120
12
64

Sclmntk.
6-20

. :i3 n ..

Stcnhoaae. Rjrbleilfr

mm

33-19

61-19
fi20

3261

3li3?

& HfM!.

,... 60'HO

. . 32-a2

C*Hi^O»

196 ...J 00 00

10000

10000 100 00

lOD'OO

100*00

Li(*l>i^ & Katie uTiiJyipd thp ether pirjiareJ bj (1)? Sehanck^t unalj^U fl wa» mitde
«tth iheppuduct olUiiitted by (1) ; * with that prfpnrcd (2) ; r with the pruduirt obtained
from erythric acid- Stijtihftuse's anfltysia a wnfttnnde witli the jiiniJuet ubtuintJ hy 2 ;
b with thit frono j[J*or«eUiG idd ; Hochkder & Hddt aiulyied the ether prepured hj t.

Becompottifluis. J. OrselUc etber heateJ on plaliiiuin-foil nirlU into
an uil, an<l g-ives off thick suftocatin^ vapours. — !?. It tlit^salves io ^irurui
nitric aciJj ami the llquiil, if ^itrongly heated, gives off y€'lluwit!i rt'd
vapf)urfl ,aiid ig afterwards fotiu J to coutaiii tfxalicucid. (Scbuhek.) — The
ether dissalves in fuming nitric acid, forming a dark Idood-red liquid froiu
\vbit:h it is predpitated hy water in its t>rigitial state. (Marx, Sihtr,
60j 127) —3. It dii5Solree« in oil of vitriol, and the solirtion when heated,
aseunied a dark hrown colour, givea off snlphnroug aeid, and deposit 5
hrown flukes on being mixed witb uater* The cob I ulk:Llinc solutmu
becmnes browu when exposed to tlie air. (Uoeren, Kane, i?L"huni-k.)
When the ether is heated with alkalis or baryta water, alcohol di-sti!.-?
over, and the residue contains orcin and carbonic acid. (Schunck.) Tbo
ammoniacal solution becomes red by absorption of oxygen. (Hecren,
Kano, Schunck.) — 6* The aijueona or alkaline solution instantly reduces
a solution of gold but a flilyer-solution ia not reduced by it till boiled with
ammonia, a metallic speculum being then formed and the .solution turn-
ing red. (Schunck.)

Cbmblnalifm^. Orscllic ether diasolFes y^ry sparingly in colcf^
abundantly in hot water, crystallising in shining laminse as it cools.

It dis^flolves In cold caustic nlkaliB und their carbnnates^ in baryta-
water and in hnic-waten und is precipitated without alteration by acids.
Itdisfolve^ in ammonia without deconipoiition, if kept front contact witli
the airj and cryslallbes in elender needles when evafKjrated.

A solution of orsellic ether iu the smallest possible quantity of
fttnmonta forms with nilnite or acetate of lead an uburuhmt white pre-
apitate (Kane); it precipitates basio acetate of lead, but nut the neutral
ftcetate of lead.

T PbD ....»»...>.* U2-4 .... 79-37

20 c 120 0 .... 12 2G

12 H .„..«...». 12*0 .... 1*23

g O » . 61*0 .... 6-54

Kmie,
«0*j>*

ii^?a

J -32
6-36

C»H'^0*t7PbO. ....,.,..,. 978'G .... lOO-OO lOO^Ofl

The ammouiacal solution of tha ether precipitates nitrate of silver*
np&re decomposition SJ.)

Orsellic ether dissolves very readily in alcohol and tther^ but not in ,
■^Beetle acid.

LECANOJUC ACID*

3?T

The aiunioniaoil eolatiou cliati^s on exposure to tUe air less quickly
than that of crytbric a<;ic!, but ulti mutely assumes a dark wine-red
colour*

Telerytbrin dissolves very readUj m water, The solution forma
nearly wliile precipitu-tes with the *5aUs of the heavy metals. The preci-
pitate foriried with basic acetate of lead, han, after drying at 1 OO', the
ranipoaitlon C^H^O^*,5PbO-

Jt dissolves flpariiigly in tt^mhol, hut is insoluble in ciAcr.

Lecaiioric Acid*

piiimcK. (1842.) PhlL Mag. J. 20, 495; Ann. PFmrm. 41, 157;
Fhtam^ Cenlr. IS42, }t^U\^Aiin. Fhmm. 54, 261; Phmm. Ctntr,
1845, 7'2L— J uH. Fhann. m,ll,^PhiL Maff, J. 33, 25T»
acuLEDER & Hklut. A}uu rhmiti. 4Rj 2. — Pharm. Centr. 1844^ 49.
iBtej^house. PhiL Ttant. 1848, G4; Ann. Phmm. 68, 59; Pharnu Ontn
1848, 31 a.
aKcKEK. AfUh Phutm. 68, 112; Fhmm* OerUr, 184&, IW.
fBnuAMBT, Vompt. cJiiuK 184ft, 128,

Sourca. In various lichena of the genera Lemmrat Tarlolaria^ ^c.

Ptr^amitmu L The finely divided plauU are exhausted wilh ether
a displaeemenfe appariitus; the ether distilled off; and the greyish
ellow ret^jJue waishod in a larnje funnel with cold ether., as long as the
ther is coloured by it, then boiled with water to remove the orscllato
of ethyl which has been ftjrmed, and recrysta Hissed froiu warm akoboL —
If the acid thus obtained is contaminated with parellic acid^ tbe mixture
iinist bo treated with l*aryta- water, the dissolved lecanoiate of baryta
filtered from the insoluble parellate, and the solution decomposed with
hydrochloric acid. (Sehunek.) — 2. Eve ma Pninagtrl is covered with a
mixture of ammonia and bydrated alcoliol in a ves.^el which can ho closed;
and the liquid after a few minufea U strained through a cloth, washed
w*ith ^ its hulk of water and neutralised T;ith acetic acid, The acid is
then precipitated in green flakes, which are washed with cold water by
atation, dried at 100^ and crystallised from a small quantity of
oiling alcoholi The prfcipitafe j* swmiHimrs contaTnintttctl witji n body ingolabk in
fther, to remoTP which, it must be dieted in ether and the eihrr distil ltd from the
liltratf^. (Rochleder & Heldt-) — 3, r'hoi»ped IRocetUu tuictoria h
fmace rated for a few hours with a considerable quantity of water; an
ixceas of slaked lime added; the whole well stirred round, and left to
Bttle; and the clear pale yellow* liquid decanted and filtered, Tho
esidne is mixed with half its weight of water, the liquid cspressed after
Im quarter of an hour, and both extracts kq per saturated with hydrochloric
aid; and the white gelatinous precipitate is washed by decantation,
ollected on linen, immediately dried ou a plate of gypsum, and dissolved
warm (not boiling) alcohol, whence the acid crys?tallises on coolingp

• m 2a«H'0« - 2H0.

S7S FRIMARY NUCLEUS C^^H"*: uXIGEM-NITCtEtTS C*«IpV1^I

It ike if6l crjiialUntioii i« out <|tiile colomrleae, it oaittl li« ndiliM
stud digested mhh animal cbarcoal. — Lecanoric mctd cannot W adfd
la^eoasly prepared by boiiiog with water, init^mncb as n Jarg« mJ3
of It IS tlier«bj df^tjmposeti, ami tlie reBtalting^ aci J, even after ij^H
crjstatlisatkm from aknihaH is ooi c{uUe fri>« fruui a resioocis and^^^
iabeUQce, from wbich it ean be fn^ed qqIj by trealju^ot with ^H
baryta- water. (Steu house.) ,^H

i^mpertin. White needles united in radiating^ gmapt, InJERI
and tastd^s. Reddens litniu^,

32 C.-. 1^ .,. i^'Sr ....... 5»90 59 92 . 5d4S 60 35

HH ,._ 14 .... -1-40 4 57 ,., 4 60 „.. 4^40 iW

HO..., U2 3^23 . UU - 3A'4i . . 3tflS .. Wfli

CWH'W*_318 .,..100 00 .,.,,100 00 100 00 100 00

Aecordttig to ScbatidE, il U C^^'H'^O*^; acrordJAs ^ St«tilui«ae; C^*0*|1
Geriufdt gave die fonatils C^H^'O'*, mhidh cr plain i the c(iiif«T«T9Q lalo 9f«Bl5eiffl.

Btcompmition4. 1. By dry dktillation tbe add yields at^I^cid di»tj
late wbicb toon fiolidifies into a nidbting mikss of orciii and Itarfl
Rmal) quantity of cliarcoal. (Scbunck^ RoeMeder & Heldt, StMiho
Heated on platinmn-foil, it bums with st yellow flame witboat Kfafi*
aoy reeidue. {Steuhouse,} — ?, Boiled wttb water it yields
acid^ which by coDtinned boiling i^ converted into orcin. iScbon
Rocbleder k Heldt, Strecker) :

The acid boileil with alcohol yields orsellate of otbyl. — 3* By ^niiii
boiling with potash, ammonia, baryta or lime- water, it yieldt orcin
a carbonate of the alkali (Schiuiek, Rochleder A Heldt); it yi«ld« in til ^
^rat instanea orsellic acid, wbtch^ by further deeoiiipo^ftion, U fvm]ni
into earb^mic acid and orein, (Sten house, Strecker.) — 4, When mtmUmd
with dilute frulpburic acid and left in a warm place, it h ^mnflifttlh
converteJ into nrdn. <li>chnnck.) — S. Whi'H boiled with nitrie irii
it emita red fnmcs and tbe resultin|j iyrup eontiuns a lai;r<» ^nnm^tr ^
oxalic acid. (Sdiunck, Rothleder ife Heldt,) — 0. With < -
it immediately assumes a deep red colour, which ho^. i^'k.'

ehangea to brown and ^-^idlow, and en ni pi otely dts;ip])ear9, if the cili^fi^
of lime has been addi-d tii excvns. I** ihi» iY,irti4iii^ » dAtk frctn »aMtf«»
nlet) fomviud by oxidati^fi) of ibr lot^iinoric leld. — Tbe ciihlouriiig ia firtHloDeHl, tiiii*!*
M, itiJute solution of rhlonde of limr ?« }»oured into ai> alii>tii:ilti' ftit iJkaltii* cittwt (^

the Uchi-iiA. — 7. The solution of lecanoric acid in C4iuttic amiuftnii
assumes on exposure to tbe aim splendid red colour, nliiin&icly rhaujrttf
ti» parple*red. (Schnnck, Rochleiier<k Heldt, Stenhciiiii©,) — g, Th^M
mouiacal solution forms with nitrate t»f silver a wbita pri^ctpitaiie ^h*^^
JH reduced when heated^ with formation of a metallic «f»eciilntti. The »«b^
tion of the aeid in potash reduces terehloride of gold iritli ibo ai4 of heat
(Sehunek.)

Combinaliont. Lecanoric acid diffsolres in 2^00 pte, of ho3m
water and separates in crystals on cooling. Tbt g^el|Uttio«i %m
ieparatod from the salts contains 1 At* witter Intimately co '*
which ogcapes alter 6e^eTft.l \\o\ir« heating to J 10"*. (Schiiock.)

^r ^*"^ LECAWORIC ACID* *- 376

^m lintntmlh^s alkalis and fnrm^ witli them soluble cryetalligablc salts;
^^it expels carboxiic acid froni alkalitie carbonates. {Schanck, Stenhouse.)

^P LeeanoraU of Baryta. — When tbe acid is disBolved in a very sll^'lit
F excels of btiryta-water» carbonic acid passed through the liqufdj the
I s^olutiori filtered^ aiitl the precipitate, consisting uf carbojsate and lecano-

Ir^te (;f baryta, ejthaaated with hot alcohol, the aolation on coi^ling d^positf |
ehiuin^ blender needles united in sjtars (Stenhou^c.) In the solution
of the acid in baryta- water* aWhol produces a ytilQW jelly which is ijo| I
decomposed by boiling with the alcoholic liquid, imd afterwards dissoivcf '
completely in water, (Schuuck.)
I B*0 U% ... 197;i 19'49 1

i 32 C ...,,„„ m^ _ 49 «7 49 2?
I 13 H ..,-.„„ nn 3 :t7 3'Hi J

I 13 O., ....,, 104 0 ... 27-03 - 27-43 I

C^^H^*BiiOi* 385^6 .... lOOOO lOO'OO I

The acid acts with linie- water in the same manner as with baryta-]
I water, (ycbunck.) The aninioniacal solution forms with cblonde of'
^KcaJciuin a gelatinous precipitate sparingly fcoluhle in water and iu
^■ftfcolioL

^m Lfcunnrrdt of Lrad. — When s-ohitions of lecanoric acid and neutral

acetate of load are mixed at the bnilin*r heat* a white precipitate li |
^^ formed which is somewhat soluble in aJcobol, and after washing with I
^■Bleoholj cun tains 37*7 p. c. carbon and 2T.> p. c hydrogen. (Rticbleder I
^* & Heldt.) [U apptars to coiitBin orteUate of IcmL (GeifMrdt, Tr. 3, KOO.)] Au I
alcoholic snlutimi of lecanoric neid does not precipitate neutral acetate |
I of lea^i (ScbuiJck,) It precipitates the biii-ic ai;etate of lead bat not
! the neutral acetate. (SteiihoaseO

^m Au alcoholic solution of lecanoric acid is colon red dark purple red i
^Mbj a drop of frrric hydnichlorate; water atldeil to the liquid throws I
^B^own a light purple precipitate. Ferrous salts mixed with a large I
^P^ quantity of leciiuoric acid art^ not precipitated by ammonia in the cold; \
^^ but on boiling the dark yellow liquid, a brown precipitate of fet^tie
Ucanoratf ts prod need. (Schuuck.)

The alcolmlie solution of the acid added to an alcoholic solution of

\ ^upric ftcttittf, prruluces aftei* a while a light apple-green precipitate. It

does not precipitate mercuric chloride, nitrate of silver or chloride of gidd*

I (Scbunck.) With aniiuonio-nttrate of silver, it forms a precipitate

> which soon dec^omposes. (StenUouse.)

Lecanoric acid dissolves in boiling acetic acid more readily than
bin boiling water, and crystallises in slender needles on cooling.

It dissolves in 150 pts< of 80 percent alcohol at \S*5'', and in 45 pt^.
of boiling alcohol, forming orsellate of ethyl; it dissolves iii SOpts, of
«theratl5'5. (Schunck.) i

380

PRIMARY NUCLEUS Cni'": OX If GIN-NUCLEUS €'*WO\

Picroerythrin,

C^*H"0" = C"H'0',C«H*0\*

Heeren. (1830,) Sdm, 59, 325»

Bc^^^XK, FUL M^jff, J. 29, 2G1* /, pi\ Chan. 38, 4li>; Ank^Fksrm.

CI, 75.~FIiiL Mag. X 33, 253*
SiENHouaB. PhlL Trans, 1848, 75* — Jni}. Fharm, 09,76,
STREiCKEftp Anut Fkart}h 68, 110.
LxrEE^T, Cmnpl. rffid, 31 ^ 355.

Erypi^H^ — Frepftred by lleercn ia lUe Linpure staU at JTr^/AWn -4(//fr,

Fommtimi* By boiliug erytbric acid witli iraterr

Ilecrea coDSlders tlie presence of alkallE to be itccefs^iry.

Pi^jjarathn. 1. Whey erytliric acid ie treaieil for a iiiioK
witli boiling water j and i\\^ liquid evaporated, a brown, g1uiiiioii8» L-™_ _
i^weel mass ia obtain o^l, wbicu gradually becomes erystalliDOj aii4 aJbv
wasbmg witb water, yielda pure wbite picroerytbriu, (ScUudcL) —
2. Erythric acid is uentntlised wilb baryta- water or lime-iriti
liquid boiled for some time, and tbe resulting orscUic u^id eepa
hydrochloric acid; the inothcr-lj<nior, after being considembl;
trated by evaporation, yields in the cold, after a few dsja,]^
crystals of picroerythrin, wbicb are washed with cold water, miiid ncrp-
tiillii?ed from hot water. (Sten house*) — 3. The light brown IoolJJe^
liquor obtained in the preparation of eryibnc acid (p, 382, 2) yielii
when evaporated, a gummy residue having a hitter-sweet taite. Oi
treating tliis residue with cold water a light brown cry^taUitie maMii
left^ which is to be washtd with cold and diatsolved in boiling water c«i*
iaining a little animal charcoal; the eolution^ fiitered from the €h«m«l
Yields after evaporation, yellowish cry^^talUne picroerytlsriiij »kiel
becomes white when washed with eold water, (Scbunck.)

Ehnoft}—
i/ydbviSl

Lon^ coiotirless needles arranged in stellate groo]M (SA«-
bouBe); white crystalliDc mass (Schunck). Has a peculiar sweet i*^

Froptrtlti.

\ ~ ' crystal]
!:trojigly bitter taste, (Schunck.) Reddens litmus slightly. (Sdiiiiick^!

24 C .
14 0

144

16

112

53^94
4Mi

Sehonck*
52SI ,
e 0a ,
41*41 .

40-81

C^H"*©",.,.., 272

100*00 lOOOO

Ae(»rdin; to UefUirdt, it h C*'H»0»^ which re^ttlrea W% &€« mAm

(IWif#, 3.704),

DtcofnpoKtlu^ns. 1, The compound melti» xvbon hi^ateti iu it gliAito*^
und yields a sahlimalo of orcin. It burni with a bright flauie a»<) iritli'

c^*H^t3* \ cTtt^Ki^ ~ mo.

ERVTHRIC ACID.

881

^

o\x i nesi due . ( Sch u u ek .) — 2. Piero c r j tU rl o la n o t al te red by b ui i l ng
with water (Scliuiick); only a very small i^uantity of orcin (and parliapa
also of erythroglucb, wm formed after 36 boar3\boiling. (Slenhouse.) —
3, Boiled with excess of alli;a.li, baryta or limej it yields orcldj erytb-
rogluciu and carbonic acid, (Slenboasc, Sduinckj Fhil. M^^, J.
33, 253);

c^WHx^^ + 2E0 - ci*H^o* + cm^«o« + aco*.

I

4. Tbe ammoniacal solution quickly imn^ red on exposure to tbe air*
(Heeren, KatiOj Scbunck, Stenliouije,) — 5. With chloride of liino it
produces a blood-red colour, which cjuickly changei^ to brown and
yellow, (Stenhouse.) — 6. Boiled with nitric acid, it ia decomposed,
with formation of nitroua acid. — 7- It dissolves in oil ol vitriol, and the
solution gives off sulphtirous acid when heated. (Schunck.) — 8. Nitrate
of silver in not precipitated by the afineous eolation, and on boiling the
liquid, the glass becomes covered with a silver speculum. Solution of
gold boiled with picroerythrin, is decomposed, tho gold being sepa rated
In metallic scales, or, if potiish be aided, in the form of a black powder.
(Schuncli,)

Comhinaiiom. 1. Picroerythr in dissolves sparingly in cold, readily
in hot water.

The alcoholic solution imparts a deep purple-red colour to ferric
Baits; but the colour is destroyed by ammonia which completely preci-
pitates tbe ferric oxide.

With aqiipoas picrocrytlirm ajid neutral ocetAta of leJiJ, Schunck obtmixed n*>
predpitatc; but tbe biiBtd acetate jielded a precipitate contBinlng 68 94 p. c. oside of
lead. Sten house could not in any way obtain i kad-eompoutid of eoti»taut
composition*

PicToerythrin dissolres in alcofml and in tthn\ It doea not yield luiy
compoi^nd ethr r by boiUng with alcohoU ( Sch u nek*)

N
^

Erythric Acid, C"H*»0« •

S; Nees V* EsENUECK, (1829.) Br. Avch. 16, 135,

Kank. Phit. Tram. 1840, 277; A** Amh Chim. P/*yf. 2, U ; Am^

Pharin. 29, 31.
£eircKCK, Fhil. Mng, Z 2f>, 261; J. pr. €hm. 38^ 449; Ann, Pharm.*

61, G4.
Stenhouse. Phd, TimiM. T840, 72; Ann. Pfmrm, 68, 72, |

Strkcker. Aim. Phann. iiB^ 111,

First obtained by X. v. Esenbcck, m a *' remarkable resin*' from
Lti^mi^a tarktrm; by Hccren (1830) in a state of greater purity and
described as Er^ihnn; analysed in the impure state by Kane as ery-
thrilin.

Occurs In greatest abundance in Ro^ctUa Montoffnei (regarded by
Sch nock as IL fmetorld^ var. fnciformiM). (Sten house.)

♦ = 2D«HW + Q^m^Hy - 4HO.

FEUumi mxxEus c^b**: mmasi-mcuxm

I vii^ eold Mid diisolTed io bat wmler . TW '
W filtnisMi frMi ike i«mBtT liUrk or Urovs rcfidw

M tm* wxtt ak^ol \^ mmtammUmmy^ tummmml^mHimW^U

Aricaaii* i Ill i .iei^lieiifermimdd): tlic linU ii

til* Hinte liMtal ai la tk» int iMidt af pr^puv&M rf

ilt rtimme oC cold vBler« tbe etytlim fts»d s-pvmles ciut, (H«tra<)
— 4. T%e lidiett b ittanerrifd in m miall qasatity of eold 9iw%mg wmmmal,
m»i IjMAded with It fur hohm tl»«; tke tefiiid r«iijii4i& eo^ti^Q diw
olitat]kt<i It dHiitfd witb wftttr; cli)onil« f»f li^om pr> cuid

" " foerellir acmI ; ike i- t«iW

driit ^omi : nlttc^ & elif^til »rid rea<tiiL

HwfiJCTi ■■firatiw «f ib» errllirii: acj4 cociTert^ t^d tsb t

W|«nl» IB the Ml?ernlf»t fim e« eeetl»f . PttnSciitMM ai ta itf
^«<roi»fi QietlHiil. (Heet«u)

Fren X^^acnior* UtrtmrHif tbr rnrthrie ««»d i§ Um tmAf ^iiAt«ii<l W
&t». Tlie ndieB is dtgestc^'with dceM; tlie akiolifilic tmim

omatikta It ouatf^ wiin wMtr; coioi
wUh wmmmm U mMc4 to jirecifuuie ;
ffcrwapfc good ihcrim (ff^j ^^
rItldneaeMi, added la taScirtil eoai

lulxl^d vitii vmler; «jid tltt jwttiMtati ticatod wltk etiier, wli>cli dl^fthci
ddon>pbjLl aad rocc^lie aod and karei iai|iiij« eiTtlirie add. (UvifOL)

tMnaaeopir fi4imi]». (Herr^fl.) From llie Uilltag aleobolie
il aapaiatie^ la stelble gnM]« oa conlbijr. (ScUtti>ck.> Water |»f«^ptt3
H mm the akoliolie telattoQ in the forai of a itUY, laodcmiai lai
jaitefeia. (Stialiettiet} At a tempefatare toiaevlat aSove I0a*» it BfHi
iDto a tiaatpafiot gajaaij wmm wMA koeooMi hard aad brittle oo ceiK
laf. (Hetrea, Kaae.)

ft lediieoa liimos (SeUmiehl; it doea not (Stmheoee.)

toe
22 M

teo

tie
ft

*«J fti-ft

$<ii ^... &^&t

c<m«o*

421

C^tS^*0*^ ia order t9 cYiklun tk« te»aaotMi*a bt

DmompogUioHi. 1. The aeid hnlad in
' AJi eil/ taUiffiale of mtbi adl altnnalelf

Owlaidl

idlie fralkt afwj«U*
earho&ked. (I'^

^ (HM|^y

mrmmc acid.

SSS

^chtiiicTc,) — 2. In eoiitact with tbe air, H bumi witUDiifc residue and
with a bright sooty flame. (Heeren, ScUunck.) — 3* It dissolves id mine
acidf with evolution of nitrous vapours, and fortns a yelbw liquid, which
ik^sumes an orange -colour on addition of ammonia. (Hecren,)— 4. It is
dissolved by oil of vitriol without charring, hut ia not precipitated by
water in lU uriginal statCj inasmuch a« the precipitate form« a brown- red
pigment with ammonia on exposure to the air. (Heercn.) — 5. With
chloride of lime it assumes a deep red colour^ quickly changing to brown
and yellow. (SteuUouse.) — 6. When boiled with water, it forms pier o-
erythrin. (Scbunck.) — 7. On boiling the solution neutralifled with
baryta or lime, tb** acid is resolved into orsellic acid and ptcroerythrin:

C^H^O^ + 2 HO - C^m'W^ + C'^H^O".

A^dording to Stenbouw, the produeU of this iltcom position ire pieroerythnn utd
CTjthrin, which crjibiLlLse in miciceouti Lamintt* and erifihriih aeid wbicli hiu a <tronflf
bitter liste; tbii latter lubiL&nce wai resolved hj bdUing with wateti into rjirbonic acid
mud orcin and probably coniiited of impure qrwllic aciJ (compare Strecker*) [Iht
erolution of Cdrbonic mid wbicb, according to Stenhousf, aceompanlrt the form alio n of
|lTcrc>erjthriri from rrythrit' add^ U explained nccording to Geilmrdt's furnmla, by the
eqttiitton: C"IP«U'« r 4HO = ZCf »- + C^H^H^* (Gprbardt'j picromtbrirO ; ai bow-
rf er the dccoEnpoiition of erytbric ftctd LikewUe gjroducf« on^lUp add, which wb«a
boded ^Tlh wAter, iii iinmcdiatdj resolvtHi ioto carbonic add and orein, the carbonic?
acid apprnf* riritUef to he the reiult of a lecondEiry dcaJtn position. L<] Ervthrio
iki"id boilud with excess of liino or baryta, yields iho [iroducf« of decom-
poaition of picroerythrin- (Sehnnck, Steunonse.) — 8. In contact with
oaoi^tie ammonia, or more slowly ^?ith carbonate of auimonia, and exposed
to the air^ it gradually aa.^umei a dark wiuercd colour (Heercn)' purple-
red (Schunck), Heercu*s erythriu tliu^ t routed yieldi*, in addition to
lichen- red, which dissolves with violut colour in alkali8, a browniaU-
yt.*llow ftub^tiijice^ and a pigu»ent whteh does not turn violet in contact

I with jiotai^lj, but yields Ijclicurcd when hifatcd, — J>- Erythric acid boiled

' with wood*^|"irit r»r alcohtd yieldu ori^ellate of ni ethyl or orecllale of
ethyL (Stcnhoimei Streckcr.) — 10. The alcoholic eolutiou fitimw with

I tfedijuichlorido of iron, a puqde-red mixture, which is turned yellow by
xiuimoniii^ but without precipitation of ferric oxide in the cohL GoM-

^^»iduliun h nut reduced by it, even nt the boiling heat.

^M Comhinttlimt*. 1. Erythric acid dissolves in 240 pl^. of boiling
^B^ater, and separates for tho moEt part on cooling in Hakefi or as a
^BpyMtalline powdtrr. (Schunck,) It diesolves in 170 [»ta. of loiling water,
^Hpd feeparatea as eoon ns tlie tenipcrature t^ink^ a little. Ii is insoluble
^BWflrong bmling' hydrochloric acid, but dissolves with tolerable facility in
I boiling acetic ncitt and easily, without alteralioPi in cold ijolutjoas of

tcaui»tic and carbonated alkalis^ forming a cotouvlc^i^ ntpad. (Heeren.)
The alcoholic «olutjon of erythric acid forme with an alcoholic Eobtlou
W neutral acetate of lead a white precipitate of yariahle comtitntion*
rStenhonse.) — Sdmoek foood in it 59 -U per ttut of PbO, 27, U C and 21 Ti H- —
Tbe at<-oboLic sQUition of tbe acid ii not |irecipttmted by neutral iicetale of kad.
tSf!bunek.)
The alcoholic solution doea not precipitate nltrafe of silver, but on
addition of ammonia, a white precipitate is forme d^ which turne black
ou boiling, and deposits a speeular coatina an thegla«a. (Scbanek.)

The acid dissolves in alcohol, especially wliea haittfid and in €ther.
(Schunck.)

Erytbrin diiiolvei in 2^20 pt«t of boUing tdrobol of fp. gj, O'Sl in S2'5 pU. »t 12%
^ ^ttt ii inioluble in ctber (HeerenJ.

I

S4 SHBaJZ 9IICL1S9

I. Pk^ 2, II; Am.

'-f-'Mnictia. 7^ aHbOK mwinBUg » vitcr of tke mleokolic extnd

dligkil J sspemtaniri
jeDov predpiufte, wUA
Bj s»l stm mal W mMtkiim^ witii wmter, tlm £^
«£«;»£ jL sx^mijr aKmnmok ^vtbk. a»l tte aolBtiiNt deeomposed whh
auonu^ ic lairaziL sbl fixaEcvL Ik ^ifiA j^Oow filiate npem*

SBF inaKic via ctiiigaar rf SKsnu jiel^' wIkm treated witk hfdif>

il is pafe j^ow, geMnUf
to Vemci<L

•^ C - ISi — <;•» 66-52

:i H i* — *•!< 8-25

i *' 4S — 2|-4f 25-23

C-HN?^ ^ . :« — lOt^O 100-00

rtKuarrv^-^ & L-nJe J^K/Te 10<!>'^ not ^ny portion Tolatlliung lllj^
1^ ^c5cr ▼^^ iri;^^, it k «wT€rt<d into picroerytluin.

h iktscC^H^ tmcHt is alkiliiie liovids, but without neatndistng thev,
jbul ^ Tc^rircziki^a frk-oc tke soSntion by adds.

T: A..TrKi>fs^ Vj QMiluc decMnposition, with metallic oxides, fonuif
<v^Tr,Tv»trif w^ ?r"i^ *^^ tbe ido<4 part^ bare m green colonr,

it> <»*xc«v»x :x tbe rnsaZjcsi posablc qoantitj of ammonia formSy wi4
liitr*:* ^: '^wd, * lyuf crwn pnlTcnilciit precipitate, whicb wben wijW
an.: ,:r^f^.; %\ liV ."is C^H^V,»PbO.

Krx :yr!'. r a:???:>« in a)«»bol and in etber.

<^i

ERYTHROGLUCIN,

386

^^^^^^^K Addendum to Ei-^ihrw Acid,

^^^^^ Erythrogliicm. C^H^W

Kenhouse. FML Trans. 1848, 76; 1849, 3S9; Jnn. Pharm. 6Bf 78;

F TO, 225.

Strecker. Ann. Pharm. 68, 111.
ScHDNCK. Phil. Mag. J. 7, 33, 254.

Lamv. N. Ann.Chim. Phj$. 35, 138; abstr. N. J. Pharm, 22, 43;
Ann, P/utrm, 84, 3G9 ; /. pr. Chem, 57, 21; Pharm, Cmir,
1853, 302. — Further: N, Aufi. Chim. Phj^s. 51, 232.
Waoneh. */'. ^r. (7/wjJt. ei, 125.

pBtudQQrcin, Sryffluf^int EfjiAromannite, PhyciU,

Source, In Protococcus vulifaris.

Formation, By boiling erythnc add or picroerythrin witk excess ax
^yta or lime Q>. 382).

Preparation . 1 . The e 3t tract of Leeanora Mantagnfl (p. 38 2) obtained
rlth milk of lime^ m boiled down in an open pan to about one-third or

[ie-four(h; catbouic acid paased into the cooled liquid as long a» a preol'-
bitate Gontiniiea to form; and the solution, aftor fiVtratLon, evaporated to
» syrup over the water- bath. Thii ayrnp confiista chiefly of orcin and
rythrogluciD, mixed with a rather large quantity of red colouring matter

ad a resiuous substauco. The orcin and the greater part of the colouring
batter are extracted by cold ether; or the syrup is mixed with three
imes its volume of strong alcohol, from which, after a while, the erytb-
.Ogluciu separates in email cry stale. These are collected on a cloth
liter I pressed, washed with cold strong alcohol, which dissolves the orcin
' fld the greater part of the colouring matter, and recryslallised two or

hree times from hot alcoboK — 2. Protacoccns vulgark is boiled for some
kours with water, and the filtered and decolonsed solution is evaporated
a syrup, precipitated with alcohol or basic acetate of lead, and the
lltrate left to crystallise* — Or, 1 Ik of Protococcta vulgaris is digested
|t a temperature between 50" and 100^, with 2 lbs. of alcohol of 85^;

he liquid decanted; the green residue strongly pressed out; the liquid

-ain filtered; nml the alcohol distilled to one-half. The mother-liquor
the phycic acid whit.'h is deposited on cooling, separates, when the
liquid is again heated, into two layers, the alcohol at the same time
evaporating. The upper layer is strongly coloured; the lower, which ia
less coloured, yields by evaporation a crystalline mass i*atu rated with a
black ayrnp, which must be uressed between fine linen, washed with very
cold water^and recryatallised from hoi water, (Lamy.)

Properiiei. Large colourless transparent crystals having an adaman-
tine lustre and belonging to the right prismatic system. Fig. 29, often

3P3 \

WJtb bemihcdral development of au 8'Sided pyramid (P, qoPo& . ^ ,)

€ (P : P) = 123* 43; « : 3 (P : «P=^) = lOr 29; 3P3 : oop^ =

VOL, XIL a a ,

386 PRIMARY NUCLEUS C^m^: OXYOKN-NUCLBUS C»*aW,

I

138* 42'. (Miller.) Large rectangular priBitie acumiot^ted witli wetml
fuces (Lamy); according to Lainy's later determmittionB, thej belong ia
the squaro prism alio system^ eryietals cut at Hghfc ftfig^lea to the axit of ibc
nkm, exhibitiitg with polarised Light the system of coloured m^ |ifc«-
lar to crystals with one optic axis, {JV- Ann, Chim. Pk^s. 51, 531;
tee tbia memoir for deUib of the cryslalUue ftjrii>») Sp. g^r, 1*59. (Laijiy.) Il*
taste ia very sweet and cooling. ^Lamy.) Index of refraction =li'4i.
(Stenhouse.) Does not exhibit circular polarisation, (Lamy.) Melts U
112^ witliout giving off water, and volatilises partly Mndeeotii|iB«el
(Laniy.) Does not act on Utiaus. — Its ta^te ie sweet, Uut leflt«o '
that of orcin. It does uot lose water at 100\ (BteaUouse.)

rib 11 I

S ten hauler Scliunck* LsiOf*

eC .,.., 49 .... 39*34 39-42 ..,. 3**-6S .... 39-10 ^ »«

10 H 10 .... 8-20 8-48 .„. 860 .... 8 23 _ Wf

80. 64 .... 52-46 6210 .... 51-72 .... 52 6J ._ »^l

0'il''W ......_. 122 ..,. lOO'OO „....„ lOO'OO ... lOO'OO „„ 10000 .«* lOHl

Stetibause gave the cmpm^^a) formula C^'^H'^^'*; accordifig to OerhAnit*# I
(^UfjifiOJi ^ ^,|^ which Tefiuirc»4 09 p. c. C, ei7thro|^li:tdn shouUbe === ortm ^ tHO.
Lamy deduct* from hia owa analysei the formula r**H'*0^, «hieli n^im
3^-33 p.c. C. 6^40 H Aud 52^42 O. The same formula was obCaitied by EtAlt,
{€&mpt- rmd, 41, 452). ~

zsK^

Betompomilmu. 1, Erythroglucin euhjected to dry dtsttllalioti
off an odour of burnt augar, and yields a liquid which does not cml
on eooliug, but dissolves in water and in alcolioL (BlenWu^a.) flbc^
to boil at 1G0° without perceptible decoinpo-ition^ gi^ii^^ off an odrtor 4
burnt dour; as the decomposition advances^ the 1>ojtir)j^ point grailiullf
rises to about W<ff but the ninsa does not swell up : the residue tatile
retort consists i^^rtly of unaltered erythrotjlucin [phycite]^ l^^^J ^ *
substance analogous to glucose and pcjssossitig the power of r^acsif
copper-ealls, a property not exhibited by erytbroglucin [pfeyeHel
Erythroglucin thrown on red-hot coals gives off the odour of bnrtit #o^,
(Lamy.) ^ It burns on platinum-foil with a blue flame and an odtrtu d
caramel. (Stenhouae.) — 2. It is not altered by potash, ammonia, b«-
mine or chloride of lime. (BtenhoueeT Lamy.) — ^3. Fuming nitne ir*^
converts it into uitro-erythrogludu; on heating the miscture, oxalie niii
Is produced. (Stenhonse.) Erythroglucin dissolves in cold oU of vitrei;
the crystalline oompoun<l yields a soluble baryta^^alt* It is not I»kfk*
eued by cold oil of vitriol, but turns brown on the applieatioii of >*«<i-^
— i. It is not fermentable. (Stenhonsei Lamy.) mM

Ccmhinathm. Erythroglucin dissolves vety readily in waier. tk
a^oeoQS solution yields the ^nest crystals. (Stenhouf:eJ}

It does not precipitate neutral or basic acetate of l«ul, eaMcr-MlH
or amnionio-nitrate of lead* {Stenhouse,)

It dissolves sparingly ia cold alcohof, bat is insoIuUe In rjhff
(Sten house.)

CATECHIN. 387

Nitro-erjrthroglucin.
c»N*H«o»* = cxm*o\

Stenhousb. Phil. Trans, 1849, 399; Ann, Pharm. 70, 225; Pharm.
Centr. 1849, 627.

Palverised erythroglucin added by small portions to fuming nitric
acid which is kept cool, dissolves auickly with considerable rise of tem-
perature; and if the solution be mixed with a quantity of oil of vitriol
equal in weight to the nitric acid, or rather more, the whole forms in
half an hour a crystalline magma which is collected on a funnel plugged
with asbestos, washed with cold water, pressed between paper, and
recrystallised from hot alcohol. The compound is not obtained by diuolving
erythroglucin in nitrosulphuric acid and adding water.

Large shining crystalline laminaD. Melts at 61 ^ and solidifies in the
erystalline form at a temperature a few degrees lower.

8 C

4 N

6 H

48 ..

56 ..

6 ..

.. 15-89 ..
.. 18*54 ..
., 1-99 ..
.. 6»-58 ..

Stenbouse.

16*62

17-83

2*48

24 O

192 ..

63'07

C8N<H«0« 302 .... 10000 100*00

Gerhardt't formuU C^^X^Hioou requires 18*02 p. c. carbon.

The compound takes fire when strongly heated and burns with
a bright flame. The crystals thoroughly dried and mixed with sand
detonate violently under the hammer.

Oa:pgen^nucl€U8 C'*H»0*.

Gatechin.
C"H»0« = C"H«OSO*.

Rimo6. Rchner's Beperiorium d, org. Chemte. Tabelle £U. s. 606.
Fk. Nebs v. Esenbkck. Fepert. 27, 211; 33, 169; 43, 337; 45, 457j

Pharm. Otntr, 1830, 43; 1831, 417.
DoBBRKiNKR. Sckw, 61, 378; Phann, Centr, 1831, 204.
WiNcKLER. Repert. 59, 39; Pharm. Centr. 1837, 740.
BiJCHNBR. Pogg. 39, 162.
Ppafp. Mittheilungenyly mo.
Daiil8Tr5m. Pogg. 39, 163; Bertelius Jahresber. 14, 235; Pharm. Centr.

1836,201.
Stambero. Pogg 3D, 169; Pharm. Centr. 1836, 884.
Wackenroper. Ann. Pharm. 31, 72; 37, 306; Phafm. Centr.

1839,623; 1841, 401.
ZwBNGER. Ann, Pharm. 07, 820; Pharm. Centr. 1841, 408.

T. EL^.TT? ^i.r. J^r-^. F" Tif J'lir-m. iVwlr. 1911.414.
; T Tititf^st J'/,;. .It r l* pW shc-^, Cf9.tr. 1S44,159.

NsTTifcro. -=.1.1 .' f.fm. K. Kr" JVn^ *?cr l5*5<, 126.

jr.:f*-«M. r.: '■".'?«..■»"-*«•£— iflf^Tutct:--- T'nkAtfynMSirr.

>.ii.— M Ii ."rr/-r/ i. iii* hxh-his -iXTTbri cf ike vood of icons
.'«£2c:i.i f^iin X'' =tn-'Uii \c lc zi^ xi: iC -£-*^,-:« 03^<Acft« mod JrwH
Pi-T^mt .'.i.-mi- 1.TI *»sa.ri- riirrii zi G-rmz-ir. the eztnct <tf

'^•i-^irriiiL ?T fT^'Tsnr "ik nFXH^tOif »kzx^>c« of emzechBtunc
US3L Si ziH L,r r»-.:fr ir?irtar *i XfaVaaer. «« tlie eoBtxuT,

j7^,.. ■ ..P. .,^1^ ; 3<!nrw ic *!Tui>'}t7 s^ku k exkaaitcid with dkff

a & Un<3i:ku'«f3zinir~^i:i.itst. ii^ jutrzi:!! fTu**r&?cd to drrneti; tW

;firf ?^«na.n.3^ ^: TtsOki'*^ > ia*rs Kuec. 17 ^/i^ a fiFvcaif^pM qsBatitT d

-Wi^c U'i. ;L'::i. ' i.-^.-^'L Ttr.t k i^iczti. ▼ Ljri USA S«- OMBf^etelj €IM

j*.'!3*i ;a .iMT ••>*«wt WL r:"»i*L Jr N-s-s T. E«w|ieck. Gsiboot)
Tin &( ii:*iii2- s.i in.' a .r -jH frii4'"^ iv:rur: iL»: t5«^1» cascckia vkn
f^'i2*m:ii'L 1 -'nyvt un u»f ix><ciec-.>(iiiir £>:•»« s^K jie*4 aiT BOR cf

if IT:--*" ■?•■ T ;«f>': n-?».-i i .f Ti;ii?^n»:-f; 5 c i* i-.-or? mizh. 5 pc* of foli

brr^T isi. n^'i"^ -x 2—2 : 7"i-^ "*{•>•.. w. i "*; *:•«.: f^Lj t«:ij*^ wi ill wiier.
j-^f-:.? 1.1 i :. ■■Tii. 4 1:1.: -7 :ji: r-^? .-.■• 'Xj^f^i. _^f;*r wisilrjf w~iheoM
ri.ir I*'. 7i- ■. i«:t: :•;■- n-i-? <: ■^i.^ar u-i it**/* ir 7-: % fc'rinl< J*^

.•la*" ■.•a. - • I- : n ?,- v ui.-.i s .•Trairieu n '~xtt jn'stwv^zn zf ?srr«nijar rf

■,••.•.":,•*:•> ■ ^'i : :« '^ » i •' '..!■• i« . :* '.a :ii"~ ■£•*•! v li m'l :* i

& filter, wasshed and dried, — As thus obtained, it is Btill impure. It t«
therefore dissolved in wai-m wat<^r and couipletaly precipitated by
neutral acetate of lea<l; the lead-coiupaund decomposed by sulphuretted
hydrogen^ the sulphide of lead (which retains the impurities), exhauBted
with a large quantity of water, at 90*^; and tbe catecbin which ci-ystalliaes
on c4»oting, la pressed as qui(ikly as poss^ible between bibulous paper and
dried jli vacuo over oil of vitriol. (Svanberg, Hagen.) Neubauer
ndopts a similar method, omitting however the partial decoloration with
basic acetate of lead. —4, Finely pulverised catechu is washed with
cold water on a filter by displacemeni till tbe water runs through
colourless; it is then quick ly dried between paper, and dfgested with
warm alcohol, so long b& white specks of the acid make tbeir appearance I
as the residue is dried. The alcohol is then distilled to one-half; the
resulting brown precipitate coHected on a filfer; the filtrate evaporated
to one- half at iO^, and then left to cool; tbe greyish brown catechin
which separates after some hours, dried between paper and dissolved in
warm water; tbe solution mixed with a sufficient quantity of basic
acetate of lead to render it colon rleas; tbe disjsolved lead-salt decom-
posed by sulphuretted hydrogen; and the solution boiled and filtered i
it then deposits cofourlese catecbin on cooling. (Dahlstrom.) Wlnckler
removes the dissolved lead- salt by means of sulphate of soda and filteri
the liquid from the sulphate of lead while still hoL Zwenger evaporates
the alcoholic solution to one-third of its bulk (without distilling,
because the mass jumps violently); presses between Hneu the yellowish
brown paste which is obtained on cooling; dissolves the residue in
boiling water; filters; redi^solves the slightly coloured acid which
separates on cooling, in boiling water; precipitates the solution, while
still hot, with neutml acetate of lead; and treats the precipitate as in
Svanberg^e process (3),

5, The catecbin which separates from an aqueous solution of catechu-
tannic acid exposed to the air^ is pressed between paper and re crystal Used
from hot water, (Delffs.) — In a tan. pit in whu-h a particularly red catechu wai
u»ed, Th. Cooper found the k&ih^r covered with a whitish crust which Wft» regarded &i
m mgn that the tanning vfas complEte, M^heu thli depoiit wiis washed with cold water,
diuoWed in a trehlc riuatihU of boiling w»ter, and filtered hatf the filtrate on cooling
f leided cattschln, — [According to Neobauer, ratcehln it not formed by o^id^Cioa of
c*techuunnic add (vid. wup,)^.

The tiUers thron^b which a solution of catechin u to be passed^ must
be previonelj washed with hydrochloric acid, because the catechin
would be coloured by tbe presence of iron or of alkalis.

Hydrated catechin obtained as above is rendered anhydrous by
fusion,

Zwenger. Svanherg. I

14 C, „..,,._ B4 .... 60'87 ».,.... 61^36 .... 61-66 I

6H »„ ... 6 ..., 4'35 4 83 ».. 4 72 J

6 0 .^.. 48 ... 3478 >... 33*81 »„ 33-^2 J

C"H«0» 138 .... 100*00 100-00 .„ 100*00 1

lioEnerlc with idlc^lic and ox|heii2oii:: adda,

Decomposkioni. 1. Catechin heated above its melting point, ftwella
np stronglvj gives offinflanimable vapours having a peculiar penetrating
odour like tTiat of burnt horn, and leaves a shining very combustible
charcoal When subjected to dry distillation, it gives off tM^^^m^^^;^

390 PRlMAEy NUCLEUS C^H"; OXYGEN- NUCLEUS C**H«0*,

ami carbonic ox:Mic, and wattr passes orer containing pvr^catodiiD mM
0, volatile oiL (Wackenroder, Z weaker) — Exposed to ifae atr m di|
moist state, it t^kes up ax/geu and gmduany turns brown, with peculitf
qaickoesa m contact with alkaJii, and tben precipitatea a Bolulion d
gelatin . The colonrless eaturaled aqueous solntion scquirea a tf^moo*
yellow colour hy a few hours* eiposuro to the air* ^WackeoMer.l
When a mixture of catecbtti and water is heated in cootjbct with the iif|
a dark red liquid is foruied, which when ev^aporated, learea a ret e»1i-
tinous masSj easily sola bio in water (Svanber^); the solution precipitiU4«
gelatin (EaenUcck), and according to Gutbourt, contains a fabftaaet
intermediate between catechiu and ryblc acid. Catecbin e^tpoted to ikt
air in contact with potash or ammonia takes up oxyg-en and becAmtf^
first rose-coloured, then bright red^ then dark red, and ultiuialeiy blifk,
japoufc acid hein^^ produced; this tran^ormatifjn Is accelettited by heattcf
with excess of alkali* — ^. According to Neubauer, catechin is e^nr«rtc4
by exposure to the air iuto catechutannic acid. When the ethi*r«tJ ftitiMI
of Bombay catechu was repeatedly crystallised from waier^ iImm
remaiuedj after the first crystallisation, a reddish brawn mot}ier4t<|iir
which precipitated a solution of gelatin and appeared therefore t# conlik
catecbntannic acid; the mother-liquors of the following orrnlaltittliMi
were yelbwish, but on exposure to the air and especial ly if erKpanlrii
assumed a reddish colour, and acquired increased power of precipitativfE
a solution of gelatin^ On further evaporating the entire liqaidT it
aaanmed a deep brown colour, like an aqueont extmet of mniibj
catechu^ and when eFaporti^l to dryness, left a residue etx:i4*tly resenibitof
the original catechu. A solution of }>erfcctly pure catechin, whicli doei
not precipitate gelatin, acquires that power hy boiling for several loan:
it is difficult however to render the transformation uniia ooiopht*
(Neubauer.) IT. — The solution of catechin in cold alkaline carboaa;Ui
becomes red when exposed to the air^ a rubate of i]i« alkali bein^ fumifd;
if the liquid be heated^ japonic acid is produced at tfa« sMsm tiat.
(Svanberi^j Zwen^^er, Cooper*) — 3. Catechin dissolves gtmdllilfy a
nioderately strong nttric acid, giving off red fomc«j and fonni m yif^t9
liquid containing oxalic acid. (Ej^enbeckj Waekenroder, T'.w^mfff}^
4» Catechin dissolirea in oil of vitriol, with partial decomfi'
a yellow-brown liquid. (Esenbeck, Zwengor.) The -
heated, assumes a purple colour and ultimately Wcooi^ Ui*L
(Wacken ruder.) T When c»iecbiii is boiled with dilute stihiHuHd mad (t fC «Iil
ritrinl to "li pU. w«ter) a cinaamo Decoloured bodf s«piirftt«». wtikh* «1«f n «ln«i It lli
»fr ftt the ordinary tcmpentturo. containi L^^W^O^^ + 3Aq and |:ivrai9fl' S At «•!»?*
im\ [The Biibstanre dried at 100^ yiddcd 5S-17 p. e. C and S*4^ U («ri^• SS'U C
a»d 5 '21 H), and the quauttty of water given off at IM^ wai 14*4 p« <!.« tli« ttkiMd
quantity ror 3 At. being )4 0 p. r.] Tlie Aoltition Altered froni tWs cnaVMi-
coloured itibstance, after b^mg freed from salphurie add bj ni«ailS of ^at^Mliil
bstr^ta nnd from andeeompos«H catecbin by repeated |>recipita^n wllb tteiiafevtf !■&
does nut contain tugar or anr mb^tanoe capable of redudnf a •olotliMI ol mxitd
copper. Cate^butauntc add boiled with dilute sulpburie acid atto jndidi m biowa ^^

itance appartnlly identiral with that just mentioned. (Nenbatltr*)^^ 5* Tln

aqueous solution of catechin treated witli chlorine, flrsi mmnmrn M viw'
yellow colonr, then decomposes and becomes colourleaa. (WadcvBRiivJ
' — it. Tr gmduuUy reduces the solutions of the noble tDetaU, or imatf^
diately if heat bo applied.

With water, a. ff^nikd Oai^itiH*

CATECIIIN.

391

TjpfH^'*, Whit© ligUt lamiiiar mais, having a fumt silky lustre|
Jfiee^ from a hot-saturated fiolutioo by iflow cooling io slender

"iieedles acuminated at tho ends, and often united in tufta. Melie at a
gentle beat; nt 217°. (Zwenger,) Has a purely as trigont tastej wUb
sweetish aftertaste (Esenbecl;) ; tasteless (Wackenroder) ; bitter and
elji^htly astringent {Zwenger); sweetish (Biichuer). Reddens litmua
eligbtly. (Esenbeck, Dablstrom, Wackearoder.) Neutral te litmus*
(Bobereiner, Zwenger.) A fter drying in vacuo, it contains 3 At water;
ID vacuo over oil of vitriol, 2 At; and at 100°, 1 At. which escapes when

.the substance is melted.

At 100*i Zwtn^cT. Hagen.

14 C. 04 M« 57-14 5S-64 .... 5(1-8S

7 H 7 .... 4*76 5-06 „,. 6*20

7 0 5C .... 3fi-10 36*30 ».. 37'95

C"H«W + A<i... l^? — 100*00 100-00 ,... 100-00

TheetEcess of hydrogen and oxygen in Zwenger'fl aaaJyais of catechin
Jried at 100^ over ibe quantity of hydrogen and oxygon iu anhydrous
BteebiDj ia to the total quantity as 1 : S'H. (L.)

la vacuo over oil qf Httitti* I>elii^

14 C... 84 .... 53-85 ........ 54*23

e H 8 ..., 5*13 5-43

8 0..,.„ 64 .. 4l0i 10*34

CHHW + 2Aq ,.,. 156

100-00

10000

In vacm^
U C 64

g H ^ 9

9 O 72

Cim«0» + 3Aq .... 165

.... 50*91 .*..... 50-90

.... 5-45 5*58

..., 43 64 43-52

100-00

100-00

IT. According to Neuhauor, catechin dried mi lOO*" is anbydrons and
bas the eompoaition C*^H''0''; and, the air-dried compound conta-inji 3 At.
water, the quantity given oflf at 100" being 14-34 p* c, (by calculation,
13 02.)

17 C

9 11 ......

^ 7 0 .......

At 100*.

. 102 ...
, 9 ....
. 56 ....

SVQ% ...

5*39 ...

3353 ...

.... 61 14 .

5*27 .

.... 3359 .

Kewbauer.
ft. e,

... 61*20 .... $1-37 .
... 5 17 .... 5*51 .
... 33*63 .... 3312 .

if.

.. 61 18
.. 5-10
.. 33*72

[ c^m*a^..

. U7 ....

100^00 ...

100*00 .

... 100*00 ,... 100*00 .

». 100*00

I

a nrtd b were prepared from Bomb&f cfltecb!}; a by extriction wiib etber
(methfsd \t P^S^ MB); i by ntrAcitii^ mik boillog water from the residtKi left after
digestioti with cold water (metbod 3, p. 388); e &tid d were prepared from Gambu^
caiteuhUj c by citractton with ethers d hy extraction with witer^ Sec, flccordiog to
Wackenroder'a method (2j p. 388). The namhers in a ore calcnlated from Ibe analjrait
of the hydrated rornpomid (infra). A direct analy^i« of the same preparation whicli
had he^^ome yellow by contirined drjini? at 100", yielded 6262 per wnt. C and 5*24 11,
indicating decompose tioo. Neu ba tier *s anal jsei of the compound dried aI IG0% agree
feri be«rly with Svaaberg's and Zwenger'a inalysci of tbe melt&d cttechm (vid, tn^J.

^ IttO .. go 1134 . U-29 _ %VU ^^[

a from Bombttf catecbn by eatErftdioA wiili esfa«r ; ^, fnMi GA^titf iiiiirii i^J

^. ^t/^ota fa^^^Tft. Hydmted catechm di^salTes in l€CHMIpCV
wAter ftt 5"* (BucLoer), iu 1133 pts. at 17^ (Wackeorodcr), sadia 3«f4
pts. of boiling water (Buchner, W%ckenro4er); the hot ^U^rsted nltlioa
solidifies OD cooliDg ia coDsequeuce of the fieparaiioii af &fmSm
needlce. — Dry catecbin mixed with 2 pis. of cold wat^r Bwelli op
aad forma a tbtck pulp which at SQ" forms a clear solation. (Wiekf«-
roder.)

CatechiQ dtdsolree without deoonipofiitiuti in dilute aatphnrio amt a
heated hydrochloric acid.

Ill tbe dry state it ahsorbs ammotiiaca] gaiS, but girea tt oW compictel?
when heated or \n Tacno. (S van berg* Zweuger) In aqaeotis solutiiat
of aminonia or the fixed alkalie^ it disdolvea witlioni de^umpoisiuott li
Erstj forming % coloiirleaa Hcitud,

In baryta*waterj nme-wsLter, or in acetate of I>aryia or Itme, it im
not form any precipitate, even on addltioo of ammonittr. (Witekenrodcf,
Zwenger.) It fcmi^ with acetate of baiyta. a white precipitate iiijoIdKI^
in water, which gradually tnras brown on exposnre to ilid mlr. ($m>
Wg,)

With bichromate of potash, it forms a yeUow-brttwn precipitili
which^ according to Waekenroder, is not soluble either in Mtaili or ii
hydfochiorio acidj but according to Delffflj diasolTea in bjd
aeid,

CaUeJtin with L^ado^kU, — a. Aqiieooa cateehin forms with
aoetate of Jead, a precipitate which » afier being waabetl with waJer, 1
ita white colour, eren when dried in yacuo. (Uagen )

^H. 2 PbO »...„ , .., . 123'* 60*34 . €? 07

^B 14 C..^.. ,»....„„..„„ » 14-0 *„, 22 60 ■: I

^^ 7 H ««,„.__„™. ... in ,,,, IBS \'^

?0. „,. 560 ■ 1511 .. 1406

C"H*0»,2PbO + HO 370 6 100 00 |Q0 no

h, Aqneoaa catechio forms with neutral acetate of lead, :
whito precipitate whieh Hfterwarda turns reddish (E^enbeek), 4amd
gradually durinf^ washing and turns yellow in contact wit4 iIm Mr;
hence it must be quickly pressed and dried in racuo over oiJ oCT
(Sraoberg.)

1^ PbO *.,, Ill a .... 44 75 „ . .. 45-U

^K C^H'O'.., 13a-0 ... 55-25

^^ C**H*c^.TbO ....... ^4%'* ... idaoe

^^^^^^^^^^ CATEMIN, 393

^. Nenbauer, by treating a moderately warm solution of catechin
with neutral acetate of lead, obtained a nearly white precipitate whicli,
after being wasbed and dried &s quickly as posiible, was found to
_eant»iti:

Aiim', Nmbftiter.

2 PbO ...„»...„.,,. 223-6 .... 67 24 57-44 I

J7 C „.. .„ 102*a „.. 261& __ 2e 26

9 H »»...,.,... 9^0 .... 2*30 _..,.. J '97

7 0 ................ 560 ..» 14-31 14-33

Ci?HW.2PbO ».. 390-6 .„ 10000 ........ 100-00

The compoiuKl it Tcry unsUblf , ti«ccimLa^ broini when dHcd. f ♦

A weak al cob olio solution of catechfn forms with fnrom iuiphaie a
lutlfiil green liquid, without precipitaticm (EseabcLk)- at first there ra
no action; but afterwards the liquid a^suQies a green colour and deposits
black precipitate; on adilin^ acetate of soda, the colourless mixturo
nmediatcly aasuinea a violet-blue colour, find yields a blue-btaek preci-
"^fiitato very soluble iu acetic acid ; an alkatiue solution of catechia
immediately foniis with ferrous sulphate a violet-black precipitate.
(Wackenroder^ Zwenger.) With sulatious of Jennie oxuk it forme a
copious green precipitate, changing to brown; ferric hydrochlorate in
excess acquires at first a dark green colour, but becomes colourless imrae-
diaiely afterwards and yieldi a brown precipitato; if the catechiu is in
excess, the mixture assumes an intense green colour^ but afterwards
becomes colourless from reduction of the ferric oxide, and sometimes
exhibits a greyish green turbidity. (VVackenroder, Zwenger.) — C*/pnc
acetate turns brown when mixed with catechin, but does not yield a
precipitate; on adding ammonia, a dark brown pfecipitate is immediately
formed. A warm solution of catechin immediately forms a precipitate
I which soon turns black. (Svanberg, Zwenger.) The alkaline solution
added to excess of solution of euprlc sulphate, produces a tine green
colour, and after some time a oinnabar-culoured precipitate; if the cate-
chin is in excess, this precipitate is formed immediately. (Wackenroder.)
— With ntercurous nitrate, it forma a copious white precipitate which
after war ds t u rn a grey from red u ct i on ; with j^; ^'J'cw ric n i tra tci a d i n gy w b i te
precipitate which afterwards turns reddish. (Esenbeck.; The precipitate
formed with a mercuric salt dissolves in acetic acid, and on adding
hydrochloric acid to the solutionj a precipitate of calomel is formed. In
a solution of corrosive sublimate, a precipitate is formed which dissolves
in acetic acid or in common salt. (Wackenroder.) — ^ Nitrate of sUver is
not precipitated by solution of catechin; but on lieating or on addition of
ammonia^ a black precipitate is immediately formed, which does not
dissolve in nitric acid or lu ammonia. (Svaoberg.) — C/ihride of gold or
solution of chloride of gold and potassium forms with catechin a red-
brown precipitate, wbicli dissolves with yellow colour in a large quantity
of water. The hot solution reduces the gold. (Esenbeck, Svanberg.)
Chloride of picumum and sodium forms with catechin a yellow liquid
^^which when heated, slowly deposits metallic platinum. (Svanberg.)
^fe Catechin dissolves readily in akokul and ether; in 2 or 3 pts. of boil-
^^ng alcohol; in 120 pts. of cold alcohul; in 7 or 8 pts. of boiling ether
(Buchner); in 5 or 6 pt«. of cold alcohol, in 2 or 3 pts. of boiling aleob

394 PRIMARY NUCLEUS C^^H*" : OXYGEN-NUCLBUS C"U*0».

in 7 or 8 pta. of boiling ether. (WacketiToder,) li diwolTCfl io
a£id but not in oil of turpentine*

Catocbin does not precipitate eolutbti of gelatm unless li h^
with Ixydrocbloric or acetic acid* (Bobereiner*) It does uoi
the vegetable aJkaloida.

Apptndix to Catechin*

Rubic Acid, C»*H«0".

SrANBEBQ. Poff^. 3D, 171; Pham.. Oenh\ ime, 8SS,

^rniatlon. Bj the action of the air on a eoluii on of i

a-^ueoiis alkaline carbonates.

FreparaHon* Catechu is dissolved m aqoeous carboimte of ^
and the liqaid left to e\'aperate in the air without application o'f b«ti
TLe residue is finely pulverised and stirred up with water; th** «oltiti<w
filtered after a short time; the excess of carbonate of potash c&rdi^j
decomposed by acetic acid; the liquid filtered as quickly as posetbU
any rubic acid that may have been precipitated^ and Vbe filttwla
with alcohol, wliich seimrates rnbate of potaiah. This salt is wsafai
alcohol, dissolved in water and mixed with hydrochlone aeidj imi
precipitate is quick ly washed with water, and dried first In vmene
oil of vitriol, afterwards in the drying apparatus.

Changes into japoiiic acid oven during the waablit^ and dtjiif it
vacuo*

Eubate of potash forms with the salts of the earths and hfcrt
metalHc oxides, red precipitates which dissolve parti&llj wben wwM
with water.

n C lOB .,.

5H b ....

Af .„„.. 108 ....

10 O _ ,. BO ..»

35 B8

i-eo

2S-5S

.. 36*04

lOO'OO „».... lOO-OO

Japonic Acid. C"H"0^".

SvA}t&Eii0, Po^- 30, 168; Pharm. Cmir, 183G, 88$,

ForntaUon. By the action of the air on a sol at Ian of
cans tic potash.

Prtp(trati<m. A solution of eatecUin in
tar nod black by exposure to the air, is supertatu

km m

itmt«d wtlki«ltoMU|W

895

¥

evaporated nearly to dr^meas, and the residue is treated with alcohol^ whicti
diseolres acetate of potasli and leaves acid japonate of potash. I'his aalt
]fi washed several times with alcohol, dissolved in water and mixed with
a alight excess of hydrochloric acid, whereby tho japooic acid is preci-
pitated, and only & stnall quantity remaina in t^lation, more however as
the excess of hydrochloric aeid is greater.

Properim. Black, When recently prepared, it dissolves in warm
water and is afterwards deposited in black grains* The solution reddens
litmus^

24 C

8E

10 O

144

8

60

62-07 (il'34

3 45 ., 4 22

34-48 34^14

C^H^O*" 232

100-00 » lOOW

(^ Japonate of potash evaporated to dryness with excess of acetic add,
is converted into an acid ^alt. With the hydroch I orates of haryla, linie^ ,
alnmina, ghicina and yttria, it forms bulky precipitates insoluble in cold
dilute nitric acid* With sulphate of oopper, it forms a dark green]
preeipitato.

Japonaie o/Siivir* a. Add.

24 C ..
f H

TOO ..

144
7

log

42*48

2*06
31-86

£seo

Sviinberf,
. 48-23
. 2*47
. 32 24

C**H'AgO" .. 339 .... 100-00

h, NeutmL By precipitating nitrate of ailv^er with noatral japonate i
of potash. Black precipitatOj which is decomposed hy potash j but sot]
by bydroohlorie acid.

C=^mW. ^ 230

2Ag „„......,..*...„,.... 216

Svtnherg*

51Ii7

4843 ....... 48-22

C*<irAg*OW*_ 440 ... 100*00

Japonic acid is inaolnble In alcohol

396 PRIMARY NUCLEUS C^*W : OXYGEN-NUCLEUS

GaUic Acid.
C'*H*Oi'' = C^*H"0*,O* or C«H«0%0'.

BcHEBLE. (17S50 Opmc. 2, 224.

RiCHTEE. -lV. Ge^efutiimk f/, Ohemie. 1, S2; II, 07*

Trommsdorff, a. Tf\ 8, 105.— A^ Tt\ 2, 142.

Daw, Journal of th Ruyal huiitut ion, 15^273; jI, ^eA/. J, 5€7*

Bouillon Lagrange. Ann^ Chim, GQ, 156; N. GeM. 3, 023,

DoRPFtTBT, Bertiiollet, Proitstj Fernai^i^ez k fioUILLOK La6IUL5G&

A.GthLB. 220.
Ffaff. X ^W*;. 5, 327.
Senturner, SchuK i, 410,
BERZEUua, ^ntk Chim. 94, 303.

Braconnot. Jn». Chim. PA^i. 9, 181; JV'. Ti\ B, 2, 303,
Chevreul. M^m. du. Mu9, 182S. Cah. 11, 37*.
Brooke. Phii, Ann. 6, 1 1 a

DofiEREiN^R. ;?cA(i^. 61, 380; Pharm. CaitK 1831, 204.
Wackknrooer. N. Br. Arch. 28, 14 — /. pr. Chem. 23, 209, — Amn.

Fkarm. 31, IS.^Pkirvi Cmtr, 3 841, 477; 1842, 3 — J; pr, CiWm

24, 33.

Pklouze. Ann Chim, Ph^i, 54, 337; Phami, Ctntr, 1834, 33€.
LlEBTG. Ann, P^iftrm. 10, 176; Pkm-nt, Cetdr, 1854, 746.— ^Jtn. i^iUm.

26, V2B and 162; /^/*am. Ctntr. 1838, 530,
RoBiqcET, y. Pkarfn 22, 487; ./. ;?/■. Vh^m. 81, 125; M^erL $9, 3*;

i*/*am. Crnfr. 1836, 634. — J«H, OAiwt. /^Ay*, 64, 385 and aM;

Phufm. Centr. 1837, 514.
Harff. i^, ^^* ^i-cA. 5, 2$\; Phatvn. CVw/r. 1836, 324.
Bley. N. Br, Arch. 2G, 169; Iham^, Onir. 1841, 619,
LARocqcE. /. Pharm 27, 1!>7 J J. pr, Ckem. 24, 34; Ann

39, 97; -PAai^», C*?ifr. 1841, 716.
Barrf^will. Oompt.rmd, 17, 739; /* pr, CA«in, 30, 370.
STENHouaB, Phil iMag. J. 22, 419; PAarm, Centr, 1343, 225.
Ph. BiJcHNER. jij^w. Pharm. 53j 175 and 349.
Wetherili.. i\^ /, Phinti. 12, 107; J. pr Ch^m. 42, 247; fAi'm

Caitr. 1847.749.
A Stbecker. Attn. Pharm, 90, 328; J. pr, Chem. 62, 434.
W. KNom Plm^m. Ccnir, 1854, 860; 1K55, 657, 737.

i

aei^«iiiu:kiiBj qonUuuiii«t?d however with Unnic add. First prvp«red in thmfmitwtim

Sources, In galUnuta (Sclieele)i in the Sumnrh and I>Mdim C^lm-
house); in tbe gumniy exiicktioD of the ^u much (Feruandei); la (Mmi
I/s^toc^$tUj Fhtret A rnict^, Scntcn Sabaifillce, Badijc IltUd^rl dw ifli
ni^rit B, Chichici atifumndfis. It Ipfcacntnhas and (^rtfm Aufmihtm
tpuriits; in green and black ten, in tlie acorn 8 of Qttenneus |gyyJ^pi (bM
in oak -bark, catechu or kino), in the ^hell of the fruit of Ttrmu^id
Chfbuia, in R. BisioHm, in tlio frait ot Anncardia hryof^iii; ia R S^mfm,
the leaves of Coriaria mfrtifofm, the frint of ^Myrius rim^^nia anJ Bf^
oiisfia f£€fi$a, in Sanda\-^nc»d, \n Lycofus europ.j Lmwt^ lai^i^.

GALLIC ACID.

397

U.

'FuL Uvm ur&i (Kawalier); in l^ad. Plumhaginu europ.; in Acaju-niita
(Vicrra de Mattoa); in the hark of tbe pomegranate root (A. Latour d©
Tri^), m mftngO'Stfcda (Avequin) ; in the fruit of Mima pqradmam
(Boufi^ingauU), in rhubarb-rout (Brandea); in Flore& Amkir^ ^nd Hadise
Sirycknog Nwi^ vomica; and probably in moat of the aetringent parts of
fklants. (HigglnSj Sdnv. 5, 46 )

Formation. From Quereitannic Acid. 1. By boiling with potaab-ley
or diloto aulphnric or hydrochloric acid (Liebig)^ witU simultaneous
formation of a hydrate of carbon (Liebig), of glucose (Stass. Ann. Piiamu
00, 205; Strecker):

»,
¥.

2C«H^O« + 16HO - eCi^H«0»o + C-^H^f3»^
{compare Knop, FAarm, Cmtr. \%hft, 74%,) — 2, By fermentation. (^'J' Tannic

Preparation. K An aq neons infusion of gall-nuts is evaporated to
drynesa; the pulverised retiidue exhausted with absolute alcohol; the
liquid filtered; the greater part of the alcohol removed from the yelJowiah
filtrate; the residue diluted with water; and the liquid evaporated to the
crystallising point. (Richter.) — Thi« process yields but a emalUiuantity
of^gallio acid, and according to Pfaff, contaminated with tannic acid, —
Infusion of ^aU-uut^ is mixed with acetic acid to decompose the gallate
of lime, and then shaken up with ether. There are then formed three
layers, the uppermost containing gallic acid, which may be crystallised
by evaporation (Dobereiner,)

2. An aqueous extract of sumach is precipitated with gelatin; the
filtrate evaporated; the residue exhauated with alcohol; the alcohol
dietilled off; and the residue digested with ether. The ethereal solution
yields an abundant crystallisation of gallic acid which may be rendered
colourless by recrystallisation and treatment with animal charcoal.
(Stenhouse.)^ — -An alcoholic inrusion of gall-nuts is precipitated with
solution of isinglass or white of egg, and digested for a quarter of an
hour; the alcohol removed from the filtrate by distillatiou; and the
residual liquid is boiled with charcoal dust, filtered, clarified with white
of egg, and slowly evaporated; the gallic acid then crystallises from the
brown viscid mother-liquor. (Diirfi'urt,) — ^ According to Trommsdorff,
the acid thus obtained is contamiuated with extractive matter, — BarrueJ
At Th6nard precipitate infusion of gall-nuts with white of egg, filter,
evaporate to dryness, dissolve the residue in water, filter again, and leave
the solution to crystallise by evaporation. — The product is small,
becaUie, as slmwn by lierthollet {A Gtld. 6, 226)* the precipitate
formed by white of egg likewise contains gallic acid, whifst a small
quantity of that acid remains in the liquid, and its crystallisation is very
tunch impeded by the presence of albumen* — Braconnot did not obtain
any crystallised acid by thii procesSj hot an inconsiderahle brown residne;
chiefly consisting of the salts contained in the large quantity of albumen
used tn the pro<ei^s — Gaultier de Claubry {Ann. Chim. Pky&, 10, 235,)
states that he obtained a large quantity t*f gallic acid by precipitating
the infusion with bone- gelatin, evaporating the liquid, and exhausting
the tee i due with alcohol. ~ Infusion of galls is mixed with carbonate of
potaah, whereupon tannin is precipitated iu combination with carbonate

\ pota

3M PRIUAKT NCCLEUa CT^**: OZfaiN-Nl/CLSITS C**ttH>*.

of imiImIi; the iltmtek pndpitelei wttiia^eetal#or \md; ftii4 tbii
ftfecipiute U deeomiiofled witi nlphofic sad. (Rtcliter, S^niu&cr.)-^
[TiesQ m^tbmlfl mre ada|»ted for llio ibtoetkni, but not for ibo prvfAmtiat

Davj botb the infiiiioii ol gmlls willi ^^twnate of bftrfta; fltso tk
iiliitsii'greeii solution of galkte of barjrtii ffoui tli« IhesqIqUo mmftmik
of barjtft irith taanie &cid ancl extnicttvt niaiier } preci^ilotfo 1^
Iwr^ 1^ ntlpburic actd; Bltert; evrnpormteo; dkoolveo Uio iwUm la

ftloolio^ wbkh leoTOi giioi unJisa^jlved ; and i^iei eimpmmJtea 10 ^
Cfyst&Hmog point, --FLedleT (A. Tr. d, 1, 52) digeets fnfosioii of ptti
wtlh hydrmte of dumitiSr wbicb be supposes t4> tuo op l&o teimio ooi
ftnd le^re ibe gallic &cid in tbe H<|iiid to be f^rapomted. BbI, aeoonfiif
to Davj and PfaC a lat^g^ ^aantUj of almntna likewise precipilmtoi lb
gallic acid; and If bjr cbaaoe a portioo of tbe acid retn^iiic in oolnlM, k
oonseqnenoe of tbe quantity of altiniina irot being sulleient lo prectfilolt
It ooDipletel/, tbii portion of acid (according lo D^ry) ei»iitahi« ilomtaa
— ProQflt precipitates infmion of gal la witb solution of protikeUofUe d
Im, remoTe^ tbe tin from the filtrate by sulpburett^ hjdrogett, ui
evaporates. Tbis proce^, accortling to TronimsdoFC, jieldd ottly |^
of gallic ae idf because the free bydrochloric acid e^cerU m d^oamfmm
action, aud also l^ecanae a large portion of tbe gallic acid ti prmpUilw
together with the protoxide of tin.

3. Pure qoerci tannic aeid precipitated by gulphnrio nr bjdroeblm
tad la digested for a d^y with a mi^tnne of 1 pt. oil of vitriol or itivv
bydiocbtoric ncid and S pta. water, tbe water being renewed af tt
eraporatea, and tbe liquid m eraporat^ at a gentle beat la ibo emUl-
li^ng point If strong ackl be mod and the liqaid bdJed, tbs gmllk oeM oblMiii
■maU in qo4tiitf, anil dark eoloQffd. The crjalaU havo but little colovtti
are easily perificd. (Steubouie.) — Liebig precipitated tbe soltttiun d
qnercitannic acid witb salpbarlc acid; add^ the prectpitate. after it Im
teen wiiflied witb dilate sulpburic acid and pressed, to a btitling mtxlin
of ] pt, oil of vitriol and 2 ptf. water a« long m it didsolven cooiBliUh;
and boiU tbe liquid for a few minntee On cooling, it mmmti
strongly coloured ga^llie acid, wbicb must be several ttme^ recfynilBBi
and tben precipiUited from the boiling aqneons ^olutifin bjf itrtll
acetate of lead. Tbe washed prccipUate ia s^spendl^d in water mi
decomposed by snlphuretteil h>^rogen, tbe sulphide of lead extftta| a
deconipoaing action. Wetherill bfdla 50 grmg, of dry tannte add will
500 cubic centimetres of a mixture of solphnric acid ftf sp. gt. 1 81 «itk
four times ita bulk of water, till tbe liquid crystal) bcs on cooling; ^
tbJ5 process lOOgrras. of tannic acid yield Bl gnns* of gaMle add.

4, Tannic acid or infusion of guild h added to an exeeaa of \

— Co&jree ty pouadefl giUi-nut^ freed from the 6 nest powd«>r, are enbii
With water; tbe infuaion evaporate<] to an extract; and ihi« txUwei
added by smull portions to boiling soda-ley of sp. gr. 14 lill tbo fnibiij
ccaaea; the strongly coloured liquid, after being left to eool for a »btk
is gnper^atn rated with acetic acid; tbe brown ctratallino prect p'ttatt i»
rejjcatediy WLiahed with cold water and dissolved In lK>ilin^ water/ tad
tbe solution is treated withaninial charcoal and filtered, Tlte add vitir^

GALLIC ACID*

399

P^fkatates on cooling, has only a brown colon r after soveral recryst^lH-
inoiUi ond cannot be decolorized hj animal charcoal; but on di^solvinj^
it in aleoliolj tbere remains a brown reaitlue, and the solution yields by
evaporation, nearly colourlefis crystals, wbich may be purified by recrys-
tallisatiou. By ttjii procesgj 10 lbs. of gall-nuts yield 12 ojs. of pure
giiUic acid, (Bueliu©r*) Liebij^ and Link dissolve the giillic acid obtained
by treatment with potaah-ley and precipitation with acetic acid, in water
containing just feullitient bydrochlorie acid to remove all the potadi, and
cryetallj»e it repeatedly till tt burns without reeidne on platinum-foiL
In this manner, 100 pt^. of quercitannic acid yield from 5(( to 60 pts, of
gallic acid.

5. One pt. of pounded galls ii digested with 3 pts. of cold water, and
the filtered Liquid m expo#e<l to the air in o\ien vof^aels set in a warm

fflace; it then becomes corered with a film t>f mould which must be
rcquontly removed. After being evaporated to one-half, the liquid \&
decanted from the crystaHino sediment, left to turn mouldy again, <fcc.
The sediineuts consisting of impure gallic acid are washetl with a small
quantity of cold water, then disstdved in hot water, filtered and crystal-
lised. (Scheele.) [This method yields the largest product. J, L.l — Tromras*
dorff boils the sediment together with the mould with alcohol instead of
Wftier^ filters, adds water, and distils otf part of the akohol; white gallio
acid is then dcpos^ited as the liquid coo^s, and brownii^h acid on evaporat-
ing the motlier-liqiior, the total product amounting to f of the weight of
the galls. — Accord iug to Bracounot, the infusion of galls is set aside
for some months in open bottles, the mouldy crust removed, the crystals
aeparated from the liquid by pressuro between linen, and the liquid
evaporated to a syrup: it then deposits an ailditLonal quautitj of gallic
aciA Powder of galls which has been exhausted with boiling water,
when left to itself in the moist state for two months, and then extracted
with hot water, likewise yields a small quantity of gallic acid. 20 lbs.
of galls thus treated yield 5 pts. of impure acid^ and when this impure
acid is dissolved in boiling water, treated with purified animal charcoal,
Eltered (ellagicacid then remaining on theHltcr), cooled, and the remain-
ing mother-Hquor further evaporated and cooled, 4 pts, of the pure acid
ftro obtained. — According to Bracoanot, also, entire gall-nuts con-
tinually moistened with water during a month in summer, swell up,
become covered with mould, and are reduced to a whitish pulp, and
when this pulp is freed from a brownish liquiii by pressure between
linen, boiling water likewise extracts gallic acid from it, A similar
method may be adopteil with powder of galls* — ^Biichner obtained by
Braconnot's process, a yell*jwish white powder, which when treated with
hot water, yielded a turbid liquid running turbid through the filter,
but dissohed in boiling alcohol, with the exception of a residuo probably
consisting of ell»gic acid, and separated therefrom in pure crygiah,
amounting to l^lb. from 10 lbs. of ^alls, (Compare further, Martins,
rfmrm, Cetttr. im], 224; Fr, Miiller, iV. Br. Af-ch., 46, 152). Wittstein
{Vierklg<ikr$chj\ pr, Phat^i. 2, 72) obt^iioed, from Chinese gall-nuts
which had heeu moistened in the powdered state with water and exposed
to the air for 6 weeks at a mmlernte heat, scarcf^ly 17 per cent, of gal lie
&oid; but, after additiim of ordinary gall-nuts or beer-yeast, nearly
50 per cent. — Steer {Witn. ALud. Ber. 22, 249 ^^ Ckem. r/<i^J857, 430)

Eitirs^ up 100 lbs. of the best Turkish gall-nnts pounded as finely as
pussible to a thin paste with water; leaves the mixture to itself f<^r 10

mM Mhm cxtnete dim dt

e^ircnd jmaa m s

liS mO tW gsllic ada bu «pnleA

^hm i%t»iMJ witk dinilW wiltf;

■ tWiiaai tram 100 Il«. oT ^lUoli

&«■ imi^ ieAVt» lli« Uinlttt

— Keat (^i;22. jIm. ^. 34, 9U) ^giUlii
tk ether mad dkillt, attd tliM i»btiiBfti

kj Tmam 4> llatea {J. Pkmrm, 17, ^25) Pr

aaii ii oJrtilaiJ W extntiioa vtii «aier« l^Oin^ witli white af igf^MJ
evapn^g tha 'filtKase: pmlwi, 10 per eeai. (A? eqaia, J. J^kam.
17, i».)

Ta detect Umm wi faeidtaaaie adi ia gallic aeiil, WaektatoJir
(X Br, Af^y iddi ialpliAte af 4|aiaa»% wliii^ ihea prodocea tariuiitf

Pr9p€tUa^ CtTataHlen &MR t!bi hot aqaeooi aolailaa ia ileaiff
white aOkj mtMiUm (Braeoaaat); ia praat WtcMigtEi^ to the doubt v Mem
pffiiMtir vptea. Fig. \m (oP . T . xT . scP « P^ ); et«av«|e
paraliel Id j^ lect d'tstuiel psfmllel ta a; jr ; a=0J'; ^ : r=ia|*
M : »=S4'; p :i=:l«Or; y : a^lir; a : m ahool 150°. (Bmok^
Ann, 9, 119; oHapare Waekearodtr, J, pn Ckemu 2a> 2W; QnM
JUw, tatmL 3, M.) Cobark^s. Hai a faanli, slighllj acid Ia«t4r .~
reddeafl litnitm. Blej (JT. Br. Ard^. 0tf, 169.) GiTea t^ 9'4i p^
(S AL) water at 120. (Pekaae.)

14 C ^.^ S4 ... 49-41 _ 49-19 . „ 4!>l$ 49-^7 .. 49*24 .... 4f^l ^ 49«
leO _^^ «0_47^ 4SS6 47 18^ 4T-0i tJilS 4e-99 I?

c»*H»o«. in ^i»m ^imm . \mm imm loooo , leoo^ _if

Tli« iriii tnalfMd % Eeknue iti<i by li«big vu pivpAird bf & ; ^

fmni cnniAcH by 2 ; 5 from iviiiAfb bf 3 ; «od e from dibidiTi bj 2,

i>K#fapoiMofif, The dry scid carofnlly heated to between f IO*sai
215% gtrcA off pure carbon ie wcui ga^^ anil yields a sitbiimmte ef pm-
gallte aeldy witbout any other prod act:* ^^

CMH*0** - C«H*0* + 2CCP,

it likewise gives off carbo tile acid when quickly heated to 250*;
eaee, boweTer, no pyrogallic acid dubHmea, bat water divtib
mftilgaUic acid remains in the retort. (Pelouie.)

2C^mH)i« - C='H^O» + 4C0" + 4Ba
• Wiitar ud meu^llic acid »re dir«jft furmed iit the

m

GALLIC ACID.

401

f«etweeii 225'' and 23$""^ the acid melts and boils, and, after three bours,
jrields a red-brown masB with ft blackish lustre, ^hidi diesolvee aJnaost
completely in cold water, and precipitateis a solation of gelatine, but not
the vegetable baaes (the ffaiiAumic add of Beneliu*). At a still higher tern-
peratare, the residue con&iits chiefly of metagallic acid, insoluble in water,
bat soluble in alkalis. The decomjifiMtion ib not *o aimple w it is giTcn by Fdouzc ;
water aiid gsUhamic acid ane produced at every stage of tbe dtstiVlation. (Robiquet;
camp. Braconnotj Wackenroder.) [The largest amoiiDt of pyrognllio
acid is obtained by mixing the gallic acid (34 to 36 p*c*) with 2 pts. nf
coarsely pounded pumice-stone^ and beating in a stream of carbonic acid.
J, L.] By rapid distillation there is obtained, in addition to pyrogalHo
acid, a crystalline granular sublimate of a scarlet or brown -red colour,
(Wackenroder,) — 2, Gallic acid burna in the air, leaving a black, com-
btistiblo charcoal. (Scheele.) — 3* Tbe aqueous solution remains unal-
tered if excluded from the air; but in contact with the air, it decomposes,
with fonnaticn of fungi and a black humus-like substance. (Pelouae,) —
4. Gallic acid remains unaltered in contact with alkali s, fio long as no
oxygen gas conies in contact with it. but in contact with oxygen, it
decomposee, the more quickly and strongly as the alkalies are in greater
€xces.% proliably because these bodies have but little affinity for gallic
acid and rather dis[»ose its constituents to arrange themselves, under the
mHuence of tbe absorbed oxygen^ in the form of other compounds, such
ae humus, carbonic acid, and perhaps also acetic acid; the peculiar colours
produced at the same time are due to the foimation of one or mora
coloured products of decomposition not yet investi gated, — The tints
thus produced are : with a ^mali quantity of ammo^ntij : yellow; with a
large quantity, re4 brown; with a small quantity of pota^: green, after
a while; with a large quantity: first yellow, then re<i and brown; with a
small quantity of baryta- waiter: reddish yellow; with a large quantity:
blue with greenish blue flakes; with a small quantity of il/wtt^ia* water:
pale yellow; with a larire quantity; greenish blue with blue flakes; with
i^ small quantity of /m^-waterr reddish yellow; with a large quantity;
violet-green with flakes of similar colour, (Gm, 4 Anfl. ii* 164.) — Caustic
fioda acts with aqueous gallic acid in the same way as caustic potash ;
carbonate of potash acts m a similar manner, but more slowly (Biichner;
see also Wacken ruder, S. Br. ArcL 27, 257.) When Schecle*s gallic
acid is added to thoroughly boiled lime-water standing over mercury,
white flakes are formed, and with a larger quantity of the acid, a pale
red solution; oxygen gas passed ap to tbe etolution is quickly absorbed,
the liquid assuming a greenish blue colour; if hydrochloric acid be then
introduced, no carbonic acid is evolved, perhaps on account of the great
dilution, but light blue flakes are separated, (Gm.) According to Chev-
reul {Dia. dt& Sc. naL tO, 530, and Metn. dm Mm. 1825, 374,) oxygen
g^^ is absorbed the more quickly and abundantly, the more the alkali is
m excess; 0*2 grm, of gallic acid mixed with a small quantity of aqueous
potash absorb in a quarter of an hour, 7*5 cub. cent.; in 15 hours, 14*5
cub, cent, of oxygon gas, and produce 10 cub. cent* of carbonic acid gas,
which may he expelled by hydrochloric acid. U 2 grm. of gallic acid
mixed with a larger quantity of potash, absorb 10 cub. cent. ; if more
potash bo added, 14*5 cub, cent.; and, on a still further addition of potash,
more oxygen is absorbed, in all, 5S cub. centimetres of oxygen gas;
similar etfects arc produced by baryta added in vaHons quantities.
When aqueous gallic acid baf turned green by tbe action of a small

Iuantity of alkali and air, it is not coloured red by a larger qoautity qt
VOL- XIL "i t>

402 PRIMARY NUCLEUS C'^HW ; OXYGEN-NUCLEUS C"B«0*,

alkaH nal^s it can absorb more oxygen; the green matter U tHerelbil
difierent from tbe red (which ia produced bj the fbction of m l^rgm
quantity of o^iygen ) Baryta- water oeutralised with Beheele's mcid m
oolonred green by oxygen gus; if iho baryta be then precipitated by la
exactly ecjaLvalent quantity of aulpharic acid, the green Bltrate yielfli M
evaporation a very acid and harsh- tasting reaidue, which predpitalM
gelatin J ia free from eulphuric acid, and dissolves in wat^r, alcohol UM
ether. Hence Cbevreul concludes that tnunin is formed in this dea^M
position of gallic acid; but the tannin doubtie^a existed ready formed ii
the gallic acid which he used, — According to Dbbereiaer, 100 pte. m
gtkllic acid abiorb 29 pte, of oxygen gaa, (Gitb. 72, 203, — Whou i
mixture of gallic acid and alkali which has been exposed to tbe air^ ii
distilled with dilute sulpburic acid^ acetic acid p^i^ed over. (Bouilln
Lagrange.) — 5. Gallic acid mixed with exceaa of bicarbonate of Mnd
and exposed to the air, forma a blaisb liquid which ultimately n^unies w
indigo colour and form^ after some time a small quantity of greeniJi
blue jdcdiment, When gallic acid ia heated with exeeas of bicarboiiiUI
of lime, carbonate of lime is precipitated, and the liquid, colourbs^ at fitf^
ass times a dark blue colour, and yieldi dark blue flakes on addition ol
alcohol or ether-aloohoL The indigo-coloured solution a^isnnies a m
aniethyst-red colour when treated with acids, but becomes blue again m
being neutrilised with lime. — This product of the d&compoftitioii m
gall 10 acid is called by Wackenroder, gilkrythrok ^li, and by BerseUafl
ajfinogaU'w acid. It is also produced when gal late of baryta ti^ros bJH
by exposure to the air. I

0. Gallic acid is dccompoaed by ekhvinf* {Proust ) Cb1orine*watii
forma with aqueoua galUc acid, a light yellow liquid which after a wbiU
beoomes brownish yellow^ then decomposes completely and beeoiM
iKilourleea, ("WackcnroderO — Qallate of potaab ii violently aitaekil
by bromine and yieMs a brownish rcsin^ {Cahonrs, JV. Ann. Chim. I*hm
19, .'iO?.) — 7' i\^iim dcirf heated with gallic acid forma oxalic acid. -^
8, It ig very quickly oxidised by i&dic aci<L (Millon.) — 9, Aqtieoui
gallic acid mixed with bichromiU o/ poi^ijsh immediately turns browirj
and grasbmlly deposits hrowri flakes insoluble in hydrochloric add.

10. When it is quickly heated with oil of vih*ioif pyrogillie
enblimcj, together with a small quantity of yellowish red fli
insoluble in water. A mixture of 1 pt. gallic acid and 5 ptA. oii of
Titriol oare fully heated to 14 U^ becomes first vellow-bn^wu, than wte-
coloured, and ultimately deirk wtne-red ; it then contains dligtc tad
rufigallic acids. (Braconnot, RobiqueL)

lU When gallic acid is boiled down with a solution of 2 pt& oblMidl
of calcium in 5 pts. of water, carbonic acid ii cuntinuoutily giireA Iff^
anil when the liquid attains a temp<vrature of 120' or 132^ a <>a|
yellowish white precipitate ia formed consisting of small polvi
crystals. Tbe precipitate h washed wiib hydrochloric acid aei diei
with alcohol, pressed between paper and drieti at a temperaturv
25"" and 00"; it tastes like chloride of calcium, with an aftrj
gallic acid, reddens nioi«}t litmus paper, and imparts a jterminonl
stain to moist paper at the point of contact. After bring dried at
does not give off water at any temperature up to 1,30'. Immeraod
irater the cryiiftat^ become opaque, give up ehloride of calcium
with a «m»ll ouantity of gallic acid, and yield a pulpy mai
when collected on a filter, exhibit^j Iho projjertiei of nnaltt-r^il giffi"
acid. Tbe crystal^ when carefully heated, yield, first a hamh

queoui
hrowirj i

fliatttfH
nil d^

3

OAl^LIC AQW.

403

%i[iiid containing a lartife quantity of hydrocblorlc acid, and tHeo rosa-
coloured vapours, which condenae to a traneparent liqaid con tain iQg
water, kydrocbioric acid, nnd a very changeable red siibatanc©, wbioh
lziipaTi£» lo coUoQ a red, or, after impregnation with bsisic mordantSi a
yigIqI colour* The reiidye contaitia char(*oal, and when treated with
water, yields a mijcture of lime and chloride of calcium. Subjected to
4ry disldlation* it yields pyrotfallic acid, (Robiquet,) — When a decoo-
iioa of gall-nuts la precipitated with chloride of calcium and the preci-
pitate is exposed to the air for .several months, It hecomes brown Uh
Macic and deposits a powder, oo which fihiuing crystals resembling
boracic acid collect. These crystals are permanent in the air; dieijolve
jreadily in water and alcoholj melt when heated; then turn brown -blacky
«well up and take fire, emitting an empyreumatfc odour; give off hydro-
chloric acid wheu heated with oil of vitriol; and when dissolved ia water
and mixed with hydrochluric acid, deposit a white powder, which
behaves like ellagic acid nn<l funua a yellowish white precipitate witb
protosulphate of iron. (Hiinefeldt, J. pr, Chniu 7, 232 J

12. Gallic acid reduces/rrrtc gaits, and forms with the resulting ferroao-
ferric oxide a bl:*ck-blue compound. (Chevreul, Pog^. J 7, IT^O When an
alcoholic ^olutiua of gallic acid is mixed with an alcoholic solution of dry
ferric; ^aulphate and heated to between Qif and TO"*, the li*[uid assumes a
£ne blue colour, and deposita ferrous sulphate together with resinous
drops which solidify on cooling, (Persoz, Compt. remL 17, 1064;
liicbner,) Gallic acid, or an alkaline ga 1 la te, forms with excess of ferric
jydrochlorate, first a blue- black precipitate, which imruediately redis-
Dives with greenish colour, while the gallic acid is decomposed; if the
ilicacid is in excess, the precipitate likewise disappears, and the whole
the ferric chloride ia reduced, (Wackenrodor.) When gallic acid is
owly dropped into excess of ferric sulphate, no colouring is produced
* only a transient blue tint; in a solution of ferric oxide mixed with
bloriue, no blue colour is produced oven by an excesa of gallic acid.
V'ben a ferric Bait is added to exceas of gallic acid^ and the mixture is
reated with neutral acetate of lea^l, a bine precipitate is formed, irhich
iflsolves In oxalic add, forming a colonrleas solution; the solution contaioa
E>tb 8e»quioxide and protoxide of iron. The blue colour is restored by
letal© of soda. (Barreswil, Oompt rend. I7j 739.) In a solution of
rne chloride mixed with ferricyauide of potassium, the smallest quan-
bty of gallic acid produces pruseian blue, (Wackenrodor, A^ Br. iL*cA.
7t 26J).) — Ferric acetate, or a mixture of ferric hydrochlcimto and
oetato of soda, forms with the Bmalleai quantity of gallic acid, a blue*
lack precipitate soluble in a lar^^e excess of acetic acid; the liquid
BTnains hiue black and transpareut.^ — An alkaline gallate in excess
wms with ferric hydrochlorate a blue*black liquid in which common
bit or acetate of soda produces a precipitate which dissolves in pota^'^h^
orming a brown -red aolutlon,^ — A solution of ferrous sulphate free from
irric salt U not coloured by gallic acid at first; but on exposure to the
tir* the mixture gradually assumes an azure-blue colour, and after 12
liours, a blacK^hlue precipitate separates, the liquid retaining its blue
lolour. If the solution of ferrous feulphate [s mixed with a small quan-
ity of caustic alkali, alkaline carbonate or bicarbonate of lime, it
^mediately acquires an azure -blue cotrtur on atldition of gallic acid, and
^rwards yields a precipitate soluble in acetic acid. — A aolutioii of
ferrous sulphate mixed with acetate of soda is immediately coloured

2d2

Gaud iaaDT M H

ttf

r ^ wlpfcam mmL — If mAm^^om M-
H to tfia. of rater w« treated ii ii

i<iM,M4 ilftyM- to mnmm ^ mtm

.—Tbe Goifmtm mm £tM.
(Miftfal) C>*li>ll>0», M«r

T, S or 10 At. of m tiM» to 4f At C-

la
LtWftiraadI
6ce mMT this deoMipociiitm do«« ■«! life

I rf tk mSkaSm tbt iS9 •oliiVle m wslfr.

— 1. Mijdmicd gmllie aol

. tti^v^ to »Ufmlioo« into a

yeotol; lad ihm eepsntej ^ ii

tli<r tmmllBii pMiUi

jcT Mfii^ wain; vfceMe it errnaniMt oo eooliagL (Bndttii:)

nm wM pwywwl W (1) ii a wbita mwder vilfa a vBiht liifi d

gmjkh ;«IWw. CLiel4) It eff»nM fi«i ik« ai^atoiiir .olliiSt k

eonbtMlioa witli wmtir of ctjiteUMaliafi. (tMiattgi,) Bf t^^

' Sl»4«r i^^oa«l pnmm. Tbe soIqUob kms a ^7o» a^il mifllioa^n

> ioat not gtFa wMmmj ikm^ at 100*. (Bidiaer).

•

»• C»«B*0«»O>, tMl

ri»crii,««

m UALLIC ACID. fdll

^^^^cl^

" Liebig
& Olto.

Cryif^UUed, Bucbner.

i c „.... S4 ..

N U ..

. 44-92 ... 4616
. 7-49

„ 4-81 .... 4 "82
.. 42^78

14 C ....... 84 ... 40^97 .,.. 40^95

N 14 .... 6"85

tH 9 „

11 H 11 .... 5"36 .... 5-38

10 0 .»........_ eo ..

UO 96 .... 46-82

?»H*(NM*)CP 187 ..

. 100-00

* 2Aq .... 205 ... 100 00

Wheo immersed in acjaeous ammonia and in contact with the ait, it
idually tarns red and ultimately brown. Hence it oanuot be prepared
5j saturating hjdmted or aqu^ona gallic add wftL ammonia. (Rubiquet.)*
— If the alcohol used in the prepara-tinn (2) contains a little water, the'
liqntd saturated with ammonia decomposea in contact with the air just
like the aqneoas solution. (BQchner.)

Gallate of Potash, — 1. When an alcoholic solution of gallic acid U
mixed with alcuholk potash^ a white precipitate is im mediately furmcdj
which at first rediesolves in the liquid. If potash be added till the
surface of the liquid becomes covered with ^reen veina which do not
disappear on stirrinf^, soft white flakes separate ont> which may be
freed from oxcesis of gallic acid by washing with alcohol and dried
at a gentle heat. If the slightest escesa of potaah be added, the
liquid acquires a dark green colour, and the colourlaaa ealt at fir^t
obtained aoott becomes dark green and greasy. ^ — The m\i cannot be pre-
pftred w i th aq neo us iol u ti o n s .

2* Quercitannic acid is added by small portiona to boiling potaah-ley
of ep, gr. 1*30, as long aa brisk effervescence ensuea; the liquid, after
boiling fur some time is saturated with acetic acid* and the gallate of
potash which crystal Usca on cooling is washed with a amall quantity of
water, repeatedly boiled with alcohol j and obtained nearly colourleaa by
recrystnllifeation with addition of animal charcoal. (Buchner.)

White crystal line powder, soft and loose after trituration; the acid
obtained by 2, ia slightly brownish. By continued exposure to the air
it becomes covered with a greenish film, but ia not perceptibly decern-
posted. Does not give off any water at 100^ It disaolvea very readily
in water with alight brown colour; the aolutiou has a strong acid ruc-
tion, and if concentrated, deposits the ealt in slightly brownish needier
on addi ti QD o f al cob o t (Buchner.)

2 KO 94^4

42 C .„.. --. 252*0

IS H . ," 18'0

30 O »P. ...» 240 0

2CWH*KOW» + C»*HW^ + 2Aq . 604-4

BUohner.

(1) (2)

15-61 .,

., 15-29 .... 15-46

41 '69 ..

.. 41*65 ..., 4208

2-78 .

.. 3-24 .... 3-lfl

39-92 .,

,. 39-82 ... 39-28

lOO'OO

100-00

100-00

I

GalhU nf Soda. — Prepared like the potaah-salt. I . — White granular
crystal line ijowder, easily arduble in water; the solution saturated while
hot yields needle-shaped lam i nee on cooling. The salt gives off 22 03 p. c,
(6 At.) water at 100°. With aqueous alkalis it behaves like the
potash salt. (Biichner.)

PUMAiT TOCLEtS O^H«; OXTOEK-NUCLILS C^H^O*

N«0 ,. 31

5 U ____ &

1614 ,. l6to

43'7& » 43 13

2 60 „ 2 90

37*51 _,_ 3r»7

C«H*>*0«' _ 192

100 00

10000

^iry<4._ Fiee gdlie aoid and gall&ta of iod» ^

U, With bfixyta water not in excc^, of vilJi «
iTiLlNfn of clilorido of bar i unit gallic aci J forms a etmtm
wiaim pffBcipitilfft, which igaicklj tuma blue in cont^^t wttli the air.—

procipitated carbonate of bsirjria b added to a h6i%
ai|iieoti3 at^lotion of gmili<i aeid, bm long aa e0«rraeac»
canc% ftsii th« wxtore b dilnted with a largQ qaantitj of watar md
k&Sbi^ ^bm pak ^«ll«w filtiaU deposiu on evaporation, ^l^nder ae«^
wUek iiiwfH HI ^nuali^ till near!/ all the wuter is evaporatai
win te KfiM ifpMiiiiii hot fliMi ^ tirjaUk b UA to cool, oo more uji^i
a^an^tt^ Ml^eaftk lelk to cnponle^*on1aiieoii«lT, aalt id effl<Mt«ccttcBap^
^rvL tht czTttals ar« feeed from the mother-liquar, wa^^ wt^
lloiM, sad fmieklj dfied. — Sleader need tee, apparently bdonfiaf H
At tMCBjLttMf vyaleikL While with a hrowniah trnce oq thif mIm^

hig%ttMl mIeikL While with a hrowniafa imge ou thif ituiM^
» Ml tm df «■▼ water at 100% lint beoomea dimeitH to dkaolrf il

r in aleoboL

ft.0
HC —

$€••

ti 0

2rf5

il 7fr

B*t2

M'2S

BUdhner.

.*- si-ii

3*31

a«SaEiH>>> ^ Hf — l^-«

tOOHM

100-00

_ Gallic add seta apoQ atrontl^-aalta io (hi

«« liafjtanalta. GmUata of $troQti& la prepared ift tk

la lb» Wjtft^it but the fiolaliin luaM be eTap<tfil«^

WiiH cm^K mora «>Inble in wmiiccr than Ik

[WiBM aa^on leddena litnnta Tbe mIi ir|0

lit^ jofla mC gm off wmter^ bnl is af^erwar^ diiniH l«

ia YioIeC. In^olable In alctolioL (Buehosi^)

ii

Ml

20 7t

•^ 3*71

C«W^rO» ^ «M — ***

(afiA with eUoride ol eakiMi

A emtallmr aalt ia ateMtf

of line, na in ika]

»tk m^ cscppii^f thai oo wmler ia ^Mti^
irtoaiTf of ttae^ — ^^^Q ^e jrallov crafts w^
k at Iff » t^ i^ «lo«> >^ gtto or walcf, ^

GAtUC Acm.

407

becomes difficuh to dmahe in water. From the aqueona solution, alcohol

I throws down white flakee wh^ch beconio bluish green by expoaure to

the air.

CuO

14 C .....,,...

8 H ....„...„,

28 .

., 84 .

......... 8 .

.. 12 97 ..
... 38-89 ..,
... 370 ...
., 44*44 „

BUchser.

...... n-m

3B62

379

12 O ,.,

96 ..

...... 44-50

Ci^H*CiiO^" + 3Aq

216 ..

... 100*00 ..

..... too 00

Gallate of Magnema* — a. B^m. Caicitied ma^eefa immersed id an
aneous solution of i^alHc acid, abstracts all the acidj so that a solution
r forric oxide afterwards added indicates scarcely a trace of gallic
oxide.

6* TrUm^ie, — Magnesia stirred up with water ia added to a boiling
alation of gallic acid, till the acid reaction ie very nearly neutralised,
r more magt^eaia be «dded than b required for comptet« neutral isation, the liqaid
ecoQiej grei?iir It must then be decntited and boiled with a small qnnntitr of fallic acid
nJntion, which takes away the green colour. Tbe filtered liquid m evaporated.
ind the residue is freed from excess of acid by alcohol. Yellowisb or
^rownish wbitej heavy^ slippery to the touch. (Biichner.)

3 MgO ........

14 C

... 60 .
... 64 .
... 9 ,
.. 104 .

... 23-35 „,
.,. 32-68 ...
... 3-50 ...
... 40-47 ...

BUrbner.

23'S3

32-20

9H..„, .,.

13 O

..... 3-48
.... 40-49

*''■"*' " **^'

C^^H'Mg'Oi''

+ 6Aq „

. 25? ..

.. lOOOO ..

..... 100 00

c. Magnoiiia is added in a boiling solution of gallic acid in such quantity
to leave the liquid still strongly acid. (Buchner,)

8MgO

42 C ,

m H „.

....f... **..»H"«w*M« ***•"•

1^0 „

252 ..

26 „

.. 2205
.. 5i7I ,
.. 3 58
., 39-68

BUehaer,
.... 21-90
,. 34-n

.... 3-61

38 0.„. ,

-— -* *»

wa ..

,, 3978

2C**H"Mg*0»" + C**H*Mg*0" ¥ IGAq ,. 726 ,... 1 00^00 .... 100*00

d. Recently precipitatetS carbonate of magnesia added to n boiling
Dlotion of gallic acid diasolvea at first ; but when a larger quantity is
Ided, the liquid becomes turbid and deposits a Leavy powder baviug
tarcely any crystalline character. If the carbonate of niagneeia be
Ided in small poriions. as long as eflerveacence ensues, the liquid then
ecanted, and the precipitate boiled with aqucons gallio acid, it becomes
eHowtab white after pressing auil drying, and dkaolves in hydrochloric
eid witLout giving off carbonic acid. (Biichner.)

7MgO
42 C ......

25 B .

37 O

Bllcbner.

140 ..

252 ..

25 ..

266 ..

,. 2049

.. 36 89

3*66

.. 3896

.... 19*61
„„ 35*10
„.. 3-65

.... 41-04

C"H»Jlg»0» + WC^Um^^^ 4- l4Aq.„ 683 .... 10000 .... 100 00

•"i^ . li: ~:-

r- . ■ i- •

1^ : .' .' 1 r: i:

V -^ ••' rvii' *■ -

v.* •':'. •■

l.-..i:;t.

T .' L

il ^4

3]:j

--^

51 '.i-

wi*'

22 0

- r*^

■»»f",

■*72 •'

.W J! .

:.M!

GALLIC ACID»

409

Galhte of Afit%mf>np, — Tartar emetic formB with gallic acid, or an
fclkaline gallute, a wljite«HgbtljcrystaUiue precipilate* The precipitate
obtained with free g-allic acid ia permanent in the air after waishing ond
Irjing, insoluble in water^ and containa 43^21 p. c. Sb^O^, 29*04 C and

"1-92H; it iadierefor«5C^*H*0^",4Sb'0^ + (JHO. (Biicbner.) When ignited
out of contact with the air, it yields a black pyrophoric mass* (Bottger,

"Td/n 2. 4L)

Gnllate of Bkmuih. — A solution of maguterium bumuihi in a large
quantity of acetic and a little nitric acid, forme with exce^ of gallic acid,
, yellowish precipitate, which, when dried at 100"^, containjs 51 42 p. c,
&roj[ide of bismuth. (The formula CJ*H*Q»,Bi03 + 7Aq requires 51'41 p.c.)
31ey,)

GallaU of Elne. — An alkaline gallate is mixed with the eolation of a
piQc ^alt, or free gallic acid is added to an eatceee nf ncetate of zinc; and
lie white bulky precipitate, which becomes more crystalline after a while,
waehed and then dried at 100^ Pale grey, insoluble in water and in
Icohct, (BiichDer.)

4 ZnO... 162

14 C ,..„. ._ 84

4 H ,„,.„ 4

ft O «.»... 64

BUchneri.

51-59 50*74

26*75 ..,...., 26'25

1*27 .,. 1-24

20^39 2177

C'*H*Zti«Oi^2ZnO ........ 314

10000

100-00

Aqoeons gallic acid digested with recently precipitated hydrated
..xid^ of ^inc diestdvea but little of that Eubstance; the yellowisli green
[fquid yields on cooling silky needles of a zinc-ealt. The mother-ljquor
Contains free galUc acid. (Bley.)

Stamwus Gall ate, — When ammonia is added to a solution of proto-
bloride of tin till a permanent precipitate forms, and the liquid is then
nixed with excess of gallic acid, a white finely divided cryaialtine preci-
pitate ig produced, wbich after drying forms a ubite light powder, iDsolablo
water. (It is not produced in an acid solution.) (Bucbuor.)

Btlchner*

4SnO..... 268 .... 63*81 6E'10

14C,„ ...... B4 .... 20-00 ,.. 19-80

4 H. ......_ 4 .... 0 95 ...... 125

BO. 64 ... 15-24 16*85

C^<H^Sn30»2SnO*., 420 ... 10000 10000

Bley, by mixing protochloride of tin with gallate of soda, obtained a
recipitate containing 55*51 p c* SnO*

Gallate of Lead. a. Qttadribaeic. — Obtained by dropping aqueous
gallic acid into an excess of a boiling solution of neutral acetate of lead.

I The precipitate, which is white and flocculent at first, but becomes light
yellow and crystalline on boiling, is washed by decantaiion and dried at

^^ 120^ (Liebig, Biichner, Streckei-)

410 PRrMARY NUCLEUS 0*W'i OXYOKK-NUCLEUS C'-H'O'^

4 PbO

14 C ...

3 H „.,

Licbig,

BU«hner.

Streelcf.

44?-i ..

.. r5'74 .

7009

,... 7646

. . 7603

84-0 ..,

,. li'25 ,

.».» 14 52

..„ 1412

.„ 14-39

3-0 ,.

.. 0-51 .

..,» 053

*.. O'SO

.«, 64$

56*0 ..» &-50 .

.... 8*76

... 8*S3

„. tl5

C«ii'Pb50i%PbO .... &P0'2 .,,, 160 00 _,,... 106*00 .. 100-60 _. 100*00
AccQrajiig to Liebigj it is C^^U^Pb^O^^, whkh reqaires 76*90 p. c> axid« of letd.

B. Bihmic, — OLtAined bj adding neutral ucetate of lead to an exoeoi j
of warm oque lus gallic acid. Tbe precipitate, if left Id the lit^uid, gradii-]
ally changes to a grey shining cryetaJline powder. (Liebig, Biicnner.)
Gives ott I At. water between lOQ^ aaJ 160\ {Liebig, Biicliner.) In the
fre^h state it dissolves readily in strong acetic acid- (Buchner,) Wben
touched with burning bodies^ it glows like tiuder^ and^ aXtex carbon isatiou
yields a pyrophorus. (Bottger.)

2 PbO .„ » «.,

....... J23-e »

^».. 84-0 .

...MM 5*0

.. 58*13 ..
.. 21 'B4 ...
.. 1-30 .„
.. 18*73 ...

Lieblg.

57'96

21^66

..... 1-70
..... 18-08

BuebDei-.
57-75

14 C „»

4 H ...........

..„ 21 82
1-47

0 0

, 72*0 »

18^6 1

Ci^H^Py'O"* + aAq

i .... 384^S .

.. 160-60 ...

.... 160*00

100-00

QMatt of Its>n {p- -iOS). The compound of gallic acid with f€jTOi(K
ferric oxide is obtained of the finest blue colon r by adding ^llic acid t^
a mixture of 0 At. ferrous salt to 2 At ferric salt. The oxide contained
in it is therefore 3FeO, 2Fo*0', corresponding to ordinary prussiao bbr.
(Barreawil, Compt. reitd. \7, 739.)

Gallic acid forms with cuprk oxide a flesh -coloured precipitiio

soluble in excess of gallic acid : it dissolves also in carbrnate of potitlif

i forming a grass-green solution, (Fr* Miiller, iV'. Br, Arch, 0S, 120,)

lAfNlorailig to Bley, the brown-red precipitate which is fomied on adding

• meefaito of copper to excess of gallic acid^ contaios 47'50 p. c. CuQ| hat

if the copper-salt is in excess, it contains 50 05 p,a CuO (compm lAU),

^ Gallah; of Cobalt. — a. Polijham, — Oxide of €olmIt extimeta
acid fnim its aqueous solution, — 5. Bmic. — Obtained by w
hydra ted protoxide of cobalt to a boiling aolution of gallic acid in sucl
quantity as to leave the liquid still distinctly acid. Tbe salt when diy
Las a dark blnish red colour. It is permanent in the air. (Buehner.)

10 CoO

42 C . .,
20 H _,

32 O ....

20
250

41-50

27 ^8S

2-21

28-32

BUi'hueri
. 41*61

- t7-»i

» 8*24
. 28-16

CoO,SC»*H«(VO« + llAq .. 904 .... 100*00 „.,.„ 100 06

e. Bvbasic, — When an aqueous solution of acet&te of cobalt il
evaporated ot€t tbe water- bath with excess of gallic acid, » light cnniioi
powder i^eparates^ inerrasitig in quantity ns the acetic acid erapoimliii
This powder is washed with water and dried over nil of ritrioj. WIma
dried at 100% it becomes continually darker in oolonr mtA loaot wtlflit*
(Biiehner; <»(op. fikj.)

G\LLIC ACID-

411

2 CoO ,„,. , ..„ 75 2 .... afi74

14 C „^„ 840 .,., 29^S7

10 H ... ,.,„ 10 0 .„. 3 56

1-1 O ,„_...... 112^0 .,.. 39*83

BUrhiier.

. 29-69
. 3-5 1

CMiPCiTO"' + 6Aq,... 281-2

100-00

Gallate ^fI^"^ickeL — a. Baste, — Wbau hydmte or carbonate of nickel
1 added to a boiling aqueous aolutiou of galiic ncld, various basic coin-
ctnuds are formed, according as the liquid remains more or less acid. If
Eie liquid 18 still strongly acid, a dart green Leavj powder la obtained^
—sy to the touch. (Bilcbner, ^omp. Bkj.)

8NiO .„..„,„ .„.. .....*«*, «* 300 a

42 C ._..._ 252*0

26 H „ _. ,. 26-0

38 O ..,.. 304-0

34*08 ,.„.... 33*65

2B54 ....... 27-a3

2-94 3-04

34^44 35*38

2Ci*H^NiW^ + Ci*H*Ni=0*« + 16Aq .... 882-8 .... 100-00

100*00

h, 1. The acid filtrata of a yieldi, after evaporation to dryness and
^traciioQ of tbe free gallic acid by atcodol, a coarse browo-green
Dwder. — 2. When acetate of nickel is boiled with excess of giiWic acid,
Ugbt green powder ia preoipitated, permanent iD the air. (Biicbner.)

Meiruroua Galhie, — Mereurous oxide forma with a hot aqueous
^ solution of gallic acidj a heavy white powder. (Harff.)
^^k h. Mercurous nitrate forms with gallic acid or an alkaline galUte^ a
^B^liiie precipitate which becomea yellowish during wa^^hing and drying.
^■l dissolvea in strong nitric acid, and is not decomposed Ly boiling with

r

1 n^O „..,....„ «-„, 145'#

3C'*a«0»... 51*0

74-00 .„..
26*94

Hftrf.
7376

3EC"H"Bi»0** + C"H*Hg»0^'' + 7Aq .... 196*6 ... lOOOO

M^rcurk Gallate, — Obtained by mixing mercuric nitrate with gallio
acid or an alkaline gallate. It is red at Brst^ but after washing and dry-
'ug forma a ruat^coloured powder. It diaeolrea in nitric and In hydro-
bTorio acid.

8 HgO „ 864

3 C^HSO*" * &101

4 HO ......,......._......... ..,.. 36/

61-38

38 62

60*72

2C^*H»Hg3o»" + C^*H^Hr^^** + l2Aq „. 14 1 0 .... 100-00

Amfmnio-fnercaroui Gallate. — Mercnrous gallate forms with ammonia
> black insoluble powdericontaiuiug 87 71 p* c. tn^rcuroue oxide* (^HarC)

Ammonm-mercmic GallaU, — Dark grey powder containing 73*se p. c
mercuric oxide. (Harfi.)

6l^«i off 10*^ |bC

eryiteli* kii
lidia „

(IMS.) .tem. i^krm. S3, tTI.

i ^/^mwmmmm mmmi wmi tk

4^3

k girm rin to otMiAa^rmble trdalMia il
fat oliOifeed bjr «9«|>ot«tioii o?0f tUmltf^

|i«ftl^ it wisk ftiwklj Ika 4lMilr«d in wmtmr, ibI^^ witJi icetic tf4
ftoJ pit^ipfMid % »e«lnl««W« of lei«i, which t^mvi dows « ti^

CREUDONIC ACID.

413

5 PbO,. ..,,..„. 559

36 G „„«. .«.»»„. „ 216

11 M ,,... .„.- U

17 O 136

Biicbner*

60'e4 „. b9-m

2341 ..,<... 22-86
I 19 ........ 1-34

U75 **.. - 15*81

3Ci3H'PfaO*.2(FbO,HO)...... 922 .... 100-00 100.00

The calculation is thAt gwen by GeHtardt (TVai//, 3, 876) ; Bucbner fiTc* the
armuia C>*H^0^2PbO.

Chelidonic Acid.

Pbobst. (18380 jifin. Fharm. 29. 116.— P/^im. C<?nfn 1839, 209,
Lehch. ^wti. Warjw. 57, 273. — Xpn Chem. 38. 180, 19L — Fharm,

CmU\ 1846, 449.
10TSTEIN. N. Br. Arch. 05, 23.

Sofircei. In all parts of tbe CMidonhtm majm, m gmall quantity, aseo-
plated with malic acid and another acid, probu Uyf umanc; moet abunduut
tLe floweriDg time. (Lerch.)

Frtparation. 1. Tbe freib or dried herb or tbe root of Ch^lidanium
mfljus is exbauBted with warm water contaiiiing carbonate of «ada; the
clarified liquid (or tbe recently expreiieti juice) is supersaturated with
itric acid and predpitated with nitrate uf lead> not in excese; the preei-
ijtate, after beiug waehed with water, and repeatedly treated with very
ilute nitric acid to remove tbe lead salt of anotber nctd^ i^ decomposed
jth hydrosulpbate o£ soda; and the liquid 19 bailed with suLphtde o(
lad and animal charcoal, the exccis of eulpbide of eodium bein^ deoom-
led by an acid. The filtrate is somewhat cnDceiitrated and dilute
Iphurie acid added as long as cheEidonic acid continues to separate; and
he filtrate, after further evaporation, deposits an additiond quantity.
(Probst.) — 2. Lerch coagulates the expressed juice of the herb by boil-
ing, acidulates the Hltratc with nitric acid, and precipitates the cbcli*
donie acid by addition of nitric acid not in excess, (If too Little nitric add
be added « targe yrUow flukefl separate tvhich Bcttle duwrv but slowly ; if too much, no pre-
cipitate ifl formtfti,} llutatelri me^ ] drjichm of nitdc acid sp. ^r. 1*3 to 2 Ibit. of jylcc.
Tbe precipitatCi containing colouring matter and a lime-Falt which cannot
fbe removed without loss by wiishiog with dilute nitric acid, is suspended in
' aterand decomposed bypassing sulphuretted hydrogen through the liquid
br several days ; and the liquid is neutralised with chalk and evaporuied
111 a crystalline crust forms : it then on cooling rJeposits tbe greater
rfl of tbe lime-salt almost pure, in needier having a silky lustre. From
lime-salt^ tbe pure acid may be obtnined by repeated crystallisation
dilute nitric acid; hut it is better to decompose it with carbonate of I
ammonia, and mix 1 pt. of the cold-saturated solution of tbe ammouiacal
aait with 2 pts. of moderately diluted hydrochloric acid] the mixtuie ,

iflait

-•CF

1>« _ II

acid. 7k

hMtai ■ A» M^— t. b a MHodr attMb.! ly atn^r mtric add; l« J

(L«^J

„ rtofcil„ ,
IB eoU Oil of nlM ^
— ^ rMowukt ttl nm
rat &e bofliatitiC^

i^niwadaO wmid^k

if WM Willi puttiii, oxsit? u^ 9

iftiat

WHfc r*Ar--i, ff^rmtd CMwiamie «^-lft
tf dbtUiwii mU iiMLiaUjreTapoMmldi|M«lil«|
M ^ CL (3 At) m«r at ll»» ^mmi
r MilaliM MkUT MM jidib «nH niifM
_^ t tke cativv liqm iabi « mltii mmm^ aaJ gin rf

rtl BL «. (t At) water at lIlT ar ^w i>i] of ritrwa* f Lmk) CHk
Idlbii liiliiliafr acid tJiofiieii ia Ibe air %rm at eidtaavr tmm^

1, j^Moa. oyM«^ «^^Tbeia4 ditioltaa apiri»gl/ in ^
m&f tAmwJMmtH ia liH waler^ so di^t tti<^ fdntioix solidifiet na eoofiil-
(Lffdu) Ii ^miiwm ia !«€ pis. rf wai^j nt 6" and b 2S |ila irf biii%

The acid dioolres in lijdfDeliUne and ml^hnne aciib mot« atminiflrilr
tiiaB m water. (Ufeh.)

Eb4j Tbe Chdid&maUt are citvtdml jnto aiOMtsmv tfVlUr,
I^f n^rri/, C"H*MHJ^* (see vii. 2QAI Uihamc C»*HIIKP,lia i*
WQ'' MO, and acit£ iai<s 6*H'M0" + C>*HM>«»,

CHELIDONIC ACID- ^

415

H^ The hihask ch el i donates are formed when the acid is neutraliaed with
^» melaJlic oxide or a carbonate; witix alkalis or their curboiiatee, uribsisio
^■pitlta are npt to form. i^Tri^t of llio bibai»ic ealu aire sola file in water und
^Krys to] J livable; tbey contain severiil alotiii^ of water^ which are giveu oOT
^Kt or above 150'; the ammonia and silver ^aalta however become anhydrous
^Mt 100^, Thofie which contain colourless baees are themselves eulour-
^■eaa. They have no action upon litmus. — * The motwbmic salts ar©
^^broduced by heating the biba^ic fialts with abont ^ of their weight of free
^Kbelidnnic acid or a dilnte mineral acid. Jf the acid is in excess, aeid
^■iK'lU; are [vroduced. 1 he monobasic saAts are resolved by repeated recrys*
^BalJisation into acid and bi basic salta. — Tho trihanc salts are formed by
^^B^eating' the biba^ic salts with a caustic alkali or alkaline carbonate,
^fffhose whieb coniain colourless bases have & fine lemon yellow colour;
^■hose which are soluble impart a deep colour to the water. Most of
^■Item contain several atoms of w^ater, which do not escape at 100^ They
^^bftTe 00 reaction upon litmus. They are decomposed by continued
^HMjtMt with water; tho^ of the alkalis absorb carbonic aeid from the
^^■b and yield a bibasic chelidouate aad a carbonate. — The existence nf cbee^
^^HlShattc saIu biL» ^ven rise to the BuppodtioQ that cbelidonic acid h& tnha«^ic ariii (vid.
^^■Uriiardt, lYaHi, 3. ^5!;^) [perhiips curreetly^ even though there b no knoivti mU to
^Hmicb the formuk C'*lIM*0'' can be poiiitivelf aadgned, L.]. According to tkf;f«-Hus«
^^Hfl^ KiBumed » hjpotlietical anhydroas chelidonic add ^ C^*BH>^'j the bi basic cbelitlo-
^Hbtes (rented vihh rimtitiG ulkalb or alkaline earhfmMtfs jield a ti«w add, chehdmic aeid^
^Hjlbii^ iit the hjriJothftlcal anliydrou* st»te is C'*H'-0*<^, nnd is rcconverttid itito cheliilooic
^^pcid, as BOiin tiA the third B.toiii of base united ftitb it llndd an opportuniCy of unitiug
^^vith atir)t1ier acid> evt^n if as feeble iS carboaie acid, tehrb. 5, 2^3.)
^H The acid chelidonates crystalHse from the solutions of the biba«ie
^B^t0 in hot hydrocblortc acid, in delicate needles or scales which do not
^K^v^e off their water of crystallisation at 100°, They redden litmus,
^Knd may be recrystallised, but give up their base when repeatedly treated
^Brith hydrochloric acid.

^B ChdidoTKite of Ammonia. ^^^ Bihmic, — A boiling dilute solution of
^■lie hibaste lime-salt is neutralised by carbonate of ammonia, nnd the
^^lltrate evaporated; it then on cooling yields the ammonia-salt in snow-
white ai I ky n ecd 1 es. The s o 1 n tio n aban d on ed to s p on tan eon a e vapor ati on ,
IltimatelyeoHdities to a transparent mass, wbtch when coUi^cied and
rained on a filter, yields the salt in long capillary crystals resembling
knot of the finest silver- white hair. — It etttoreaces in con tact with the
ir, gives off 14 23 p* e. (4 At,) water at 100", and then exactly resemblea
ulphate of tjuinine. (Lerch.) .

At 100«. Lffv^li. i

14 C... 84 ... 38*53 ._.. 33fi7 I

2K..,..*..»^ 28 .... 12^85 ]

*0H. in ».. 4*58 .., .- 4*72
12 0 9* . .^ 44 04
C^*a^(NH^fOi^ 218 „„ 100-00 I

The fait does not ^ive off ammonia, either when exposed to the air
at ordinary temperatures, or when heated to 100°. Healed abo\'8 100"*,
it turns brownish and gives off carbonsite of ammonia; the residue does
%Qt contain any other acid. By repeate<lly evaporating the solution
ind fedtSBolving the residue, it is converte^l into the acid salt. It doea
lot form a tribaaic salt when treated with carbonate of ammonia or
(stustic ammonia. (Lorcb,)

416 PRTllART XICLEUS Om^: OXIGEN-HUCLSUS C»*H*0*,

of tfao bibaitc ^t La coloured yelloir hj paUmh mmd solidifiei in » ei^
IftUine mass, — 2. When alooholie potash is added to m atbtof
I flolotiap of the aftU 6, the jelluw miiittire becomeg torbid uid dtpoiiti
fttnber^oloared crystal of the tribasic salt, wiitcli^ wheQ repesiecly
wasLe4 with warm alcohol^ bake together into a soft mmher-Gahmel
jnft^ which, if difisolred id the smMmt pomthie qoantitj of hoi^
water, yielda crj^taU on cooling.

Dark yellow; efflores<!€e in the silr, hot d^^ea not reacrt upon litmis^
Absorbs carbonic acid from the air, beoomeiS moi^ and ihca exkibita fti
alkaline reaction. (Lerch.)

L Bibame, — Obtained by neat rail sing the acid with carbonic aadj
crystallises in amall Aoocalent^ aggregated needles j dJSdolves itadily b
water. (Probst*)

ChflidofmU of Soda. — a. Triham. — Reaetnbles the potash ««dL
h, Bibmilc. — K Obtained by neutralising the acid with carbonate
■oda. — ^2. Tbe dilate solution of the Hn»e-salt is precipitated by ei
bouate of soda, avoiding an excess, which would be indiciited l^ iht
liquid assuming a yellow colour. — Delicate silkj nee^UeSt vbieb
effloresce rea<iily in contact with the air« It giYOa off 15*5 per ce^.
(5 At.) of water at 100^ and 5^5 p. e (2 hi.\ more between \W
and 180°* (Lcrch.) After drying at 100^ it drusoirea in 15 5 pirt* 4
water at 1 50", and much more abundantly in hot water. (Probst.)

I

2N*0_, _ ._ .. m

14 C „„, 64

3 H 3

11 O B8

Tjerch.

26-16 ....,*.* 26-79

35-44 ..... 35-SS

1-27 .»..,.. 1 35

37-13 .^^. -^ 36'48

Ci*H*Na»0*3 + Jkq 237 .... 100 00 ...... lUOOO

c. Monohmic, — ^The aqueous solntion of a is minced with aboat | |i

of chelidouic acid^ the mixture bmled, and the needles whicU aefiaimiSM

cooling, parifieJ by recryMtalliaation, (Lerch )

N*0

14 C .
7 H .

15 O .

Ai 100-.

31

._. 84

.,„„_..., 7
120

Lerch.

12'81 1266

3471 ...,,,. MM

2*a9 „..„„ 3' 1 6

4t-8l 49 81

C^H"N»0« + 4Aq ..... 242 .... 10000 ...... 100*00

d. Add (p. 415). — Delicato needles or scales.

Ai im\ Len^

NaO ...,.,.......,. *. 31 .... 7 13 ., J-U

CaH^O**... .,-, .- 404 .... 92$?

CHH>NftO^,C*'H*0^- + 5Aq .., 455 .... 100-00

Ch^lidomUf of Bitrgia. — a. Tribrmc, — The aqueons solution oC I
salt h v% mixed with amnion ia^ the yellow uiixtnre hejitod art • -i^tpJ"'

with cblortde of barium; and the Icmon-yelJow prccipit4*t€ ^ ., . ., , r ^4iM

CIIELIDONIC ACID,

417

rith water. — Lemon-yeJlaw fpowder- Doei not give off its water of
crytstaJlisatiott at 100"^. Absorijs carbonic acid from the air. Sparingly
soluble in wator, iuioluble in alcohol. (Lercb.)

Ai]OQ\

3 BaO 229-8

14 C 84 0

r H 7-0

15 O ,...„.,..».. , 120'0

Lenk.

5213 .,. SI -80

19-06 XS-88

I 58 1-72

27^23 ., 27-60

C^*E-Biiaoi3^&iO + 5Aq.... 440-8 ..., lOOOO lOO'OO

h JSibasic. ] , Obtained by neatmHsing the aqueous acid with oar^
ttnato of baryta. — 2. Better: by adding baryta-water to the aqueous
eid till tbe salt separates out* — 3. By double decomposition of the

iime-salt with a baryta- salt. — - Hard transparent crystalline grains.

the solution Las no action upon litmus* The salt does not give oS
By water at 100*^, It dissolves very sparingly in water either hot or
ttld. (Lerch.)

2 BaO

At 100\

. 153-2 :

64-0 .

. 4-0 .

. 960 .

:.. 45 43 ...
.. 24-91 **..
... 119 ...

... 28-47 ...

Lerch,
45 15

4 M

,.44.....t......<

...* 24'7l
..... 1-25

12 O _..

..... 28^89

Ci^H^Ba^J^

+ 2Aq ,..

. 337-2 .

... 100*00 ...

... loo-oo

Ckeiid^naie ofStrotiiuL — Obtained by dissolving carbonate of etrontia
tbe aqueoui^ acid. Crjstallige^ on cooling in blender needles, wbich

Iter drying appear interlaced like wooK Afier drying at 20iJ^ it

lissolves in 240 pts. of water at 16'' (Probst.)
A cid. — Slender needier or scales.

At 100% Urch,

BaO ...„..„ 76-6 .... 15-94 .- I6-2a

0»H^O» .„„.....„.... 404-0 .... 84-06

Ci^H»B*0i3 + C«H^O^ + 5A(i 4806

lOO'OO

ChelulonaU of Lime. — a. Tr^am. — 1. Produced from 6 by boiling
rith ammonia, almost without ehange of form. — 2. When tbe solntion
f i La mijced with Liine>water, no action tahea place in tbe cold, but at
be boiling beati the li<jaid assumes a yellow colour, tbe alkaJino reaction
f.the lime-water dii^appears, and a yellow precipitate separatesj the
idition of lime water imiai be continued till tbe liquid remmna alkaline.
-An adoaiJEtwre of ewboimtc of lime is ujimvotdnble. — 3. Prepared like the
b«lt. — Yellow powder, soft lo tbe touch, sparingly soluble in
r, ineoluble in alcohol. (Lerch.)

At 100%
3 CM

7 H ZZZZZI!ZZZ"Z

15 0 ..- . ....

. %4
. 84
. 7
. 120

... 2847 ...
... 28-47 ..

.... a-37 *..

.... 40-69 ..,

Lurch-

..... 28*88
..... 28-^4

2-75

..:.. 39-53

C»*HK:#0«,C*0 1- &Aq ...

. 295

.... lOO'OO ,p.

100*00

41? ROtAKT 5tCL£LS C^fP^z OXTGSK-NUCLEUS OW0«.

iL MAetir — OecsR n tbe Im^ of OMufewtMK M^'au. For tbe pn-
pnom. «r :a^ 413. Gitcs off 5 At. wmtcr at 150% the aixth at 200', m
^. I^^<ri p. c. -f A:. ' It ^isolres spsringlj in cold, abnndutlj ii
UlEzlt w-iier. vMbce i: crrstallises for the most part od eoolin^; it is

Ati&r.

Lerdi.

2CaO _ 55 _
14 C ._ _ 84 —

2H . 2
I+C -_ S# _

25-22

37-84

0^ _.
35-04

.. 37-45
1-12

OiFCrO= _ 222 —

100-00

^I00\

Lerek.

2 CO 56

* e ... 8

HO la?

... 20^29
... 30-43
... 2-90
... 46-38

20-28

30-68

304

46-00

c«e=c«=a= • eAq 2:6

>.. lOOHW

10000

^150*.

Lereh.

2C*0 ....^ 56

c*tPo^ - 1:5

..- 24-24
... 75-76

24-07

C-HWO= - Aq — 231 _. 100-00
c. -IriJ . Sv^^-ier needles or scales.

a: !•»*=,
CjO

11 H

*r o

:

Lerch.

29

6-62 .-«

.... 6-52

„„ 168 .

.. 39-71 .:.

. 39-92

U .

2-62 ...

.... 2-65

216 -

5105 ..

50-91

.. 423

. 100-00 ...

100-00

CtriTi.f.t :::' •/* Ztn-' ■:inl P:*i4A. — WTien an andilated 8olotion(^*
ibe biKi^ic r:2:^>;il: :< mixed with an eqalvalent quantity of carboiaii
of l:nie. 1 A:, of *:n;e i* pr^vpitaied, and a trihasic chelidonate is fonwi
cor.:*:r:nj: 2 A:, calo'um and 1 At. potassium. — In a very JiUtt
solu::or. :he wh ^*e of the lime is immediately precipitated bj ctHxwiie
of jvtd^h. ^Lerch »

TvV :' 'i-.rf ;•' J/':t.*»'t — Obtained by dissolving carbonate of
ma^rr^e^ia in hv: a uuvus chelMonic acid, till the liquid is ueutnli^
Crv >:;!*/» st'^' V » c - ". r.j, in bifurcate needles, which effloresce in the t^r.
and ;if:or virvi: 'J :i: liK' . dis^soive in 79 pts. of water at 16'. more reid^lj
in hv*. wa:er. .PrvW;.^

Frxm a ni:x::;rt» of chrome-alum with an alkaline chelidonate^ *a^»
havin;: ti tine b-.^-'..: i:n.\?n cnour is precipated on application of he*tof
addiiivui v>f ammonia. yLervh.)

By SA^uratiniT the aque«->QS acid with oxide of rinc, a liquid is fomfi
which has an acid reaction, a sweetish astriogent taste, and jiewU

CHELIDONIC ACID.

419

eryatals as it oooU, These crystals^ afti^r drying at lOO'', dissolve in
140 pU. of water at 1 4 ""j more readiiy in hot water* (ProbsL)

ChdidanaU of Lead* — a. Sfxhmic. — The salt c mixed with ammonia
i addled to b.ifiio acetate of lead. Dark yellopr.

1.

iPbO 6r0*8 . .

^ C'*HW> ..... 166-0 .,..

IL

mU 6PbO 67-08 ..„

VJ'Bi Ci^HO" 15'70 ...

Lerch
al lOO*.
81*03 ._ 80-06
W^7

P*a30'",6FbO . 836^8 .... lOO'OO D+HPli^O^ 3PbO 82^8 ,... IDO'OO

Ciilcahidon I is bf Lcrch ; II bf G^rh^rdt {TraUi, 3, 763)*

6* Tnbftsic. — L Obtained by treatinj^ c with ammonia. ^ 2. The
blulioD of bj basic chtjlidonate of lime, mixed ciold with basic acetate of

id, yields yellowish white flake.^ can tailing 2 At. water, which are
iven off betweea 150'^ and 100°, the salt then turEiug yellow. If the
alutioa;! are mixed at the boiling beat, the auhydrous g'llt is produced

once in the form of a yellow precipitate. — temon-yellow ariiorphous
nwder. darker if mixed with a; decolorised and decomposed by acids;

soluble in water and alcohol, soluble in lead-sails*

3 PbO ,

14 C »..

2 H ...

10 O ..,

PrfcipiMe^ hoiting*

335*4

84-0

20

900

6602
16*?5

0-40
15-93

Lercb,

67-06

15-90

0'62

16-52

CWH'Fb»O"pPb0 501-4 ... 100 00 .- 100 00

Prfeipit&itd cold, Lercb.

3 PbO ......»» ... 335-4 ,... 64-57 66-03

CHH30W_,^„^...,, ,,,,, 166 0 ..., 31-96

2 HO 180 .,. 3-47 ...,.., 3*60

Ci*H*Fb^^PbO + 2Aq .., 510-4

10000

e. Bihmic. — When a eolntion of the lime-salt is mixed with nitrate

lead, the liquid becomes turbid and deposits small ahining crystal I i tie
ilea or elentler needles, which are insoluble in water^ and dissolve in

l*fialts and in strong nitrio acid, but not in faming uitric acid.

After drying at 100, it gives off 4r23p. c, (2 At) water at 200^
Lerch.)

2 PbO ,....

14 C ..»„...

Ai tm\

,.,.. 223-6 ...
,..., 84-0 ...

. 57-40
. 21-55 „..
. 051 ,...
. 20*54

L«rch,
20-8i

a H ,

2*0 ...

.... 0*68

12 o

,.... 80-0 ...

C>*H«Pb*Ot» ...

...,. 3»0^6 ..,

. 100-00

2 B 2

430 PSDUXT occurs OV^z OXTGd-MJCLEUS G^VO*.

ix r

_ 20-61

— o-«

^ 23&5

S4-6S

.— 20-48

4 H -- -

A-«

. . . 1-0?

i±o

»6-0

23-81

C^E=ftrO= ^ 2Aji 407-6 — 100-00 lOOOO

WkissL iL» B.i'LZXiQ. 3£ Lcszai viih ftrons' nitric mcid, an acid alt ii
fTjtaai^ wijieii kgmt iht tzilosie salt when treated with alkilia.

J^ I'M Ci«5*A»»s£e. — The a^neoos add diasoWes iron.

Ci^*£:^3£d. — m. The eolntion of iron in chelidonic leid
paases «o & kix^ker ^srrree of oxidation daring eraporation, and depoaiu a
G£j pfiiJ:w p;«eip:iase. — 6. The bihasic sodarsalt forms with iqocoa
aesitzJeslicAt c€ irott, a din^ jellow precipitate, somewhat solaUeii
aoECie acai a&l ia excess of aesqaichloride of iron; it does not dimniil
za we»rxt as 1^3\ az^ if set on fire at one point, boms away with i
^oz^liir l%^t. kaTia; chareoal and 9e9i|mioxide of iron. (Leich.)

Lerdi.

Ff50» 80 »- 32-52 32-60

C-HV»» 166 ... 67-48

C-^ir-0^,Fe=0» 246 _ 10000

ter:r:£> 'cli-rk-i-rc-w:: slz i v-pi^ue, bai recovers its pale jellow culuar
af:=r s.zir i.ce: -..c Leiiinr the li*]aid, the changes of colour lake plaa
2L:r£ .*::i.y. T-e A*rk brv:»wn liquid forms with ammonia a rostj
tr. in i-reci .ii:<*, w-i-h bec^>mes black when treated with a liw
cziniiT c5 aazioiiii .pry:;iblv from formation of protoxide of iitii:
Ji* :-;Li. an^r harizr r>?>;.vered it5 p%le vellow colour, fornix nid
ann-i-a a rri-lrwn precipitate containing 57 65 p. c. FeW, 7 32C
I 3 H ai:i ;o j-6 0 ; iLe or^acic sr.bstance contained in it corrc5pi>fliiJ
lif- :. re :. :"::e ::n::-:a CH*0=*. ^Lerck) [It probably contains nitrt.^ci
in u.e ::rzi zi aiiiziv-ia cr of an amide.]

Ci-r-.V*.r.:4V y C-X'p r. — The hot solution of dielidoaate of eoii
mlxoa »'.:i: 5;ili'iia;e *.«! *x«j per. yields by cooling or by slow evaporauufir
ctvy:>*:: crv^ia orys:^? spiriii^Iy solahle in water. (Probst.)

r-.: .f .:v /\> 'rv^ .. _ ,1. 7n>vV.— AVlien the aramoniacal *uln-
iIvT. v! :ic I .V;i* 0 .::r.e-sa!: or tr;b,'.*!C pcta^^h-salt is precipitated w;tli
t:i:r.;:o vf ?:.vor, .. '.t:!::: yellow jaeoip late is formed, which beivmrf
4::.v:. >V. c^tr. .;ur:::j £'.:ra:;v>::. a:: I when drie*l in vacuo over vil ^'i
vi:r. !. :is> ,::.:;> a yo".!o«-l«rv^wn colour, and i» then no lon^'er solul»!t' ia
a:v.:r.. :..;». 0:. iu:\;:u- ilie hot >*..!utions, the decompoiitiun Ukes flaw
jt.H :..vn* ;-.;".okly. la vvr*«4;i<a».'>r of this tendeucy to decooipobition, ihe tn^Hat
of o.r.v:. :\:V. =Ni I'j vvr. bj>ti03 vaHe* br morf thsn 1 p^r ceot.j the perttnuttffi
»U»«x-ov.w<r r"v.-«;<i %«r.ei :r»m Oi-OS to 68*85. (Lereh.) [ Lerch'i f^Mouk

MECONIC ACID.

4S1

i

C»H=0>t>.3AgO rtquirea 67*70 per cent, of oiide of silver; the formijli C^^HAg^O**
Tecjuirea GB'9l p. c. A» the salt decompo^ei daring titration, tbe unalj^sis ta^y be
eapected to give more silver thmn the formula requires. L.]

Mihiisic. K Obtained bj dissolving oxide of fiilver in cbelidonic acid,

2. When the bi basic lime-salt is precipitated bj nitrate (*f silver, and

eated to the boiling point, the Bait crystallises on cooling from thd

IS ill ting solution, and may bo purified by recryatallisation* — Long,

ioorless eilky needles, resembling acetate of silver. Permanent in tbe

ir at ordinary temperatures, and not altered by beating to between

100' and 130'. Between 140° and 150**, it decomposes witb i^light

etonation. It dissolves in water^ ammonia, and strong nitric acid, but

,ot in alcoboK

2 Ago,
14 C .,

2 H ..
10 O ..

232 ...

84 ....

........ 2 ....

, 80 ....

ffydr&ted, FfOlwt LfTch.

5fl^29 2 AgO .,., 232 .... 57'0O .... &6-& .... 57-oa

2M1 14 C ........ 84 .... 20-04 20-48

0*&0 ^ H 3 .... 0-74 0*78

20 10 no 88.... 21-62 2174

C»^H5Ag30i3..„ 398 .... 100-00 + A<i ....... 407 .... 100*00

100*00

- Cheiidonate €>f Sllvfr and Calcium. — On mixing a concentrated
Smmoniacal solution of tbe bibaeie lime-salt witb a concentrated Bolution
m nitrate of silver, a ligbt yellow precipitate is formed, wbich alters bat
little in dryings and is decomposed by water only after continued boiling.
(Lercb,)

bAgO...
[ CaO ...

Anhydrmt.

232 „

...,. 28 ..

.„ _ B4 ,

.. 56-63
.. 672
.. 2014
.. 0-24
.. 17-27

2 Ago ..
CaO .

14 C .„..
2 H ......

M^fdraied.
232 ....

..... 28 ....

B4 ....

2 ....

54-47 ,..,....

6-57
19-72

0 47

18-77

54-04
10-70

1 H ilL

1 ..

72 ..

076

10 O ....

..... BO ....

'•HCaAg^O" ........ 417 .... 100-00 + Aq.

426

lOO-OO

Cbolldonie acid dissolves at 12* in 700 pta. of alcoliol of 75 per cent,
liebter, Probst)

I

Meconic Acid,
C«H*0^* = c»H*0^0*.

fEBTipRNEii. (1805.) J. Tr. 13, 1, 234; 14, 1, 47 j Qilb. 55, 72;

57, 183; C4, 05.
uijj. AfiTi^ Chim. J>2, 228.
CHOtiLANT, Gith. 5S, SA9.
EoBtQiTET. Ann. Chhn. Phps. 5, 282; also GilL 51, XtZ.^Ann. Chim

Phy^ 51, 236; also /. Phanft. 19, 67; also Ann. Phat-m. 5, 90.—

Ann. Chim, P%#. 53, 425; also J". Pharm, 20, 79. — Prntm. Cmtr,

1^33, 209.

A. VooEL. Schw. 20, 196; I^eperL 4, 40,
John. /»Vr^ Jakrb. 1819, 15fi.
LiKBTO. Po</ff. 31, 168; aleo Ann. Pharm. 7^ 37* — Ann. Pharm, 26, 11 B

aad U7\— Pharm, Cmir. 1804, 202,

UH.

nSL nmt. m, mi.—Amm.

'«rt^i

IKijiltsiiilitt

wtoiitii W gy^p^nitiaa^ ie ieft totnpoiii
I MfamJ ct3r«tmls oT ipMi»ak addL lb
te if harpM. yiMm whm c^tpocilii i
r ail. (Sertorver.)

tii» iMifer it I

t%y ■■■■■!■ tad iitereJU be wot w^ pm
raf iijwi— »aiirflai^ ^gjFgtfq-lwt of tlwi wieeiHi^tr of tai|tiii

1*. fy^lin- (.Auc Hm. /'JlfS. 50, f50) ^roc^eds in tbc same wmr
«■ Oiilfttmi, bttt MCi bftTjta^vitef biitttid of efiIond<? of Ufiui]i,W
■iinii tfcegwt<r|«t of tke bremi uoJoaiing matter from thtppd^
pilite ^ iM|)cHiiil M&^ witli ftleoboL

S. Op^B is exlaa^ra viUi strong alcohol nod tlse ttnettifte uM
wit& cUuri^ if baiimor vlucli pf«dpit»let nearly all Ih^ meco&ie ^
at Mvlj Mn ImjtU svlt; litis lali m Iben w&^heJ with al^oM mi
iiiiM|iii nl kj MlpLirie acid. (Merck» MfptH. 32, 87. )

C Tbe filtered decoctiou of 100 pt«. of <>piiim is iH^Ilod wlili 3 purf
■agMfiiai the liqmkl filtered; tUe grejr pow4cr whkb r^m^itnii «• iW
iltei% frrad from eoloanDg malter and morptitiie by mean:- b^

tfa» lenalaing powder, coofiktiog of baite meconate of muyi : 1- .*.

m a vmaU qnaotitj of cold re ry dilute sulpliunc acid; thi^ tx^luLios |)if-
dpilabed hj chloride of barium; the liquid ag^in Altered ^ and ^
nddidh |>recipitaie of enlphale and mecontite of baryta decofnpHclVj
loog-^oiittaaed digestioQ with dilate Eulpbutic aeid; alUr wnick lli
li<|uid is diluted with a large qtiantity of water, fill end und «Tiipoiiliil;
aod the cotoared crystals thereby ubuihied are wusht^d h ith ^ Bnmll t|(uat^f
of cold water. (R^^biqtiet) — Or the miigDe via- [irecip) tale, aftf f i^
exhausted wrtb ulcohol, m trealed with a fimall q«:iuiity of ci»M ttjt
dilute sulphuric acid to remove the exeeps of u»ugtic?sia; the Iiq9il»<
decanted; the residue heated to the hoilin^ poitit with au i»i«w of*
mixture of 1 pt, oil of vitriol and 2 or 3 pts, of wuter; ibc lipoid fillertdsi
Ihe boiling beat; aud the still brown crystals of the acid whtdb i«|ttiiit
pa coolitig are collected. (Robi<iuet.) [These eryacdj iu« ninlwtiy t»«*

5, The deroction of opiDTii freed from morpbine by aeuMOttk ■• it •* l
I precipitated by c\x\onA%til caidvwrck; ix^wtl tbo impure o^it^al wbb^mm^i

MECOJJIC ACID.

423

amounting to about 8 per rent, of tbc opium, b carefully washed and
suapeuded in kIx tiuics its bulk of hot water, th*?n mixed with hydro-
diloric acid tiU it is converted into a cry^jtalline powder of pure
^econate of Jhne* 103 pta. of this powder are ihen decompoeed by diges-
tion with water containing 36 pl^, of cry>tiliised oxatie acid, and the
filtrate is decolorised liy animal eliarcoal. (Winkler, Ittpert. 45, 460.)

6. Opium is exhausted with dilute potash; the filtrate preeipitated
by ehloride of calcium; and llie precipitate waiibed with water and boiling
akohol (accordiD^ tu Robiqut;tt it h better to e^huust the opiura with water at. 33" ;
neutralise the extmct mih coaraely jioumled mnrhJe ; evaporutc to a syrup ; mijt with
i^uceDtriiCed solution of chloiide ot calcium, whereby the mt'conate of hme is more
Ci>ropktely separated in proportion Wi the liquids are more concentrated ; then wush the
(rempitflte with wuter and press it), ] pt. of it is then suspended in a mixture of
pte» commercial hydrochloric acid and 20 pt«. boiling water ; th<j mixture
at a temperature short of 100*, and frequentfy shaken, till the
Ae is dissolved; and the acid meconate of litne which separates on
Irng, is Cidlccted on liueu^ washed with a small quantity of water, and
redissolved after presf^nre in a niixttjre of 3 pts, of hydrochloric acid and
pt«. of hot water, aroidtng elrullition. The liquid then yiehls on cool*
eryatab of meconio acid nearly free from lime, while the mother-
in consequence of the excess of hydrochloric acid, contains
ly any meconic acid. The still coloured crystals, after being
aahed and presf^ed, are dissolved in \G pts of hot water; the liquid is
rained througU linen; and the tiitrate is mixed with two thirds of the
nrigiual quanlity of hydrochloric acid; on coojitjg it yields crystals of
tneconic acid free from liine but still coloured. These crystals are
fiospended in cold water* neutralised with carbon ale of potash and
heated to 100^ wiUi gradual addition of water in qtiantity just sutHcient
to dissolve them; the soluti^^n which solidifies on cooling is well pressed
(the liquid which runs off yields impute meconic acid when treated with
excess of hydrochh»nc acid); the expressed ma^s, which is not yet quit©
^^vhite, is redissolved in the tinml lest possible quantity of boiling water; the
^Kcilid mass obtained on cocding is again pres^cl; and this treatment is re«
^Hpeated till a pure whit<? product is obtained. Lastly, this pure meconate of
^P^t&sh is dissolved in 16 to 20 pts, of hot water; the acid meconate of
jipolai^h which separates on cooling is mixed on iincn with a snjall quantity
« of cold water, pressed, and redissolved in 16 pts, of hot vvater ; the
solution is mixed with 2 or 3 pts, of hydrochloric acid; and the crystals
©f pure meconic acid which form on cooling are washed with cold water,
and reerystaHised from solution in the sraallest possible quantity of
boiling water, (Gregory, Ann, Pkarm. 24, 43), —The mother.tiqtior
Cipre&sed from the poUsh-salt, *ttll yitHd* * qmantity of impure meL-onic acid whea
treated with hydrocljloHd acid, Paper^fiUera [probably tm account of the iron cMnttilned
!; Ill them] cannot he used in any pari: of the process, (Gregory.) —The chloride of
[ caldnm precipitate su.Hpended in ten tTmes its htdk of water is mixed and weli stirred
JLho witli hydrochloric acid at 9(1'' till the; greater part of it is disaolri^d ; the hot liquid U
^Hptrred throagb paper which has bfien eomplrtely freed from iron by hydrfH^lilonc acid;
^H^tiedelirate neHles of acid meconate of lime which separute on enormg are pressed be-
^Kpecnhneri, difisolveJ in the required tjuaiitity uf w^jter at 90", decompogfd by a qn^ntity
^Hpf hydrocldo'rie acid equal to half t but uf the cbluride uf cwhi'sm precipitate ; and the
' iiquid if heated for a few secoitds, hut nttt to 100"^ and then left to cool ilowly. If
I lighicr cryitals of the lime-salt should form above the more denMy inierlaccd c-rystnl*
^Hftf mrconio add, the former ti my he fivpnnift'd nuHmnieaUy \ orif ihe^rysOilUKation %mkm
^^Mtifj^ t(Ht rnpidly to Admit of this mode of sq^umtiun, the whole muH be rcdiit^ohed in
^^lol w«ter, aoil the remnindcr of the lime reranved by fresh Uydrorldorir acid. The
r crjatitlt of the acid obtained in either way — whkh should btirn away without residue

L

MC

H ^ «
4 « «

115 - M

- 5M

W»Wr l«*pt»»«»^ i«tly into earbonfc and ftTf^mec^Die «*

**^rii«titT ^2^^; and iH^tw^ii SOO^^a^^^^ SET ii .^ooj-j
^ 2Sl i'TQm t20« I'l 230^ nil evalutioii of g^ opMi ^

MECONIC ACID.

425

be anb-grey crTstallmo acalj resldne consists of cotnenif; aeiil [whence
&mes the water 1 (Gm.)] If tUe mecrtnic acid li immediateVj exposed
n a stroBg heat, it yteltls iit first abimt 20 per cent, of pyromeconio acid,
Hither n^itlj water end acetic acid, tben carbonic acid ami a vcrj
umll quantity of combustible gafi, t*jgetber with empyreumatic oil, and
I la^, lon^ white needles of parapyromeconic acid {a so be tan co reqiiir-
pg further exam 1 nation), wliicii are difticnU to fu^e^ ha^*e a strong acid

otion, are sparingly soluble In water, and likewise r«dden ferric salts,
fibiqiiet.)

Dry nicconic acid melts between 1 50° and 200", and is conTerted,
rith frothing and evolution of pyromeconic [and carbonic] acid, into
■rown comenic Rcidj which at 250'', gives off pyromecontc acid, carbonic
cid, water, a small quantity of acetic acid and brown empyreumatic oil,
ben assumes a black brown colour, and ultimately leaves a light combus-
l»le charcoal. (Wackonroder) — Me conic acid subjected to rapid dry
still at ion sutTefs the same kind of decomposition as com en ic acid, and
mlds the same substance resembling meL'LgalHc oisid (xif 384).
''inckler.)

% Meconic acid rapidly be atetl in a spoon boils up, emits dense white
Hmcs bavin I,' a slight empyreumatic odour, bnrns easily with a yellow
tmc, and leaves a small quantity of cbarcoaL (VVackenroder )

d. Pulverised meconic acid diesolres in hromlne-watert with rapid
rolntion of carbonic aci 1; atfil the liquid^ after a while deposits beautiful

stals of broniocomenic acid :

C«*H<0" + 2Br - C^^fH^BrO" + HBr + 200=,

Tben chlorine is passed into the aqueous solntion of bibasic meconato of
nmonia} the monobasic salt is formed^ and chlorocomenic acid remains
I the mother-liquor. (How.)

4. Meconic acid is quickly decomposed by nitric acid, the mixtnre
sing projected froni the vessel if large quantities are u!»ed, and a large

Quantity of oxalic acid is formed. (Hobiouet.) When nitrate of eilver
precipitated by aqueous moconic acid, nitric acid being added in
|uantity rather larj^r than is required to dissolve the nieconate of silver,
ind the liquid warmed, flakes of cyanide of silver separate without any
-Tolotion of nitrous acid, and oxalate of silver remains dissolved in the
eid liquid. The only products of the reaction are carbonic acid, oxalate
' silver, and cy.inide of silver, the quantity of wbicb is however less
fcbe excess of nitric acid is greater, (Liebig, Jvn. FkatTn, 5j 2 86)

5, Oil of vitriol exerts but a slight decomposing action on meconic
acid J sulphurous acrd being evolved only after lonj^' boiling the liquid,
ftnd etill retaTniug its power of reddening ferric salts. (Robiquet)

G, By boiling with water and aqueous acids, meconic acid is eon*
rertedj with evmution of carbonic acid, into comcnic acid :

his evolution of carbonic acid is observed even when the acrd is dts-
iolved in water; and if the boiling be continued, it goes on for several
days, till in fact the trauRforraation into comenic acid is complete, tbo
liquid theo acquiring a red-brown colour. When a meconate is boiled
^■twiib excess of eitber of the stronger acids diluted with water^ thia

426

PRIMARY NUCLEUS C»II" : OXYGEN-NUCLEUS C"n«0<,

evolution of carbonic acid Je niucb more rapid, anioanting to m kind
eflTLTvescencej atid the liquid remains ctdourless, (RobiqneL) Liebi|
also obtained a dark brown extraclive a€Condary produrt hj WiliB
meconic acid with water; but on beating tlie acid with strong byd
cbloric acid, brisk effervescence ensued and colourless cotnenic acid wi
formed; bence tbe formation of this acid appears to be indepcndeut
that of the brown eubsttmce.

8. Meconic acid boiled with a ooccentratad solution of potasb, ii^
regolved into oxalic a^id, carbonic acid, and a dark brown aobetA^ee'
reaeniblitig bumic acid. {Wackenrodor.)

9. WhcD concentrated aqueous solution of bi basic nieconat«
ammonia is boated for some hours with excess of ammonia to a teuiDen
ture below ilie boiling point, comenamic acid is produced. (HowJ
ati, 393.)

CWH»CKH^)SO» = C^H^Oa + NVl^ + 2H0 + 2C0^.

CombiRationM. Witb Water, — tf. Cr^BtaUktd Mtconk ^ctd,-
White micaceous crystalline scales {Sertiimer, Robiquet) ; rbofnbiQJ
crystals (Merck). Small right rhombic prisuiB, having their oeali]
lateral edgrs very much truncated; cleavage parallel to n. (Wacken*!
roder, J. pi\ Ohm. 23, 205,) The crystals give off their water at I00',|
(Robiquet)

Ci-H<0»*

6 HO ».»»..»

200 .

........ 54 .

... 78-74 ..
». 21-26 ..

R<jhiqiiet.
...... 78-5 ...

.... 21*5 ...

Lkbif.
. 786
. 21-4

C"H*Oi« ^ 6Aq ..

254 .

... 100-00 »

...... 1000 ...

. lO(>-0

hu Aqufoui Meconic aeid. — The acid dissolves sparingly in

water, but in 4 pts. of boiling water; from ihv hot solution in
contain in;r bydnndiloric acid, it crystalliees mure readily than froti* pa
water. (Robiquet*)

The Meematfi are either (iib<mic (neutral) = C'*HM'0'*p
= C"H»MK)". or monobasic = C^*H=*MO**. (Licbig.) The trib*
dults are yellow; tliose of the alkalis are produced by milling the %cM
with excess of alkiJi. — [The meconHtes of tUe nlkiilU d«mbfd bj CboiilAnt Mil
ciU^d la m^Rjf sjfstemfttic works, a|i|^ear In Jmve t'ontnined pirumrCTmic in'id inaimtti'hl
na thc-jr wert! prrpured with »n acid ohtniiied by difitUUtif mn'otiatp of barjU witlll

boradc iiA;id,] The salta heated with boracic, pliofipboric or sulphuric aeiJ
yield a subHuiato of pynmieconic acid, but not when healed alon^l
(Choulont 5f others.) They redden ferric salts. {Seriunier.) Tb«yl
ar« less aoluble in water than the pyrouieconates. (Robiquet.) Thef ]
tire insoluble in alcohol (Sertiimer.)

Mecfmnti of Ammonia. ^^ a. litbasic, — Obtainotl in How*» pn
for preparing uieeonic acid (p. 424). Slender rwdiaiittg need lot hafin
& fijlky luitre and acid reaction* (Robiquet) Contiiin« variable ^tisml
titles of water of ervstallisation and gives off from 0 to lt> per oeat ill
100"^. (How.) It liissolves readily in water

^^^^^f uicom

C ACID.

^^^* At loo^

How.

14 G 84

2 N 2S

10 H -^...., 10

14 0 _„. .. 112

..» 3&'89 ..

..„ 1196 ...

.... 427 ....

47-8S .

.... 35*51

12 09

4^73
47-67

C'^H3(NHT-0'* ,- -Ul

lOO'OO .,.

lOO'OO

4Sf

The aqueotid Bolytion may be heated nearly to the bailiTtg |ioint
without deeouipaaitioa (p. 42(>)«

h, Monohtuic. — Wlieii chlorine is passed through the aqueous sol n*
tloti of the salt a, hard graniilHr crystals soon collect on the edge of I
the vesseli and these, wheti recr^'stiilllsed from boiling water, form thick
lUfcdles concentric ally grouped. (How.) Sparingly soluble in water,
(Robiquot.) Gives otT 7*56 p. c. (2 At) water at 100". (How.)

Ai 100*.

14 C — ..., 64

N ^^ 14

7H.....«.. ,„„... 7

14 0 ...... ...™.., in

How,

3870 38-57

6*45 6*21

SE2 »..,.,. 355
ai'63 ...... 51*07

C»*H»fNH*)0** 217 .... 100-00 ........ 100-00

Meconate of P*Au^, ^' a. 7*W6a*td. — Produced by adding caustic
potufih to the solution of b. Yellow.

L Bilituk, — Crutlo meconio acid is heated with water, caustic
pota^ib added till the liquid aasumes a yeilowfsb green colour^ and the
resulting glutinous mass h treated with water till it dissolves. The
solutioii coagulates on cool rug to a uearly solid pulp, which must be
pressed and recrjetallieed. — Colourless silky needles or lannnaj, sparingly
eoluhle in cold, more soluble in hot water. (Liebig, MurtdL 2, 847.)

(For the drcomjiosition ae« pftge 425).

c. Jlonolimic, — Separates on mi icing a cold-saturaled solution of h
with a small quantity of hydrochloric ncid, in slender needlee, from
which all tbe potanb muy he removed by further treatment with hydro-
chloric acid. (Robiquet.)

Mtcofiate of Soda, — a. BlbaBk, — The impure baryta-salt is digested

aqueous sulphate of soda^ the filtrate evaporaEed, and tbe crystals

led with alcobol; or the alcoholic tincture of opiun» rs precipitated

^y acetate of soda and the precipitate mixed with uarm alcohol.

Sranular crystals. (Serturner.) Slender needles containing water of

crystallisation and soluble in 5 pts. of water. (Stenbouae.)

b, j}fonob<i^ic, — Obtained in the prejiaration (b) of meconic acid.
Crystalline grains^ dissolving witb tolerable facility in water, sparingly
ID ai}neou3 potash and in absolute oicohol. (Robiquetj */« Chim, med
1, 364.)

Mecomttt of Baryta. — Tbe pure acid does not precipitate baryta-
water. (Robiquet.) It forms with excess of haryta-water, a thick, light
yellow gummy precipilatej which is insoluble m water, but soluble in
acetic acidi and the bibasic p«jtafib-salt forms with chloride r>f bariuni,
white flakes im perfectly soluble in waterj but dissolving readily in aoetio
iicid. (VVackenrod:^r.)

B ibitsic, C ' *H * Ba^O** + 2 A q . — D i ssol V es s< pa r i ngly i n water, read i fy
baryta* water forming a yelJow solution « (Liebig.)

4M PintAKT NUCLEUS C»*H»: OXTGKN-NUCLKUS C»«ffO«-

slfw ImI elowlj in scetie ^Id, — 2. Oblalnecl in tbe

water, wkile iakcsfloliibk in ^eetie «ckL

& JiaMc^ C*fl'Cft*0"-i.2Aq. — TBesolatjoij of Uie bilnm; [
e^t M^etatatrntod witli UDinotib fortns with cUluri'le uf oik'tta a
j^Iov ffliafipiwiw pre^ripiuilft. (Liebig.)

c MmMt. e*H'CaO'*-hf Ac|.— 1, The aqiie<m« acid ititnd ip
wilh a lolatk^ of eblonde of calciiLin tjot too dilute, iintl left to ftia4
fori

and diiSDlfw I

of ineeoiiic acid (nMtliod 6); when freed &om admixed gTTCsni ir?
wcgyiunkatiqo m«i boilio^ waiter acidulmted with h jdj-oehloricadl U
lamw btovtt dnaliig lamios. (Ltebtg.) — 3. A mixttire not tooditottif
bibuie nwwrointg of potwb and ^loride of catcinm, de|*a3ii6 wb^ iCirfrf
m ctjstalliaa powder, wbicb diasolTes slowly in water but 4|Qickh !■
aaeticacid. (T^'ackenroder.)

Tbe limfHali mibject^ to dry distillation, does not jield ^jttmt
mmn aei^ bat mdj «Q|ijTBnniaiJc prodncts. (Stcnfaouse.)

MetomtU if Zimi and Amm&nia^ — Precipitated for the wort ptft
to^tberwitb norpbine from tbe opiam-d^oction; and rv^maiDt brbiW
wb«a tbe morpbiaie W dis9C»lved oQt bj alcobol; aDatber portion rfoaaia
dla9otT«d in ibe aauMUjacal iltn^ta andciTBtalJmo wben it l^^^twrnd.
(BoUqpel.)

JTarMMi^ ^ Mm^mem. — Tbe aqueous acid boiled witb
"= iocw aacaoiljr iolabi© alt. (Ore, iSdbip, 59, 23§-)

wtmmd

iffiw ily y niWa.— Tbe aqae^aft tod doe* not pr«cit»iute |ttri«.«»lte a«d«te
J^iBii via Tflbift md, cvi{>ar«l«d, lesTes a ^mst ip^Qgl j- soluble la water*

Mmmfh ^ ^^^ — Tbe bibasic pata«b-8aU forme witb salpbiitcf
tine* a «a|Mova wbiCe precipita.te fneolmble in water luid lo aabMiif
line, Tciy w^ms^m^ eobbk m acetic, but readilj in aiirio acid*

IfafHifr of !%«. — Tbe wbite precipitate formed bj tbe pntail ah
im aolatioa of proioebloride of tin, djj^oWes readilj m exoe« aC ^
latttr. tWac^iaiioder.)

Mhtmtwk if tfod, — Meconic acid a«lded in altgbt ex«e« to Mflttd
acfflale of kadC tbrows down thick jellowiab while &ke% iaao]ay»f«ii
ia bol water. (Stenbonse ) Tbe flakes are likeviao Inaolable is mrii
Md Vid ia acetate of lead. (Il^ackeoroder.)

Prkimiim\ Stealuma.

liC .n. , ^ «4 ^ 1*»4 ie-5fi _

SH _- «.. 3 .«. 0 67 0 6S _

ISO .. ^_._ iw . 19 n ........ lass _

Robiqpit.

CMtlPbW* * tAi|-. 5f 7 -.. lOOOO _ .., IM^eo _ 100i»0

Bc^biqnct iof« wt «f bcvw tbft »li wbicb ht>m'
tftloa i«w« wtib tbe ftifwab C«H*Pt>W* s SiwiboL
I m wJt, Op lb* oibcf b«n4 be ebcueed B43f« b*^
r «m «wit- of iNd-eside. bi tbi fom «r <fc*p-TrIlow
Fn»e«iA to Mttttii aflitola «l Wd feadmd ib^^^

MBCOHIC ACID,

420

Forrous enlphate forms with meoouata of aramonia a clear oolourlesa
miatture, whicb, wbeii exposed to the air, quickly becomes turbid and
aaeum^s first a yellow iuh red, tlien a dark red colour (Wackenj-oder.)

Ffiric MtaonaU^ — Mccwnic acid and ita saltu impart a bri^lit red
colour to ferric suits evea wWu very dilute, but form uo }jrecipitate.
(Sertiirner,) ^ The reddeuiug is disstin^^aiabed frt*m tUat which hydro-
atilphocyaoic acid produeea in ferric ealta by the fiu-'t that the coltmr of
tbo latter ia lighter smd luach miited with yellow. ^ — luk and wntiui^'
with iiik are aUo reddened by uiocoaie acid. (A, VogeL) — The rediloii-
in^ ia uot destroyed by torch lo ride of gold (which didtiuguiahes it from
that produced by hydroaulphocjanic acid) (A. Vogel); or by boiling'
with nitric acid and a little alcohol ; but quickly by chloride of soda and
by tutromuriatic acid. (Waokenroder.) It ia also destroyed, the ferric
oxide being reduced to ferrous oxide, slowly by sun lights quickly by pro-
tt>chloridi3 of tin (A Vojfel); slowly by sulphuretted hydro^'en, and very
little by boiling with sulphurous acid, (Wackenroder). The decolorised
liquid slowly recovers its red colour by exposure to the air^ immtsd lately
when treated with nitrous acid.

Aqueous raeconic acid does not act in the cold on recently precipitated
ferric hydrate, but di.^aolves a smdl quantity of it at a gentlo bea-t, and
m considerable quantity at about 80''^ chiefly in the for to of ferrous
oxide, eo that the filtrate on cooling depo-^its ferrgso-ferric meconate ia
the form of a reddish ponder. {Stcnhou^e.}

To obtain ferric mecouate in the solid state, the solution of the pul-
verised acid aad of sesquicbloride of iron in ether free from water and
alcohol are mixed ; and the red-brown flakes which, after a few minutes
are deposited from the deep red mixture, are waslicd on a filtc^r aud
dried. If water b pretent* blood -red drop* uf liquid &e[ijinitc ii»j»teaxl of fljikea.
— The browa-red powder thus obtained is much less eoluble than it wa^j
before drying. It dissolves with tolerable facility in cold water and
alcohol, more quickly isi hot water or in water contain lug acid. The
blood-red solution is converted by ammonia into a clear yellowish red
mixture, whereas potash or soda precipitatea the ferric oxide. — ^ The
"brown-red powder contains in 100 parts; 30 82 Fe^O*, 26*00 C, P»5H
and 41-330.

A mmo nio-ferric Mticoiiaie, — On mixing neutral meconata of aiutno-
uia with a alight excess of a eon cent rated solution of ferric nulphate made
ae neutral as poaj^ihlej this salt i 5) precipitated in a few hours in the form
of a fine, amorphoU'S, orimaou powder^ which must be washed on the fiiter
with watfir, as long as the water tukes up any sulphuric acid. The
powder retains its colour when dried in the air at ordiuarj temperatures;
but at 100% it becomes rod-brown and dull, without however any reduc-
tion of the iiei?!|uioxidc of iron to pmtoxidc. It dissolves flparingly in
cold water and alcohol, but very readily in hot or in acidulated water.
When the aqueous solution is heated to 50*, part of the sesquioxitle of
mm is reduced to protoxide^ and at 109'', the whole, the Ikjuid being at
tb@ same time decolorised. The blood~red BolutioUj if quickly heated, is
coloured deep yellow hy ammonia, without precipitation, whereas potash,
soda, or lime deoolorisei it, with evolution of ammonia and precipitation
of hydrated sesqaioxide of iron free from protoxide. (Stenhouse.) — The
erimson powder contaif is in 100 patts: 23 Q^Fo^^ 3'4dK, 31-24 0, ZB^TB
d 3d-m 0. (Stcnhouise.)

^&iii

¥CC1JZ3 C*fiP: OEXT^ClMCCCLSri O^PO^

of poCiili foms
whkk rields reiy
l) Waekenrodtf
. & Kzsn vkite precipitaxe. inaolable m
- 3 MKCXL ^fKJtikljr ia Kitric acid.
— TW ^<K itfsi 'wMiti' SB cbmsbU £re» colov to
fc riqyBE- bm vrtaoBt alter m wkile a ptle TeUov
v^rmoDK. IftioiipB^ — 'STst mekk •£ cof pei.. h forms a greei'idk
yslu^ jjuBLiHr.m* viia rrv'ei «f a jazcv ^Baatirr of pTromeeMiie add

^ i* pvccipitaled bj
h^r tW free add iaVkili

cpanngij solabk ■

— Ti* »r •£ »d EX5 poca^ «aU form witk aeicm

1 "jacr» OTHSTT i£ T«^T-sa wihe cmidix ftake&. whidi dissoln

Tsadlj n riirr a=L*L areor aci &»£ ccoukw mls^ bat are iiuoIaUe ■

JT-ryiti.'Lf *r >r« & T'^nmr. — Wbea aevtral nitrate of dm

s It- *Sj7«:a2f^ I J mtK-jnSr a=<£ exanlr aevtraliwd with ammoBit, tk
Tiixii "i^rjimf* a=i£ uic a T*>wi^ vkite p«Ipj precipitate is tbnwi
(u Vl Tiif &iitf 5kJi 3f locabifti Vt itptaiidlv boiliiif the salt b witk
r-sak ivrriit&f i£ ▼*!»?. Aser crrw;. h detc«tatw when heated It
JsBf J^^ ?*sa£rj jx cicse ricv aoi. h«t is u^olnhle in water ani it

M .. Itii _ 16-10

>> -. If*? 17X2

, --£..vr*:- J^ ..■«•» ._ 100-00

} T '.-»v Ti»f fcit*-'*^ i^-** - ::r=i^ w:iii nitrate of silver, a snow-

^\ i 7.->.-.:. -a:,' ^:.oi .:.•** !>:■: '^«;-•w cri^ialline when washed wii:
^.,.^ ^^.-i- > r.tr^fCTi*£ -Tt" 5 Vj 't<il:rr with water, and when keitid
jJ;J[« ^.-^ J ~ ^I»f•,:^ ui a?o.ai>.-*5ef w-.u.<*i desooation. leariD/?52'2Sp.c
,/'^r.; ^^v;r lj=y^ ^ii-"7i.i-». T, 240.^ — Urt»iy forntaij obuad
jtmt^ -rl^-w^ * L*i c«i«r MiMTsarr &&iue- cucmBista»£«». a white precifntiaB.
« fcv** ^b-'x »»««?- «*^ *•'■** «!»a.i« tK i.-cm ••^ tt-aiac CTrstaliiae luctn«, and ••
■a sJi-i: 33nrifc."0.>=* jc*v-jif 4? SiS per oeai. of white iilwr.

i V:

>-i-t «r : !< ■ . Liebic.

•, - >4 ?l^-?> - 20-00

'1: 1 _ i^4> ... 0-4S

. it i-l> 52-2S

^- :-: vr*^^-- *•* ''"^'^^ 100-00

y^ j^. : ^si.:'^ rf»i-.> :t aI«i-ioi v^^'tiinerX less reidilra

ETIIYLMECONIC ACID.

431

Conjugated OompoundM of M^onie Ami,
Ethylmeconic Acid.

J. How. (1S52,) Edinb. Phil Shtni. 20, iOl .—Ann. Fharm. 83, 357-

Fonnntion and Prepnration, Hydroclilorlc acid gm is passed into a

olution of niceontc acid in a^bsolute alcohol, till the liquid ramea stfoxigl J J

coolitig, a precipitate forms consisting of thread-like crystals wliich

be washed with cold water and recrjstallised from hot water,

' ©nlj recti ^ed fipirit is uicdt mecooAte of ethylmrconic add lep^rnieft nftcr % longer

me only and in a less crystollinei «tale. The mutberdit^uar cautftitia bietbyltuei^mc

pad.

Properties. Small ehining eqimro needles. Does not gi v^e off any
rater at 1 00'', The aqueous solution has a etn*ng acid reaction and
filiates albumen*

IB C*.. ,

. lOS .

... 47 ^3« _
... 3'5I> ..,
... 49*14 ...

Bow,

47*26

B M

8 *

3-71

14 0,

in .

.... 49*03

C"H*0'^

„„ 228 .,

,„ 100-00 ....

100-00

Dfompmiiiom. 1. Melts at 158^ or 1,^9 ", into a transparent yellow
liquid, yielding at the Kinie time a sublimate consisting of shining fhornbic
IVysials. — 2. With alcoholic ammonia^ it forma meeonamic acid; caustic
iTomonia in excess decomposes it rapidly, — 3. Heated with alkaliea it
yields nieconates.

Omi h'mat ions. Ethyl m eeon i c ac i d di ssol res read 1 1 j i n w a ter.
It eatpele carbonic acid from the carbonates with efflorescence. The
^ih^lmcvomiies are hihauo (neotnil) = C'H'M^O^* or numobmie (acid)
eC^^K'MO^*: — the acid appears also to form salts with ejtcess of base,

Ethylmtconatt of Bf^ryta. — a. JSiMsw. — When the boiling aqueous
glutton of the acid is exactly saturated with carbonate of baryta, the
Hrate deposits the ealt in small yellow needles.

2 BaO .. ..,

_ 210*0 ,

.. 42']8 „..
.. 5782

How.
.., 4189

C»^H*B»»Oi< _

.,.. 36:V2 .

... 100-00

In other eiperitnenta, How abtAined from 42 to 44-5 p«r ceat. of hi.TjU, n lutlc
II bATUi^ probibljr been formed together with the ahove,

6. jlfoitt«>5a*i^. — When carbonate of baryta is gradually added to
r&ter in which solid ethylmecouic acid is immersed, the acid quickly

; jeUov ah. aad tk

qoutity if

^ IlmtjoB; and oi agia

«r mt m gentle hetK

^ whidigiwif

-j^—T

- 25«
~ 2-3*

Hov.

»17

36-20

2-63
. — 33-00

^ -

'i--l

-i

r« ^ IMM

lOHM

of Vanrta £[>nii8 with acein
^Tik sslpkue of copper, a nb

rjie «f iron, a brown-red moft
«r IB exoeas of Uie iromnlt

T >^ T^f^ EdkjimMaaje add koated witk eaa

:iL TBTTig iW a^aeoos aolation of the ^^

t£ mtwv. a pnopitate is fonned which vk

mSac vKer^^Mlds oa cooling, smaU duiif

xnayt BeKuwanalterodindajlight Gm

. 3#» — 32 23

_ r _- 2-08

- ;• _. 32-23

33-46 _

• •♦

How.
31-92
2-20
31-94
33-94

.^^Ar-'

i:^ ._ 100-00

10000

i£iT-^xi«»:nJr *o£ 5aittres resJDj in ordinary alcohol, less i»£j

ji s3fcvi-xif ijr*i 1 rafc£i:T in fd^.

— If lif i^'a.i':^ xiei in t^e preparation of etbylmeconic aciJ i* **
ij*.t.i.-f. li-ic- '-? irrfoaied, after the fealhery crystals of etbvlmeet*
i^i'L. & >s5 ;^i^:A..:i>e precipitate, which sometimes separates aUfri
:it n. -.It -•-::,::..• vf cihTlmeconic acid. This precipitate, when panfi*
':t rfr^:i:ei ^^I-ucs in a *mall quantity of hot water, forma i »ia
azi.r: i. ii-s jic wier. rerr soiable in water.

^100'.

52 C 192

12 H -.... 12

28 O 224

C^^HK)".

428

How.

2 80 2*92

>2'3S : 5241

100-00 loO'OO

BIBTHYLMECONIC ACID. 4?^S

The wann aqneons solution supersaturated with aiiimoDia, turns
yellow without separation of meconamate of ammonia; on addition of
strong alcohol, the liquid deposits small yellow radiated crystalline tufts.
On evaporating to dryness, there remains a substance, only a very small
part of which is soluble in water; the soluble portion forms with
hydrochloric acid a precipitate consisting of needle-shaped crystals. —
When treated with bases, it does not yield salts, but is decomposed more
jquickly than ethylmeconic acid.

Biethylmeconic Acid.
C«H»0" = 2C*H»0,C"H»0»

H. How. Edinb. Phil. Tram. 20, AO\.—Ann. Phm-m. 83, 357.
Biethylomeeonic acid, Didihylmekon§dure,

Formation and Preparation, 1. A mixture of meconic acid with
absolute alcohol and oil of vitriol is kept in a state of moderate ebul-
lition; and as soon as the residue in the retort has become syrupy, it is
ponred into a large quantity of cold water, and the rose-coloured pre-
cipitate thereby obtained is several times crystallised from water. —
"When the quaotity of sulphuric acid used is rather large, the product appears to consist
diiefly of neutral meconate of ethyl 3C^H»0,C"HO". (How, N. Edinb. Phil. J. 1, 212.)
— 2. The acid mother-liquor obtained in the preparation of ethylmeconic
acid and meconate of ethylmeconic acid, is evaporated at 100° as long as
acid vapours continue to escape. The residue, which forms a thick oil
or viscid mass and crystallises on cooling, is recrystallised two or three
times.

Properties. Colourless, flattened prisms. Melts in boiling water
before dissolving. Has a strong acid reaction and coagulates white
of egg.

How.

(1) (2)

22 0

12 H

.. 132 .
.. 12 .
.. 112 .

... 61-56 ...

... 4-68 ...
... 43-76 ...

51-22 .

4-88 .

43-90 .

... 51-34
4-84

14 O

... 43-82

OaH«0"...

. 256 ..

.. 100-00 ....

.... 10000 .

... 10000

Melts to a yellowish liquid at llO''. Boiled with aqueous ammonia,
it forms hiamidomeconic acid.

Biethylmeconic acid decomposes carbonates with effervescence. Its
neutral salts are C«H"MO".

Biethylmeconate of Ammonia. ^ solution of the acid in strong alcohol,
through which dry ammoniacal gas is passed, coagulates to a nearly solid
yellowish mass, which, after being pressed and dissolved in hot alcohol,
forms on cooling silky needles united in radiated groups, which dissolve
•readily and with yellow colour in cold water. Acids added to tie
solution throw down the acid in its original state.

TOL. XII. 2 F

434

PRIMARY NUCLEUS C»H»: OXTOBN-KUCLEUS C"tt«0*.

£2t:

N,
15 H.

Dritd

.... 132 ...
... 14 ».

... u ...

.,. 112 »,

. 48*35 ..

. h'li ...

, 3-49 ..

. 41-04 ..

How.
.... &'46

14 O

mm

■rm

C*KH

ifNBW*

.. 273 ...

. loooa ..

...... 10000

MifiJiylmemnatt of Barifta. — The aolulfon of the ammoiiiacat
forme with cbloride of barmtn a yellow gektbouj precipiUite wliicti li
in^luUe m water^ bub didsolvea readily in excess of cUlaride of bfij-iam^

At 100'.

B»0 ,„ 7fi-6

C=5H"(V' 2170

How.

23-68 2354

76*32

C^H'iBnO'*

323'fi

10000

I

The strontm and lime salts resemhTe the liaryta-salt. In a solutioo
of s^lphnte of magnesia^ the nmnionia-salt furnia a crystallme precipitate;
with sulphate of copper, & green gelatinoua pim-ipitate. Ferric mitt
colour tlia acid red. With uitrate of W/ver^ the ammoaia-ialt foniui
yellow gelatinous precipitate insoluble in boiling wnter.

Biethylmeconic acid dissolvea readily in alcokoL

Meconaimdi€ Acid.

ft. How. /oc. cU.

When a solution of ethyhuecoaio acid in wann water or alcohol '«
mUed with aqueous or alcoholic ammonia, the liquid n^mm^ a tWp
yellow colour aod bccuitiei filled with a yellow ten ii*gelali hods bodj«
which, after washing with dilute alcohol^ driee up in the air to an a1I10^
phtiua mas3. The solution of thia substance in hot water forma wiih i
gmull quantity of hydrochloric acid, a white precipitate, which diasolTii
in hot waterj and the eolution, on couHng, yields meeonamidic seid ia tko
form of a white crystalline crust.

I.
g4C..

7N,.
3^ H.
78 O

504

39
624

39-84

3 -OS
49*34

11.
14 C.
N..

5H.
12 O

84 ....

14 .,

5 ....

06 ..

42-21
7-03

48^25

i

3*M

C**Nm"0^... 1265

100*00 C"NH*Oi3

It?

Actx>rding to How (1), the corapoimd i» CWN^H*^^?^

Athylm (iconic acid and atitmoni* by climiimtion of ilcohol ; '■'■
C^N^ll«0« + 6C^H«0-; icqgrding to Gerhirdt (H), it b n

audtt'o'*.

Boiled with pot&shley, it gires off ammoni&j and the
meooaic acid.

OALLAMIG ACID. 435

AnmdvUi^-^onipouhd. — For the preparatidn; vtd. rap. -^ OoBSists of mioro^
8«Mia round grains or oellnled. When dry, it may be rubbed with
iifroulty to a powder having a fine yellow colour. Disfiolves readily id
loi water, with erolution of ammonia. Gives off ammonia at 100^
blackens and melts at a stronger heat.

84 C

16 S

63 H

504 .

224 .

63 .

... 36-23 ...
... 1624 ...
... 4-52 ....
... 4801 ....

How.

86-42

15-98

f78

.... 42-82

75 O

600 .

C84NieH«07«

.... 1391 .

... 10000 ....

100-00

According to How, it is C^^7n^(SR*)907^ + 3Aq.

When decomposed by hydrochloric acid, it yields a quantity of sal-
ammoniac corresponding to 10'4 p.c. (9 At.) of nitrogen.

With baryta-salts it forms a yellow amorphous precipitate insoluble
in boiling water; with nitrate of silver, a yellow gelatinous precipitate
which blackens in drying ; — both of variable composition.

if. Oxyamidogen-nudetts C"Ad*H*0'.

Biamidomeconic Acid.
C^*N»H«0»° = C**Ad»H«0«,0*.

H. How. iV. Edinb. Phil J. 1, 212; Pharm. Centr. 1855, 360; liebig
and Kapp's Jahresber, 1855, 494.

When biethylmeconic acid is boiled with ammonia, biamidomeconic
acid separates and alcohol is evolved :

20H»0,C"H20« + 2NH» - CWN*H«OW + 2C*H«0«.

Greyish white powder, which has a strong acid reaction and expels
carbonic acid from its salts. It is readily decomposed by caustic alkalis.
I)isso]Tes with difficulty in cold water and in dilute acids.

May be regarded as bibasio meconate of ammonia minm 4 At watet:

C"H2(NH*)20" - 4HO = CiWH^Qi®. f.

Otytmidogen^udem C^AdH'O*.

OflUamic Acid.

C»*NH'0» = C"AdH»0*,0*.

#*. Ki^op. Pharm. Centr, 1854, 857; 1855, 657, 741.

OMnnitudure, GaUustdureamid,

PHpttration. A boiling solntion of 8 oe. of tannic acid froiii CfaineB* .
gall-nuts in the requisite qaantity of water, is treated with a mi:|tQr0

2 F 2

436

PEUMARt NUCLEUS C^*H«,

eon tain ing^ to erery 5 ox. of strcm^ atniuonis, the fttoun d vi.
ralptiite of ammonia obtained IVom 3 drams of the cmrraalcvwfnf^
lions being bo adJDsted tbat tbe liquid nuLy still matS. IbliMltf 4
ammonia; and the liquid is kept in a state of bnsk ebiUite vl
bcigtiifl to tnni thick. After the soltition baa oooled to 40", ullAini
acid gms is p&ssed into it, whereu;>on gallamlc acid ^epaimtas^ m 9m
tlie whole to sotidifj into a crystalline pulp* Tbe raoUief-liqwr «rt*i^
lijdrjIamiEiviucte of pingmttic acid >tid prob&blj^ also tliAt of ellji^ add*

EFroptfiiti. Colonrless cryBtalllne Imminm baring a fittj Isia
Iteddens Utmns. After drjring at BQ^^ it does not give off loy nii
at lor.

U C.
N

BO

%4

14

7

64

CNNH?0«... 169

8-28

414

37-8S

100*00

4f*yo

4*29
37*84

Decompo$kianM. 1^ When boiled for some time with dilnie ta<ki
yields gallic acid and a salt of ammonia. — 2* By boiliog with ]w^
ley it is decomposed in the same manner as galito aeid» '

Comhtnations. Gal lam ic acid diseolves in water mixed with Ufii
quantity of strong hydTochloric acidi and crystallises titialtered oq b(?Ua|
Decooi position take^ place cmlj a^er cotititiued boiJin^,

Reep^ctiu^ Che crystals ftrst c&lled bj Knop ThmmigtmsmMamrit iWa Giif^
r^urrttmidt then GdflMtiitrfAjr^r|^;aminami<f, but oaw regmrd«d as ■ wifetf^ 9
Pkarm. Cbifr. IS52, 417 ; U^4, 858 i 1855, e£l and 8^7 (ooffip. Tteae t^dV

Damaluric Acid.

STiDBLEB, (1850.) Ann. Fharm. 77, 27. — J, pr. CSIflU, 51, li-
/^Aam. Oai^n 1851, 10.

From iafrnkic (a beifbr) md ^upov*

Occurs in the urine of the cow, of tbe horse and af bil .
the solution obtained in the preparation of tanfjlic aeid (xL IJ
agitating the oily mixture of carbolic, taurylic, damalnrie aad di
acids with carbonate of soda, is evanorated and distilic*4 withi^*'
acid, a distillate is obtained having the odour of butjnrtc acid, a
ing of a heavy oil and an acid aqueous solution, Thia diatUlila
with carbonate of baryta yields a filtrate^ from whtcb tkera i
first crystals of damolate o( baryta, melting when heated aod i
9700 p c. of baryta,— then crystals of damaluntU of haijtiw
ly, crystals which contain 4446 p, c. of Wyta, and art pfofctllft
tiire of damal urate of baryta with the baryta-s^h of l>iitjTJ«^ ^i-i*-i.
peculiar acid.

TANNOXYLIC ACID. 437

Damalurio acid is a colourless oil^ somewhat heavier than water,
and having a peculiar odour like that of valerianic acid. Reddens litmus
strongly. Decomposes carbonate of soda.

Damalurate of Baryta, — Very small white prisms which when
heated, do not melt, but leave carbonate of baryta in the form of the
crystab. Blues reddened litmus paper.

Stadeler.

BaO „ 76-6 .... 39-16 39'19

CMH"0» 119-0 .... 60-84

C"H"BaO* 195-6 .... 10000

The baryta-salt forms with basic acetate of lead, a white precipitate
consisting of microscopic needles arranged in spherical groups, and with
nitrate of filvery a white powder not blackened by light.

Silver^Malt, StSdeler.

14 C 84 .... 35-74 3538

11 H 11 .... 4-68 4-68

Ag 108 .... 45-96 45-70

4 0 32 .... 13-62 14-24

""^ C"H»AgO* 235 .... 100-00 100-00

Oxygen-nucleus C"H«0«.

Tannoxylic Acid.
C"H*0" = C"H*0*,0*. ?

Ph. Buchnbr. (1845.) Ann, Fharm. 53, 369.

Formation. By the action of cold potash-ley on querci tannic acid
in contact with the air.

Preparation, A cold moderately dilute solution of potash is saturated
with quercitannic acid, and the solution, after exposure to the air in
shallow vessels for some days till it has become blood-red and opaque, is
precipitated with neutral acetate of lead. The red precipitate is freed
from carbonate of lead by means of acetic acid, the colour then changing
to a fine carmine-red; and the admixed tannate of lead is removed by
repeated treatment with acetic acid, and finally by boiling with dilute
acetic acid, till ammonia no longer forms in it a precipitate of tannate of
lead. The tannoxylate of lead is digested with alcohol and a quantity
of sulphuric acid, which leaves part of it undecomposed, and the acid
mother- liquor is evaporated over the water-bath; it then leaves a red,
nncrystallisable syrup^ which dries up to a brown-red mass when the
evaporation is complete.

The lead-BsAt (preparation above given) has a brick-red, or in the moist
state, nearly a carmine-red colour. It dissolves very sparingly in strong
boiling acetic acid, forming a reddish solution which deposits reddish
flakes on addition of ammonia.

438

PRIMARY NUCLEUS €?mU^

0*96

IL

n PbO , 122f-i

mc »„ M6-0

19 H 10 0

4H O ._„,...._. 544 a

C»*H*CM»,3PbO _ $18 4 _ lOOOO C*«H»»Fb"0** ,, 1928*8 „,. lOTOO .,. lOHl

C«]mlAliaii l; It iccording to Bochner ; icconlinf ts> II (GerH&rdt, TV. J, (51^
tla«salttft4C^H4firai^,3(PbO,tIO), « formuU which r«pre»^u tancoxf tic idij «

Primary ^udeut C**W\

Naphtha, c^w^

Lauiuent. (1 837<) -4?»n CAm. i^Ayr 84, 32 1 . — ^nn, PJUrm, 2J., m

— /.pr. CAm. 11, 418.
PEtirETiEii & Walter. J, Fharm. 26, 554.^ — N^. Mr, ArdL 21, li!,-

I'harm, Centr, 1840, 880*

Cootained in tock-ciiL

Prtpm^ion. 1. Hock-oil of Amiano is eubjecte'l t^s repeated la^
tional distillaiioDy the operation being stopped it; eacb case «& lotn •
one-tbjrd of the liquid bas p&ssed over Tlie rolatile fjortion is rwtiiri
over pbosphoiic aciJ (p. 439), (Pelktier & WaUer) ^ 2. TIi# meW
k treated with oil of ritriol before distiMation, (Pell^tirri Wite.
p. 435). — 3, The most volatile portion of the empjreumattc oil fAmwd
by repeated fractional distjUalton of bituminoua shale (p. 442 r, t*
fied bj agitation with oil of Tiiriol mnd TectlBcatiay iiver hydn
poUsb. (Laurent.)

Ana i

Proimrtifs. T ran i'prt rent, colonrles*, mobile Iiqoid. That whii '*
prepared by the third method lias a peetiliar em pyre mnn tie otliMir. TW
oil obtained hy the Best method b<>lla between S3^ And ^H'^; hf tk*
second, at 00°; by the third, between 80'^ and ^^''^ Sp. gr. of ibttM
(J'7I4. Vapour-tleneity of the firetj 2'B; of the second^ 3-42.

14 C_....

14 R , ..

84
11

i4-2e

Laanent,
84 f 8

l4-»» _ U#

C»*|J" ... 98 ».. JOO'Oa

nn ^^ 100 00

Wf

VoL DciiJdtj*

C-T»poiit .».»».»..„. 14 *, .»„ 5-8240

Hfus -,.., U ............ I»'9702

KA|»bth£*v«pour ...t 2 .^... - #794f

I » 3*3971

Aeoording to the batllnf point ^tii* 5?), thi^ fomiitta of n«phtha tbcrQld I>« C^i
which however requiret 87 50 p. t. C md 1 2*^0 II t the boilitig poizit i - -

NAPHTHA,

439

Bt^omposiiioni, 1. Naphtha fakes fire on tlie approRcb of a bnmin^

Loily, evett at s*>me distance, and huros with a bright, but aoinewhat sooty

flame, (Laurent) — 2. With chlorine m aunshiite^ it forms hydrochloric

acid and condenses. (Laurent.) Chh^rine pa^tied tbrou^^b it at a gentle

beat cocverta it into a yellowieh oil heavier than water, w^hich burns

Irom a wiek» exhaling an odour of ht^rse-radiMh, cannot be distilled

ritbout decompoBitiMn, but is not altered by acids or alkalis. — Broimne

cts iu a siniilur manuer, — loditie h ohnndnmly diijsiplved by napbiha

nih the aid of heat, and on c<ioling, the exceas of iodine sejiarates in

^e crystalline form, the napbiha not beings perceptibly altered. On

treatiug the <!bloriiie'Compf>und wiih iodide of potassium, a eub&tance is

formed which appoara to contain iodine. (Felletier & Walter.) —

3. Naphtha is hat Jitde attai-ked when heated with nitric acid; but by

uonti lined heating, ampelic acid ii proiiuecd. (Laurent, Pelletitr &

Walter.) Oil of vitriol, hydrochloric aoid and potaeh do not exert any

^ mction upon it (Laurent.)

Napiitha ia slightly soluble in alcoliol of 33°. It mixes in all prnpor-
lioos with ether. Gaoutehouc immersed in it^ swells up and h^om^
,ey, but does not diaaolve. (Laurent.)

Appmiix io Naphtha^

Eock-Qil, StrtJi^l, Bergi^t, Bergifaitam^ QmHnut&l, Petrohvmt Bitumen
tiiUdumt NaphUf Biiumtne ti^uide^—izi tli« |iur*r BUte, K&phtha. . — Espen-
kally a mixture of a variable numV»er of volatile oils consist ing
pf Cand H in equal nuniliera of atonjs and gencnilly mixed with paraffin*
|— According to Felletier ^t Walter, the naphtha, naphtliene and naplithol
Jpid.in/A olitaiiieil from rock-oil by distil bt ion with oil of vitriol, are
Contninod in it ready formed.

Crude rock-oil from Amiano of sp. gr. 0*836^ yielda hy repeated

rectiiicntioii in the water-bath at a very gentle heatj about 0 3 per cent,

of the pares* oil of sp gr. 0'753 at 16 , wbicb begins t^) hoil at TO'', but

n^oes nc»t boil constantly till tlie tempemture rises lo tll'^; it mixe« with

^Epold absolute aleubol in all proportions and dis^^olvea in 7 pts. of alcohol

^bf ap. gr. 0-83i. The vapour at 20 3"" has a tensinu etjuivalent to 7 cub.

^Keut. of mercury. (Saussiire, BilL univ 1832^ 100.)

^K AmiQUft Naphtha is amber-colouredj of sp. gr. 0-^4^ very mobile;

^naa astrong but agreeable odoar; contains 85*67 p e. C auil 13 I7p- c H;

Wg^ioa to boil at 125% and is in full ebullilion at 130% the temiierature

then rising qnickly to 270% at which point J of the licjaid have paMed

, over. The distillate obtained between 270" and 300' is y 1 lower and

©ily» hut tolerably mobile; above 300% there passes over, fin^t an oil

which solidifies to a tremuluus maa,*3, then a buttery nia^s, which yields

paraflin after tie oil has distilled over; and in the retort there remains

cliarciial having a metallic lustre. By repeatedly rectifying the liquid

which distills over between 125^ and 270, taking each time only tbe

£rat third of the previous di&tiilation. pure iiapbtlia i^ obtaiited, b<uliog

at h5'\ and amounting to about y^j of the entire quantity of rock -oil

The rectitication of tbe distillate of higher boiling point, accompanied by

dehydration with phcisphoric acid, doea tiot yield oils c^f constant boiling

jioiut, — When commercial naphtha is mixed with cold oil of vitriol, the

44t)

PRIMARY NUCLEUS D^H»*.

acid becomes red and ellgbtly heated; and the oil dee&nted ihereJroqJ
wheo again mixed with oil of vitriol ^ does not Inrcyine heated or a^aiffl
any colour^ the sulphuric acid only bocotiiing^ pale- red; if thia treatuseM
be repeated four or five times till the sulphuric acJd no longer keeOHMfl
coloured, the decanted oil may be J^eparated by repeated di^illation JnM
oil«j of tolerably conetant hoiliu^ j>oint, and with peculiar facility mtm
oils whose boiling points fluctuate about 90"", U5^ and 100". (TtM
Naphtha, Naphthene and NapkfhoL} Amiano naphtha is therefore a mixtufd
of pa raffia with at least three uils^ naphtha, aaphtheae and naphthoQ
(Pelietier & Walter, J. Fhmnn. 26, 549.) |

Wben pur^d white rock -oil is di&tilled with f pt«. ef water and HmcJ
the first I which pa^sei over boila at j^5°7^ is but little attacked m
strong eulphuriG aeid, and becomes inodorous and iudifiereut to nitric mI|
when shaken up with water; the next f boils at 172%^ the l&#t riaH
gradually to 232^, but^ like the firsts is colourless^ tnobile, and not enipN
reumatic. The residue separated from the water and dietiJled by itaeli|
yields a yellow oil boiling at 310% which disaolves for the most part w)t||
brown colour in strong enlphunc acid, becomes continually thicker^ ao||
ultimately leaves a brown oil^ from which boiling absolute aJe^lMH
extracts paratHu and an unsapouifiable fixetl oil; from the residue «tlia
extracts a brown indiflereut resin, (Unverdorben, Sckio. 57, 243.) I

Native rock-oil from Baku has a sp. gr. of 0'835 and begins to boil ail
140"^^ but cannot be separated into liquids of constant boiling point dTfln
by oft- repeated fractional distillation^ the distillate obtained at a certaitl
temperature being resolved by subsequent distillation into liauida oil
higher anrl lower boiling point. The oil thus obtained is mobile^ mA
after being shaken up with strong sulphuric ucid^ which takes away adi
empyreumatic odour, smells agreeably aromatic; it has a sp. gn of O^d
begins to boil at 80"", but is in full ebullition only at 130"*. — ^ Rock-ot||
which had been distilled over water in Baku^ smelt very much like otifl
of turpentine^ had a specific gravity of OS and borled at 110^, (HiiiJ
Poijij. 3G, 417.) -- Blauehet and Sell {Ann. P!uirm. 6, 308), by dist^H
Persian rock-oil with water and frequently changing the reai^^|
obtained : 1. A small quantity of liquid of sp, gr* O'T40, boilin^^fl
94°, colourless, and aromatic; 2. Half of the entire quantitv, boiling «M
138"^ (on repeating the distillation, the first -J boils at 118*); 3. Aa aij|
boiling at 187°^ and having an aromatic odour; 4. After all the watafl
has passed over, a yellowish oil boiliug at 220°; on rectifying over limoil
the portion which first passes over boils at 215^; sp. gr. 0*849, {Pw imI
anaJy*w> Bee pjige 442). According to Thomson {Thmn. Ann, IS, 307 jl
BchuK 29, 374) Persian rock-oil is transparent and coloarless, of sp. ^.1
0'83G, boits at 160% the colour becoming darker and the boiling poiati
rising to 172% and contains 82-2 p, c C and 14*8 H. — Oregor™
{J. Pharm. 21, 536; /. pr. Ch^m. 4, 1) found the rock otl fruoll
Itangoon (Persia) to be dark brown with a tinge of green, buttery all
ordinary t em jicra tares, liquid at 40% of sp. gr 0-880, with a not unpl«4*l
fant odour of floivers and smoke. When distilled, it yielded, firt t a |ttliJ
clear, mobile liquid having an agreeable odour, then a viscid ftmm
yellow liquid having a slightly amoky odour, and finally^ &a the neall
on the retort rose to redness, a pale yellow di^iillate whick aolidMoll
at ordinary temperatures The second and third dtstillate^ oontaiadl
paralfin a^ previously found by Ohristison, the first likewise cnntaioedl
eupione. — IT Warren De la Rue Sl Hugo MUller have exatnined rock-etll
jw eartli-oil from JBurniiyh,. knowB in cgmmcrce as BurmtM n ^pkiki^^m

NAPHTHA.

441

L

^San^oort tar (Proe. i?^y. Soe, 8, 221; Chem, Qaz. 1856, 375). This sub-
stance has at ordinary temperatures the conslatetjce of goose-fat; it is
1 lighter than water^ haa a greenish colour, and a faint, not nn pleasant
odour* It containa 96 per cent of volatile constituenti. When it was
distilled in a current of steam, first at 100"*, and afterwards at Uigher
temperatures, U percent, passed over at 100\ consisting entirely of a
Tolatilc oil free from solid hjclrocarbonSj from 110' to 145^, 10 percent,
of liquid nearly free from solid matter; from 160'' to the melting point of
lead, 20 per cent, of liquid which contained an appreciable quantity of
eolid matter, but retained its fluidity at 0 ; at a higher temperature,
31 fier cent, containing eufficieut solid matter to cause it to solidify ou
cooling; and at a still greater degree of heatj 21 per cent, consisting of
liquid and solid substances; and finally 3 per cent, of a substance having
the consistence of pitch. The portions which distilled above 14d^
yielded, at the temperature of a freezing mixture, a quantity of suHd
matter amounting to 1 0 or 1 1 p. c. of ilie crude tar. — The solid products
of distillation yielded by fractional crystallisation from alcohol, at least
two substances difleriug in their physical properties, but identical in
composition, {either C'^H" or C"H*' + *).— The liquid products of distillation
were found to contain benzol^ toluol, xylol C^*!!"'^ cuniol C^"H^^i£c, toge-
ther with other hydrocarbons, apparently, belonging to the series 0'H" + '.

Roch(>U fi'Qni tht Tegern^e (quirinus oil) is brownish by transmitted,
dark olive green by reflected light, viscid in the cold, mobile at 20°, of
sp* gr* 0*835 at 20-5 '. Has a strong pen etrn ting balsamic odour and
but little taste. Yields by fractional distillation : 1. A nearly colourless
distillate having a strong odour of flowers and somewhat of oil of tur-
pentine; ^ — 2. A yellowish distillate of leai powerful odnur, mobile at
9% and solidifying for the most part at 6^ into a soft crystalline mass
which when filtered at 0", leav^^s paraffin on the filter, while the greater
part runs through; — 3. A reddiah yellow thickish mass consisting of a
small quantity of oil, pamtlin, and a resinous substance; in the residne
there remains a difficultly combuitibJe charcoak (Kobell, J*p9\ Chtm.
8, 205.)

Rock 'Oil from Niihtfloiv near Kalusz in Galicia is of a yellow- brown
colour inclining to green, of sp. t^r. O'P60, of the consistence of an extract,
and not completely fluid below 61°; that from Tmscawiee, of similar
colour, a p. gr, OSOO and thin syrupy consistence, did not yield paraftin
by fractional distillation, and was not coloured by nitric acid after recti-
fication; the first portion of the distillate which then passed over boiled
at 274"^, lost its offensive odour when treated with oil of vitriol, acquiring
an agreeable odour like that of flowers, and turning red; when repeatedly
distilled with oil af vitriol and a small quantity of nitric acid and washed
with putash, it yielded a transparent colourless liquid, having a pleasant
odour i*{ flowers, nearly tasteless, of sp. gr. 0 722 at 15", boiling at 1 10%
nnd not altered by acids or alkalis (perhaps eupione)* (TorosiewicK,
M^eH, 55, 15.) — Rock'Oil from the mineral water of TridkoHnec,
cannot be obtained of lower specific grav^ity than 0720, even by repeated
fractional distillation; it boils at 90^; has an agreeable odour, is very
inflammable, and burns with a white flame which does not deposit soot*
(Torosiewicz, Repe^rt. 61, 398.)

The oil obtained from the asphaUiferoiis limeatone of Travers by
repeated distil Jation, —after being shaken up with -j'^ of oil of vitriol,
decanted after standing for a week, freed from sulphurous acid, exposed
lo the air, shaken up witli a solution of caustic pola^b in 20^ pts. of

442

PRIMARY NUCLBU9 0*H".

water, tlien witU 9 measttrea of air; then with 4 or 5 measures of wmt«
Ihen^ after the oH hm been de&iDled from the milky liqaid, a^o tbakeil
up with air and water tid tlie water h no limger rendered milky, ^«|
becomes ns infulorouB nn a fixed oil. (Saaa^ure.) — WUeo ilie empifren^i
matie oil from hitaminotis ghak is dL-tilled, it begins to boil at 1110% anil
llie boilinji^'^ point pradutiny rises to 300*; but even if the dieiiUat^*
fractionated at every 20°, and then distilled apHrt. no oil of con^taut boillngl
point t% obtained, the boiling point of earh fraction varying only 5" fft*ml
the beginnifig' to the end. The meet volatile portion boila from 80* lt|
85^ (|) 430); that from 118** to 128"* is very like the former, and whstl
«et*eral times distilled with strong nitric acid, yields a eolourlesa oil||
which boils between 120 and 122*, and k probably C**H^* (g- v.), TbiJ
portion which boils at 16J^' appears to be identical with eupionftl
(Lanrent, Ann. Chim. Ph^A. 64, 321.) [C^H^*, the boiling of which hf\
calcuLition ebould he 165^? L.]. Compare Volekel, (Ann. Ph^rm\
87, 139/)

To pnrify commerciol rock-oil, B^ittger a^iLites 2 lbs. of it ^llj
from i tu 6 oz. of fnniing oil of vitriol, and leave^t the mixtore m
closed veasei, sbakinir it freqaontly; the foreign matters are the
carbrinized. On opening; the vessel, a large quantity of enlphur^itif
escapes ; the transparent colourless oil is decanted with a si pi
repeatedly ebaken np with water and then with 3 oi. of quiek Mmm i|
lamps of the size of peas, and then decanted. Tliu oil tUtts ohtaisil
may he n^d for prefer viu!^ potasiiLum and sodium. {Ann. Ph
25, 100.)

llrrfrntan*

^ C 87-21 „.. 8&'65 .... %2Z .... 82-08

H 12r9 ,. 1331 .... 14*8 ... 1231

«» 8^71
,-. U-29

^ lOOaO .... 0896 ... 9r 0 .... 94*39

1 ... lODOe

■ DumM. Bl.ncb.ta.Sdh

Fowntm^

^l C 85*92 .... 8388 .„. 86 43 ...

^B H . }tit . . 14-29 . ]:i*(»e

, 8583
12*80

H !»S04 .... 98 17 .... U9i9 ...

. 98*63

V Hes*. PelkUer & Wsltcr. ]

<r. A. c. a, *.

S, ^

C T9 82 to 81*83 ,... 84-20 ..., 65-85 .... 85*58 ... 8S-3 ....
U 13*50 13 20 ... 142? .... 14*51 ,.. 13 U -. 13-1 ...

84-1 .... UU .«. 1*1
13*1 ,.., 13'3 ,- U^

B3'32 .,.4*5*02 .«. 88*47 ...100*36 .... g8-75 ... 98-7 ,,

97 9 .... i^ri _ mi

Bwttrrure «n*lys*d rork-oil fnjm Amkno : fl. Bjr e^ plosion wliH oifiiv

b. By puft^ifif the Tatiour of the rucli-oil reftifieJ «C tlitt hrnt nf ||ic mwuw
thfougfa a tube fHled witU €iipppT'turiungii, wbrrcbr ht obcatrie^] fUar«x}n|i Jinii m
biisttble ^i. Thomson bur»ed crude rock- oil, Herrniinn rveti1i«il nil frttm
ip. gf. «*?(!, wuh 0 Hide of copper (Pof^. 181, 380) ; Dumni'it Pemiati oil fai4
lea in coritiict witb potasviam CiU Ihe metjiL remiincd (Terfectly brigbt {Anm^Ck
50i 2.19) —The oil a AntljrHed b]r Hl»tich«t St Snell dlitilled at 94% & at 21 5'' (\
Heu aaaljt^d % a the flr»t dittillate of crude rock-oil t ^ tl^at frym Iklm distill
WMtef} e rock .oil puri^ed b| fiQ.ci\Qt^«kl dx^ulUtion (p* 441), and agiljaUon mith

NA.PHTHA.

44S

I i^h

w

^■•cid, then wilh potAsb, »nd Ititly with itrotig iulpUuric »cid. Pelletier & Wdter
itiialysed : a. Crude rock-oil from Acniaao, which Uej^ani to boil at 125^1 ^^ tbat whkb

Rlitilled bet^fen 100° nnd 115"; c. that between 115* ftad 120*^ j d. Chat between
£0* >nd 130" ; «. thil between 140*" mnd 150^
Dfcompmiiifm^ of Batk-oiL I. Paaaeil iLrougli a red-bot porcdain
ttl»«, it yields ver^ dense charcoal baving tbe metallic lu&ire^ an eoipy-
renmatic oil contarntiijT a crjetalliue euUstance in solution, and gases. ^
2, Naplitha from Amiano eet a^<?jde in a bell-jar filled witL oxygen over
mercurj did not absorb any gas in the course of a year, but after C years,
1*62 grni.=2*I45 cub. cent, bad absorbed 0"44 cub. cents, of oxjgen, and
formed \*'S cub. cent, of carbonic acid; tbe oil wos elill colourlej'S, but a
solid deposit bad formed on tbe uides of the vessel, and a fine dust of
galpbide of mercury on the surface of tbe mercury, (Saussure, I^Qffg^
^57, 370] Ann. Pharm. 3, 157,) — Exposed to air and light, it is very
owly altered and hardens into a substance which is not asphaltum,
■3Eygeii gas saturated with vapour of rock-oil, and mixed with more

IOXVgen, explodes violently \^ ben an electric spark is passed llirtiUgb it.^ —
BTlie oil burns in the air with a white flame which deposits a large
iaantity of soot. (Saussure.) — 3> With chlorine gas. it forms hydro-
Dilorlc acid and a fuming liquid of sp, gr. 0 884, more soluble in alcohol
l&d more easily decomposed by acids [than the original liquid t]
(Saussure.) Purified rock-oil from Buku, fields when satn rated with

' oblorlne gaSj a large quantity of hydrochloric acid and a liquid contain*
ing chlorine. (Hess.) It forms with chlorine only a small quantity of

I hydrochloric acid, the oil not retaining any chlorine. (Serullas) —
4. Iodine acts violently on rock-oil, even at ordinary temperatures.
(Guyot, J. Chiwr, mm, 12, 48T.) With chlGfrkh qf iodtne^ ro<'k-oi1
bee^im-^s strongly heated, with separation of Iodine and strong evolution

^■fif hydrochloric acid, part of the hydrogen being replaced hy chlorine;

^^Uie beinif^uid mass, after being treated with potash^ which takes np the

^jiwline, leaves a light yellow liquid heavier than water, with whitieli
flakee floating upon it. Both tbe liquid niid the flakes, if passed, after
being purified by solution in alcohol, through a red-hot tube, yield
charcoal, carburet ted hydrogen, and a large quantity of hydrochloric
(icid. (Sernllas, Ann. Chhn. Phi/s. 25, 313.) — 5* Fuming fiftrie acid
imparts to naphtha from Amiano merely a yellowish colour, without
further decomposition, fSaussure.) Concentrated and fuming nitric acid
«4;ts but slightly on rectified rock-oil. When rock oil is gradually added
to nitro-sulpburic acid cooled by a freejting mixture and left in it, with
frequent stirritig, for several days, the oil^ after being washed wilh water
anil then with carbonate of socfa, exhibits the properties of nitrohengol.
Previous to tlie washing with carbonate of ^oda, the odo^^r of hitter
almond oil is disguised by a pungent odour. It seems as if the moat
volatile portion of rock-oil confiiste^fof olU of similar character to benaol.
When n on -recti fled rock oil was u^cd, a brown oil was also farmed having
^ penetrating odour of musk. {R. Wagner, l\*i^L Jout-n. 13(J, 311);
eomp Warren de la Hue, B^pert rf Pat ittvtnt , July, 1^55, 57. De la
Hue & Miiller, by Ireiting tbe most volatile portion of the distillate from
Rangoon tar with nitric or nitrtieui|diuric acid, obtained nitroWnzol,
binitrotoluol and terailroxylol {Proceedings of the Moyal Sociei^f, B, 221,
eom/j. page 440) — ^ Tbe portion of ehale-oil which bolls between 80"" and
150'^ yields ampelic acid (p. 27*2) when heated with nitric acid.
^La-urent.) — 6, Chromic acid exerta a violent oxidising action upon

^m, *tt)— T. €W<

lyriakled Wftm it itti i
^M wfcinikeloli

1 oalj with ite^ of V«i
«f nKk-4»l from T«|crai«i it

mmeAy^ oohmr. tlie tlmi d

^QS&iftT of n^i«l

* I- pt. of nttfTp it Invei h lit

m imsHt eolovrleM dktiliiSt

"MMiB, so^sirev m deeper jdlovvobofh

wmd if afterw&itlfl digested wttb itnif

&|^ Attk brown or erwm aineUijst-ni tit

L with poteib. It haa ao mgrmlite oiwe.

^id ififlt «f oO of torpetitiiie, eait«t ray

gr. »T7% teils Wtweea 04° a«d a^, wick ik

• villb ft >M4y flmne, eolours 9tmmg uiUic loi

had viih tt^^vi^golf i^ ivpatira, &iid wbeolcttarf vHI

sni^ gndsllf tatae It bn^wD . The liquid portioi d

bte ihm>d ficMi tb« mimlEii, le^Tes wl

rlia& dJstii]Miu(,

iA HwmilwwM qiaringlj in boiling &leobol IW
fowii «il asd ft fifttftJI quantity of paf&ffifi ; tW
bkkbfttfttmirait odoor like th^t of nmfi4 k

vast fftit €ttii*«tflJ, fy flbftking up with j pt. sulphum mi

rk Mi^ ft an^ ^iiftfttitj of oil bowerer remaiii^. Hi

pbaiie acid by water, dissolve ei narttallj a

■ooM-like enMftnoe ; mud the Bolntion win

af«t ft akiuig btiule m^sa, which gires ofl^ ammuntA «ki

ItMMi, dinolvei in water^ nitric acid ftod anueoiifl aletld,

Miafallic aalt&. Wlten the oil Is treated widi ftni|

[ftilftlMft it plMiii »d diitilled, the first tbird of the dtsUIUte

[«f ft y^ownA oO, of ip.gr. 10S12, which smells like riuidd

' *e sad stroog eftlphuric acid dark red, und is doGOBipoaai lif
when heated ; it dimQhm sparingly in boilbig iJoftM
liapfttftti^ agftiQ &s the litj^uid eoole.

Cbai&mafi'^M, 1. Water acquires the odonr of rock-oit

< ikmAwmg iL Hock-oil from Amiaiie diMoWes when beated ^ of fW

I p)bfw«a ftnd ^ of $ul(^htir, the greater }mrt separftUng again ia ^

\ dystalline form as the liquid cools. Of Iodine it lakea op at moti ^

— It abaorba 2f vol. hydrochloric acid gas md an e^oaJ quafitttT d

ftmmoniacal gaa. (Saussure.) It absorbs a entJtll quaniity of ga«Mi

fluoride of silicluni. (Benelius.) Mixes in M projmrtiona with h^wA

carbonic acid. (Thilorier.) Absorbs olefiant gaa io karg« ^oslifiis^

(Hess, /'p^r;. 36, 420.)

It mixes in all pnjportiona iu absolute alcohol, dtawkltva in 5 pta«i

alcohol of 41' 6ni. and in 8 pt3. of 3(i Biti, at 12'. Mixai la aO ft^

tlons with ether and volatile oils. (Saussare*) — Left ta eoQlMi »^^^

icohol and nitric acid for eight wc^ks, it doea not yield ftoyef3nriala(l '

VTbe oil of sp. gr, 0 87 to 0 &3 and having an enspyreamlk «*«f

lite oil tit iwax, v^Vuc^ ^u&^^ ov^t ^rat m the diatUiatioii ol ntk-^

CENANTHTLENE.

445

ywld^, when shaken up with | vol* uitno acid of ep. gr. 1"36, a turhid
mixture » the colour of which becomes eomewhat lighter after a while,
and from which a portion of the nitric acid ia dejiositedj clear and of a
yellow c^jlour ; with 2 pts. of atrong aulphurie acid, it ylelda a dark
brown mixture, on which afterlwodayt!, a transparent colourleas oil floats.
It dissolvea in 100 pta. of warm alcohol of 0855, separating for Uie most
partaa it coola, and In 2 pta. of ether of 0 75* (Anthon, lieptrL 54^ 77*)
Reicheubach (Schw, 60, 19) distilled 50 kilogrammes of coarsely
pounded coal from Oriamuyi near Briinnj with water, aa loug as oil
continued to paaa oyer with the watery vapoura, repeatiiig the operation
eight times, and thus obtained from 400 kiL of material, 150 grma. of oil.
The coal oil thus produced is transparent and greenish yellow; boila at
167"; haa a ap. gr, of 0'835; emcUa and taatea like rock-oil; la not
altered by exposure to air and light. It burns without a wick, and with
a bright sooty flame. Placed together with iodine under a bell-jar^ it
a^baorba vapour of iodiue, becoming brown* red, then turbid, and ultimately
dear, a dark oily iorline-compound being then deposited. It dissolvea in
eold nitric acid of 1-35, acquiring a reddiah colour and becoming clear,
with aeparation of a greenish brown deposit. With atrong sulphuric
acid and potash^ it behaves like rock-oil It does not diasoWe in potash-
ley of sp. gr. 1 '36, but yellowish-red drops form after a while below the
oil It ia insoluble in water, which howev^er acqulrea ita odour. It
diBsoIves in d pta. of alcohol of sp. gr. 0^84, and readily in ether. With
^Mpoutchouc and resins, it behaves like rock-oiL

Fomiadon and Preparatt^^n , 1 . By repeatedly drstilling conanthol
OT€f anhydrous sulphuric acid. (Bonis*) — 2, By the action- of sodium
on chloride of cenanthyleno* Sodium in small pieces is thrown into
chloride of ^nanthylene contained in a tubulated retort, and the action
16 assisted by a gentle heat* As soon as the quantity of separated
ehloride of sodium becomes so great as to interfere with the action, the
liquid must be distilled and the distillate treated with freah sodium ; to
remove the la^t portiona of chlorine, the product must be repeatedly
rectified over perfectly bright sodium. (Limpricht.)

By (1): colourless oil which floats on water and smells like caproene
(oleene, xi, 411); boila at 50^ but the boiting-point does not remain
constant (Bouls); — By (2); Transparent colourless liquid, lighter than
water, having a peculiar, alliaceous, but not very strong odour; boils
at 95^ (Limpricht.)

tEnanthylene, C^*H».

juis. (1855.) N. Ann. Chim. Fk^i. 44, SB.
utPRtciiT. Ann. Pharm. 103, 80-

14 C

14 H

84
14

8s*n

14-29

Boaii,
853B
1430

Limpricht,
... HI

£^W*

98

100^00 99'68

1000

Tlie product examined by Bouii, ifreea in atl pcspects with capro^ae (ih 41 1) |
bt boilmjE point calcttlated from the fonnwla C^*H" (tu, 67) i* 70* [L.].

Soluble in aicohoL

FfiMAn mxLsirs

ip»Mifk^. C^H^.O"*

Tour. /iU Mmy, J, 33, 81.— Jn.
43. aOi.— n^rs. CMBr. 1343^ MJw
BftvTA^un. Amm. Mam. 35. 231.

dmSt, mttmfUi, Bf^rm 9f

I*

Cbtfr. 1847, 137.

%1

Bj Ifce ilfx <ltifcillifttw 0f etttor>«iL

1. TTie yeUow oilj dMiIlml« o%tm]n«cl hi fl* Iff
diititlmtioii 9f csstor-oil, it setiumlcd frooi tiie wmt^v^r )ii|iiiil and i^lM
with ire «r dx t]iQii« its Wlk ef vmter ; the dMlll^te ci»iMtiif i
fBoancM, witk mi^ q^aDtitl^a of aen^leio^ <Bruuilli vtic «eld isd «^
Altj scids !■ fehttken up with 6 pts. bj weight of wa.t«r, whiel dimM
oitt t]>e gremter pa^rt of the acrokiii, mxA «^iti drstiUrd with (knr^ vilff,
till no mora oilj liqmid reinsifi.4 ; thb dbtillmte U ehAiceu tip wttb ^ftk
Ymrj^w^tJtt till it no tooger exhibits sn Md reaeliati, tbeti dieewtfd iil
^•tsUed; and tlie portion which goes orer between 155'' ssd 15a; n
€0il«eted ft]»rt ibeiow Ur. >ett>ktn dbUb orer.) l*|,e pure oiAaiithd tl»
ohtaliied ie dehydmted by cUoride of nlotum (fioaey^ Wt]li«3BiM.)<-
2. TUiey heat^ the i&Emathol parifiec] bf dbtill^tiao in water, to 130* 0
the waier-b&tb, and paases carbonic »eiii iliruugh il till tlie oilberif
acroleia is enUrelj de^royed, then dloii]^ in the wftier^bntb at 155^ wd
tlrie* arer cbloride of calciam. — 3. The prodact of the dry di#iilUlMi
of oidtor-oil is shmken op with % aolnlinD of mrWinate of |>ot&^^ wb«^
ft so I lit um is farmed, which , when heated to the bciilin^ ptitot, jic^df IM
imiattthol a9 ft lepamte lajer od the surfafe; this lit^utd ia tbeit r0i>e^
and ttmted with a moderately eon cent rated salution of bnntpbtteaf hA,
whieb diseoWes the o&n&ntho), and leaved «& oil? liquid tftnelliiif tikt i
fixed 0iK The eolation on cooHd^ deposits surpbile of omftnthol tal
eoda^ which mu^l be dried ftnd deconi|ioi9e<1 with irftmi wmler eatHUDit
hjdrocblonc or anlpharie aeid. (Berta^iai.)

Pmpettm. Transparent, colourless, very mobile, Sp. gt.^^^T^
H&a a ^roDg, not unpleaimDt odoar and tattee aweel at irti, but ite
wards persistently sharp. Refracts liiiht strongly. Bmla between l^f"
and 158^ (Bun^y) ; 155° and 156' (Winiamaiio), At 155" (Tii>:
Vapour-density =4-130 (Basey)^ from 4 08 to 5 OL (Bouia,)

14 C ... .
14 H

.. 84 .
.. 14
. 16 .

12 2«

» 73-49

12-t3

14^

WiJltarowm.
«*. 73 40 _
«.. 12-10 .^

» I4'J3

TOtf.
73-11
1^43

3 0

C"ll**t>»,M.

... \\K

. . V^ Wl

^..^ lOO-DO

>... 13M3

I#t4t

^^^^^§ C-varH3ur ,. u*.,t 14 . fi<82ia

^^^^F H-gas U ., ... 09702

^^P O-iffla _ 1 ..«„...... 1-1093 J

^^r (EhDiithoUTapotir... Si 7'lf03S 1

■ I ......... S951T I

^ TBom cHc wUb but jr rone. Acporditig to Tilkf, it itray be regard ^3, tfli ftcduut of
pbe def^ompflftfimri by potd<b iind bj hfdrochloric acid and altx^bol (9 & 10) a4

C'*H^O.C^'*H'»tP ; but ihm ifiew ii nob aocortUnee wltk th« hwlmg point *nd ?A|M)iir-

dfiiuitj (fid. p. 23). L*

■ Btcompmiik fii, 1* Wlien llie liqaid ia sn Ejected to contiiiued dietil-
H^tiot]^ the Wiling point rises and tbe residue in the retort exhibits t
■ereater amount of carbon. ^Tilley, Bonis.) — 2. In contact with the at r.
Hi absorb* oxygen and turns sour^ when shaken up T?itb oxygen, it may
pibsorb as nmcU as 10 per cent ; at t!n* boiling point, tbo absorption goea
kn faster. (Busay.) — When o^nanthol^ which m kept cool, ia gradually
ptiixed with a 4Uu.ntUy of bromine sufficient to render the brown-red

colour pennauent, and repeatedly distilled with water, a colourleas liquid

is obtained^ which turns brown when dried by chloride of cakinm or over

bil of vitriol, antl after being freed from dit^dclved hydrobrouiie acid by

Ibaustic soda, contains 40"DO p.c. C, 6 '53 H, and from 4i'B to 4.> 7 Br.

(O^ 1 1 "O^ requires 43*& p. c. C. 6'7 H aud 41-4 Br.) On distilling it with water, &

brown resin renmins iq the retort. When tBnunthol is mixed with iodine

ntid i,h(f;iphf>rti.*f a violent explosion enBues. (Limprichl ) — 4. (Enanthol

Kb converted by cold nitric acid of ordinary strength into raetcDnaiithol ;

when distilled with 2 pts. of a njixture of I voL atrong niiric acid aud 1
_1 vol, water, it is gradually converted into ceDantbylic acid. (Buggy.)
Mrhe dijitUi^ite fiiill cotitams stuuII qoiitiltties of two other ^olaliiencid* [probjibly caproic |
HCid, L.]t and an oil which maj be separated by «ittuiating the icid distillate with
Rmrjta aud dbtilling; it ia lighter tb»n water, smelb like French cintmmon, and tnrni
Bioid in contact witb th« air ; it is therefore prob^ibl j oil of cinnamon [but oil of ciatit^
Bmo it he»viei- thaniVHter. (Gm,)] B<rffides oen anther Ik «ddf oxalie »Hd ii f^roduced
Ksd tt reddkl) yellow re ai u toltibk in alcohol. (Hussjf,) When n&nantkol m heated
Krjth 2pti} of strong nitric aoid« great heat h produced /red vapours are^dvea i
Poff, aud the greater part of the oenanthol i« destroyed. ( Bussy.) W hea '
CBnanthol is added by drops to strong nitric acid contained in a retort, a
Tiolent action takes placei and a mixture of nitacrul (ix, 502), cunanthylio
^scJd, capniie acid and nitric acid distila over; the liquid in the retort con^

■ tains <Bnanthylic and caproic acids. (Tilley.) — 5. With chhrinet cenantbol
I forms hydrochloric acid and chlorGjnnnthol. (Williamson.^ — 6, Glluanthol
I dropped upon crystallised chromic acid takes fire with violent explosijn;

dilute chromic acid converts it into c&nanth^licacid. (Bu^sy.) — 7* With
fuming oUofvitriolj it forms a conjugated acid which y j el (fs crystal lisa hi #
fialts with baryta, Itme, and oxide of lead. (Bouts.) — S, When repeatedly
disliilod over anhydrous phosphoric acid, it yields Qenanthyleiie, (Bonis.)
-*— j>* With ftfntacklondc of phmphorus^ it becomes strong Jy heated, and
yields a distillate^ which when freed from chlorophosphoric acid by
repeated washing with water, and from excess of c^nanthol by agitation
with acid sulphite of soda, consists of nearly pure chloride of eenan-
thylene (J-*H^*CP, (Limpricht.) Ac4xjrdinj to a forroer «tkitent«nt of Limprkht,
the diMillate^ after bein^ repeatrdly diatilled with water and dried oter oil of vitriol and
caustic »uda, contuined 53 '9B p. c. C, 8^70 B* and 3 1 00 Cl| agreeing with t^ie formuk*
C*H^K:i'0^ — 10. CEnanthol dropped upon fused hydrate of poiaih, givm
qR hydrogen and forms aenanth^late of potash. (Tilley.)

P5t

I>aat» f ite^ fay doM Ml a«t «

kj^xte of pstefii and kyliile rf

^ it^ mad csoimsst it ista s alt rf

lik* MMe, CUV iC ft lite

•ointiott of poiiib, «•-

alt of OMiiilibTfioiol

* bjftgtpltfdiftilk-

Hsftled wick tfaeMi

Ljfc acid mud aa ml, wldeh, whm ind

77-1 pw €> C, and 1 2*7 IL fWiUUawt.)

lor wrenJ boara wlili atcoliolie poti4

of polaA aad aa ail wbidi could noi bo 4U1IU

Aa bai^ pool qoiekljr risiog to S00^ Wkiit

^^ lia oil whiefc im pmed over eosuiaod. «6v

of ttlms, 8?-^ 11. e, C and 10-87 Hi Uio foll««-

1 » tf 1^ <^ C aad 10 43 H. CHnaJitljo] boil«d b

lEe poteili, ji^dod laaaaUi^lato of poladi iri 1

' 9jTw^ oil, oalr tiaoBo of whldi paseed otot oa diit&Llin^ 7 :^

— Boom ioaad m Ife portion of tlie oU botliag between 129 loi

lir, otemcd fcy tibo aclioB of bjdmte of potaeb 00 oBBaailio!, ^T»

PL c C aad 14 S7 H.

IK la aa alnnfcaikf aolatioe of <Baaalliolf iBnanlhjkte of etki^ •

* fej tW aedoa of i^diaeilme meid gm. (Tinej.) — J t. ^tm^

' af vlveri iHioa it ia mLsed witb auunotkim lal

aitzaia of lOins adltwl,a wUte pree^taAe la formed^ which U rediiovj %
, md ^neto tiM Yoaod. (Biuof.)

With w*ter, — a, Hydfai^ of €EnmUk0l — U^

to 5^ or 6^ depodii eoloarloo9 eiyotaJa, vfcidi vfai

r, jidd a hiiltlo ntaao reoemMiiig eaaiphor, s "^

\ in aleohol tod io aeetie acid^ la&olahle ia

14 C 84

15 a 15

a 0 . .„ ,. . _ S4

_ lt'52 »..

-.« IMS
.. lt-4€

C»*H**0» + Aq . ._ Its

.., 100-00 «„

.». 100^

4. CED&tithol diseokee tct^ qmringlj in water, impariiag its o<lo«r.

C^aaalAa/tfM -.4mwwifa, — CEnaiithal absorbs a^large quaiitj^of J17
amnioDja«aL ga% becoming bot and viscid, orysiala appfiMaring to fins m
it; ■afaooqaeDtly howerer it recoTers iU mobility. (TiUy, lis^riekt)

(Lunpficht-)

<ZnanMoZ «^A Bisulphite of Ammmia, — 1 . Th<> mwL^
canantho) with ammonia is dtsaolved in strong a) c^bol, a^ llio

attinited witb sal pbn roue acid gas. It ihea depooitaacn.

'fXTf or, if the £o) niton is ratber dilate, dl&Uaot er^ilabu -^^ t. QSatt-
r shaken up with bisnlpbite of ammonm amd the pmdiiot u &•
in boWiBg alcoWi, ^Ueace the compound ia depooitea ta Ibof

dtalbocnottki

(EXAMTIIOL

449

le itate by cooling or evaporation. (Bertagiiini.) Siimll wUito prions,

j^ley.) Lcsa cryetallino tlian the potash and ioda-conipoundsj

"tingly soluble in waiei\ (Bortngniui.)

Tilhj.

11 c ,. ,..

.. 84 ,

.» 43-1

N ..,.,

. 14 .

», 7*1 ..

.... 6-8

17 n «^. .........

. 17 .

... 87

a s ,_.,.

, 32 .

.. 164 ...

.. 168

6 0,... ,

. 48 .

... 24-7

C»WW,NHa,2S0^,

. 1S>5 ,

.. 1000

Heated on plattnum-foil, it meltSj gives ofT white fames, blackens ami

Inrns with fljime, f^ivhig off the odonr of cDtianthol. It ilccoin poses

idually ill contact with water, or m aqueous or alcoholic solution,

aore quickly when heated with water, into ©nanthol and Uisnlphite of

Imintonia, Still more quickly is thia decomposition produced by acids,

jTilley.)

Wkk B U ulph He of Potash . — W h en n^n an thol i a &h .i k e n up tv i r h
Baulpbite of potash of 28^ to 30^ Bni. a pulpy ma.?s i.^ ftjitiictl which
[tadually becomes crystalline^ and after being dried and disj^olved in
Jeobol yields smalt noedlos. It dissolves in warm Uisulphito of potnsb,
3ertagiiiai.)

Jf itk Bimlphlte of Snda, — When i\\% crude di^ til lute of ccnanthol
shaken up with bi sulphite of .soda of about 27^ Bm., a thick crys-
ullino pulp ii formed. From a solution of anmnlhol in warm dilute
^ulphite of soda, the compound separates in cry slab. On recrji-taU
BiDg it from boiling aiceholj crystalliuo laminie separale, ^hich lill tho
itire liquid; these are pressed; w^ashed with cold alcohol till lliey no
pnger smell of acrolein, and recrystallised from hot water to froo thcni
' i>Di a small quantity of sulphate.

Crystallised from alcohol it forms aggregated lamiuco which have a
rong lustre and become white and nacreous when crystallised fiom
»ter. They are greasy to tho touch and havo a alight odour of o^nau*
bol. (Bertagnini.)

14 G

.... 84

.... 33*59 ..
.... 7-20 .
.... 13 55 ..
.... 13-13 .,
... 30-53 .

Bertagnini.
3577

17 H

„« 17

7-17

2 S ...»«.»

N»0 ,«,.

9 0 » .».,

.,. S2

.», 31

.... 72

1:^^47

...... i:ii9

30*40

0*H**O^N*0,2S05+3Aq

.. 236

.., 100^00 ..

lOOOO

It IS decomposed by chlorine and bromine at onlinary temperatures ,by
iue only when heated. When the aqueous eolation is heated, (cnan-
ol separates out; the decomposition is accelerated by tuldition of acids
or alkalis, but is not produced by acids without the aid of heat The
compound dissolves readily in water and in warm alcohol, but not in cold
silcoitol. The aqueous stdution forms with bfirium, lead and silver salts,
c*>pjous precipitates which contain cBuanthol ohemically combined.
(Bertagninl)

Glinanthol mixes in all proportions with ahoholMiA. oilier*

N

b.

vgr. XII,

% ^

450

PRIMARY KUCLEUS C"H".

MetenanthoL

BussY, N, J. P^iamv. B, 321. — J. pr. Ohm,. 37, 96- —Marm.
1848, 170.

When 1 pt. of tenantliol is eliaken up witli 2 pta, of ordinary fill
acid at 0^ the liquid acquires Oi transient ro60 colour; and on jKfUxh
the mixture after *24 hours into a dish and leaving it in a cool pi
beautiful crystaliifiatiiiii like nitrate of annmmia forma on t!i«
and sometimes the whole solidifies into n soft oiictuous maa^. After tb
acid has lieen decanted and llie mass pressed hetween f>aper, a Lan
brittle substance remaitie, wbioh mtxj be rauderad neatral by rep«ftU
melting in hot water.

Between 5^ atid 6^ it k solid, white and Inociorous. At UigUct
peraturea it melta into a transparent colourless oil, %vhich hmis nt SStf'jl
after being heated to tbe boiling pointy it does not solidify tiU
time after cooling.

14 C

UH.»

2 O

.,.. Si .
...... 14 .

16 .

., 73-68 ...
.. 1228 ..
.. 14*04 ...

Buaay.

.... i2*2r

...., 14'I!

D<H*^0' ..

... 114 .,

... imm .,

10000

j^Relnted to oenanthol in tti« wme mixmtf M beusoia to bicttr •linood oil.

Exposed for several days to a temperature between 10" luid 12", H
liquefies, and if kept for a longer time at that temperature, it doc^ t\oi
fiolrdify if after wards cooled even to — 12- or —15% hut only whenexpo^^l
for a considerable time to cold, a moderately low temperature being tht^n
su^cieat.

Metcenantbol U insoluble in water, diaaolves sparingly in cold, mm
abundantly id boiling alcohol, and crystalliaea out for tbe mo»t piyft m
cooling.

The so-called Hydride of (EnanthyL
C'*WH} or C*«H«0*.

"Tilley. (184B.) Ann. Pharm.01,]m.

Format ion and Pt'fparation, X pt. of tenautliol 19
5 or 9 pts. of hyttmte of potufth, and the mixture is left to «tMfl ftud bt
to 120% whereupon the liquid beeomes thick. A large quantity of w%m
is then acl(le<L and the residual oil freed^ from every thing #alublc il
water, is distilled with water; it pa^see over T«?ry dowly, jti> tbftt ihf
di«t illation is not completed for several days,

rrojtetiUi^ Colourless^ mobile oil, having a ^nt odonr of Ictmoa''
Boils at 220% but becomes coloured at the eamo time and aequins^ a
Jiibrentodoar.

(ENANTHYLIC ACID.

451

.I.-

11.

Tilley.

*c

. 156 ...

. 78 79

14 C ...

». S4 ...

. 79-24 »..,

... ;^*2S ... T9'43

»?=

, 2% ..

, 1313

14 H

.., 11 ...

. i:^2t ....

.... i:i 34 UM

. 16 ...

. 8-08

O

.. 9 ,„

. 7 55 ....

.. 7*33 .... 719

1*80*.... 198 ..„ 100 00 C»H"0 106

100*00

100*00 100-00

Pftrkaps A ketone (Gm.)* Therefore probably C^H^O^ (Calc. L) L. Calcula-
on 11 )B fj-om Tilly's formula.

DecompotUiam^ 1. Tbe compound burns with a bright eliglitlj
Oty flame, It k difficult to burn with nxide of copppp j Tilley^s anidy»F« were

ere fore made wiih pecoliiir precautinn 2. When adcleil bj drops to StfOOg

iHrio add, it dissolves and oxidises quickly, forming a?nanthyUc acid,

Jthout any secondary product, but not so quickly aa a3uantbol —

When heated with potasb, it gives off hydrogen and yields cBDauthylic

md together with a piteh-Uko enbatancej the decgmpoaition take^ place

rly.

(EaanthyUc Acid, cm'\0\

^ATJttENT. (18370 ^wik Chim. Fk^$. 66, 17^, — Fharm, CaUr,

1838, 280.
ritiLEY. Ann. Pharm. 3&, 160,—/. pn Chem. 24, 2B7.—Pharm. Centr.

1841, 837.— ^tm. Phfit-m. 67, 106.— PAajm, Ckntr, 1848, 645.
lussY. N. J, Pharm. 8, 329. — /. pj\ Chem, 37| 96. — Pharm, CtniK

1846, 170.
CHNEtDEB. Ann. Pharm. 70, 112.— Pliaj^. (kntr. 1849, 476,
U^BACUEn. J?m. PAiirw*. 73, 200. — PhatTrt. Crnir. 1850, 274.
Iraziea & GossLETH. AfiH^ Phaji3u76,2QH.-^Phan/i. Cmtr, 1851, 201.

First obtained by Laiinsnt in an impure ftate »9 ez^hie amd ; called n^oteic atid
' BerjEetiiifl. Occurs in the fufeUoil of upirit obtdued from rice or maije (Wetherill,
hem, Gaz. 1853, 282).

Forvmtion. By the oxidation of cenanthol in the air or in orygeu
3. By boiling tienantliol with nitric acid (Buasy, Tiiley), or with
Dhromic acid {Brazier k GoasletK) ; by boiling cantor- oil with dilute
^acid (Tillcy), or chromic acid. (Ar^biichcr.) By heatiug the distillate ob-
lioed from castor oil with nitric acid (Scliaeider, Ann. Phai^i. 70, 112),
that from oleic acid with strong nitric acid. (Laurent^ Redtenbacher,
inn, Pfmrm. 59, 41,) By the action of potash on cenauthol (p. 448),

Prepamltm. I, Ono pt. of oenauthol is di^illed with 2 pts. of a
istturt} of ] vol, strong nitric acid and 2 vol, water till the greater part
m paafied over; tbe oily di^tiHato decanted from the acid water is
.tlimted with baryta-water^ aod evaporated to tbe crystallising point;
and the baryta-salt which crystal Hsea out is decomposed by sulphoric or
pho,T(pboric acid : Lbo a-nanthy)ic acid then rises to the surface in the
form of a colourless liquid. An additional quantity of ojnan thy late of i
baryta may be obiained by washing the reeidue in llio retort with water,
wbich exuact« nitric aod oxalic acid, and neutralidng with baryta water.
|Eiiaffy*) — 2, When otjnanthol u diatUIed with strong nitric acid ai\d \.W

^fBm

m m hmrjimm,

MMb tlMI to ttf

tlMI to

of At tv<»>nri^

mmmmAjh^ of Imry^ €ij^

Thm iBotlici^liqttor it i|^

palp bepQsneB mh^ till

_-) — ^3- Ambtiutoflft

lalef villi' an equal bulk v( ^idch

Atm tmkm pta^ m dial tije mm

m H ^iM«idbwi, mUrnr wlikh dio fist*

tW iMiivcr €«iilaii» tke oSi tdt

m «ala^ liqmi, MJ a dilek fitsja^

— "-^, jielda a laig« a4£tk«a]fnii?

. (Til]^.) — 4. Oastor^tl ii buM

af a mrxtitre of 4 ^U. ycfcniinaii i

12 pta. of vatcr; on b«atiag tk ski*

telcet pfaee; aad as mmkii ■# Mie li^

affile vana lalstamis aildetl ffiii

an tkai BO salpfaoi^tcs nvld fomL it

aati4iies in a l>Iaek ntttt. Tk

A^esi the oily padiotttwyA

wdi^ ia «ilamte<l iritia earbosatt if

aBd iKnM witli aJeoiiQl. Tlio Glad

tslo a ctjslalluie itsaa«» wibieti aitt

'led fmn kol aleoliol el SI |K

(Aisbicti^r.) TbiiMiMMa

aCpikrtjPcad4> (Bfaaier lb O—htl )

Stf-

oll, harln^ ao QQpleaaat ate
inl ia te ooML bat becottiing itroti^r ai 1^
(Bawy.) &t a pccaliar siromatic ^onr, mad a pofMi
I iHie. (111%^) BcgiM to boil 9X liB\ but doeoBpoMtfi
» wiiB ■■Wnliii la OMOnad dktillaUcm, (TiUej,) Bdk H
(Stalker, £€M.Sbi«.)

Laonat. 'nilify.

14 C 84 _ <4-«l etrf _ €4-44

14 H u _ le-n — 10 ?i ... 10-71

<?W _ 130 ..- 100-00 «„^ 100-00 _. 1OO-0Q

1. CEaaDtJi^lie acid bums wlib &

(Tmrr,)Z-t. Hratod wiUi luda-kr, it forms & neotrai oil, (AtJbitkm^
— 3, Sl»le«l afilh potaBh-linie, it jie\4» gaseous anti Hqtiid hfdi^auim
of t^ fofnata OH'* (C^boafs, Cb«/>*, r«M<l. ai, HI )-^4. Wlai
diFtllted with peatacblori«)eof pbo^>lioru3, it j\eUU ctikin4e of onsaaitiTi
if resolretl by water intci Jijrdrocbloric and ci?iuuii^jriit ^A
___m CQ^pi. rtntK t.% 724*) — 5. A eoni^entnii^d toratM 4
iiiit!iv1ate of potafili di^eompoaed l»y a eurrent nf atx Bii«M*«arfb
,31% ^toi off bydfogen and carbonic acid gaaot, vbOo mmmat*
Mie'anA Vi«aA«m^le ^l ^«^*fe>=^ ^^^ formed, ud u oQ ite ti

CENASTUYLIC ACID.

453

ll-e iprface, whiclij when tUiitilleil with potash, lcav*?3 c&naii(!iylatc of
potash, and fields a JbtilUte cons^iatin^' mainly oFcaj^royl C^*ir*j and a
Bjtlnicarbon C'*H** boiling at ITO^ (Brazier & Gossleth.)

CojnUnatioiu. Qilnanthylic acid dissolves in concentrated nitric aehl
ind id precipitated therefrom by water. — With salifiable bases it forma
■'ae (Enanthi/lfjics.

(Eminth^luU of A^nmonia is very soluble in water, (Bussy-)

(Enanth/l&lc of potash, — Obtained by saturating the acid with
irbonate of potash; does not crystallise; h very eokible. (Til ley.)

<En&nthyhU of Baryta (pp. 451, 452). — White nacreooa senles.

liwsy, WilliamHon, Anbiicher.) Lancet-shaped tables. (Tilleyj Has

► very faisit, slightly bitter taste; inodoronsj but when rubbed between the

Ingers, it imparts an unpleasant odour of perspiration. (Bnssy.) Di.<?soh'e3

^^ 51 pti. of water at 23** (Bussy); very tjasJly in hot water; still more

easily in hot alcohol of 85 per cent. ^ and crjetaHises out alraost completely

"en cooling, (Arzbacher*) Dissolves in 3D2 pts. of alcohol (Bussy); inso-

*Til>le in ether,

BBiiy, ^^^"^"^- , '^^^^'3r. Schneider. Arxh,
■* Ban. a. &♦

BaO r6*6..„ 3fi-77.... 3&*80.... 3870,... 38-50... 3B'2a.,.J9*34.,..3927

.C 84-0.... 42-51,... 42-68,... 42'45,... 42-52,„. 41^68 Al'W

\n ,.. 13'0..,. e-5S.... £-51.... 6*85... 672..., 6^80 7'n2

rO 24^0..., 12-H.... 12ilL... 12*00...h 12-26... 1S*20 11 57

Ci^H^BiiO^

197'6,...10000,„.100 00....10000 100*00....100'00

100*00

The sjilt analjrsed hj Buisf wai prepared from the acid obtaiwcd by 1 ; TiUey'a
att a from the aciJ prt^pared by 2 ; fi from 3 ; Aribiicher'a salt from acid -i ; ScLneidcr'd
ilt from the di^tiLljile ohtjiiied bj heiiting rdpe-oil wilb nitric acid ; and WiUinmsou'ii
EH tUe ^dd obtained by I be actluti uf putoth on o^naDtliul (p. 4'18]<

(Enanthylatc of Lmd^ — The potash-salt forms with acetate of lead
, lemon*yellow powder, wbjch i:^ insoluble in water, but elightly soluble
lit boiling alcoholj whence it separates in email scalea on cooling,
H'iltey.)

fEnanihf/l<U€ of Copjyer sepamtes after a while from a mixta re of the
free acid with acetate of copper in needles having a fine green colour
ad silky lustre.

(Stianthf/hie of Sihfi\ — The acid neutmlised with ammonia forma
ritb nitrate of silver a white precipitate insoluble in water, and turning
brown on exposure to light. (Bussy.)
I White flakes, wbidi yield by dry distillation an oil and a solid

^■nibetaQcCj which crystallines in needles from hot alcohol ; both are acid.

As

13 11
iO

108 ..

, 45'57

84 ...

13 ...

, 32 ..

. 35^44 ....
. 5-49 ....
. 13-50 ,

Bussf. TiUef. WiUianjion* Schneider, Arab,

45'o0 .... 45-60 .-. 45-55 „.. 45'44 .... 45'3l

34*82 .... 35-33 ........ 35*20

5-62 ... 5*61 ., 5-66

l3-y6 ... 13-41 13-50

CfO^... 237 ,.. 100*00 ... 10000 .,./ 100-00 lOO'OO
lanthylie acid dissolves in akohol and ether.

454 PRIMAUT NUCLEUS C^H".

CEnanthylate of Ethyl.

Tilled* (I84L) An?t. Pharm. 89, 162.

Williamson. Ann, Fhann, 61, BS.--I*harm. Cmtr. 1847, 29T.

Frepamtion* L Hydroclilorlc acid gas ii passci) tliruagK a aolnttciti

of asEmnthylic acid in atrong alcohol ; the licjuul diatilled with aqueoui
' carbonate of potaah; aud the diatillatG la washed with water, ftttd nnaltjr
dehydrated by chloride of culcium in a 8tre:im of carbonic acid gui
(Tilloy,) 2. Hydrochloric acid gaa is passed throug-h a solution of j
1 vq\. cfioanthol in 4 vol alcohol^ till the liquid becomes brown isb and
fumes atroogly^ and the cenantliylate of ethyl h then Eeparated by ,
addition of water. (WilUamaon*)

FropfTiUs. Colourless oil lighter than water. Solidifiei In a frceiiof |
fnixture. Ha3 a peculiar agreeable odour^ and a hurfilog taste, (TiJley.)
Has a pleasant fruity odour; distils readily and completely, but witfi »
eoaslantly rising boiling point. (Williauisou.)

Tillev. ifttteen irettPf^n

Ul" a«J 18*>*. 190*iiWlW*.

18 C

... log .

... 18 .
... 32 ,.

... 6S-35 „.
... 1139 ,
,.. 20-26 ....

.... 67-62 ...
1157 ...

..... 20-81 ....

..... ^8-2 .
.... 117

.:... 20*1 ,

.. IJ84

18 H ......

4 O

„ 20*3

CWH^W...,

„. 1&8 .

... 100^00 ,.

100 00 ..

1 000 .

.... 1CM3 0

Burns with a clear non-fuliginous flame.

Insoluble in water, easily soluble in aicokol and Hher^

(Enanthylate of Phenyl
C^H^'O* = C"H*0,C^*H"0'.

Cahours. Compt raid. 38, 257*

Produced by the action of chloride of cenanthol on phenylic alcohol
Oil boiling between 275"^ and 280^

Appmdit to (EnaTtthsfiic Aeid.

(Enanthio Acid.

LllBfci & Pklouze. (1836.) Ann. Pharm. W, 24^.— jtnis, Okm^l
PktfK. 63, m,—Fofjg, 41, bll.^Phorm. Ctntr, 1S37, 20.

MtLDEW, Pogg^ 41, ^m.^Fhm^. CaiiK 1837, 809.

Dblppii. Poffij, 84, ^QS,~Ann. PA^rw. BO, 2m, ^ Fknrm. i\n(f
1852, 93*

CENANTHIC ACID.

455

I Produced in the fenmantatlon of wine and grain.

I I'reparation, 1. (EnantJuc e^fj* is boiled with potash -ley, and the
Kaflnlting cenantbato of potasli is decomposed by dilute ealphuric or
ntt^drochlorio acid, the acid then rising to the surface in the form of an
oil. It is washed with water, and dried with chloride of ealeiam or over ]
ail of vitrioL (Liehig & Pelouze, Delifs.) — 2, The fusel-oil obtained in
be first distillation of fermented grain is rectified over diiute carbonate
^' ^oda; the residue Is boiled with water; and the filtered solution is
aposed by dilate iulphuric acid : the acid then collects on the enr^M^a I
be liquid iu the form of a fatty layer which ia washed with water,
'Ived in alcohol, and the solution left to eT^aporate* — 3* When
tfied fusel-oil Js distilled with dilute potash-ley, and the residue is
aiied with eulphunc acid, oonauthic acid separates, and may be purified
by washing with water and crystal ligation from alcohoK (Mulder,)

*
Fropeftiei, DaMlin^ white, soft like butter at IS'S*', above whicli .
iperature it melts to a colourless oil. (Liehig <fe Pelouze.) Buttery '
nais. (Mulder.) Yellowish oil^ which at low temperatures solidi^es into
i indistinctly crystalline buttery mass. Crystiilliaes from alcohol in a
friablo mass. Melta even at tbe heat of the hand, or at all eveute
slow 25°. (Delffs.) Tasteless. Inodorous and tasteless. Reddens
litmus.

I. IL ^mltt ^"^^^'^

[4 C U .... 68-85 18 C lOfl .... 68*35 .... 68-24 _. 68*58

,H ,. 14,.,. 11-48 18 H 18 _ 11-40 .... 11'55 ..„ 11*61

I o 24 .... i§'6r 4 o aa .... ao-as .... 20*21 .... 19-ei

^wo*.... 122 .... lOO'Oe G^»fl*»o*.,.. 158 .... 10000 .... 10000 ... 10000

Cabul&tion I la from tlie farmuk proposed bj Liebif . DeltiTs regAfd* oenintiilc
sid AA identictil vith pelargonic acid (II), irhii:h 'wlew agrees with the coinpoiitron of
I buriam a»d silver valta mualytu^d by hitEt> but ia opposed bj^ the ftd thml oenajitbio
cid ii di!coini)oeed by heat hito water and the so-called ftnbydroaa oenanthic odd.
leeording to tbisT d^aantbic acid should be mbaKiCr and the fprniuU gift^n by Liebig I
Cjfc PeloD^e sboold be doubled {cQmp. Laurent, Cmnpt, rend. 21^ 857). Ddffs'i view
la also irrecondbble with the compositian of cblorcenatithic acid (p. 460) [and with the
boiling point of oetiar^Uuc ether. J.L.]- The Urge Tariationa iu the inalytca of the
I palts by Lie big & Pelous^u and Mulder and DelfTi, abow either that ibose rhemista

I e;Eamiiied different bodk»j or tliat the cenanthates bare but little per man ence ; perhaps
tbey yield pelargonic acid whea decotuposed. Mulder's uialyses agree ne«rlj with the
formula C^'Hi' MO* [L.].

hDeco7nposki&Tts, (Enanlhie neid is reaolved by hent into water and
nhjdrons oenatitkic acid. (Liebig & Pelouze.) — Bj verjr tilow evnpQ-
ration of alcoliohc cBnontluc acidj f.f/. in a dee}* cylindrical glass,
hvdrated cenanthic acid is obtained as'a transparent oil on tlio snrfacc ojP
the liquid [doeg not this oil contain alcohol 1 Gm.], while crystals of lltQ
anhydrous add are formed at tho botltfhi. (Mulder.)

Combinatimt^. Mulder assnines the existence of a hydmted CBnanlbfc
acid, whldi he describes as a tmospareiit colourless oil of ip. gr* 0^861,
and supposes to be converted into the anhydrous add by gentle beating
or hy the action of chloride of calcium* The eep« ration of the hyd rated >
acid into the aoliydrous add and water ie also eiiid to be induced by

II drtJpping the crystals of tho anhydrone acid into the hydrated acldi ^^

k^_ J

lff«Uer.
X 12 -_ I2-*l 11-15

ailtsi

.▼as s rnmsj 6otp j

pottikUoetti
mto m pslpj

caBBl^res 31 VifTnig ciri>ooatc o

Lc iLiu. ja mllUz^ :&c ^mm with mleolH

iisu ^-^s-9^iaerdki3ZBr Bfedles. (Mi

[Tiiiir ic*t£ 3: ThftnTBr caibooate of f

sLeahuL tke liqmid solidi

« ««ciiSJL_: m?i- iDA. "tit t^-^3l** fcsc locii:^^^! are perrv^tadli?-.'"
v.. T r« ." r.^2? ];r^* ^ - 3^v rirT^^gg«:g-:Hz wyji the f

. J.- zi". - r-ut^ ^ -rJxar7 "i-'Oi^T^ncar-Sw tal«k white flakes

f. . iir-:- . : => -•**.«'"5»i. Qju & ij^-rvT-it ia»£ m ba^Le sait. — A«
T«». r.r. *w T :;. i?in2i:::i« n « »ia. 3 ms & ?c-ciT:tate wkirb wbci

- . -. • ^ .. ^..UTta 'T cT.:3:ixarf :t f»;«i* f^rs* with aee

r -. -. ■ • *^ — J.:xi:j.c jcki acts with &cet&te of

c. • ... ' .-^:? -v* n «•• LCd-jtic sMLxai.>a of x-:«c&:e cf cc

I.* • ;.. r t;_i .-i.;f- :i.i?:-i'-' 1 ":«.i^2;r w-xr«er. Mid l<^ -cie^ la

jLa 2.0- .i-:^--: =* ' 1 '-Q- '* c::j.3-.j.*:-* vf $«>^ fv>n!u with aori
»4ii:T:.:j.:::^- .■'.^:;i-i-TX .i i ■«• :'i:ti. cf vx.u- cf c.Tper. ^Mi

ffiMANTIUC ETHER.

437

. 192 &0-CS 18 C

liH ,...»».„ 31 ». 8 Ifl 17 H

Ag ,„„„ I0a_ 28-49 Ag .

GO , 48_ 12-67 4 0 .

108 ..,. 40 75 51 -lO... 41-04

17 .,., 6^42 B'09 ri-5l

108 _ 40'75....35-67.... 27" 14 ... 40'4»

32 .,,. 12'0S 13-37 ... ir96

QUH^UgO*..., 37S.„ 100*00 a^H^^AgO*.... 205 ..,,100-00
CEnantliic ncid diaaolres readily in akohol and €ihef\

ioo-oo...aoo-oo

CEnanthic Etlier.

L „

^■LtEBia & Felouze, Ann. Fhami, \d, 24 K — Ann, Qnm. Phys. G3, 113.
■^ —Fogg, 41, 511.— Pha}^. Ctntr. 1837, 22.
^^CXDER. Fogg, 41, 582.— P/mrm. Ctnir, 1837, 807.

Stick EL. */, ;>r. CTfrre. 9, lfi7.
t: Ckeutzuuro. /, ;>r CAi=w. 10, 3S2> — Fharm.CentK 1807, 574-
^ AtTDERGiER, JuN* tf, Fluu'm. 27, 286,

">ELFFS, Po^^. 84, 505. ^ji/fj». Fharm, 80, 200, — Fharm. CtnU\
3 852,93.

LiiEBtG, J»«p i^Aarjn* 80, 200.

fEfmnihdihej't Wcii\fuaelutf Huite de mare de raitiWm

This compound is the source of tlie odour of all wind's and cjvuBes a

fingk drop of wino iu a bottle to be distinctly smelt, whereas aqticoiH

^Icobol baa but a very faint odour ; it must not however bo Cf»nfi)uuded

rith tho bouquet, whiob is different in ditTereDt wines and absent alto-

etbor in many, (Liebig k Pelouze,)

Fonnation and Frepondioii. I. When 5 pta. of sulnbovinatc of
tash are be a ted with i pt of cenanthic acid, the mixture fuses, and at
l^O'^ an oil rises to the fmrface, consisting of cunantblc ether and excess
ofceuautliic acid, which latter may be removed by heating with carbonate
of poUish. (Liebig & Pelonze.) — 2. This ether is rIso obtained in the
preparation of French brandy from wine and wi Tie- lees. The wine'Ieoa
are distilled with half their bulk of water; the resulting distiilate, of 13^
Cartierj is redistilled, whereby a distillate is obtained of 2*2'' Cartier, and
at last, when the diatil late shows only 16*, oenanthic ether pussea o> er
with it; 10,000 pts, of this distillate yield only 1 pt, of amantbic other,
(Liebig ^ PolouKe, according to Delechampa,) - — The rough, ehiirp-tosting,
colourless ether containing conanthic acid (sometimes however colnured
green by oxide of copper), is shaken op with acjueous carbonate of ?oda,
ftnd the .milky mixture is heated to tho boiling point; the amantljic ether
then rises to the surface and may be removed and dehydrated by chloride
of ealcjum. (Liebig & Pelouze,) — 3. When the residues obtained in tlid
di^sttllation of a/tetmnf brandg {Wthvnder-hrmintwmi) are n^raui dis*
tilled, comparatively pure alcohol, becoming turbid when mixed with watrr,
pusscj over at first, then alcohol containing fusel oil, tlien a watery liqo'^
rendered turbid by the presence of oil ; the two latter liquids uii
ield, when mixed with water, a con.eiderable quantity of oil (^150 \

458

PRIMARY NUCLEUS C»Hi<.

of brandy jield more than 32 pruii:!.) In ono prepa.mtion a aygtslliii
unctuous mass was obtained, {AuUergier.) — 4. Fioel-all obtained in tb
fir.st distil latitm from fermented grain, and etill relaiQiDg a gr^enii
colour of oxide of copper nfler otie rectification, Is itg&lii rectified Q\i
at^ueous carbonate ot ^odn. The cDoauthic etber tbua obtained, still
cot>kuii8 mi oil not decomposiblo hy potiiah, "which also pas^s over in thr
deconi posit ion of oinantliic etber by potasb {ritl. inf.) ; jt haa a very peofl
irailng odour like tbat of Phdiandrium and a sbarp taste. (For ii*_r —
positipQ, vid. Ptfffff, 4 J, 5820 (Mulder,)

Pro pert ieji. Triusparent colourless oil, of gp. f^, 0*862, bavln^ a
strong, intoxicating, vinous odour and a fatnt dijiagreeable taete. BoiLa
between 22,5^ and 230°. Vnpour-dengity 0^a (Liebig Sc PelouKe;) —
Yery mobile oil, colourless at firsts but assuming a yellowish tint wWaj
exposed to ligbt , bas a very penetrating odour and sliarp nnptea^imt
taate. Less volatile than the volatile oils. (Anbergier,) — Fniel-ojf
obtained from the lees of Jena wine h light brown, Tiscid, and depositi
a lar^e qnantity of ^stearoptene at 4^ Sp.gr, 0'S56. Haa a somewb^
nn pleasant odour like tiiat of cheese from reindeer's milk, and
extremely nauseous taste, ei:citiug violent irritation in the tbroat. Fou
drops make a sparrow nneasyj but produce no further iymptomi
(StlokeL) — Fusel-oil from the lees of Austrian wine haa a penetraiiii
ethereal, vinous odour and a mild vinous taste ; a few drop^ of it i]»|!
to pure alcohol the odour and tabte of French brandy. It U leas vola
than ether, more volatile than the volatile oils, (Creutzburg.) ^ — Q^n
tbic ether obtained from a distillery in Krenxnach ia yellowish anil
slightly acid, begiiie to boil at 2 40-, and exhibits a constaat boUing point]
at 246V <^"<^f<JUfth passing over between 246"* and 250". Thii jMirtion, i
after being freed from a little acid by agitation with earlK^nate of «Dd%
is colourless, and of sp.gr. 087 at 13^ Boiling point 224% wiib tho
barometer at 27'' S''. Vapour density^ 7 04 2. It lias a plea^nt vinuuj
odour, and its taste is faint at 6 ret but afterwards produces irritation m
the throat.

. I.

n.

Uthig &

D^

'so

. 108 ,.

... 72-0

22 C

, 132 ...

„ ;0'97 .,

... ;i*Li ,„,

;oii

. 18 .

. 120

22 H

» 22 .

. ll*»3 .

... n*^2 _

n$t

. 24 .

... 16-0

4 O

.. 32 .

17-20 .

», 16 95 ....

l/'il

c^a^)*..

160 .

., 100*0

C-H3S0*

. 188 ,.

100 00 .

... 10000 ^

lOO-Ol

Cflleaktion I is nccording to Liebig S^ Pelouse: II, according to Delffi (c
pt|^e 362). raLculntion 11, p.Yt9 lh« Tfipour*den4itj G*5 Dud boiUitf^pmni WJ^* TImI
fcrmtjln I doubted corrcaponcU to * yapoor-denwtf ™ lO'Sy^S. [L.] [Acatirdtflf ••
J, a«n«utliic ether skauld be composod of i vol. aahydrous aeid i&bd J toL
tftpour^ J. L,]

DtconiposUioHs, I * <Enanthie etber becomes yellowigb wh^n U

Aod leaves a yellowish reiitduc by distillation. (Dems.) — Whendi^

jl first pasties over unulteredi and then yields a dtstilkto bavin

empjrreunmtic odour; the residue in ihe retort becomt^s more audi

yelhjw as the dit^tilhttion goes on, and at lait a very light rhi

ttemains, (Aubergier.) — 2. When kept for some time, it tumn h

j^nd acf|uire4 the power of reddening litmus; it burnt with a yelk

fmd SamQjijii leaves no tedium* (^Su<sk^l.) — 0. Boiled wiUi iwi '

AKHYDKOUS CENANTHIC BTHBR. 459

it yields alcohol and CBnantbate of potash. (Liebig k Pelonze, Malder,
Delflfe.) — With alkalis it forms saponaceous compoands. (Anbergier.)
— 4. It is not decomposed by alkaline carbonates or by ammonia, either
in the form of gas or of aqueous solution. (Liebig & Pelouze.) — It doea
not dissolve in potash even after long boiling. (Stickel.) — 5* Heated
with iodine, it emits a peculiar vinous odour. (Stickel.) — With chlorine
it forms hydrochloric acid and clilorcenanthic ether. (Malagnti.)

(Enanthic ether is insoluble in water. — - It imparts to water its taste
and smell. (Aubergier.) — With ammonia it forms a liniment. (Stickel.)

It dissolves very readily in alcohol, even if very dilute; also in ether ^^
(Liebig & Pelonze, Stickel.)

When the peels of 40 ripe quinces were distilled with water, a watery
liquid passed over smelling strongly of quinces and haviog drops of oil
floating upon it; more of these oily drops were obtained on distilling the
water, but they altogether formed only one large drop. This oil has a
very strong odour of quinces, and when distilled with potash-ley till the
residue becomes inodorous, yields an oil having a similar 'odour; the
inodorous potash-solution is rendered milky by sulphuric acid, and on
heating it^ an oil separates out which boils at about 10^ dissolves readily
in potash, and is therefore probably oenanthic acid. (Wohler, Ann,
Pharm. 41, 239.)

The so-called Anhydrous (Enanthic Acid.

Liebig & Pelouze. Ann. Fharm. 19, 246. — Fo^^. 41, 571. — Pharm.

Centr. 1837, 24.
Mulder. Po^g. 41, 582.—/. pr. Chem. 12, 265.

In the distillation of oenanthic acid, water and oenanthic acid pass
over first, but at last anhydrous oenanthic acid, which begins to boil at
260^; but the boiling point rises gradually to 294"", the liquid at the
feame time becoming coloured. After fusion it solidifies at 31 . Inodo-
Tons and tasteless. Reddens litmus. (Liebig <fe Pelouze.) According to
Mulder, this compound is left when an alcoholic solution of oenanthic acid
is left to evaporate slowly (p. 459).

14 C

13 H

84 .

13 .

... 74-33 ..
... 11-50 ..
... 14-17 ..

Liebig &
Pelouxe.

73-63 .

12-19 ..

14-18 .

Molder.

... 73-22
... 11-73

2.0

16 .

... 15-05

qHHllQS

113 .

... 10000 ..

100-00 .

... 10000

It absorbs 1 At. ammoniacal gas. (Mulder, Pelouze, iV. Ann, Chim,
Fhy$. 13, 259.)

HaJfflLga

l«,iT.

IVS^^*l

— .j-l;l. ?'Jii:-Ti. -"^ I;.— JiiZ-TR. iT'^'L-. 1S». ,>M>.

:« : :l»^-^ -. ir->* ^c j^-gj _ 35:3

:,H -. I*'* ~ <-?■* 17 H 4.74 _ 5-3J

* 7- :4:-i ~ li-:* ic: 49-51 ^. 4s;4

:y _ U^ ?^4 *0 8-93 _ S4l

c^^'**:^^^ -. i^r-« _ i<^^<^ c*^H~CHo« ._ 100*00 ... iftKJ

tfrrTiis* Xd<r*-^-C-''H'H..'<^\ CAlc;.Utica I corn.*| oada to DrJli's i*« •

**- ciildrid:^ of (enanthylene.

4n

CWoTmnanthic etlier blackens ut a etrong heat and gives off bytlro-

cliloric acid gas, a hcterogeDeous li(|iilfl tbcn disliirmg over, wbose boilings

"point rma as the distillatioa goes tm; m the retort thtjre remains a very

acid pitch-like muss. The ether i^ slowly decompfised by potash-ley, but

[Completely after some days; the liquid contaius hydrocUlurate and acetate

■nf potash HTid acids separate a?nanthic acid from it.

Jt dt^olves in 15 or 16 pts. of alcohol at 40^

% Chloride of ffiaantliyleiie, C"H»,C1'

jiMPRicnT. Jim. rimrm, 103, 80.

Fonn^timi, By the action of pentachloride of phosphoms on ceu&E*
lliol.

preparation. When 1 At. a>nanthol is gradually allowed to flow

liuto 1 At. petitacbloride of phosphorus contained in a tabulated retort,

ireat he^tt h evolved, and a portion of tUo resulting chlorophoaphonc acid

Mis over immediately, A^ soon as the decoiu position of the penta-

Horide f5 completo, the liquid rs subjectod to fractional distillation, tho

ortion wbicb boils above 150^ bt'itig collected apart as long as H passea |

ivcr colourless; in the retort there remains a small quantity of a brown

Ihick liquid. The la^t distillate u washed with water to remove adher-

liog cblorn phosphoric acid; and the oil which floats on tho water is

Ifthaken up witU bisulphite of soda to remove undocom posed ojnatithol,

then dried with chloride of calcium and rectified, the portion which boib

between 180^ anil 200'^ hemg collected apart; on again rectifying this

portion, pnro chloride of cnnanthylene passea over at I B7°.

P? -opert rV^ , Tran sparen t, c o 1 o u rl esg, m oh i 1 e 1 i q u id , 1 igb ter th an w ater,
having a not unpleasant odours like that of mnanthol. It boils at 191%
The boiling poiat rtnd oW wns. ]8r% but acorrectioa of 4^ ii mide for the columu of
aercnrj oot Immersed in the ijr|ULc].}

14 C

.„. 81-0 ,

,.. 49-4 .
.... 82 .
... 424 .

limpricht
4885

14 H ,

2 CI ... .„

80

42-5

0*W*CI^ ....

.... IG8'8 ,

... 100 0 .

98-90

_ The compound gently heated with Bodium is decomposed with violence,
ntelding oenanthylene and chloride of sodinm. — Boiled for some time
'with ethylato of sodium or alcoholic solution of potash, it is reeol red into
Ijydroddoric acid^ cblora-nantUvleno C"H*^C1, and a hydrocarbon, pro*
l^bably C**H";

a*H»*Cl= - 2IIC1 - 0*WK

U is not perceptibly decomposed by acetate of silver, even when con-
linuoasly boiled with it or heated to 250"" in scaled tubes, (Limpricht.)ir

WFO.

C«S^»\>.

Ckm,

zzim. 'hr 2ii:i=iztr i Ai. Cif pexfeclij dry oramnUijbte i

wjxt . J&> li fibB^^iiiii ifii^ TifceacuMi bcpna ipoBUaeodf,

rss li f^^oiiaiiL i£ iisc. sni h is nerri j neeeanry to heii ik
use K ?3tt iisK. Ix c<Mr re;^>ects the proees u eoi-
t£ m^yito>^M bwi«Mc add ^p. 04). i£i»
* * * ; the potuh^L

^. 0-91 mt 14". At orfiBBj

like tkai of aakfliw

odour; if lufi ■

lliierbtt.

It C 14 -. «^4« 69*20

IS H U -. 10-74 10-51

JO 24 _ 19-S4 20-29

e--H=0= lil — lOOHM 10000

"«dL£ Lxa1j& h be^TH like other anhydrideoL With eusc?

Benzoic (Enanthylate.

Ch::zzi i: Mjxebbju /oc. eit

Prc^uced bj the mction of chloride of bensojl on GenanthvliM d

C^louness oil of sp. ^. 1043. Smells like cenaDthjIic anhjdriJe
Wlen recent] J prepared, it has no action on litmoa paper.

Malerba..

2SC 168 .... 71-79 7185

18 H 18 .... 7-69 7-58

6 O 48 .... 20-52 20-57

C»H'H)« 234 .... 100-00 10000

In contact with the air, it quickly becomes filled with crpuJ <
iCDZoic acid.

riMELIO ACID.

4m

Pimelic Acid*

TRENT. (1S37.) Ann. Ckhn. Phsfs. 66, 163.—/. pi\ Chan. 27,51<J.
—Phann. Cewir. 1838, 280,

OMEJS. Ann, Phartti 35* 104, — P!mrm. Ctnii\ 1840, 615,
Kadcliff, Ann. Pharm. 43, 353,— PAam. Cttdr. 1842, 907.
Gkrhaiidt. y?^(^. ii^/ry*i. ID, J 3.

Sacc. Ann. Pharm, 51, 22L — Plmrm^Cmtr. 1844> 876.
Mar8h. Ann, Fharm. 104, 121,

^Li.

Pimeiime acid^ FimeliiMdurt.

Fof^mation. By the action of nitric acid on caprylic alcohol (Bouii),

iJeic acid, linseed-oil, wax or spermaceti. — AJ.so, according to Sacc,
when a mixture of pure succinic acid and excest of subem acid is heated

t" '

2C*H«0« + C^«^H'W + 20 - 2C»<H«0" + 400^ + iHO,

^refiaration, J. The hard cfystalUue grains of piraelic acid con-

inatetl with suberic acid wliicb are obtaiued in the preparation of

ipic acid (x, 434), ur© freed from adhering' euberiG acid by elutriatioii

iTitb water and washing with cold alcaUol, and rocryittalJised from boilin^^

water. (Laurent.) — According to Bronieie, pimelic acid occurs, not so

much in the acid mother-liquor of f?uberic acid prepared by Lauren t'ii

tthodj as in the waeh -water; and crystal lii^eu therefrom by slow evapo-

itjon* It is purifietl by repeated crystallijiation from boiling water. —

jirfih separatea the suberic acid as completely as possible by repeated

^ystalli^atiun ; conoentrates the mother- liquor very strongly; presses

e sejHinited mixture of acids lie t^' ecu bibulous paper ; dissolves them

water ; mixes the warm solution with a quantity of strong aqueous

.rbonato of soda sufficient to impart a slight alkaline reaction ; treats

e conceutrated liquid with chloride of barium as long a^ subemte of

ryta is thereby precipitated ; and miies the liquid decanted from the

precipitate after cooling with a warm concen Crated solution of eulphato

ipper. The pr«cipiUitJon must not b« perfomi^d mi tcM) high a tempera tur^^

rime Ihe piinolale of copper as it septrates, will partial If fuse and take topftber,

light blue precipitate of pimelate of copper is suspended in water

.nd dccomfiosed with sulpharettod hydrogen, and the liquid is evaporated

to the crystallising pointy the tirst portions, which possibly still contain a

little suberic acid, being set aside, and the last portions being regarded a$

|>ure pimelic acid. — Sacc, in prejjariug suberic acid by the oxidation of

linseed-oil with nitric acid, obtained from the inolherdiqnor containing

iilLrie acid which was left after the first crystallisation of suberic acid, —

first, fre^b quantities of suberic acid, Bud then larger granules or hard

yellowish plates of pimelic acid, which were purified hy distillation. -^

2* When I pt. of wax is boiled with 2 pts. of nitric acid till the whole

h dissolvetl, granules of pimelic acid separate first as the liquid cools.

(Gerhard t,) — 3* Eadcliffe digested spermaceti with moderately strong

4Si PRIMARY NUCLEUS C»^ll»: OXYGEK-NUCLEUS O<0iW. \

nifcrio acid till the wbole waa dissolved ; the Bolution when erspomted

and left to cool J yielded, besides succinic acid, wbitts gmiiules of pimelie
iicid. If the digeatioQ be continued, tUo pimelio acid diminislica itt
quantity and tho succinic acid increases, so that it ij only the nioiber*!
litjnor of tbe Fuccinic acid tbat tbea yields pi roe lie acid. — In aaotLer^
Ciperimeut, Hadcliff obtained an acid wbicb separated ia transfmreQi <
crystals, arranged in groups like cauliflower-heads * this acid dissolved J
readily in water and exbibited the composition of adipic acid, — 1
4. When a mixture of succinic and excess of suberic acid h boil^i witfcl
etrong nitric acid, and the excess of suberic acid ia removed by eTapi-l
ration and coolings tlie mother-liquor yields yeTy beautiful pimelic adj
without any trace of succiuio or etiberlc acid. (Sacc ) [1 L.J

Properiieg. White granules of the sixe of pins' heads and cora|
of fimall crystals. (Laurent.) Needle-shaped crystals groupetl in liird
warty, stellate masses, (Marsh.) Hels no smell, but a sour taste.!
(Laurent.) Tastes sour, somewhat like tartaric acid. (Marsh.) Meltti
at 114' {Laurent); at 134^ (after drying at 100^-). (Bromeie.) Wheal
perfectly dry, it softens at 112^ and melts at 114^ or 115^ (aspecimeQ.|
imperfectly dried melted at 00"), and solidifies on cooling, into a luitilel
mass of needle-shaped crystals, (Marbh.) Distils witbont dec<>mpri?itbtt '
at a high temperature. {Lauront,) Boils at a bigh temperature apparciiiW i
between 230° and 23ij'^, turning slightly brown, and distilling in the form ofl
a transparent oil which forms needle-shaped crystals on coolings, (MuhiIk)'

I At 100*, LaureoL BrotneU. Kadctifl; OerUv^l

14 C ,,. 84 .... 52^50 51-78 .... 51-75 .... 51*09 ..„ 52*0 J

12 11 ,. 12 .... 7-50 __ 7 55 ,.., 7 55 ,... 7-52 ..,. 7$ I

8 0 .«...*, 04 .... 40^00 40^67 ,... 40-7tJ .... UiU ..„ 40-1 ■

c^*H^»o»„„ 160 .,„ 100*00 „ 100 00 100*00 ._ 10000 ,„. looi^

DecompasitifmM. When fased with hydrate of potnsh, it gircs nf &|
large quantity of water, and at a stronger heat, hydrogen ;nis : tlttl
residue turns yellow, contains oxalic acid, and when disti fled wfth ful*!
phuric acid, yields a volatile acid having the odour of valerianic ttei^l
and forming a silver-salt which blackens quickly when exposed to ll^hLM
(Gerbardt): ^ 1

. C'^H^^CF + 4 HO = cm^o* + C»H»*^0^ + 4ir> I

Chmhinatm^, Pimolic acid dissolves in 35 pts. of water at IS*, tcijI
easily in boiling water* (Laurent.) It h more soluble in wntc^ IbJ
fluberie acid. (Bromek) It dissolves in heated oil of vitrioL (Laureiit.)!

Pimektes. — The acid is bibasic. Only its neutral salts, C«*H*^^^0•J
are known, Nevertheless, a solution of pimelic acid boiled with tlid
recently precipitated carbonates of baryta, strontia, lime or magtioiij
even for a considerable timej does not dissolve a eufficieut tjnantity of thj
bases to form neutral salts. |

PimfMe qf Amm&nia dissolved in water gives off ammonta mhM
boileil, and when left to itself for some time, especially in m warm idoe^
(MArsh.) I

Plnuhtf t>f Baryta. — Ohi%m%A by boiling the aqueous add wltll
farbonato of bar)^a, (Laurent,'^ \

PIMELATE OP ETHYL. 465

Laurent.

2B«0 153-2 .... 51-89 5107

CMHWO« 142 0 .... 48-61

C»H»B»«0» 295-2 .... 10000

The acid neutralised witli ammonia does not precipitate the salts of
baryia,8trontia,lime or magnesia (Lament, Bromeis, Marsh), or manganous
oxide or f inc^xide. (Laurent, Bromeis.) — With zinc-salts it forms a
white bulky precipitate, which, if sulphuric acid is present, appears onl^
when the liquid is heated. (Marsh .) — With Uad-aaXta a white preci-
pitate (Laurent), apparently insoluble in water and alcohol. (Marsh.)
With fefrie salts a light red precipitate. With mercuric chloride a
white precipitate. (Laurent)

Fimdate \of Copper, — The ammonia-salt forms with cupric salts a
green precipitate (Laurent); a blue precipitate insoluble in water and
alcohol. With acetate of copper however no precipitate is formed, the mixture of
the two salts leaving^ only a syrupy mass when evaporated. (Marsh.)

Marsh.

2CuO 79-6 .... 35-86 35-2 .... 34-25

C»^H'0(y 142-0 .... 64-14

C"H»Cu«0» 221-6

Pimelate of Silver. — The neutral ammonia-salt forms a white preci-
pitate with nitrate of silver.

14 C

10 H

84

10

.... 22-46 ...
.... 2-67 ...
.... 62-04 ...
.... 12-83 ...

Bromeis.

22-19 ..

2-64 ..

62-19 ..

12-92 ..

RadcUff.
.. 28-37
2-89
.. 60-00 ...
.. 13-74

Marsh.

2 AgO

6 O

232

48

. 61-15

CMH»Ag«0»

374

.... 10000 ...

100-00 ..

.. 100-00

Pimelic acid dissolves readily in warm alcohol and ether.

% Pimelate of EthyL

Marsh. Ann. Pharm. 104, 125.

Obtained by the repeated action of hydrochloric acid on an alcoholic
solution of pimelic acid. The portion which is yolatile below 100® is
distilled off; the residue neutralised with carbonate of soda; and the dark
red oil thereby separated — the quantity of which increases on further
addition of water — is dehydrated by means of chloride of calcium. —
The liquid thus obtained has an agreeable fruity odour and the following
composition :

VOL. XII. ^u

lUCLEUS C^W* : OXTGIS-KUCUO Cif"*?.

ac.

SIB.
$0.

20
61

61*11
29^61

.. . 61 44

<^H*0» 216

tO«*IN»

mi m h^mU |M«eg omer wbicfa dl^rv»M with orWii

le c „_

16H,...«
8 0

§4

5r44

9 10

iBMT to llie ethyl-eompotiod, mad rBJir^oiM the Mme kiii*l &f t
I boilcHl.

T- Pimelate of Amjt

JIjvV. iiiHi. /'Aam. 104, 124.

IgsebpuBediutomdolQtjoQ ofpiiBelSeMlill

; tl» fOftton whieh boib below 130^, dictUM *€; lltft*-

:«a vitk mb^ portion of amylic alcoliot; kj^rndilom aal«|i

^i9ed tnt^ tlie Bqmii; and the portion robtile Wlciw ]30*i|aia W<

" Tte dark ped retidue begiof U> boil at 2eo', Imt iJm loifitf p«»

fiqiiM,

to
lofetber

, tod a dark rrd oIIt ]ti|iiicl
with iLat wbicL i/ extmctod

ybcken^ r«»diie in the r«toH, it reHiBed^ the portlcm wkiek Mdi M*
ISO' beiog rejected, ati4 tli^t obtained between 170' ii»d SOQ*, fiflia^

a^rL

Dirk red aooiewhat otlj lirjald, hairiTi^
mpleswit odoor.

a p^setmlAj; hit li

MA«k.

34 C

52 H ^

g 0 «.

. . 204

52

,..r. 64 .

10-47 ..

f*7iS4
^ 2l-4€

C*HMI^ ,.

300 ..

.. im*OQ ,„

lA^iHl

olnble in water, wlable in alMoi and efA#v, f

TEREBILTC ACID. 467

Oxyge^irnudeus C"H"0*.

Terebilic Acid.
C^*H"0« = C^*H"0*,O*.

Brombis. (1841.) Ann. Pharm. 37, 297.— Pharm. Centr. 1841, 399.
RiBOURDiN. N. J. Pharm. 6, 185. — Pharm. Oentr. 1845, 213.
Caillot. Ulngt. 1849, 353.— J^. Phil. Mag. 86, 67.

Terebie acid, Terebiltdure, Terehitu'dure, Terpenthin9dure (Bromeii). Acide
iSrMgve, Acide Uribilique (Rabourdin).

Formation. By the action of strong nitric acid on oil of turpentine
or oolophonium.

Preparation. When oil of turpentine or oolophonium is boiled with
nitric acid, a violent action takes place. When oil of turpentine is used,
the mixture is thrown out of the vessel; oolophonium acts more quietly,
and after a few days, the whole dissolves, forming a clear liquid, which
when mixed with water becomes turbid and deposits resin. After
evaporating to dryness, and treating the residue with water, nothing
remains but a small quantity of resin; and the acid solution, which is
almost free from nitric acid yields by evaporation a yellowish syrup
which, if left for some time in the cold, deposits crystals of terebilic acid;
they may be washed with water and dried between paper. (Bromeis.)
— When a small quantity of oil of turpentine (obtained from Pinus
maritima), is heated with commercial nitric acid, a very violent action
takes place at 60"^; and if more oil of turpentine be added in successive
portions, the nitric acid being however kept in excess, and the liquid
being ultimately boiled, till the resin which separates at first is com^
pletely dissolved, a saffron-coloured resin is precipitated on addition of
water, and the liquid after being evaporated to a syrup, yields crystals
of oxalic acid. The mother-liquor diluted with water in order to preci-
pitate a small remaining quantity of resin, and then again evaporated to
a syrup, yields terebilic acid in a few days in the form of a granular
msLsa; (if no such product is obtained, the syrup must be mixed with an
equal volume of nitric acid and evaporated over the water-bath to its
former bulk). The granular crystals are washed with cold water and
recrystaliised twice or three times. (Rabourdin.)

Properties. Four-sided prisms with oblique terminal faces, and
having a strong lustre on the lateral faces. (Bromeis.) Crystallises
from the alcoholic solution by spontaneous evaporation in transparent
colourless rectangular prisms and acute or wedge-shaped octohedrons; from
the aqueous solution, on cooling, in small cry^jtals united in groups like
cauliflower-heads. (Rabourdin.) Melts with some difficulty (Bromeis);
at 200", without loss of weight (Rabourdin); fumes slightly when strongly
heated, but does not sublime. (Bromeis, Rahourdin.) Its taste is purely
acid. (Rabourdin.)

2 n 2

438 primahy nucleus c^h'*: dxyghm-nucleits cmm'^

At 100% Bromeif. RuboarJia.

14 C 84 .». hZU 53-20 .... 53"03

10 H 10 ,... 6-33 -» 6-70 ..» 6 13

SO... U ..» 40'5l .»»,« itJ-OI .... 40-54

C1*HW03 .„. 158 .... 100 00 10000 .... lOOOO

The behaviotir under the influence of lie«t make* it doabtful wbetlier
exainined by Bromeis wsa the s*me as that exaijnined by Rabourdizu

DtmmpnsUiom^ L Tbe cicitl wLen boated^ deeompoaea witti aligKt
lUumesconce* (Bromela.) When lieated to the boiling potnt, it givej < "
rirkmic aciil and jielda a distillate of pjroterebiljc acid^ without lejiriij
anj residue in the retort, (Rabourdin.)

2. It ia not altered by boiling witli nitric acid, but oil of rii
bhickens it. (Rabourdim)

3. According to Caillot's reacarcbea^ which are known onlj
abstract, terebilic acid, in presence of excess of bases, takes up 2 or 3 /
water and forms two new acids; with lime, cupric oxide, lead-oxide
silver- oxide, diaUrebates are formed, — C-*K^^0',2M0 ; with potad
soda^ baryta, strontia, nia^neaia and mag'tianous oxide^ mett^tr^batm
C^*H"H*,2M0. When hydratcd oxide of lead is dii?solved in terehi^
acid or terebilate of lead (obtained by dissolving carbonate gf Jeid "^
the aqueous acid) the salt C"H^OV^l*bO ia formed, which dissalvcj
water in all proportions and when boiled yields C^'H*0*,7PbO,

Comhinaiiom. Terebilic acid dissolves sparingly in eold water, but ilf
much more soluble in boiling water. (Habourdin.)

The TerfHtalfs are soluble in water, the ferric salt only being dilEeii
to dissolve; the terebitates of the alkalis and earths dissolve very pjuilj
and crystallise with diHiculty* (Rabaurdin,) The amnioniacal solutic'
does not precipitate a solution of chloride of calcium, acetiitc of lead i
n i tra te o f fill ver* ( Bromeis. )

TerebrxMte of Lead. — a. Bmic. — The aqueous aoktlon of b di
a large quantity of oxide of lead, forming a basjic salt which ctys
with difficulty. The aqueous solution does not prenipjUite basic icetaCc of kaJ,

&, NetUrai. — When oxide of lead is dissolved in the aqueous acid
inch quantity as to leave the liquid still acid, and the solution is tU
evaporated to a syrup at a gentle heat, white crusts form on eoolii^
cnnsiiting of crystals aggregated in cauUflower-like groups, Di^olr
readily in water. (Rabourdin.)

Ferric E^lis are precipitated by alkaline terebilates; in diloie soltitia
a blood- red colour is produced. (Rabourdin.)

Tfrthilate of Silver, — A strong aqueous solution of nitrate of sUf
is preci[iitated by an alkaliue terebilate in slight exees«| and tho
pitate is washed with a little cold water, pressetl between pAn
dried by beat in a dark place. Fou resided needles having m '
lustre* It blackens when exposed to light, enitecially If mr^'U,
(Rabourdin.) Bromeis, byniixin^^ terebilate of ammonia with a sli^ii
excess of nitrate of silver and evap<^irating, obtained, as lh«3 liquid eooliij
needles grouped in tufts mid having a fine silky lustre; they dc
posed at a rather high toiiijieraturc, and when slowly healedi left silvi
in the furm of the crvstals.

CULOKCENA.NTllYLENE. 459

11 c

Ai 100\
Si ..

.. 31-70 ..
,. 3-40 ..
.. 43-77 ..
.. 2113 ..

Rabourdin.

31-61

3-44

43-89 ...

21-06

firomeis.

9 H

9 ..

AgO

7 0

116 ..

56 ..

. 44-22

C»H»AgO« 266 .... 10000 100-00

Tcrebilic acid dissolves very readily in alcohol and in etliet;

Terehilate of Methyl C*«H"0« = C»H»0,C"H»0'. -^ Oil having a
bnming, but not acid taste. Cannot be distilled without decomposition.
— Dissolves sparingly in water. With bases it forms salts having but
little stability. (Caillot, L' Institute 1849, 354.)

Terehilate of Ethyl. C^H"0«=C*H*0,C"H*0'. — Oil, having a burn-
ing but not acid taste. — Cannot be distilled without decomposition. —
Sparingly soluble in water. With bases, it forms salts which have but
little stability and are resolved by the slightest heat into metaterebates,
alcohol and terebate of ethyl : e g,

2(C»H«0«,BaO,C^H«0) + 7H0 = C"Hi30",2BaO + C^H'O* + C"H907,Cm*0.

(Caillot; see page. 468).

Terehilate of Amyl C'*H««0»=C^«H"0,C"H»0'. — Resembles ibe
ethyl-compound. (Caillot.)

Chlorin€'7iucleus C**C1H»*.

IT. ChloroBnanthylene. C^-CIH".

LiMPRicuT. Ann. r/uDtn. 103, 82.

Formation. — By the action of alcoholic potash or ethylate of sodium
on chloride of cBnantbylene (p. 461).

Treparation, A very concentrated alcoholic solution of potash is
distilled upwards with chloride of oenanthylene for a considerable time
(the decomposition of 15 grammes of the chloride takes about a week);
-— or chloride of cenanthylene and ethylate of sodium are heated together
in a sealed tube to 250^; — the liquid obtained by either process is diluted
with water which separates impure chloroenanthylene; and this crude
product is dried by means of chloride of calcium and then subjected to
fractional distillation. It begins to boil at 100°, the boiling point slowly
rising to 150°, where it remains constant for a while and ultimately rises
to lOO**. The liquid which passes over below 100° is a hydrocarbon
(v!d, inf.); that which distils at 152° is chloroenanthylene, and above
tliat temperature the product consists chiefly of undecomposed chloride
of (Biianthylene. The complete separation of these liquids can be efl*ected
only by repeated rectification.

Fropetiies. Liquid resembling chloride of oenanthylene and having
a similar odour. Boils at 155° (observed boiling point 15i'; correction 5*).

470 PRIMARY NUCLEUS C^*H^*: CHLOIUNE- NUCLEUS C*^

U C ..,,*, ei'O .... 63-2 ...... 6.V&

13 ti »» ..„ ma . ^7 ........ ^*7

Cl_. a5'4 .,. 271 ioHt

a^ClHW, UZ'4 ..., 100*0 ....... JOO-0

Scidtutn remame unaltered iti cblorcBDaDthyleno ii.t onliiiafy 1
turee; but un heating the liquid, a violent action sudden! j tokee &!•»,
cblorido of eodium being formed together witb a bydrcMmrb^^n. pitJttLj
C^*H*** — The SBDie bydrouarbon appears to be produced hy the Action erf ilo^cit
patiLsh on chLoriKEifttitbylenfi ; tor the portion of the liquti! obuitied in tke p«|i-
ratton of chlorocm«nthyieti« ttbove dti^crib^d, whieh boiled below 100*; mwA ImmI •
cqiiUio 84 14 p, c, carbon and 12'42 hydrog^cD, betidea a certain qnacitiif irf chbcttr
SappoAiDg now that the df fi^^iient 3'4 per cent, consisted of diloHDe, arum^ fr>»A
admiJiture of cbtoroetinnthyLene with the hydrocarbon , a^d dedneUrig from t^ |»wi
ine quantities of carbon and hydrogen the quantities of lliote rirfrrnn rnrrriiumfitl
this 3*4 p* c. of rblorine, there remains 76-3 C aitd 11*2 H, or 87*5 |t, c, C tnd U'tl^
iigreeitij very nearly with ibc formnla C'*H'^, which require* 8 7 '2 p. e. C and 121 E
Tha anaijws of another speeimen calculated in m aimilftr mftanei- gmve 37*7 pi.4:aii
\2'% H. The formation of this hydrocarbon from chloride i>f cenanthfkne «a4 fna
chloroenanthvlene 15 reprefieuted bj the cquationa ; C**11'<C1* — 2UC1 = C*^M^, irf
C'*H"Ci — HCl - Qm^. (Limpricht.) f .

Chloride of (EnantliyL

Cahodrs. Compi. rend. 25, 724.

Produced bj distiUiug tEnautbylio acid with peQtaeMorMi ^
phospborns.

It ia decompostfd bjr water iiito bydrocbloric and a^uimtlijUc wcH^

aUorine-nudeuB C?*Cl»H»,

TarcUoroenanthoL
C^Cl^H^^O* = C^*CPH^SO',

WiLLrAMsoH* (1847,) Ann, Pharm. 61, 44.

(Enantbol abeorba a largo quantity of cbtorJne gm% and i« eiftfifiil.
witb formatiou cif bydroehlorio acid, into a viscid ail^ %vhicl] is «^bM
with water aud freed from hydrocblorie acid by rep^yaUnl fiolstUoB <
nleobo] and precipitation by water. — It ba9 an a§reOftlile odour, mmt'
tbing like ibat of caoutcbouc. It sink^ in water, but does not amir^
be decompoied by it, even after long immeriion. It ^uinot be aiMiiW*^
without decompoBition.

H C .„__ SI'O . 38*et ., SS-I

11 H....« p.... no „„ i*oi _ ^ii

3 CI 106*2 ,„, 4g*96

2 0 , „,...„„... 160 „,. 73<^

C"H"C1W _.„... 217-2 ... 100 Ot» ^

When Ueuled, ilWa^Vt^m %.\\t\ ^v<5^ ti^ V^4s*MiWorio ml*

THEOBHOMINK,

471

(Enaathylamide.

luiozzA Si UAhEHUA. (1854.) Ann, Pharm. 91,103. — /. pi\ Chaft.
04, 32.

<Enantliylic anliydridB fortui with strong raiiistic siniinotiia i& mase of
nail crystals which may be recrystnlHsed from bo Uing; water. — LiiiiuiiBO'
iving a pearly lustre. Melts at 95° and volatilise^J wilLout deronipo-
ition at a htgber temperature.

14 C „,, 84

N 14

15 H.... 15

2 O 10

C>*NH«0* ... 129

(ia'Pi ....... 65^32

10^85

12*40

lOOOO

Ox^azo-nurit^ns C»*N*H*0*,

p.

Theobromine,

OSKRK0BNSKY. (184L) Aim. Phart/L 41, 125.—*/, pr. Ohm.

23, 3M.—Pharm. Centr. 1341, 520,
Bley. N. Br. ArcL 29, 201 .—P ha fni, Cffitr. 1842, 303; 1840, 424.
Kkllrr. Ann^ Pkarm. 92, 71.—/* pr, CUm, *>4, IDO. — /V*an^(, VmU\

eij im,—Pharm. Cmtr, 1855, 95,

^b«

Sourcfi. In cacao^beana (WoskreseuBky), and m miiall quautJty iu
their Iiuglvs. (Bley.)

Preparatimu Cacan-b<3ans are treated with water for some time a(,
the beat of the water-bath ; tbe eotatioti is etrained tbroui^b linen, and
carefully precipitated by aoutral acetate of lead ; the precipitate, which
is abundant, b separated by filtration ; und tlio filtered liquid m frt^cd from
excess of lead by sulphuretted hydron^cu. The tiltrato lliea yields by
ev&poration a brovrn re«ildiie, which is boiled with alcohol and ti'ltered at
the Doi It ugh eat ; ike liquid on cooling deposits a reddit^h white crystalline
powder, which is obtained colourless by repeated cry^talliaation. (\Vo«-
kresonsky^ Glasaon.) Keller beats the theobromine obtained as abore,
between two watch-giasses^ whereby a small quautity of ebarcoal is
separated, and a dazding white sublimate m formed.

ProptHm. Colourless cryetaUinc powder. Microscopic cryatlliJ
belonging to the right prismatic system : (»P2; P in club-thapcd gronpo^

472 rRlMAUY NUCLEUS C'*H*' : OXVAZU-NtCLKCS CWK*ll«0*.

(Koller.) Taiites very bitter, but tbo (la von r m very aJowIjt tk^dopc^,

(Wo^krcsenskVi Gln^aon*) Sublimos witboutdecotupQ^iiion l)etw«etilW
and 235'. {Keller.)

Woikrcseiia)(j« GUmmsu Kdkr*

14 C »... 8i .... 46*67 »...,.. 40-3$ .... 4713 ^ Um

4N ,..,.., 5G .... 3l'U „.,.... S5-3S .«. 31-27 ^ 3IW<

an 8 .... 4-44 4-5S ,,,. 4*611 _. 4-W

4 0 ,„„... S2 17-78 ....... ia-?4 ^,. 17-00 ^.. IS-<Ni

C**N*H«0*.... 180 ....10000 ...... lOO'OO ...100-00 ^. lOOiM

Decojnpo^Ulmii. 1 * With clilorine io prescoc© of w&tar, it t^tm
amalic acid (xt, 433) and bydrocblorsite of tnethjlaiDiDe. (RofdiMirA
lUasiwet^, Bi^, Jii^J, 1850, 1, 206)— 2; Heate<l witb peroxjifeolM
nnd dilute sulphuric acid, it gives o^ carbonic acid^ tbe decompofttiM
when once begun, going on without further applicatioti of he?»l; %nl4
the right quantity of peroxide of lend be added and the heatiog not l«
long con tinned J there is ohtained, after eeparating ibe sulphute ol Ud
rby filtration, a transparent colourless Uqaid, wbich gives off aiMmoei
' when treated with potash^ separates sulphur from ^ylphureltcd hydnf ea.
colours the skin purple- redj and ini mediately tares blue when treihW
with magnesia. An excess of magnesia des^troya tliis colonr, wbkb mm
however be restored by cautious addition of enlphiinc acid. The hfm
mixed with excess of niagnesioj heconiea reddii»b atid gives offamooM
during evaporation to dryness; boitiikg alcohol extracts from the rmiM
a body which crystallisea from the aolutlon in rhombic prisms, is soloWt
in alcohol, h^s an acid reaction, and docs not precipitate chlofiik itf
mercury, nitrate of silver or bichloride of platinum, (Glasson,)

3. It diis^olves m hoiJint; baryta-water without evolutjoo of amrngsii;
tLc eoluljoti on cooling, solldiGes luto a white jelly.

Ucmhi^tatiom. Theobromine is fiparingly solnble in hot water. Witl
ncids it forms salts which crystallise readily. The neutral sait* in
ikeonipoaed by water and yiela baaic salts.

Hf/tlrocMoratt of Theohvmine. ^- Theobromlno dissolves readiJT ii
concentrated hydrochloric acid; ns the warm solution cools, the alt
fccparales in cryi?tals, which may be dried over oil of vitriol and c»»(ie
potash* Gives off all its hydrochloric acid at 100^. DccompoiM viA
wa,ter fonniug a basic salt. (Glaason*)

Ci«N*iiW„. 180 0 ... 63*17

CIH . ■■» 36-4 ,... ieB3 „ 16-g3

C"N*H»0^,CIH . . 216-4 ... 10000 ^

^'itraU of Titeobromine, — A solution of theobrotntDe ia .
heal<5d nitric acid deposita the nitrate after a while, on ecioling, ia si-,-^—
I humble prisma. The ^U gives ofi* its acid at 100% and la tmdi^
dccum[iOi&ed by water.

Ci'>;*H'^*,HO 189 .... 77 78

NO* , .......„« M ... 22*22 .,„.^, W^f

c»*H*iro\NO*ii....-...,. 243 ,„. iwm

BDIIEIC ACID,

473

A^ittffie of Siht}' rmd Thfobro/tn'm, — ^AveryUilute luiueous solution
of nitmto of thetibroiuiDe mixed witli uitrate of silver forms after a short
time, silver-wljite needles. TIjc double salt ia but eparingly soluUe in
water, and may thereforo serve aa a test for theobromioc. 'it doea not
aiiffer any perceptiblo loas at 100", but at a Ujgber temperature it melt!^,
gives oflf red fumce^ and after continued ignition in contact witU tbc air,
leaves a residue of metallic silver. (Glasson.)

u c ......

5N ,.

' "*"

....... 84

„ 70

,... 21*00 ...
.... 20-O0 ...
.... 2-28 ...
.... 20'5B ...
.... 33' U ...

..... 2.3-n

19-76

S H

........ fl

2*47

9 0

72

...,» 21^22

A«0 .

....«, 116

32-84

C^N'H'^O*

,N0* + AgN

0*. . 350

.... 100*00 ...

100*00

CMorophiinate of Th^d^mmhit. — A niixturo of theobromine dls-
olved in hydrocbloric acid witb bicldoride of platinum, yields prisms

elouging to tbe oblique priamatie system, and baving tbe faces «^p an
IP. Tbe salt elflorei^ceH iu tbe air, and gives oif all its water of crystal-

Bation (873 p. c. ^4 At) at tOO'. It decomposes at a stronger beat,

id when ignited in the air leavea pure platinuni*

C»^Nm«0*,HCl .,„.. 216'4

2 CI .,„.. n%

Pt „ Sfl'O

Gkaion. Keller.
56*03
18*33
2&-64 25-42 ZS'SS

C^WHW.HCl + PtCl* .... 38G-2

10000

Aqneoua theobromine forms witb a solution of corrosive sublimate,
a wbite crystalline precipita tOj sparingly soluble in water and alcohol,
(Woskrescnsky.)

Theobromine is less soluble in alcobo! and ether even than in water.
It forms with tannic acid a precipitate soluble In txtmn of tbe acid, in
Lot water and in alcohol.

Boheic Acid,

loCHLEDKR. (lSi7.) Ann. Fharm, 63, 202,— Pkat-m, Cmtt\ IBiSj 25.

Occurs in small quantity in black tea, together witb a large quantity
of querci tannic acid.

PtrparQiitm. A decoction of tea is precipitated at the boiling heat
with acetate of lead ; the filtered liquid left to stand for 24 houi^j nud
n^gain lilterod to &e|mratc a small ^cdimeul; the clear solution mixed

414 mMisT ^Ufxsus c*m^i oxyges-hvclzvs c«»tt"o*.

hj4nif«i; aEMl the fiknao left te tfifMiili.

The mldQQ is dlseolted m wtl«f » ifti lb

i» in Ticao^ tiieo dried mi 100^, 1^ tn^

tki^ivmm mmd tho reeido* imJlj l«Eft f«r tint

W^M p«lTerieed, il is of s pale j^llow colour.

i. Mete at 100^ into m mass wkich drawa imi

t^g«tker »lieii exposed to the liir, even fi*f a W

dcdi^Meeee refy qokyy. Colours ferric lijdfocliiuak

i

U€

no

10

-« 5'2fi
« &0-53

EocliI«der,

.... All

C**H"W* » 190 ..„ 100 00

Ibt tie bjpatibitiiml aolijdroQi add cbe foniiBlm C^H^,

1000

,^„ — Bj dty dw^Oation It yields a Ughi eharaotl, aod

tfitJHtia wyeh aneili of MOlie ftcM and blackeDs iron salts, U.
\ sad •loahoiie oolntioiis decompoae when erapoiaied in costiet
L the air.

Tbe ftcld did&olvea in water in all proporlioaa

Mtkmk^ ArfU, — Tte lead-salt suspended io a]|*ohot it .«»»*
woi by aal^irollod hydrogen; the filtrate mixed with watet »
troattwl wttk baiytA-water, lu mifficient quantity t<j produce a aiii|fcl
alkalm icactinn: and the yellow precipitate b washed
with iW aki vilk water Gontaiiilng alcohoL

■Irri^B

oQl of eoatitf

10 H «^^
If O

Rochleder.

l&3-i ... 44-02 , 4€*3«

84*0 „„ 24- 48 ...._ 24*32

100 ,.„ agi ..„_ S^
OfiO .... 27-99 S9*3<|

C»H*B«W" + aAq .. 343*2 ..., 100 00 ...._. 1 00*00

[ BJmi^ ^/ Lead.— a, B^asic. — The yellow precipitate <^t cnk
1>c»tieato of lead obtained in the preparation of the acid, on ntntialir
ine tlic Uqttid with animania, is euspended in alcsohol and drcio-
pt^ed by snip hurt* tted hydrogen ; tha filtrate is freed (ptm i»i-
phnrettei hydrogen by lea\ ing it in vacuo over strong pi*taAh*«t»]QtK«»
then precipitated with alcoholic acetate of lead; and the pfectphale ii
washed with alcnhol and dried at 100°. White with a ting« of grtr

2FbO

14 C .,.
10 H . *

12 O ....

22%'B
84*0
10-0

54-06
20'30

a4t

33-2:1

RochWer.
. 2115

eni^pvo*'- ^ %K^.... uas ... loooo

100^

BOHEIC ACID. 475

6. Bcuic. — A decoction of tea is precipitated hy neutral acetate of
lead; the yellow precipitate suspended in absolute alcohol and decom-
posed by sulphuretted hydrogen; the filtrate evaporated in vacuo over
oil of vitriol; the residue dissolved in water; and the solution precipi-
tated by an ammoniacal solution of acetate of lead.

Egg-yellow precipitate.

Rochleder.

4 PbO 447-2 .... 72-22 71*43

14 C 84-0 .... 13-56 14*04

8 H 8*0 .... 1-29 1-39

10 O 80*0 .... 12-93 1\14

C"H«Pb20W2PbO .... (>19-2 .... 10000 100-00

In one preparation, Rochleder obtained a fait having the composition
CMH^*0^,2PbO; but he did not lucceed in preparing it a second time.

Boheic acid dissolves in alcohol in all proportions.

ADDITIONS TO VOL. TIL

Piige 3B.

^onjiation of Oi*gmtic Cmnpomuh fmm Tmi\jamc MaUrkth^ —
m a mlxtaro of bisulphide of carbon and aalplmreUed or plios-
petted bytirogeo is parsed over copper at a dull red Leat, hydrogen
and mardi ga3 are obtained, together with a perceptible quantity of
iant gas and a trace of napUtUalin. A somewliat larger qnantity of
iant gaa may be proiiuced by tha action of a mixture of bisulphide of
bon, sulphuretted hydrogen and carbonic oxide upon iron.
Formic acid ts produced bj the action of carbonic oxide on potaab
J 4Q0); forniiate of baryta yields by dry distillatioiij marsb-ga«, olcfiiut
M and propylene-gas C4i*; and the last two hydrocarbons may be con-
srted into the corresponding alcohols by uniting them with sul|diuno
aid or with hydracids (x, 51 1^ 550), Moreover, a mixture of carbonic
lide and marsh-gas passed through a tube heated to dull redness
deldrf a small quantity of propyl en e-gas. Fur the r^ acctio acid may bo
brmedfrom alcohol^ which may itself be produced from olefiant gas; and
.estate of soda subjected to dry distillation, yields olefiant gas (in small
''quantity) propylene, butjdene, and a small quantity of amylene. — Hence
and from the known relations between hydrocarbons and alcohols, and
between the alcohols and other organic com pounds, it appears that a
large number of organic compoundi? may now be formed from inorganic

I materials, (Berthelot, Compt. rend. 43, 236; Ann. Phnrm. 100, 122.)
Si/nthah of Ifdhylic Alcohol. — Marsli-gas mixed with chlorine nod
exposed to sunshine, yields chloride of methyl together with other siub-
atitntion product.«, and chloride of methyl may be converted into
methyl ic alcohol by procesies to be presently described.
I 1 To prejmre chloride of methyl in this manner, 40 litres of chlorine
! are mixed, in bottles each holding a litre, with <Q litres of marsh-gas pro-

Fagc 25B.

478

ADDITIOKS TO VOI- VI K

viouslj purilied bypasaing through oil of vi trial ami collected over water.
Tlie bottles carefutlj closed are placed so aa to receive tbe sims r»yi]
n^ fleeted from a wail; and, as soon m t be colour of tbe ebloriDe ta no longer I
^ isible, tbey are opened under a mercury, and pleeea of bjdimte of
potash are introduced together witb a few drops of water. The volume of
tlie gas is tberehy reduced one-balf, and the residual gas which coutatfu
tlie chloride of methyl, together witb unaltered marsh -gus and fiometimea
hydroi^^en, h agitated with glacial acetic acid (250 grm. to 8 litres of tbe
resiilual gas), wbicb ab&orbs the chloride of raetbyt together with other
giises* On enbseqaently boiling tbe acetic acid^ the greater part of the
absorbed gas escapes; and the remaining portion, wbicb may be eicpeUed by
SMturating the acid with strong soJa-ley, exbibita, after being freed from
vapour of aeetic acid by contact with sticks of poiasb^ the eompoaiiioD
ami properties of pure chloride of metbyh

2. Chloride of methyl may be con verted into methylic alcoHol : m. By

■flisaolvi ug it in acetic acid and heating the solution to 200** with aeeiate

of soda; acetate of methyl is then formed, from which the alcohol jgeaaily

obtained. This methoil however is not adapted for large 4|uant]tle0* —

6. By heating it witb aqueous potash to 100' for a week :

CSFPa 4- KO + HO ^ CSHHF ^r KCl.

2 litres of the gas thus treated, yielded 2 grammes of wood -spirit, —
c. By treating tbe chloride with a mixture of oil of vitriol and mercunr-

. aulpbate or sulphate of silver at 100^; metliylosulpbate of silver is iber)
fKiriuedj from which tbe barium -salt h easily obtained, and from this,

[inethylic alcohol, or beuKoate or oxalate of methyl may l>e obtained.

[(Bertbelot, Comiyt. remL 45, 91 G; Ann. Fhnrm. 105^ 241.)

Page 271,

Prrparattm cf Formk aeid, — Oacalic acid la reaolfed by heat mUi
earhonic acid, carbonic oxide and water;

C*lFO* = 2C0* + 2C0 + 2HO.

and, as first observed by Gay-Lussac (vii, 269), ^ *mall portion of Ibt
f^irbonic oxide UDi tea with water, prcnlucing formic acid C'H*0*, New
Berthelot has shown that when ihis decomposition takes placi? in preatdet
<if glycerin, the whole of the carbonic oxide is converted into foimlo
acid. When equal weights of commoreial oitalic acid and fyrnnyl
glycerin (a kilogramme of each) and from 100 to 200 gmnimes of water |
are gently heated (scarcely above 100^) in a capacious retort, a bri^kj
eTotation of carbonic aci*l soon begins, and after 12 or 15 hours, tli«l
wliole of the oxalic acid is decomfK)sed, half its carbon beinjr given off ia
the form of carbonic acid, while the remainder prudnces fonnic add In the j
manner just mentioned, A timall quantity of thia fnnnic acid di»til« ittff
.with the wiitcr^ but the larger porticm remains in the ro 'her with

hihe glycerin, aud may be j*eparateil by distiUiog the i^ ih half a^

liire of water, and renewing the water as it distill, till (i ui 7 litir«« of

ADDmONS TO VOL. VII,

470

llquitl baTO passed over. The glycerin wbicli then remains may Iw? userl
for the convertsion of fre^h qtiarUittes of oxalic acid ioto formio a,cuh —
Ii is importaoi tlmt tlie oxalic acid be slowly decomposed; if too mucli
lieat is applieti, the evolution of carbonic acid becomes stronger, rintl
after tills bas ceased^ the temperature rises to betn-cea 130" and 200'^, and
carbonic oxide is given ofT, arising from the decomposition of the fomiic
ncid dissrd ved in the glycerin, — ^ Formic acid is almost completely re-
«oIveii into water and carbonic oxide ga«, by heating it to a temj>erature
between 200 and 250' in sealed tubes, (Berth clot, #. Ann, GhirtL Phffi^
^46, 477; Ami. Pliarm. 98, 139.)

Formiate of baryta ia decomposed by protochloride of sulphur,
pelding formic acid and carbonic oxide gas, toj^ether with chloride
" barium and sulphate of baryta, and separation of free sulphur;

4C?HBiiO^ + 3CIS = 2C-H50* + 4C0 + 3BftCl + BaO,SO^ + 29.

[Joticent rated formic acid may l>e prepared by mixing 4 At of a dry
brmiate with 4 At. water, gra*lually adding 3 Al chloride of sulphnr^
iistilliiig br^tween 110" and 120% and rectifying the distillate over a
nail quantity of form i ate of lead* (Heiniz, Po^g, 98, 458,)

Thtoformie atid. — CH^SW. — Produced an small quantity In the

Secomposition of formiate of lead by sulphuretted hydrogen, at tempcra-

"^ lures above lOO'^, especially between 200'' and 300'^. Cryalallised in

needles from the distilled formic acid, and may be recrystaUised from

alcohol. Has a slightly alliaceous odour Melts at about 120% and

Isubliraes in small transparent crystals even at lower temperatures. The
ilcoholic solution does Dot change the colour of litmus.
.1
2'

2C ,.,...

2 U .., ,

„»,„. 2 „

.. 19*3
, 3*2

2 8 .„,.,„..
2 O .......

„ 51-e ,.

Limpricht*

51-2 .»» 52-5

OHSS^O*

62

100*0

The acid dissolves in oil of vitriol at a gentle beat, giving off snlphur-
AVLS acid aud depositing sulphur. Strong b^droehloric acid does not act
upon it, even at the boiling heat. Nitric neid wtth the aid of bent
destroys it readily^ farming sulphdrie acid* Strong acetic acid dissolves
It in small quantity and dei»ositH it unchanged on cooling. Heated with
sulphuric acid and chromate of potatjb, it reduces the chromic acid to
chromic oxide; peroxide of lead is p.irtially reduced in like manner.
Fused with hydrate of potaili, it forma a reddish vellow maps which,
when treated with dilute sulphuric acid, gives off sulphuretted hydrogen
and an odour of garlic. Fotash-ley dissolves but Utile of it, even at the
boiling beat; and the solution treated with acids, gives off traces of
iulphnretted hydrogen. The acid does not dissolve in sulphide of
ammonium either hot or cold.

Thioformic acid is insoluble in wiiterj and nearly insoluble in cold
alcohol and ether; but dissolves pretty readily in those liquids at the
boiling heat ; part of it volatilises with the alcoUol vapour.

480

ADDITIONS TO VOL, VII-

The aleobolic glutton h nat altered hy ^esqiucliloride ^f iroo; it'
forms with neutral acetati? of hatff a yeUowisfa procipitate wfaitld tanw
bUck when beate^l witb the l]f|iiicl; with nt Irate of sif9^, an smDt^om
pt«ciptute, which li white at fir^t, hut eoon ittros black, and ^mtfii
putlally LQ hot alcohol, with eii^i^iratioti of luetaJIic ailrer or cnl^plLiik
gf alver*

Page 2S7.

A^ticm cf Hea^ mk CUorld€ &/ MHh^L — Wtien ehloride of mwkH
b paaiad IknMi^k m red-hot porcekm tabe^ aud the gatseoui products ii
sition, after being washed with a large qaazilftj of water U
kj^ibficUoric aeid^ and then dried over chloride of calciaiiif Sft
I lo pM into a loiig*necked vessel eontiiiatii^ brotnine, thence into a
A reeetrer, ^nd Bnallj into glutton of pota^sb to absorb the ex«M
«f broaune, the following prod acts are oblalned : 1. A contideiattl
f Mantitj «if (^iboii is deposited in the porctdaio tube together wiA i
amII <|iaDtilj of a Liquid havia^ an empyreuniatic odotir; ciyitik «f
JciliE %ie def)Os^ited in the tube which conveys ibe gmses bio lit
-ktUle. — 3. The bromine^ which is not altered in appearanev, pdk,
traftted witk YifTjr dilute potash, a liqnid bc^ivicr than vtlSt
ble in water, b«t ac^lnble in akobot and ^tlier; and iki« lif«i
lij refieated disliLkiion yields a b^iiiid hailing an oUiere&l oiMi.ml
boiling a little above 15(l^»aiid a solid product wbick nelta il iM
M^ boiU at ttO^r has MU agreea^bk odour^ is u&ctitoiia to tbe l^acb
mad vwr peraane&t Tb« aolid bodj vielded by mialTiif SJ^l
e. €mt^m l^t kyirogeo, »d « e-68 broniine, onmbcra wlatdl d« Mt
~ t» «Mji»plfl feimla. — The liquid boiling al 130^ gatt^ n$lh
«f t«» awdm^ 13*41 p. c. C, 2 23 H and 85 I Br, n^iJkm
•suly witk tin conpoeilfon of bromide of ethylene, C*il^ Bf.—
■refcaklg tb«reliDi« that the chloride of iiietJi%d ia redolrcd «t
nto «iHkjktt# CU\ mad kydroehlorie acid, bat tbt lb
al Ike mmmmt of «f|MtMnt doaUes it? niolecnle and bectad
cikyktttL A pQftioa of li abo ondergoea doeonpoirili^
of aaiililkaliii and oiker prKidDets.-^3. TW
i of bffoaiiao kao been absorbed hj tk
a of melkylCTe, bnl realty cmm»
of eukoB, tke klt«r koii^ kmd
hf iko aHm of tto ted-kot caikoa m Ibo labo on cariMmie odd ^
givoa off by tbo Mixtaiv whick yitUk ibo cblortdool laelky^ a«J
mmiUj on a «iaU oaaaticy of

ooakom by tko
" ■ aflor

#f a adxtmrr if

aadoxido

h/1.

IfETHYLOPHOSPHOROUS ACID. 481

Page 295.

Hethylophosphorous Acid.
C«H»PO« = P(C«H>)H»OV

Hugo Scbiff. Ann. Ch, Fha)'m. 103, 164.

Formation, By the action of terchlorido of phosphoras on metliylio
alcohol:

3C«H<0« + PC1» = C«H»PO« + 2C«H»Cl + HCl.

Preparation, When tercbloride of phosphorus is added by drops to
wood-spirit, a strong action takes place, the liquid becoming strongly
heated and gradually assuming a red colour (arising probably from the
presence of hydrocarbons, and scarcely perceptible when pure methylic
alcohol is used.) The addition of the terchloriJe of phosphorus is con-
tinued as long as any action takes place, and the liquid is then left in a
warm place for several hours, to expel hydrochloric acid and excess of
methylic alcohol. The compound is thus obtained in the form of a nearly
colourless, yery acid syrup, which draws out into threads, and cannot be
made to crjrstallise. On attempting to concentrate it further by heat it
is resolyed into methylic alcohol and phosphorous acid.

The Methyhphotphites, P(Cfl»)HMOS are obtained by treating the
corresponding carbonates with the aqueous acid. By evaporation at
ordinary temperatures or at a very gentle heat, they are obtained as
amorphous masses which exhibit crystalline structure when scratched
with a sharp-edged tool. When strongly heated, they give off phos-
phuretted hydrogen and combustible hydrocarbons, leaving a residue of
phosphate mixed with a little amorphous phosphorus. They are hygro-
scopic, and dissolve readily in water, sparingly in alcohol, and not at all
in ether. The aqueous solutions decompose slowly at ordinary tempe-
ratures into methylic alcohol and phosphites. This decomposition takes
pUoe most quickly when the solutions are acid, and may be prevented
by keeping an excess of the carbonate in the liquid during evaporation.

^<iryto-<aU. -~ Anhydrous; less soluble in water and alcohol than
the lime-salt.

Schiff.

P 31-4 .... 191 1912

CT1',H 160 .... 9-8

Ua 686 .... 41-8 4M7

6 O 48 0 .... 29-3 _^

P(C2H»)HBaO« .... 1640 .... 1000

An attempt to prepare a bibarytic salt, by treating a solution of this salt with
strong baryta-water did not succeed. The liquid, after 24 hours, deposited a consider-
able quantity of baryU, and the filtrate when evaporated left the original salt.

Lime-iah. — Contains 2 At. water, which it gives off at 100°.

VOL. XII. ^ '^

TO.

' . sit

_ 23-5

- 23-35

7=i=.i _ , iri-l

_ li*»

'x 9H|

— I5-«

13-M

; ^ aa-i«

_ 3€-1l

ino - la-H

-- 13-5

13-«

? :-3»^irCiC» - iJha KB-4

— imrm

^isii^n ? ^r-LDARibhi ic \ ^sitie aesc » mmam remmhu wbid achi
lerr-^tfs 5.7 ui.L -v>'. izd jivisi of wa&Hr ami cooibaBtible hydroeutai
Vcwan itl' jnii Tr. AI>*re :}a% the decompoaitioa goes on fery
riTMolj: 'lar 3o e^oinnon if pdosEpaoreciiifi Ejvlrogea takes place till tk
AiC IS oeaieft <nii>iiiefabij abure 114'. The salt gmre bj antlja
0-129 irm. yi poaaphunu ro Q-4dS zrm. of lead ; the catemlsted qoaititf
ia 0-1564 irai. -if pbnsranria.

T!ie ftiinnnn of the iinw lit «ioes not precipitate the cbloridei if
omper ami mni with ■emirv chloriife it forae a white preeiphitej ui
with nicnce 4f hItct, a precipitate which m white at fifsl bat <
▼ieUs redoeefi uItot.

KefUijio^ho^ioric Acids.

HcGO ScHTTF. Jaa. Pharwu 102, 3^.

F^*rmnt'on ajvi Prrpcrati&tL Bj the action of chlorophospborieteii

on methjlic alcohol :

Fo-c;' + :c-:i'a- = P(C-h5)hh>^ + 2C-H>a + iici.

ir.onomethylo-
phrspKoric acid.
unrl :

PO^Cl^ - 3C-H^02 = P(C=I!»/HO» + C*H»Cl + 2HCI.

bixetb\tophos*
plioric ac'd.

On mixlnpf tlio two liqn'ul?, ^rcat licat is erolrctl, vapours of hrdrocLlsif
a<M<l anrl clilorido of methyl are given off, and a dark re<l liquid rtmaim
roni^iHtin;:^ of mono- an«l bi-mcthylophosphoric acids, the former beia? ^
the <,'rfator quantity. But, if the chlorophosphoric acid be plmcni ic»
fl:iHk attarliod to the lower end of a condensing appamtos, and staaiiif
in cold water, and the wood-spirit be added by <lrops from the npf^f
rrnl, cadi a«l<lition licin^ made only after the reaction pro«?uce«nv ik<
fornn^r lias Huhsidcd, the product consietfl almost en tirolv of MznV:^^*
l«>|»h<'s|)lioric acid, which, after the red liquid has been freed fmni hvr-
diN.ric aricl and wood-sp.rit by heating it for several hoarv in th? ^a:*^
l),Mih. nMimins in the form of a colourless syrup, but bv continaed iirtH-r
(»vrr tl'«> \Na!cr huth is ^'raduallv resolved into wood-spirit and T.*-*rV:<

/y.//.f//(f///'7'/i..if;'/ft)/vV f.c/</ is very sour, attacks zluc with e rolst: 1 <;•
ilro'.:. II, and tloroniposes carbonates with facility. The aqoeow j^***
n is rcatlily tloconiposoil by boilinc", apparentiv with f.'rti:aLv*c -i
nt^\\wi\\\V^\\\^^s\\\^x\^ ^^Id. It is •olnble in alcohol and etker.

METUYLOPilOSPHORiC ACID.

46 i

Til © JiimHh^h/JhOipht tr$ F(C^ H*)* MO*, a re o b tai n f^i hy n © n tral m ng
tUe aqueous aci*l witii tlit> corrcirprtufliij|f carlonatcfl* Some of the Je^s^
sol u Me may a.Uu be obtniiieil by pn^cipitaticm. They are ca*^ily aepariited-
from the iiuinonielhybjpiKJsphatos, whkh aro much Imi^ Bolublo and .
Etparate out on tvufimiiit>u. The binjoLbylopbofpbtitea are mostly i
colourkis, (iis^ttlve \rreity reailily in water^ h^a m alcohol, not at all iti ,
[ ether^ and are precipitated hy alcohol and ether from tbeir concentrated
olutions. — Almoet all of them contain several atoms of water of crya<
ftllistttion, — Their aqueous solutious aro decomposed by evapo ration,
unless the beat is koiit very low. By distillation they yield the samo
f rodact^ as the free acitf , with a residue of plioephate.

B<trytn-BaU. r(C^H*)*BaO*, — Micaeeouf? laminst nearly intolnblo In
llcohol, and containing 35 0 p, <5» Ba and 15*6 p. o. P (by caleulatiou
B5-4BaaDd J6 2P).

8t rmit ia -mli, —^nm^'^h'^ii more aoluhle in aleohol than the haryta-

alt, and cry italltses from the alcoholic solution by gradual evaporation in

lalky crystalline lamiu?i3 arranged In r&<liated groups. Gives off S Al«

rater at 160\

l>fled oeer uil ^fptMul LimpHcht.

P _.,. ,. M4 _ I«-7 .... 167

2C^W 300 .- 160

$r „.MM**»«*.., 43*B ,... 23'4 ....... 22'7

8 O _.....,„.. ftid *.. 34-2

2 110 ..„„,„..,»» , li'O ,.. 9' J ...... 9^&5

P(C3H^)'SrO" + 2Aq 18^2 .... 100-0

Lme-mU. P(CHP)*CaO*. — Separates in warty masses, very s^!ublo *

water. Contains )3^5^ p. o. Ca and 20 s P (hv eatcnlatfon, Ul Cji 1

id 28 ft P). * II

Mtrfjnma-iktit. — AVhlte powder, sohihlo in water.

Z'm-'-mlL — AVhite and pretty readily Holuble.
Tho /ron and Copper sJh appeal* nUu to bo easily I'olu hie j inafimuch
IS the ijiiliitmn of thi^ Hinc-£alt i^ not preoipi tatc'd by tfolutiuns of iron
copper.

Imd'ialU P(C'I1YP10*, — Precipitated from the concentrated
|aeous solution by elber in fiakei containing 4ii 07 p. c. of lead (cal-
ilatiou, 45-34 p. e.),

The aokiblebimetliylophospbatee form white precipitates with salts

cobalt, njcrcury and silver.

Menomethphphosphorte mid. P{C?H'*)irO*.^ — Obtained together with
^injcihyloub^ij^piiovic acid (p. 482); also b^ the action of peutachloride of
^hosphtmiM on wood-fiplrit, cbloropbosphoric acid being firat produced, aa
akown by the eciiialiou.

PCI* + on*o^ » Poxi» + aH'ci + iici.

Vad then acting on the rest of tho inotliylie alcohol as above. The
aiotion is violeut and atteudetl with ^rci^t evolutiA>a of beat

tlft

484

ADDITIONS TO VOL, VIL

water than the bimetB ylopliotpbates. Tlie ftirrgrfur mMJt m tern mMi§ m
water at 100' tbnt] in lake-warm water* It llierefor^ sepamM as iNi
a« tlt« solution U placed orer tLe waler-batli, in lamiiue Wtic^ m itrt^
lostre. It gives o^ the grater part of its water of ffrptaliijatiaB, rvm
oo ejtpoenre to Uie air, a fartlier portbn over eiiTpliitm aeiil, hmg iti
loati^ at tBeaame time, and the whole (4 At.) at I^a"^. W^ettili0i|ij
beated, tt gsrea of combustible gases.

Cr^MiaUUed,

l4Bi|iekfc£

V,^ „ ».^.^^..., 3M

«- 111

r*H* „.■-., ..... 15-0

-«. 5-2

! Ei _......., ... 137-t

•-- 48 4 ._

..» 4S-S

8 O .. 64*0

^, »2*<

4 HO . ..„, ^ .„„...„. 3$-0

... 12 7 _

^ 14^

ItC*H*JB«W + iAq .„, 2«3'6

.,„ 100*0

Satpliocliloriile of photphonii fornix with tn ethyl ie aleoluil MM
ether. whtMe liaryta-ttit is soluble in water and pro^bly

Biitilphometliolic Acid.

$, ill; Amm, Ptom 100^ 12S-

r ^eH, Mtikj^fhrnm^^kmrie add (i. 4f J)^ Mfeikl^kMil

^...^ L Br Ibe neliea rf fvinmg tiilphiiric iiej<l nkni

liite (ejviMft of netliyl) or aeeUaaido^ milpbacetic actil being
ttltbiMWttw:

•cH.

[kl im^bftCeof

, C«X1t»0». Mbs horn ifi^Miitrae ^oly bf tHO. Iti u,,___ ,

bdjm »w Ttrr wtAiII^ wstd. and the mtiiiirc U rool^il fniis ti«« I*
tiiK, KWrtiv anv carbiuea«U U evolved, mi the projijct lh<ii (
It of «itf^e«6t w»v ^^ ^ ^ b*ai bt c^atljr iiiercs

BISULPHOMETHOLIC ACID.

485

acid eseapea nnd the product is chiefly bisulpUomethulic acid* Tbc
reaction appenrs inflecd to conmit of two stfrgea. In tho former, tlio
nascent acetic acid emiply unitee with 2S0* ; in the l:itler, tUo acetic
acid is reardved into carbonic sic id a ad mareb-gas^ ibe latter combiuing
witll 480*. (Bi^iilphainctholk acid catmot however be formed by Iha direct combl-
Diilion of mar^h'giLs wuh subihuric add. (Bocktatt and Hofniann.)

3. By the action of anhydrous sulphuric acid on ether, Thi^ wns tbe
lirocesB by which Ltebig first obUined tlie acid (inethionic acid^ Tiii, 435)* It b mErelj
ji Berotidary prodiirt of the reaction, the principal product being neutral fuljihate of
erhjl (viil, 4 13)* The 4cid thus obtained has since been examined by WetlicriU and
by RedtenbacUer, and more compklely by Strccker, Buck ton ^ Hofmann have ihown
Ibat it U id (critical with bisulphometholio acid*

II Fvqxiraimu I, Acetonitrile and fuming sulphuric acid may bo
inixed completely £Lnd almost without colour in a vessel oxtcrnalJy
iiOQled (^itlioitt this precaution, the beat evolved caii-^es a large portion of the acetoni*
trile to rolatilise) \ but if the niixluro be then strongly heated, it swells up
Considerably and gircs off a large quantity of carbonic acid gas. The
residue when cold forms a thick brown transparent tnass, which disaoU'et
readily in water or alcoboL Its aq neons solution boj!ed with carbonate
of baryta and filtered hot, yields bisulpljomotliolate of baryta in beautiful
crystals; and on decotnposiug this salt with a slight excess of snipburic
acidj saturating the filtrate with oxide of lead, precipitating the lead
with euipburetted hydrogen , concentrating the liquid to a syrnp, and
I^Ting it to evaporate in vacuo, the acid is obtained in the crystalline
Btate. — 2. A mixture of 2 vol. acetamido and 3 voL fuming sulphurie
acid (cqtjal ¥olumcs yield scarcely ftuy thing but acetic acid and sulpha to of ainmiyn in)
k heated till sulphurous acid begins to appear among the products ol
distiUation; tbc residue is dissolved in water; the free sulphuric acid
oeutralised with finely pounded marble; the liquid boiled witb carbonate
of baryta to deeunipose the sulphate of ammonia; and the filtrate
evaporated to the crystallising point. It then yields crystals of bisut-
pbometbolate of ammonia, while sulpha cutate of ammonia remains in
the mother-liquor, A moderately concentrated solution of the ammonia-
ialt mixed with a eaturattd eolation of acetate or cbloride of barium,
>ields crystals of the barium-salt of bisulphonietUolic acidj from which
the free acid may be obtnined asaboTC. (Bucktun k Hofmann.)

3. A flask tilled with anhydrous eulphuric acid is inverted in a glass
cylinder containing a little ether, and left there till all the acid Los
diaappcared ; after which the product is shaken up with water, aud the
watery liquid separated from the ethereal solution of neutral sulphate of
ethyl is treated with carbonate of baryta, &hC.j as above. The ethereal
solution also contains methionio acid. Another method is to pass tho
Tapour of anhydrous sulphuric acid into cold anhydrous ether; but the
former yields a better product* (Strecker.)

Fropertm, The acid obtained by evaporating the aqueous solution
Id vacuo, forms long needle-shaped crystals, which are highly deliquescent
and have a very sour taste. (Buckton Sl Hofmann, IStrecker.) — The
aqueous solution may be boiled with nitric acid, or chlorine gas may bo
passed through it, without any sepamtion of sulphuric acid ensuing.

I (Buckton U Hofmann.)
, The Bimlfhefhoktffs or MffMonatft are obtained by digesting the
^ueous acid with oxides or carbonates; they are all sUubie in water>

4M AOOmoyS TO TOL. Til.

A^ -fljiiff-f^ft. ^Prtpmrmiim^ p. 4tt) IH^solres with moflente fadlitr

ia c»*t i vxier. rerr trsnW io bot wmter. The b^iilinir »o!otion <lef«ifti
cy>! cr^e« prisms vith dibednl sammits, and aometi nes an indi Im^
(B. t H.) Svtauos a heat of 140' (Strecker), 190* (B. ds H.)> vitluMt
altcmiSoe.

Ai 190*. Bucktoa & iIof:nABa (rmk).

4C ..- 12 .... 5-71 ^.... 5-3t

l^H 10 ^ 4-76 5-2a

2X 28 .... 13-33 ^ 12-90

4 S «« — 30-47 ^ tO-55

12 O W .... 45-73 45-93

<?H>NB«)«.«SO»_ 213 _ 100-00 10000

/V4a( mlr.-^Eaftilr obtained bj graduallj mixing a boiling tolite
of euboaaie of potisb with a solation of the barjt*-aa1t, aroidi^ tt
evce«s of ibe laiter. The alkaline filtrate deposiu the salt in tfaiiiii;
■eedie!! or ia ^cTasaiet, accoriinglj as it separates from aolotion qiicUj
« 1^0 vIt. ( B. k H.) Anhrdioat: ctTstalliaes in long needlee. (Stmkir.)
1 pL of the silt diaclres in 14 pu. of water at 220^ (B. d: H.)

f^j.'y I juif. iPrrpxrthmr p. 455; Crjbtalliaes in reetan^nilar plitM

haTiof a notr^r-of-pearl Instre, and firing off the whole of their wtia,
aaoutisr :o 1051 p. cl (4 At.) at 150^ (B. db H.) Very thin rhwlii
tibM vkkh exhibit rerr beantifnllj the eolonra of thin pJatee^ and kn
a cMher^-praH Insire wben dry. The salt does not alter in lfp■^
aa<« or in vei^t at 130', bat gives off its 4 At. water at 140*. At i
hifhfr tesapertTaiY. it decomposes without fnsion and gives off snlpliir.
I^rlw i-V:::-Jirt wjlh the air, it leaves sulphate of baryta, whicfc
bovei'er is d £c::it to free frum a mixtore of snlphide and solpkitt.
F»^ viih hjdnte of potash, it leaves a mixtare of sulphite wU
f«}phaie ia ceaxfT e^cal Dombeis of atoms. (Strecher.) [ Accordiag to Uihi
,r3^ i2^ ac^cnw acad is sot (oTTStd ia tkii mctioo.

JC _ ..-_ 12 .. 3-8$ 3-71 .... 3-4

i H — 2 ... e-e; 003 ,_ 0-7

£B& is: .. 44-05 4405 .... 44-0

4S . 64 .-- 2«-57 ~ 20-83

1* O 96 . 30-S6 30-78

OH-E«*.SH)== . 311 .... 100-00 100-00

Strecker. Liebig. Redt^ abacher. Wctbrri
i* ^- _ 1 * . . 3-46 3*5 3.4 ^. i *

Jh — ^^ - i'"3 1*8 la ... 1*

is 64 li^44 186

16 o •^__??:*?

:.;..-,:; —Or v<u;.:5c* in de^.icato silky Qee<IIeSy vcrj (oloUt :■

water

— ..'v.'T \

OiSULPHOMETHOLlC ACID.

487

Zim-salL — Metallic xiiic dissolves in the aqueona ncidj with evolu-
tion of lijtlrogenj auiL tbe solutioa wLea evaporated yields a syrufi wliii^U
' crystal lisca with g^rent dltHculty* The solutioti h not preclpUUcd by
iilcohoh (Biicktou ^ HofmatiQ.)

Lead-ifiiL — a. Neutral. C*H*Pb»S*0»*+ 4 Aq, — Obtained by deconi^
ositig tlie baryta-snlt with eulpbtiric acid mid boiHijg the (lltrate wjt!i
ISarbonate of load. The solutiou concent ruled by evajiorationaud slowly
cooled, yields the salt in large, triinsiparent, colourless^ rhombic prii^ni?,
probably itjoniorphoufi with flie barium -salt. (Strceken) Small squaro
bacreous laminie rcitembling thoso of tlie banuui-salt. (B. it H*) Tiie
try stab do not alter in tlie air at ordinary temperatures, but at 100''
hey give off 8*4 p. c. (4 At ) water; no fiirtUer loss of weight takes place
it IGO^ The anhydrous salt tjivea by analysis 5 8 "5 p. c* FbO, agreeing
ixactly With the formula C^H'Pb^S^O*^ I'he salt dissolves rery easily in
irater and i^ precipitated from the solution by alcohol (Streckcr.)

h. nasic. PbO,Cm^Pb^S*0'^+ A r|1*^ Obtained by boiliti^r the
Central mlt with hydmted oxide of k-ad. It is much less i^oltiblo ia
fc-ater than the neutrpil silt and separates from the hot eolation in
"colourless crytstals on cooling. Has im alkaline reaction and absorb?*
carbonic acid from the air* Afte*^ dryh^g over oil of vitriol, it "^ives olT
21 p.c. water (1 At ; cdcuhttion 10) at V20\ The anhydrous salt
jave by analysiis 09' 2 p. c. PbO (t-alcuiation, C8 p, e.). The ealt was
obably contaminated with carbonate of load. (Streckcr.)

Oopper-sifL C^^IFCu'S^O^HlOAq. — Obtained by decoaipo^^in^^ tlio
MTta-salt with sulphate of copper. Crystallises ia blue rbomhic pri^^ms
rhich elHorci^co aud turn white when exposed to the air, (Strcckcr)
Teedles united in r^idiatinir groups, or email prisms of a K^recn colour,
B. fit H,) Soluble in dilute alcohol, insoluble in absolute ak^uhoh
[Streeker, B. & H.) Gives oir2C'2 p. c. water (10 At.; by calculation
i7*5 p. c.) and sulfers uo further loss at im\ The anhydrous eult
iVft by Htial)^6JS 036 p. c» CuO (calculation 334 p* c.) (Streckfir.)

Siiver-saii, — Obtaiuod by neutralising the aqueous acid with oxide
carbouate of silver. Crystallises in groups of t<leuder needtes or
iroad plates of considerable sUe^ but usually much modided and with
rounded edges. (Buckton<3t Hofmaun.) Thin colourle&s laminue, which in
tlio moist state are somewhat blackened by exposure to light. (StreckcrA
The salt sustains a heat of 140° without decompusition, but blnckeua and
froths at a biglier temperature, giving off Bnlphur(>us acid and sulj linr,
and leavtnn^ ractallie silver* Insoluble in absolute alcoboi, but may be
erystalliscd from dilute alcohol, (B. & H.) Alcohol preeipitatcs it from
ike concentrated aqueous solution. (Strccken)

2 C . -

2Ag

4S,...
12 O

di 12U*,

12

2

.,......,. 216

U

m

Duckton 9c Hofmanti* Stiecker*

1GM1
2101

2*07
053

55-41

5&'3&

BuektoQ lV U^fmann did not incce«d ia prepnrlng the crberi of hi^^ljiHomrtticlii:

lOiAm Ife Ml ^ rf mt^ifmimm^ ^^ CWmm

Jht MHuidm

ifaiM «ibd elJier.

tto nse^ll with esecM of owtie IaijU^ fiUerio^ to mmCstxJliit

mmA erftpoimiiog tie filtiate ai t^ heai cf tlic wmfer4ml&.

C<4aiirle£», modoroiis, eijitftUtiM ttll, which if pr»:t|»iUKi §mm if
ilroftE aqoeoojr MitBtion bj ftteofaol m the form of m wbito fniit'
^viter. A eon^titrmted sqneonfl oohitioii lefi to «vmpotmta k tmi^
4lfoiiti the nit in eohei arnoged la octoliedral masses, li -—^-
beat 0f 170^ wiihoal deeompofitioa.

2C ,-„«M«,M,.- n^
3 H « ^ a-t

Ba ...^ 6S'6

2 8 __ ^M« S2-0

40 320

*.. 8-13

... 46-48

,... 216$
.... 21-68

-. 2-11

C»H»Ba8?0* 147*6

.... 100*00

**.♦.♦,, 106*00

hihylohithionafe ^f Limt. — Obtained by treating the £liMdi i*

0 &f lime-water, and prcflipUfttitig the lime from llw lltnit I;

Qic acid* A concentrated aoluttoo left to ora^orate in m

^«&U BJ a solid mnni wblch docs not eijffCmllifle. Il It

MBTHYLOBITH IONIC ACID.

4&9

At 100% Hobton.

2 C 12 .„, 12-12 .„ 12^00

3 H *.. S ,.., 3"03 3^29

Oa *„ 20 .-., 20 20 1964

2S.„_.._.^_ 32 ,.„ 32-32

4 O ™ 52 .„, 32-33

mWaS^O* »... 99 .„. 100-00

Methphhlthwnnft. of Magnemi, — Obtained l>j decomposing tlio

iryta-salt wilh sulpliato of magnesia or tlio zinc-salt witli cnustic

nagnesia. — Colourless, inoiJorous ealt, wliicb eeparatcs from its aqueous

[>!ation hj evaporation In a mass of minute crystals which retain 1 At,

rater at 100\

Ai 100*-

2 C .„.., ,

4 H

,-. 12

4

U'U

4-00

Mf ,

2 s ...:. ^

„.. 12 MM».

„„ 32

..... 1200
..... 31-17

5 0 - -.

.... 40 .......

40*flO

C^H^MiS^O* + Aq ...

».. 100 .......

..... 100-00

MelhphKthiofuite of Zim, — {Prep&raiiQn, p. -ISH). — Colourlesa, inodo-
ana salt, having a bitter, somewhat ilisagreeablo ivk^it. CrystaUiecfi from
be aqueous solution by evaporation, wlien the J t quid becomes very con-
BUtrute^i, but on account of ita grdit solubility, does not form any
LTge erj'stab. It is stable at ]0D°, but decomposes and blackens at a
iimewhat higher temperaturOj omitting a mostoficusive odour.

jinoo*.

2C 120

3 H 3-0

Zn 32-5

2 S 32-0

4 O 32-0

cm^zns^o* ........ in-&

Hofavon.

10-76 ....... 10*72

2-69 2-61

29*15 28-97

28-70 2855

28-70 29 15

100-00 100-00

¥

3/eth^kbt(Jnonaie of JS^iclrl — Obtained by decomposing the baryta-
alt with sulphate of niekel. Forms a grass-grccn solution^ which when
left to evap€»rat0 in vacuo, dries up, with partial decomposition, to an
imorpbous mass of a dirty buff colour.

Methyhhithionnte of Copper^ — Prepared like the baryta- salt. Ita
aqueous solution has a bright green colour, and when evaporated at 100^
becomes brownish yellow, in consequeuco of decomp<?sitionj the dilute
solution also decomposes gradually and deposits sulphur oven whea
exposed to the air at common temperatures^

MdJifjhhUhionaft of Silver. — Carbonate of silrer dissolves slowly in
tbe free acid, but on evaporating tbe solution over the wiiter-batn, it
decern poses even below the boiling heat« Tlio dilute solution also blackens
rapidly wbeo exposed to light

4^0

ADDITIONS TO VOL. Vll.

Methjlohitlmnafa of EthjL — A niijcturc of nietiijloliilbbriatc
Ijarytii and eulphoviaatc of potiflli, yieltlej wljea di^tllied at n higlv temJ
peratore, an oily liquid, together wjtii liir^o quantittes of stilpUarousaciJ
The pioductj after behi|^^ waohed with water, dried over chloride a
calciunij and redistilled in vacno, formed a light straw-coloured liqiiij
slightly heavier than water and having a peculiar ti shy odour. It u&d
goea deeompoaitioa at the high temperature required to |»rep&i!e it*

Page 32 L

Iodides and Chloriodides of Tetramethylium.

C. Weltziejt, Ann. Fharm, Dflj L

?V/rWii/t\ — {C-H*)*N.P. — When a solution of protlodide of
methyliuni is mLxed with ait alcoholic Wutioii of iodine containing ill
much iodine as is ru(iuircd to forni the teriodide, tbo firat crop of cryt^ull
deposited from tUo liquid nevertheless con data wholly of peniie ""
{Xi 408); but afterwards crystals of the teriodide and peutiodid
deposited together and may be separated mecLan really and paririd
recryatallisatioii. ^ — The teriodtde fonns crystals belongmg to the Hgli
J>ri8matic sv'stetn, having a deep violet colour aod strong lustre ; it td
more soluble in alcohol than the pent iodide. It gave by uniUjiii
B3'7 p. c, iodine, the formula requiring 83 '5.

The Fentmdid^, (C='HV)*NF, is the only product obtained irh«
"an excess of iodine is used . It forms sniall tiibular crystals having
dark greenish-grey colour ami perfect metallic lustre. Melts at J20^tj
and solidifies in a shining crystalline mass. (Compare i, A^%.)

TtfrachUrioduh (C*H')*NICK — On heating the teriodide or |i«iii
iodide of tetraraethylium with oxide of diver, iodide of silver is imtueilHl
ately formed (together \vit!i a small quantity of lodate), and a oolotiflM *
strongly alkaline solution is obtained, containing the hydrated oxide iM
the iodato of tetraniethyliuni \

ftnd on gently heating the filtered li([nid witli bydrocbloric aeid (bed
after neutralising it with iodic acidV chlorine \h evolved, and the !*^tn*|
chloride of tetramethylium is deposited as a very loosely cobc rent, kiUQa
yellow substance smelling strongly of chloride of iodine:

(C^H*}*NIO^ + GUCl ^ (C=H^)^MCl* + 2U ^ 6HO.

Weltiten.

8C.» 4a .». 14*0 ...«^ U^

13 H, 12 ... 36 »*...... 4*4

N 14 .... 4-n

1 ^»*. »*, U? .... 37-0 »„.,.. B6*i

4 CI 142 ... 41-4 .... 3S-8

(,cni*)<Nici* „.. M% ... ico'O ..._.. too 0

Analogottf 10 FilhorB chloriodidc of am in milium NH^ICl* (IT, 4i J),
flvg«rileil m jinit iodide of tct] iraethjlium ia nrhich 4 At* I ure mhutil br 4CX

TAlMBTHTLf^HOSPHlNE. 491

Tertkfwiodide. (C»H»)*N I CI'. — Obtained : 1. By mixing chloride
of tetrametliylium with chloride of iodine. — 2. By passing chlorine
into a 6olu ion of protiodide of tctramethyliam; a precipitate of pedt-
iodide is then formed, and after^vards a colourless solutiun, which, when
eraporated, deposits the terchloriodide.

Lemon-yellow substance.

Weltzicn.

8 C 48-0 .... 15-6 15-3

12 H 120 .... 40 4-3

N 14«0 .... 4-5

1 127-0 .... 41-5 41-6

3 CI 105-5 .... 34-4 33*4

(C«H«)'NIC1' 306-5 .... 100-0

BiMoriotfide. (C*H*)*NICP. — A solution of the terchloriodide in
water deposits the bichloriodide, in shining, yellow, inodorous crystals,
belonging to the s<|aare prismatic system.

8 C 48 .... 171 170

12 H 12 .... 4-4 5 0

N 14 .... 5 1

I 127 .... 46 9 45-1

2 CI 70 .... 25-9 2G-6

(C^HVNICl^ 271 .... 100-0

Page 328.

Trimethylphosphine. (C«H*)'.P.

A. W. HoFHANN & A. Cahours. Fhil. Trans. 1858, 592; Anti.
Phaim. 104, 29; Chenh, Soc. Qu. J. 11, 73.

Formation and Preparation, By the action of terchloride of phos-
phorns on lino-methyl :

3C3H»Zn + PCP = (C»H»)8P + 3ZnCl.

Terchloride of phosphorus is added by drops to an ethereal solution of zinc-
methyl contained in a tubulated retort with proper condensing apparatus
attached (for the description and figure of the apparatus, see Triethylphosphine),
a Stream of carbonic acid being passed through the apparatus during the
whole process. As the action is intensely violent, the terchloride of phos*
phorus must be dropped in very slowly. When the action is terminated,
a hoavy oily liquid surmounted by a lighter one, is found in the retort
and in the condensing apparatus. The heavy liquid is a compound of
trimethylphosphine with chloride of zinc; the lighter is a mixture of
ether with excess of terchloride of phosphorus. The latter is decanted,
aadthe eomp^vnd of trimethjlpboepbine and chloride of sino is distilled in
a stream of hydrogem, the trimethylplM>qpbiie which then passes o?er being-

AODlXfOHS TO VOL. Vn*

mammaied with ice, Hm mmm of ^infA

tricfi?, iDobil# S^ftii k«itiir dv
srar power, snd «ti ia^atenU^ flMPia

— {fBWfeV. — FmdBCGdt 1. B/ tkeiUncifmiilMir
a^mai iiimalfnai taiua^ Bxe in coetaet villi t&e iic.«-%

I, the Berk of ikt mmt ..

^ wilba be«ili/y tftvrt^

mmj lM9obtmiBC!dkliqpfM%

fi> 2 ^tow i*«rr«iri af dry sir. — S^ Bjr&itdMi

wiIb o£ Hffmitiolh/ipfcoipfciMiiiiB, —^-^

-^ — -J liy gmdmUf iJJflif —
of irclJ fomcJ ii»

ij%fciii|imi — OijmaSmm Mkm thm ^ihjl eoB)|NHB]iii ( '4
ii MT bt mmtaAwiA Aa air k blackens, wiOi tefmtiit ^

MiPft «r InMfthylpboi^ae ia b;iinKU0i
if liiliaMj aa ncaaM-jeUow, iJidiM#

^m

letntinethyiplio^hoiiiTim. (C»H*)*.P,

p kehluaid W t^e aeiioa af loAfc ef »etbvt i
AjlBboepbiae. Wblto cry »^1^

NITROFORM. 493

Hofmann 8c Caliomi •

(C>H«)*P 91 .... 41-75

1 127 .... 58-25 58-14

(C*H«)*PI 218 .... 100 00

Treated with oxide of silver, it yields a very caustic solution of oxide
of teirametkylphasphonium.

Gold-$aU, •— Obtained by mixing the solution of chloride of tetrame-
thylphosphoninm and terchloride of gold. Crystallises from boiling
water in brilliant yellow needles.

At 100"*. Hofmann & Cahoors.

((?H3yP 91 .... 21-17

4 CI 142 .... 3302

Au 197 .... 45-81 45-98

(C*H>yP,HCI + AuCl» 430 .... 10000

Plalinum'Salt. — The solution of the oxide mixed with hydrochloric
acid and bichloride of platinum, yields a platinum-salt, which is insoluble
in alcohol and ether, but crystallises from water in beautiful octohedra.

Hofmann & Cahoun.

{(?W)*? 91-0 .... 30-73

3 a 106-5 .... 35-95

Pt 98-7 .... 33-32 33-30

(C»H»)<P,HCl + Pta« 296-2 .... 10000

Page 360.

Nitroform.
C'N'HO" = C»X»H.

L. ScniscHKOFP. Ann. Pharm. 103, 364.

Hydride qf Temitromethyh

Formation and Preparation. 1. Ternitracetonitryl, C*X'N, — a pro-
duct of the action of strong nitric acid on fulminuric acid (x, 55G), —
treated with water, yields the ammonium-salt of nitroform;

C*X»N + 2H0 » C»X«,NH* + 200=;

and on treating this salt with strong sulphuric acid, sulphate of ammonia
is formed, and nitroform rises to the surface, forming a very mobile
liquid stratum which solidifies on cooling :

C<X»,NH* + SO*,H « C^X3,H + SO<,NH<.

The nitroform is then separated by a pipette, and purified by two or
three ciystalUBations, the portion which renmins Hqpid b«iu^ evAli \\\sa^

r'lT'K :::. ._ 3iii-*-i

ssunaoasbc ioobi

C jmiuaMc.iBU. XaiflOSE CJiaiJieg 7ea£Sr za Mtfcr, ftmiiig t U
Ii» *r'qF sr* errfTTpTiVjf. f^ a tae jeZIcv colov, explode via

. 1^. r: — "f j-TT-^'.' rrrjcilr-rw viH j r^f uj be kept cnilterfd fa

Einirrr^ieiiiylic Add. ex-H*o*.

.r '\ <^^' J-

Y jTZJ.l bv the acil :i cf liaoxiJe if nitrogen on xinc-methvl. Tfc*
:-ro i ^>iirs i.TuJcaiij anite and form cryst-iliiuc needles con^i»tinc «'*
t(,r.T'.'i^\Mi Liniiroxethylate of zinc, C-H*ZnX'0*, with linc-mtibjl :

2C H=Zn ^ 5Ni>' - C H=ZuN-0\C;iPZD.

TLi.= comp^^nnd oiidjs^s rapidly in tbe air and takes fire when cxp«^
in cow-iderable qaaniity. It is instantly decomposed by water, yieiJiq
u ar-li ^' .^ and an opalcKreut solution of basic biuitromethylate of xicc:

C-lPZuN"0*,C^H Zn + HO - C-H"ZnN;0*,ZnO + C?H«.

mrnl Zinc-t^nll, C-H'ZnN^O* + HO. — When carbonic arid -'
throu^'li the opalescent solution of the basic zinc-salt joal »«••
carbonate of zinc is prioipitated, and the liq lid, after baiii^ i^
^, y'\^d& \)^ eva.v>t%lMCL cryBtals of the momud sise-«alt

a c

CTANIDKS.

At 100«.
12 .... 10-30 ..

Frankland.
11-28

2 N

28 .... 24-03

4 H

4 .... 3-43 ..

3-50

ZnO

4 O-

40-3 .... 34-77 ..

32 .... 27-47

33-86

C«H5ZnN«0^,H0

.... 116-5 .... 10000

493

The excess of carbon in the analysis arises from the passage of nitric oxide into
the potash apparatus. In bodies containing so large a proportion of oxidised nitrogen,
it is exceedingly difficult to decompose the whole of the nitric oxide by red-hot copper.

Soda-iaU, (?H'XaN'0* + 2H0. — Obtained by treating a solution of
the zinc-salt with carbonate of soda, eva])orating to dryness and exhaust-
ing the residue with strong alcohol. The filtered solution yields by
evaporation, crystals of the soda-salt containing 25*83 p. c. of soda (by cal-
culation, 25*72). The salt dissolves very readily in water and in alcohol,
barns intensely when heated, and in other respects closely resembles the
corresponding ethyl-compound.

Page 417.

Cyanide of Barium is obtained in the pure state by igniting ferro-
cyanide of barium and potassium (prepared by precipitating 2 pts. of
ferrocyanide of potassium with 2 pts. of chloride of barium) in a
close vessel, exhausting the residue with water, distilling off the
greater part of the liquid, and leaving the remainder to cool :
it is somewhat sparingly soluble in water and absorbs carbonic acid
quickly from the air. — Cyanide of Strontium may be prepared in a
similar manner from ferrocyanide of strontium and potassium (obtained
by boiling prussian blue with strontia- water); also cyanide of calcium,
which crystallises in cubes, and cyanide of magnenuw, which is loss
easily decomposed by carbonic acid than the preceding salts. (C. Shulz,
J. pr. Chrm. 68, 257.)

Page 4G2.

Decomposition of Ferrocyanide of Potassium, — In the preparation of
carbonic oxide by heating 1 pt. of finely pulverised ferrocyanide of
potassium with 9 pts. of strong sulphuric a'lid (Fownes's process), the
first portions of gas are always contaminated with 11 or 12 per cent, of
carbonic and sulphurous acids, but after a while the carbonic oxide is
given off pure. When the mixture has been heated to a certain tem-
perature, at which it begins to froth, the evolution of carbonic oxide
goes on for a long time by itself; and if the mixture be again heated
after the spontaneous evolution of gas has ceased, fresh quantities of gas
are obtained, but more or less contaminated with sulphurous acid. — At
the beginning of the action, there is formed a white mass like the residue

Til.

-i* X t FaV, «-r« 30^ mad 854 KG. The formb
a?*VJSCF -> Ea30»MyiMi»'8Fc\y, 57-4 SO*, a»i 9< KO.

'■'^ ~^ : ai&v of OElaBK «zidsr wUehy sftcr pHRBg tuoi^
^ oHiiini M fm. (GrnuB & Basdokr, in.

K(NHOFeCj», WiM
giTQi olTaauaoaiAaiHi font
Lted bj tke equation

tiae, a green piedpildt

. bjdrmte of poiul, ol

atiMs, becoiBes fint jdlov.tki

. wiA di^c eroInUoa of gas, s ntti
K fcddj vken tW solstioa is warm and eoM»
siHBcaKXV^pnies to be bcated to tbe boilia; fmL
r> bifleUbie m eold water, but dissolres rujmkf
g >^n u Ipntrd by aeiib. It Fires off 10-5 a &

Chbkh »S5 to 4*42 pec. carbon, 41<J H

^?Ha.&ias<W9.Mi3^ ta9'4fLe. bpiroeen. A fimilarpiefa^
* Vr acBCW IV fres a solatioa of cyaiuJe of jiuliwii.
a^^ 5(Mi «Ji! ai »«pL c C, 42-3 X, and 3-0 to 3iE
' jr-. Ski v*- ^- ^- ^^-^

ADDITIONS TO VOL. VIIL

Page 4.

Ammontacal Ciiproso-cupric Cyanides. — a. 2NH*,2Ca'Cy,CaCy. —
When an ammoniacal solation of hydrated capric oxide is poared into
aqneooB hydrocyanic acid, till the odour of ammonia decidedly predo-
minates; tne slightly yellow liquid heated to the hoiling point; the heat
kept up, and the gradual addition of the ammoniacal copper-solntion con-
tinued till its dark-blue colour no looger disappears, — micaceous crystal-
line laminae make their appearance after a while in the liquid. If it be
then filtered, it yields on cooling, green rectangular laminae of remarkable
lustre. They have the composition denoted by the above formula, toge-
ther with 2 At water. — On heating them with equal volumes of solu-
tions of caustic ammonia and carbonate of ammonia not too dilute, a blue
solntion is obtained, which, after boiling for an hour, deposits shining blue
laminiB consisting of the same compound in the anhydrous state. The
green lamin® also turn blue when treated with fixed alkalis or their
carbonates, even in the cold.

Anhydrous,
2NH> 34 0..

. 12-57
. 58-59
. 28-84

Hilkenkamp. Bydraied.
.... 12-67 2 NH».... 340...
.... 58-21 5 Cu .... 158-5...
.... 28-73 3 Cy .... 78-0...
2 HO .... 18-0...

Hilkenkamp.
. 11-79 .... 11-57

5 Co 158-5 ..

. 54-94 .... 54-37

3 Cy 780...

. 27-04 .... 27-30
. 6-23.... 6-76

2NH»,2Ctt»Cy.CuCy.... 2705.

..100-00

+ 2Aq.... 288 5...

.100-00 ....10000

The compound is quite insoluble in cold water; and is decomposed
by boiling water, with formation of a brown substance. Dilute acids
separate from it white cuprous cyanide, which dissolves on boiling, with
evolution of hydrocyanic acid, (L. Hilkenkamp, Ann. Fharm, 97, 218.)

Page 10.

Fotamo-cuprous Ferroci/anide2QvLKFeCy*-{'3AQ.*'^When the red-
brown precipitate of ferrocyanide of copper (Ca'FeCy') produced by
adding ferrocyanide of potassium to cupric salts, is heated with solution
of cyanide of potassium (obtained by mixing prussic acid and potash),
cyanogen is evolved, and a light yellow solution is formed, which, if the
cyanide of jiotassium is not in excess, deposits, first a deep red precipi-

• €u - Cu».

YOL. XII. ^ 'K.

.«« «, i <

■ - r vr -_--

U':

.'.-'1 'V

VAT

. »;:h j.lai.i'.-c;.-aLi:o -f f.v-ir-jeii ■ -ir ••-.

. -J.*; 4 ! in ho[ waicr or in al>«o]ute aich..!. : ■ .r.-'-
:».l. I.t-nii.n-yeJlow plates arc then iiep.'*i:<>i. 1 ■

SULPHOCYANIDES. 499

in width, aereral lines in length, and exhibiting a blae iridescence bj
reflected light — A red pUUirKhcyanide of hydrogen UPtCy'-f 5H0 (also
obeerred bj Quadrat) is obtained by treating platinocjanide of bariam
or potaasiam with an equivalent quantity of strong sulphuric acid, digest-
ing in a mixture of ether and alcohol, and drying over sulphuric acid.
The hydrogen-salt is then deposited in crystals 7 or 8 lines in length,
half a line tliick,and having a splendid vermilion colour with blue irides-
cence on the prismatic faces. The crystals absorb water from the air
and then assume the ordinary appearance of hydroplatinocyanic acid.
(Weselsky, •/. pr. Chem, 69, 276.)

PlatinosesquicyanuieSy M'Pt'Cy* or 2MCy,Pt'Cy*. — These compounds
are obtained by triturating the platinocyanides with nitric acid of
sp. gr. 1*3, removing the excess of nitric acid by draining and pressure,
and recrystallising several times from the smallest possible quantity of
eold water:

3MPtCy« + 2N0» = M^t«Cy» + MO,NO» + PtCy + N0<.

They are all soluble in water and alcohol, and all form colour-
less solutions, excepting the lithium-salt, which is yellowish. — The
pUcmium-saU K*Pt'Cy* -f 6H0 (aUo observed by Knop, viii, 49) crystal-
lises in slender undefined needles having a coppery metallic lustre but
appearing green by transmitted light. They turn dark green at 180",
and yellow at 200°, without losing their metallic Instre. — The ammonium-
•oft (NH^)'Pt'G3r* crystallises in thin needles often half an inch long. It
has a golden yellow metallic lustre, becomes steel-green at 150°, with
partial decomposition, and lemon yellow between 180° and 190°. It is
more soluble in water than the potassium-salt. — The lithiuni'scdt
Li^Pt'Cy^+BHO is still more soluble both in water and in alcohol. —
The magnesium-^aU forms a blackish violet satiny mass of microscopic
needles. (WeseUky.)

Page 88.

Ferrous ISulphocyanide FeCyS* + 3 HO. — When a solution of iron
wire in hydro-sulphocyanic acid concentrated as much as possible, is left
to evaporate in vacuo over oil of vitriol, ferrous sulphocyanide is deposited
in rather large oblique rhombic prisms having an intense green colour,
and a bitter inky taste. They dissolve readily in water, alcohol and
ether. Both the crystals and their solution ouickly turn red on exposure
to the air. The crystals are decomposed by heat, with ^evolution of
sulphide of carbon and formation of mellonide of iron.

Claat.

Pe 28 0 .... 23-83 23 56

2 8 32-0 .... 27-23 27*44

Cy 260 .... 2212

34 HO 31-5 .... 26-82 26 74

FcCyS* + 3iAq? 117-5 .... 100-00

Host probably the lalt was imperfectly dried, and the proper qnantity of water
bSAt.

2 K 2

«Oaf Titml^tkeaJtii

•^ .^ g- _ Ifrii ji^

sir/rxir'^ . tK ^« s: _ i#t*i

^ cqcv f«]p4orjmiiHie, bj dilitii

*«^ wifc mlo^kof). looBf its cdm,

"»; ^*i<* i» pit>UW J ft Iw

^ rf tk <ieeoaipo«UaB of mijh'

»^ ^J^drocjBue amd fdplwii

_ iMffciMftaMft. XerertMaa, it
> s likr MM delicmto flf aU tou i« Ai
- .F»*^ ?^ ^«^ » aodidaied witk Mf
^ ^ iHimifWMap«aTY;^^„p^ofiw«ilb
n: wwmrssiHL ?w mcchs k idD percieptible, proTkM tb
fOiM 11 iwic* nii»T: inf Tin* jhuc nw m wkhe snrtace ; -» " of ni
^►vc^ t n-fli Tnw lYitnnr ^^ :^ wcttk* it decoIoriMi ^hj^^m

^ Ji?mr samiirtrnaiin* mKiu*Tf» TOh^W in watifr^ afcoJkcl woi dkr

iitiuic viica & ^aiLTBt IT Juii ^i rrwm imx>as snlphocymaide. (CIib '

S« h^'P^'TUii'^' *f Sii^^ rnCTS*. foims pnflns cf a fine deep w<

/I sl;!Tl^^'71J:'n* fC sIJTvr fti>c uodmi.sb for poUkGsium) is mixed »^
»fii*/.n* liiiimiiiiii^ -M hcLJc ncmLr heoomee filled with coloe^
ru-^^-^ia^ ifiiinnff /c ia.»«Ti3:3oe c/ salTw. When a lamp c( ^
,i..i !itf «»•: r^-MViTJf^c w crxT** i» immeRvd in dilate aminoiiii.y
- .Ti;Tt.a.r. riiunr^ ?> » ^-•' ^'"^ *» MKtfpkons maaa rMemblio^ dum*
,. ^ ;>' t r»- I ft fr jK«*/a>fl5 ft^T. iht TeswJ beeomet filled wii^ sa0«
K-J.I . I ,T->iTA. .:T>f mmrma. Hvdy«^i<*ne acid acts like tmmt»
S*«.|n^ VJ.T »rtf .:*«>»■«■ ft»a aiEiDc«iiim is OMnpletelr decompoatJ i*
1^* » r «.7ij.T*:j/a: ic rrMsmiir sclpbocTMide of silrer. [A ama:
I^Non^.^ ;i.a tc lirt wis.«i«m sfth w« obtcnred bj Hull (riii,?:

HYDRATE OF ETHYLENE. 501

-=-Reoently precipit&ted oxide of silver digested at a gentle heat in
solphooyanide of ammoniam, gradually dissolves, with evolution of
ammonia. The liquid, which always contains an excess of sulphocyanide
of ammonium, likewise deposits crystallised sulphocyanide of silver on
addition of ammonia or hydrochloric acid.

Page 387.

Hydrate of Ethylene.

A. WuBTZ. Compt rend. 43, 199; Ann. Pharm. 100, 110.

Glycol.

FomuUion and Preparation. By the action of hydrate of potash
on acetate of ethylene :

Preparation. Acetate of ethylene (6* 1 5 grm.) is mixed in a flask with
hydrate of potash, (4*72 grm.) previously ignited and pulverised. A
brisk action immediatelv takes place, and after the lapse of a day, a mass
of acetate of potash is found in the flask. The mixture is then heated
to 180° in an oil-bath, and after a small distillation-tube has been
adapted to the flask, the heat is raised to between 250'' and 260°. A
colourless liquid then passes over, which is to be rectified, and the portion
which distils between 190^ and 200"^ collected apart

PrapertieM. Colourless, somewhat viscid liquid, having a sweet taste.
Boils at 195° and distils without decomposition. Its vaponr is
inflammable.

Wurti.

4 C 24 .... 38-7 38 7

6 H 6 .... 9-7 9-9

4 O 32 ... 51-6 51-4

C<H«0* 62 .... 1000 100-0

May be regarded as a double molecale of water u, V O*, in which 2 At. H are
replaced by the biatomic radical C^H^ (compare page 222 of thii Tolume).

Deeompontums. 1 . Hydrate of ethylene is converted by oxidation
with nitric acid, into giycolic acid C^H^O', and afterwards into oxalic
and carbonic acids. When it is dissolved in four times its volume of
nitric acid, of sp. gr. 1*33 and solution is left to evaporate for several
days over caustic lime in vacuo at the temperature of the air, a
syropy liquid remains, which, when diluted with water, neutralised with

S02

ADDITIONS TO VOL, YUU

chalk, and treated with alcohol after filtration* jielde a pr^ipitate of,
^lycolate of lime C*H^CuO\ — Tlie alcobolic liquid filtefied frotii thi|
precipitate does not eon tain any subetance capable^ like aldehyde, a
uniting with bisulphite of soda. — Boiled for some minuteii with foa
timea its volume of weak nitric aoiJ, it gives off red vapours, and
solution on cooling solidifies In a pulpy mass consisting of interlao
crjstah of oxalic acid. ^Monobydrated nitric acid acts still more via
lently.earbotiic acid being evolved, and glycol ic and exalte acids retaaiiiiiy
in solution. — 2, Pure hydrate of et!iylcne dropped on platicum-bUcI
makes it red-hot and gives off carbonic acid. A Bolntion of hydrate ol ,
ethylene in four times its hulk of water^ added to platinum -black, hIjni
causes rise of temperature and evolution of carbonic acid, and tlie
platinum -black is afterwards found to contain traces of glycolie adil.
Wurtz {.inn. Phartn. 103, 366,)

Comhinniwns, Hydrate of ethylene is soluble in all proportions bj
Wfitef' and in idcohoL

Acetate of Ethylene.

A, WuRTZ. Cmnpt rend, 43, lOfii Amu Fkni*m, 100, 110.

Acetaie qf Gly^&L

Fcrmatkm. By the action of iodide of ethyleae on
silver :

FteparQiton. Iodide of etbyl is mixed by small portions with w«U

dried actate of silver (lO ^rm. of the former to 12 ^rni. of the latt<fr;ttr*
ut»t advfcSttble to o|>er«ttt with Urger t|Ufttttuifs), and the mixture is iotrt
duced into a fla^k. A brisk action soon begins^ and the tu\m% aflsumii 1
yellow colour from formation of iodide of silver^ and giv*?a off a <
deruble quantity of gm, principally carbonic acid and olefiant ^
(arising from secondary actions). As soon as the mixture h suificiesll
cooled, a fresh portion is introdnced> and the pmc^aa c^mtinued ti
between 100° and ISO"' graniraea of iodide of ethylene have been umd
At ibe end of the reaction, there is found in the H^uk^ a yellow ntaas <
iodide of silver^ saturated with a liquid; and on distilling this mixtif
which requires a somewhat high tempemtnre, an acid liquid ptfoco 0
cob^ured brown by iodine and containing acetic acid besides netitr»l i
ducts. When subjected to fracticnol distilbtion, it begins to boil
120^ but the temperature soon rises, and the portion wbich fUstili ov^
between 160 and 200, must be collected apart. The distillati*. whio
iB still acid, is redistilled over oxide of lead» and aiain ^itbjpcted
fractional distillation, till it passes over almost eatirely brtweeri II
and )^0\ If it still conUinf a t.*aee of iodide» it mtist be rm^ifiett ot
i>xide of silver.

OLYOXAL.

503

PropeHie$. Colourless neutral liquid, nearlj inodorous at ordinary
iroperattires but amellin^ slightly of acetic acid when Leated. It ie
lesvier than water and eiuke to the bottom of it ia large drops. Boiia at
1^3°} and dbtik without decompositiou,

CaJi'uliitioii* VoL DfiriKily.

\C T2 ._ 49-31 C-?mpomr , 12 „„.... 4-5920

I H ............... 10 .... (i'85 H-ga< ....« 10 06930

I O ...^■,......... 64 .... 4364 O-gM ..,.,. .-...»■...., 4 ........ 44372

»HWO» 146 iOO-00 Tipoarofa3H»*Cy.... 2 „ 10-1222

I b-mu

» 2C^H^n< + C*H«0^ - 4H0.

icetic acid« glycol.

By bases, <?* g. potash or Imryta, in presence of water, it i«
Bsolved into acetic acid and bydratt^ of ethylene, (p. 501). 1-298 gmi.
ale of etbykne waA hf;ated with cjlccss of hydrite of b«r|tBi to bi'tween 120* and
PSO* in a iealeJ tube, and tbe product vhaa diluted with water* Batumted with carbonic
Icid and filtered. The fiUrnie eontained acetate of baryta, ^hii-hi when derompoaed hj
imlpburic^ acid, yielded 1 850 fpni. «ulphate of baryta: or 1 At. acetate of ethylene,
vieldvd 18 At , Of nearly 2 At. aectie acid.

Acetate of ethylene diisi^olves In a very large i|uantity of water, and

I alsQ soluble in akoboh

Ethyl-gtifcerintt C*\l*0^ = \.^ VO^. In the prepamtloti of acetate of ethylene

bOTe deicribed, there U also formed an oily liquid which remains in the returl «flef
he acetate of ethylene baa pauicd over, aod bat 4 boiling point a bore 23 tr. This
quid appears to be the ai'etate of etbyi^glycerinei a compound boixiolo|ous with
«t)ti (ix, 497), and contawing C^H^ in place of C^HK

Glyoxal, C-H*0*

}£BCs. it fin. Pharm* 102^ «0.

fhrm^ittn (p. 506).

Prtptindi*:m. Wben the syrupy neutral liquid oUtaiiu-d in the prepa-
lit ion I if glyoxy lie acid, iw mixed with i^ereral timoe its volume of a eoncen-
ratcd flolutjon of bisulphite of ammonta^ and the mixture lefi to ]t«e1f for
ome hours, the sides of the vessel become covered with a white crystal-
Ijpe craft consisting of a compound of glvoxal with bisulphite of sodaj
Jitid by dissolving thii& product in ibe stnane^t possible quantity of boiling
water and leaving the ISltrzite to cool quietly, the conipound in deposited
In fine crystals, which, after two cryslalliaations, are obtained quite pure,
A further quantity may be obtuined by treating the mother-liquors with
alciihol. The flodlurn-cotupound mixed with chloride of barium yivlds^
M"ter two days, crystals of thtr corresponding bariun^conjponnd, which
may also be purilieil by recry?talli^ation, and by decomposing the barium-
compound wilh the exact quantity of eulpburlc ucld required, and
evaporating the filtrate to reniovc water and sulphuroua &cid^ glyoxal is
CibtaiEied to the solid state.

604

ADDITIONS TO VOL, VI H-

Properi leg, Trauspare n i, si igh t) 7 y el 1 o w tdli , aniorpli a ns
deltqueacea when exposed to the air.

rbicb

4 C

2 H ........

Ai 100^

24 .

....... 2 ,

41-31 .
... 3*45 .
„. 55-18 .

Debiw.

,,»«. 40-2
3-5

4 0 . ,.,

.^.... 33 .,

„».. 56*3

0^H>O*

58 .

... 100 00 .

„.. 1000

The deficiency of carbon In the analyBii ia due to &d idmijitare of Ihe btnim-
com pound, wbicU could not be compLetel^ removed.

Glyoxal may be regarded ai the ildebyde of gljoiylie add (C*H*0*)- ll

between glycol aad oialm acid, in the same mantier at ordinary aldehyde between
alcohol and onLaltc acid, Cotntnon alcohol (motiatomic) by loaiog 2 At. H, ia fw^-
Terted into aldehyde , and aldehyde, by taking up 2 O^ ia converted into aoetic acid^ la
like manner, glycol, which ia biatomic!, by giving up 4 At. H, becomes glyoialr and
glyoTEal, by taking np 4 AI. O, ia converted into oxalic acid CH^O^.

Decompositions. 1 . An iiqiieous eoluti^m of glyoxal treated wiili i I

email quantity of very dilute nitric acid and evaporate*! over the water- J

batli, leaves a residue of glyoxylie acid. An excess of nitric acid, 1

' when very dilute, converts it into oxalic acid, — 2. Glyoxal i^ do4

med by sulphuretted hydrogen. — 3, By caustic alkalis, eveu

ordinary temperatureSj it is converted into a s^h of glycol ic acid : t.g,

£*W<y + CaO,HO « C^CaO*.

glyeolate of lime*

4. The aqueous eolutioti is merely clonded by neutral acetate of
hut, on addition of animoniaj a cupiouii white precipitate is formed.-
With nitrate of silver and ammoQia, it forma a beautiful speculatn
silver.

Comhinatiom. Gljoial diasolTes very readily in water.

Gii/oxal with Ammonia, — Ammoniacal gaa paeaed through ao eti
eolation of glyoxal forme a white precipitate.

Qlyoral with Bieulphile of Ammonia ~A coneentfated eoltttion
himtphite of ammonia mixed with f^lyoxal depoeita thia compound
cryBtabj the depoaltion of which is attended with considerable evolutjoo
of heat. The cry stale are purified by recryatallisation from hot water,
but the boiling must not be long continued, ae otherwise, a portioa iif tbt
Bait is apt to df^compose*

Shining pristuatio crystals, wliite, or often slightly yellowiah; very
soluble in water, insoluble in dcohoL The aqueous solutioti is precipi
tated hy acetate of lead^ but not by salta of xiaCi copper or silver.

DHmi

in vatuo.

Debtta,

% V iltt Urftt.l.n

I4.>...4iil>l..l

>Hl<>».)+4.^Hll

24 .

., 100 ...

..... 100

10 H ,

10 .

... 4-2 .M

4**

tn

1 ...... 1 It*. I'»^»

2d .

... 118

60..,

48 .

.. 20*3

4 so* ..........

....„»»..,.„

128 ..

.. 53-1 .„

nn

a(NH*)«0*4SOi + 2

Aq

238 ,

.. 1000

GLYOXYUC ACm.

50*

Glgojml mih BwdphUe of Soda, — Prfparaiitm (p. 503). Small Lard
'wbite cryataXBf easily goltible in water, insoluble in a]eohoi> The aqueoun
BolulJOTi, when boiled for some time, acquires a slight yellawisb tint; it
precipitates acetate of lead und chloride of barium. It ia elowly decom-
poaed by bydroebloric and sulphuric nctds, with ev^olution of sulphurous
acid J also by Lot nitric acid, with formation of oxalic and sulphuric
acids. With caustic eoda and carbonate of soda, it turns brown and
forms a dark -coloured precipitate. When glyoxal is mixed, first with
caustic soda, and then with sulphite of soda, the mixture remains colour-
less, because the glycolate of soda formed by the action of the caustie
Boda is not affected by sulphites.

Dried in vacuo,

4C...,. „. 24

6 H ..,....„,., „^ „.. 6

2N»i ..-,„.,.. .._ „,... 4e

10 O ....._ ,.._„ , ,.,. BO

4 SO^ 128

Debus.

8*45 8*44

2*11 , 2 Ifi

161B ....„, 1606

28*16 27*94

45*09 , 46-40

C*H5O^/2(N»O,HO,2S0^)+2Aq.. 284 ... lOOOO 100*00

Qlposral with Butdphiie of Baryta, — Pr^ptsraH&n (p. 503). The hot-
fitn rated solution deposits after about two days^ nearly the whole of the
alt in indistinct concentriculEy grouped masaes.

Dried in t^ewo. D^but,

4 C 24 ..» 5*37 „«,,„ 6*12

9H „^... 9 ,.-. 2-25 .„ 2M9

2 Ba «.,,..„ „ ni .... 5407 33*83

13 O „..„... „„,..„, „,.„„„._...„.. 104 ._ 2&*fi7 .„.*... 26-33

4 50= 128 .... 31*64 » 3l"53

C*H=0*,2(BaO,HO,2SO«)-r5HO.P 402 ..» lOOOO lOOOO

The salt heated on platinum foil, blackens, gives off sulphurons acid,

ad burns away, leaving sulphate of baryta* The aqueous solution

oiled with a digbt excess of caustic baryt% yields a precipitate of

heutral sulphite of baryta, while free baryta aud glycolate of baryta

[lain in the licjuid.

^HH>*,2(BaO.HO,2S03),5HO + (BaO.HO) - 4(BaO,SO-) + yHO + CMISBaW

gijcokute of
barjrta.

Glyoxal dissolves with great facility in alcohol and ether*

Glyoxylic Acid.
C*H*0» = C*H*0* + 2H0J

Debus. PkU, Ma^. [4], 12, 361; Ann, Pharm, 100^ 1.

Formation, By the action of nitrio acid on alcohol:

C*HW + 80 * CnVO* + 4HOorC*U<D* + 2H0,

506

ADDITIONS TO VOL. VUI,

DobtiB origiQslly regarded glyoijljc acid as C^HHy {it« inlta hftvlng indeed t}i«
[posttion 0*^14^ VI O^), and 5U{i<pofled that it was produced by tbe oiidntioD °f l^lfi
I tcid C'^HH)", that oon^mund being pjfCvioQsly fopmed by the tctioq of the l
Iftr^d on the alcLihol ; but he now {Ann. Pharm. 102, 2S) rather regard* it til
IC^H^O'^ (gijowt, C^H'O^ being the ct>i-responding atdebydc), and BUppoiea it& formt- j
r^un Trotn alcohol to ht preceded by tbat of glycol and glyoial, Mx^ordiof to tbt j
l«qtt«tioni %

glya>li
QHl^Q* 4^ 40 = C^HW + 4HO.

gljrcul. glyoiaL

C*HW + 20 = C^HW.

glyoxfll*

flyoxylic ttxM*

I ThU suppoaition does not indeed ngree with the eouiposilifin of the glyoijlateij i
Tin, the ADhydrnus state Appear to be C^H^MO^ ; but Uebaa sur^efU thut thf i% utay biia J
anhydroui giyoxylic mnd C^H-U**, r^^Uted to gly'.iJtylic ncid C"*ll*tJ^, in the %Am^mm
u nnhydroui terturie ucid (t, 335) to ordmary taztaric acid, and eontmioUig byiln
replttceable by metuljs.

Prepartition. 220 gniis. of 80 per cetjt. akobal ara poured into a tdl j
narrow fliisk capable uf lioldiug about 1 i lb of water; 100 gr^nnmes oiJ
water are introduced below the alcohol by mciins of a funnel having iU
neck finely drawn out ; and below tLis, are poured 200 grma. of red
futiiiug nitric actd, «o that the three lit^uids may remain one at>oire tU ]
other and nux as little ua possible at Grist, Tbe bottle is then do^ with
a. cork fitted with a gas-delivery tube dipping under water, ami the whab
IB left for BIX or eight days, at a leinperature of 20^ tu 22"^ till the liquidf
Lave become crjmpletely mixed, and the tee ul ting nitrite of elbyl hu
volatilised. Tbe residual li<^uid, containing nitric, acetic &aij formic
r&cidgj compound etherSj glyoxal and other aldehydes, glycolic ftcid md
Iglyoxylie acid, is evjiporated to a syrup over the' wat r-batl] in portioQA
' of 20 to 30 grniH. euch; tbe residues containing oxalic, glycolic md
glyoxylic acids, together with the less volatile aldehydes, aredi£«olved in
email qmiji titles of water; tire united solutions are neutralised with chalk;
the neutral liquid ie nuxed with an equal volume of alcohol; and the result*
jng precipitate of linie-salte pressed and repeatedly boiled with water.
The *«pcrnatant liquid containi glyoiciil and glycolate of lljne. The ^qufOltf
f extract yields crystals of glyoxyhite of linie, and a fnrtber ^ua^ntity of
this salt may be obtained by eo nee nt rating the motber^iquor. The tnh^^
qucnt rn other 4iqu u rs y id d n double «uit ofglycolate and glyoxytat^ of Ivmt^ tta^ the
Uflt cnnUin glycolatc of line (p> 509).

The hydrated acid ia obt-ained by decomposing the liitit-«Ut *tth

oxalic acid, and evaporating tbe solution in vacuo, in the fi>riii of i
viicidj transparent^ slightly yellowish syrup, which disf^olvea readily in {
water, The solution heated to 100' givea off unaltered glyoxyJic acid
together witb the wat.ry vapours. The 6yru|iy acid, when *frtroiiglr
heaiedf gives off acid vapours and volatiliees, leaving m toiisty Idack
(t^idue. I

The Clj/fixylafei C*H'MO*, are obtained by neutraHiing lbe luues of'
their carbonates with the aqueous acid.

ff/«w^M/# i/.im»ion/fi crytjtallises in hard crusts, eoDsistiiig of needle^
nJjAped cryiitafsi coiiceutikaVLy grouped.

j^

DI-YOXYLIC ACID.

60t

Gl^ow^laU of Pohtu^. — White, very deliquescent aalt, difficult to

crystalline »

Gly^^Ia/e of Lime. — (Pr^ara/io» p, 606). — CrystiUisea iu tliln
[needles or hard priam&tic cryeta-ls, soluble iu 177 pU, of water at 8^-

Bri^d in vhcuq.
4 C ................ 24 ..

3 H ...„„ 3 ....

2V%2 ...

270 ...

18*01 ...

57*57 ...

Debus {mean).
... 2l^G2
276

Ca ....,_ 20 ...

8 O .,.._, £4 ., .

,... 18*20
.... 57*12

C^H*C*0^.. ... Ill ....

lOO'OO ...

.... 100 00

Tbe salt may be be&ted to between 160* and 170° without \m^ at
[weighty but is decomposed at 180% with evolution of wiiter and car-
Ibonic acid, and formation of oxalate, glycolate and carbouate of lime,
[together with a retsiuous substance. Fmm ttiis decomposidon it uppcart 1
mcwt probable Cbut the «alt in auhydrnti^, snil consequeotl^ Clmt the formula of]
jljosflic acid h C^H^O**; ic i» possible however thut it mny coBt«in 2 At. water, wbicli j
Tmx9 ^veii olf mily at the teirpe rat lire Ht whiirli tUt sblH Utk'lf de<;omposea. In thfl^t case* I
the formuU of the lime-B«lt would be CHlCaO* + 2Aq and tliat uf glyoiylic aci^j
C*H^O' (p. 506). The relation of gljoX)Uc acid to glyoiiil is in favour of thii ^
>. Atlppositinn.

The solution of glyoxylatc of lime mixed witb ]ime- water yields a
I whit© precipitate of a basic: fralt, wdiich is decomposed by carbonic acid
fin the coldj into carbonate of lime and the iieutral glyoxylute; aud iM
' fesolved by water, gradually at ordinary teniperatureSy quickly on boiling,
I iato oxalate and glycol ate of lime :

2C*H'CaO» + CaO.HO = C*Ca^O« + C^^II^CaO* + 4HO.

Tbe solution of the neutral lime-eatt h not precipitated bj nitrite of baryCA or

I chloride of copper,

Glforiflat^ of Lead. — White precipitate obtained by adding oautnil
Iftcetate of lead to the aqueous solution of tbe linie-aalt

4 C

... 24 0 »

... 80 ...

... 07 ...
. C9 7 ...
... 2l'G ...

Debm.
76

2 H ....,.._.

2*0 ,

1*1

2 Pb

... 20 --fj .
.„ 64^0 ,

..... 70*9

8 O

. 20-4

C<H*PbW....

„. 2PJ 6 ,

.„ lOU'O ...

...„ 1000

The ootn position of this «ftlt if em i to show that the (leid i» bib»frc ♦ the formation
of a basic litne^suilt tenda townrds the iAihe oondustoti, wbirh is aho in accordauee wttb
Uie relation of glyotyUc acid to ^lyeol and glyoial. If plyotylic acid be rcallr
t:*H^O*. the three rompouads* p^lyctil C<11»0*, gjyoxylal C*H^O<, and jlyojiyKc acid
C*H^O*, will he reUtcd to eai^b other in tbe same maune? as «K ohol, aldehyde and
ALX!|i>c tidd.

Gf^oxt/latf qf Silver, — Oxide of silver dissolves in aqueous glyoxylio
acid, and the concentrated solution left to evaporate at ordinary tempera- 1
tnres, yields white riioinbtc crystal;?, which however arc always contami-l
natod with metallic silver, even if the liglit has been c:irefully excluded J
The aqueous solutign deposits a silver speculum when boiled.

c^iv=CTPa»o«.

■«:«"

milt ^RtiSir loii iJasucnM a piCHk; the wlti»y glTeohto of potaik ■
mcsmtaoM W x^zmat ;ic aSiv. aai the ^tjco&t aod is m^aaaM/td frM

4 VVn xtraa 3f ^Mi^niii a Hmt tkmm its Walk of Bitric mai d
:^ ^ Z ». ui ^ M^asaML after mrfag fcr MrctBl dajB» it eoam-

viikc^Ik,^

wiikmlcpK
the

l4i^*0Mt ^J*' vvnrff^wtcva ^* fi^tvcc aeiii TW BolWr-li^«or, aftor Wiif
)N«t«^*tw^ w-w Afci- ^« iMcIieil a tke watir fcitk, ud tW mUm
V^ i*^fc ; J^ iw« ^'viktt:^ fmiKtK aUAjde, a«ue etkr, foi«ic etfctf,
s^a 9 c-vo^ .'^i^ V^ jttMM «««r. va* fMad to coataia aitimlc^ aeettlt
M!^ Vimt ift^r Jt IJtmf. >i|p..'AfrwiAtWliwi ^h #f aa acwi haTiag tlwcm-
yv««c;va v'^Sr'^ 5y TiipMMaLT aMftiwi^ tW aolatmi to
«% V^Tft. v» &W itma&w tW I:m|wI

(Waita. Cm^ fwi.

ia ^ anklioa of akokol hj aitm
Wiw gHwJ aa4 gljoxaL (IMai^
. M. K4) Ibaal n tko

iM of

» tpoal

aolayealu

GLYCOLIC ACID-

509

lime; and by deconipositig tlie llme-flalt with oxalic acid, and concen-
t rat tug the solution over the water*balli at in vacuo over oil of vitriol,
the acid was obtained in the form of a syrupy liquid resembling lactio
acid. Cloez gave to tbia acid the name Homola^tic acid,

B. By the action of alkalis on glyoxal or glyoxylio aoid* (Debus,
pp. 501, 507).

Pi^ptrtUs. Flat crystak, having the form of laminas striated on

tbe surface. (Dessaignes.) The homolatUc add obtnined by C\ntx, fom^^d. when
eoucentratfrd »s much as pfisaiblef A colourle«ft inodorouB lyiup, of 9p. gr. 1*197 at 13°-
Wurti suggeiU that gljr colic acid rnnj exiit ia two iiotnertc modificatiqnt.

4C

4 ti _..„..
6 0 ,..

. . 24 .
.... 4 .

.... 48 .

.. 31*5g ,
.. 5-26 ..
.. 63 16 ,

Defl!taignes«

31-64

5*27

6309

C^H*0« .......

.... 76 .

,. 100-00 ..

100*00

Frtim the second nifide orformHtiqn, it iippean that jj^1jci>co1 is the amule of g Ijoolifi
acid: C^Nfl^O* = C^AdnH.>3.0= (it, 24 7). The pcfculSur acid which Horsfopd oW_
taiQtti {ii, 2MI) hy the ai^tion of chlorine on glycocolUdifTe rent from gLjcoUcacidt inas-
much aa it^ ammo uia- salt is prf^cipitatcd by chloride of Uartura. (Socoloff & Strecker.)

Combifmtumi, Glycol ic acid dissolves in water in all proportions.
The Glycolate& are for the most part easily soluble in water and
crystal lisable.

GlymlaiM of Barytn, — preparation p. 508, — Melts when heated, form-
I ing a perfectly clear liquid which crystallises on cooling. When strongly
llieated^ it swells up, diifusing a peculiar odour, and leaving nearly
I cole u Hess carbonate of baryta.

BaO .„ .

4C

3H

5 O . ,..,

. 76-6 .
.. 21-0 .
. 30 .
.. 40*0 .

.. 5^*34
... 16*71
.. 2*09

.. 27-86

Socoloff & Strecker*
........ 52*70

16*fl2

...... 2*27

........ 28-21

C^H^BaO- ..

. 143*6 .

.. 100*00

lOO'OO

Glpeolate of Limt. — Tbe liquid obtained by the action of nitric acid
dh £^)ycol yields, when neutralised with chalk and minced with alcohol, a

[precipitate, which, when recrystallised from water forme tufts and
B od ales of deli cate i n ter laced n eedl e 9 . ( W u r t ^ . ) — G 1 y oxal boi 1 ed for

|& few minutes with milk of lime forms a liquid which filtered and freed
from excess of lime by carbonrc acid, yields glycol ate of lime to tbe last
drop, — Glycolate of lime is also fonnd in tbe motber-liijuors obtained m
tbe preparation of glyoxylic acid (p. 506;. —The afr-dned salt cont^iina
2*2 p* c. {3 At.) water which it gives off at 100^ or a little aVove*

(Wurtx, Debus.)

At 120\

Wurtt,

CaO .. .
4 C .. ,

. 28 ...
. 24 ....
. 3 ....
. 40 ....

29-47 ..-

25*26 ,..

3*15 ...

4212 ..,

29*47

.... 24'fl7 .... 25-00

3 El ... .. .

5 0

.... 3*52 .... 3*40
... 42-14

C-H»CaO«..

. S& ....

100*00 ...

.... 100-00

J

SM ADMTIOXS lO TOL. Till.

23
24

3
4«

22-93 22«

?"

2-4€

sn

32-79

»eo

22-13 22-10

ibaiWike

122

— 10#-M
1 of liMe-waftcr on glyoxykte of

^fVMOf e-- Zfliif •«£& G^fsryUu ef Xinr.— Cry«UUiae« from tb
Hi^iKHDfiHci «fcK;&5Mi ia tW prvpantioa erf" ^ joxylic acid (p. 506). b
ii T«rr »LX3^ a wsxier. aai the wan»^siiazmted solation solidificf m
«»H^ 5* »>Pj wkkik. afieraoBe^jn, ebaaiseB to a crTsUllhie powder.
ASaet 'irfjt^ 5a tk air. it gms otf 7T1 p. c. water (3 At.; ale.
T-4> fL €.' as I2f. «3i retaiaiag 2 At Tbe aoIatioQ girea witii aitna
af fcarraiL ^xi«-^rsser. ckknie of eoppcr, and nitrate of sOrer, the wm
■gagriwar at Aa» <f rfi^jhte of hme >. 507).

i*r

-jf i2r.

72

11

11 H

*^»

ca

54 O

192

«-49 21-92

3-28 3-«9

17-91 18-99

37-32 56-48

eB^CiO'^K:*BCaO»^2A^ 333 — 190-99 100-90

^^jcaZoi if ZokT. — TW aqaeoas acid satarat«d at the boiling b«t
▼i^ skT^'is^^ «f x:r*c. depc^ss on cooling, crjistaliine crusts reseiDUJif
iacsa^ :c ii.x«r. :r cv*C:-xrkss c pique prisms arranged io stellate grospi
— IVe ^1 2« sm;£T4r> so^sUe ia cold water, aolable in 33 pU. of kot
w-astff . ixjcCxtie xa a^*cL It gire* off 1 4 35 p. e. (2 At.) water at KKT.

M \«f*. Socoloff & Stnx^er.

irO 49-5 _ Z7'i7 37*64

4C 24^ — 22-33 22 69

iH 3^ _ 2-:9 300

JO.. _ 4*i) - 37-21 36-67

c-B^z»o* . i#:-5 _ 100-00 100-00

trV-«^*y :/ S\Svrr. — A solotloa of gljrolide in potash fonns will
tiTTi^e :f 5c:T^r, s wihe Soor^ient precipitate which soon becomef cm-
OL.-T^. iij^^xT^ :**Aii;T i- hot witer, and maj be obtained tberefnw'ii
litr^ crT^^al^ A: Iiv" :i i-ms reddish and gires off 4*79 p. c. (1 At)
w:i:ec- , rVssiur=f« • — G^TCv^aiir c^ Klrer prrfrnvd bj decomponnf ftrtohte <rf
W-^-a •T^ ^i. i**^' '< «>«^ i<co«fo«Ki tren while still in scUtion, the bqaui dn»-
jsC-Tic r *-A fu.rs^ TV it.vc:xa hke^isp tamed blsck when erapormtcd ia J9cm» V9&
vU ,v t r- . . «*i ;:be va<3i maiae wta wo longer eomplecelj solvble ia watw. Tk
»;«^Na» *.M-o» j/ rue siui w« »« preclpttmtod by akobol or etbcr. {S^ncktr.)"
lVss»^:<* rjrcTnl-se^ die ».•»: prpfiMwi by 2. mixed tbe tolatioQ with aitnte oimhs-
t^T^-^fv: r.^ 4«ro&ra:e i^ rviihaKd sairer, aad ohriiafd tbe acid in tbe etrUMOkm hn

GLYCOLIDE.

*% IfMta Hised. D t iiilgnn.

AgO ,.., „,. llfi ,... 5C^25 ,, 56-12

4C ., „.......„...„„«.,. 24 .... 12-50 12-70

4 H 4 .„, 2-08 2 20

6 0 48 .. 29*17 2898

CHHgO* + Aq.. 192 . 10000 lOO'OO

Glycolic acid mixes in all proportioDS with alcohol and eiher*

511

Glycolainide, c*NH>0*.

I/LIGNES. (1853,) Compt. rend. 38, 4T.

Fot-madon and Prtjarathn. 1. Glycol id© ii diisolved in hot
imoiiia. — 2. Tartronaie of ammonia melts at 150°, with v^iolent evola-
lion of carbonic acid; after a while however tUe escape of ;;as becomes
rapid, and the residue form§ on cooling » thick deliquescent syrap
probably glycolate of ammonia). If the beat be contmued, earbonato of
Ammonia e^apee^ and at last there remains a residne which solidifies on
eoolingf ami when recrystiUiied yields beautiful cryatali of glycolamide.
— This compound diasolvein readily in water, sparingly in aloohoL Haa
a faint, somewhat sweetish taate and a slight acid reaction.

N »**.

... 24 .
^ H .
... 5 *

.. 32-00
» 18'6C .

. 42 68

32-10

.„..,. lB2i

5 H ..,

,.«.. 6-81

4 0

... 32 ,

..-..., 42*80

C^NH*0* .,.,

... 75 ,

„ imm .

100-00

Gljcolamide ha* the aitme compositioii ^ ^tjeocolj bal b related to it in thft itatns
QUiner 11 Uct*mide to aknitia (ix, 434; ii, 470). (D^sfAigtie*.) [But hcUmide,
N^rdlni: to Liittrviit, U laetHinate: of ammonia, whereaa glycoIamidB dors not contaia
Qmouin (Lial).]

Glycolamide when treated with potasKf d<ies in.»t give off the odour
l<»r ammonia till heat la applied. When boiled «pith potash till ammonia
Ijs no longer evdved, it yields glycol ic ucid, — It ja not precipitated by
olnliun of platinum.

Glycolide,

>EBiAiGNFS. Com;^ rmd* 38^ 46.

I

lUr© oe Kept at JDU , sw nm^ »<> g^^ i^uuinijuto 1,^ «^w»^r^, lucio reumjua m

the retort a slightly coloured maea whifh has the conaiatence of
iufpentiDe, and soli^lifics after a few ilay.'?^ it mnet be pnlrerised and
wa^^hed with hot water. White, ta^telesH, insoluble in cold, very
sparingly soluble in hot water. MeLu at 1 80^ without loss of weight.

51S

ADDITIONS TO VOL. VIU,

4C »

2 H , „.

24 .

»^. 2 .
32 .

... 41-38 ..
., 3 45 .
.. 55-17 ...

40-40

3 75

4 0 .„._,..

... 5585

cm^o* .......

58 .

.. 100^00 ..

lOODO

Homenc with glyosal^

Gljcotido diaeolvea ir potash, prodaciDg glycolic aeid.

Page 282.

Aeetic acid, — Anhydrous ace tale of soda treated wltti prf^tooblorldt
I of iulphur yields anhydrous acetic aeid :

4C*H*NftO^ + 3C1S - aCH'^O* + 3NaCl + NftO.SCF + 2S,

The process cannot however be applied to the prepnration of anliydronA j
acetic acid^ inasmuch aa the product is contaminated with other b&djt%|
especially sulphur-compounds, which are not easily separated. — ^Mer-
curoue acetate heated to a temperature between 250^ and 300^, yields
anhydrous acetic acid mixed with acetone and a body rich in oxygen*
(Heintz, Po^f;. 98, 458.)

A^:^H€U6 of Lanthannm.^^^ Basic acetate of Ian than unij which is preol-
, pitated in the form of transparent gelatinous flakes from a solution of oxide ,
orjcarbonate of lanthanum in excess of acetic acid, by supersaturating wtlli ^
' ammonia in the cold after diluting the tsolutiun with a lar^e quantity uf
t water, — is coloured deep blue by iodine. The colour is not destroyea by
\ washing with cold water or by drying at ordinary temperatuxes; but i
decoloration takes place at 80° (at which temperature the salt still '
retains water), or by continued boiling of the salt suspended in wattr;
but on adding iodine and a very small quantity of ammonia to the liquid,
the colour is restored and blue flakes of the basic salt are preeipttmted; ,
the colour is also destroyed by addition of acetic, hydrochloric, nitric or '
sulphuric acid, or of excess of ammonia, — The blueing of ba^ic acetate
of lanthanum by ioiline takes place only when it is quite free from
cerium. It is not exhibited by other basic salts of laathanum^ or by Um
corresponding salts of alumina, yttria or eerie oxide^ (Damouri Com^.
tYftd, 43, 976.)

Page 358p

Imllde of Ethyl heated to 100** in sealed tubes with an aqneooi or]
ethereal eolution of mercuric chloride, is converted into chloride of ethjU
with simultaneous formation of iodide of silver. — Similarly with tb«
iodides of mtiktfl and amyL — When iodide of ethylene is 1i«at«d for
MFOfml hours with ati a^u^vift %(iV^UQfL of mercnrie ehlorido, il dn —

fiTHYLOTRITHlONIC ACID. 513

t>ear8, iodide of mercury is formed, and the liquid, which has a strong
acid reaction, yields by distillation, chloride of acetyl, C^H*C1 :

C*H<P + 2HgCl =* OH3C1 + Ha + 2HgI.

(Schlagdenhauffen, N. J, Pkai^. 29, 247; 30, 38.)

Bromide of Ethyl heated with aqueons potash in sealed tabes to 125'
for a month, is decomposed, with formation of ether and a small quantity*
of a gaseous body. At 100^ no complete decomposition takes place^
even after heating for 200 hours. (Berthelot, N. Ann. Chim, Fhys^
43, 282.)

Page 394«

Borate of Eihyt, — H. Rose {Pog^. 98, 245), recommends for the
preparation of borate of ethyl, 3C*H*0,B0', to distil sulphovinate of
potash with anhydrous borax between 100^ and 120"*. If the materials
are not quite dry, the ether thus obtained contains water and deposits
boracic acid after some time. It does not appeitr possible to prepare in like
manner the ethers of silicic, carbonic, phosphoric, chromic and molybdic acids, or to
obtain a compound ef oxide of etb jl with alumina.

Page 406.

Ethylotrithionic Acid. C*H«SW.

J. T. lIoBsON. Chem. Sot, Qii. J, 10, 55*

Obtained in the form of a zinc-salt by the action of sulphurous acid
on zinc-ethyl. When perfectly dry sulphurous gas is passed through
zinc-ethyl, rapid absorption takes place, and so much heat is evolved that
it is necessary to cool the flask during the whole time of the absorption^
A crystalline body soon forms, and after some time the flask becomes
filled with a quantity of minute crystals, which protect the remaining
portion of zinc-ethyl from the action of the gas, so that it is necessary
to continue the actioii for a long time and frequently to break up the
crystalline mass. The zinc-salt is purified by recrystallisation, first
from alcohol, afterwards from water. It may be converted into a baryta-
salt, by treating its boiling solution with caustic baryta, and passing
carbonic acid through it till the excess of baryta is precipitated; and
from the baryta-salt, the free acid is obtained by precipitating the baryta
with dilute sulphuric acid. The zinc-salt distilled with sulphuric acid also yields
a distillate of aqueous ethylotrithionic acid ; but unless the sulphuric acid used is very
dUute, a large portion of the distillate suffers decomposition. After prolonged
evaporation over the water-bath it still retains 5 At. water.

The Ethylotrithionaten are obtained, either by dissolving carbonates in
the aqueous acid, or by double decomposition of the baryta-salt with

VOL. XII. 2 L

514

ADDITIONS TO VOL. Vlll.

SBlphateB, TUeir general fonnwla is C*HWS^O«, or MO^CH-^O*. TU
anhydrous add may be regarded as formed from 3 AL S0\ !iy the aafcati-

tation of 1 At. C*H* for I At 0; thus C*H»S*0* = S» i^'^l

EthylotrkMmiate of Sb^a , — C*H*NaS*0* + Aq. — OUlaioe.d hf
dissolving carbonate of soda in the aqueous acid^ eva|ioratiDg to dryneitJ
and extrficting with aleoboL The alcoholic eolatioti evaporated fml
vacuo over eulphuric acid^ yields tSi© salt in coloarless peedlf:<* shaped J
crystals* very mnall and uot well defiued. The crystals dried m vacttol
gave by analysis 15 21 p. c. sod i urn and 30*05 sulphur (by ^enlftlioi]
14*65 Naand 30*57 S),

4

EtJiylolnthionatf of Baryta. — Prtpuration (p. fil3). — CryatalUse«

cooling- from its concentrated aqueous solution, in the form of a colourlesi I

^ pellicle which fiaata on tho surface. The aalt, after drying over sntphurio I

acid in vacuo^ giveB off 1 At. water at 100"; it sustains a beat of 170^1

without decomposition.

4C «„.,,.,»,..,. 2i"0 ,.„ 12 39.... 12*08 4C .... 24*0 ..„ H-g4

tf H SO .... 2 'SB ... 2-43 6 H .., 60 .... Z'9G

Ba.. G8'6 .... 35-43.... 34*41 B«..,. 68 6.,., S3-86

raS *... 48 0..., 3170,.. 24-22 3S .... 480 „„ 23*68

^6 0.,. 480.... Z4'8l 2G86 7 0 .. &6-0 ..,. 27'fi6

C^H'BftS^O* ... 193*6 . lOaOO .... lOOOO + Iq ... 202*6 .... 10000

& ni§ prep&r^d bj decompoainf the xinc-sak with barfta*w«tef ; 6 hj
tbe aqueous &cid with carboaate of bar^tB.

ISItl

33*3t|

23'4l

28*11

Mthylotrithiortatr of Zin^. — a. Bask. — The crude salt obi

by the action of sulphurous acid on zinc-ethyL The exees« of

of zino arises from the action of water on tbe undecomposed dn^
eibyL

6€ „....„*,.„,. 48^0

15 H ^ «....«... 130

3 Zo.„, .,., ^ , — 97*t

6 s .„..».... ., ...,...,. .*.,„ nu

16 0 12i 0

ZiiO,2C»H*ZaS?0« + 3IIO .... 382 6

Hobfoa,

!2'5S 12-43

3 39 3'M

25 49 ..„« 25 'fS

2&'09 ...*...* 34-80

3348 33-91

100*00 10(NM)

h, Normai, — Obtained by crystQll i sing the hasie salt jnst de«crib«j|1
first from alcohol and then from water. Minute, colourless,
crystals, having a peculiar odour and a fomewhat Litter taste. Dti
sparingly in water, either hot or cold, and nlm in ethor; nearly ttia
in c«ld alcohol, but njoderate solubly in boiling aJcohoL On ev»yior
the aqneoua eolution, the salt crystallises out aa a i>ellicle which Ooalii
the surface. It contains I At* water of crystaJlisatioB, wbidi ii
not give off at 100°.

ETHYLOTRITHIONIC ACID. 515

Hobson.
4 C 24-0 .... 14-41 14-48

6 H 6-0 .... 3-60 3-69

Zn 32-5 .... 19-62 19-57

3 S 48-0 .... 28-82 28-69

7 O 56-0 .... 33-65 3357

C<H»ZiiSSO« + HO.... 106-0 .... 10000 10000

Eihylotrithionate of Copper, — Obtained either by doable decom-
position of the baryta-salt, or by dissolving carbonate of copper in the
free acid. Crystallises, both from the aqueous and from tbe alcoholic
solution, in greenish blue deliquescent needles.

4 C

Dried ut 100^
24-0 ....

15-33 ...

3-19 ...

20-18 ...

. 30-65 ...

30-65 ...

Hobson.
15-18

5 H

^ 5-0 ....

8-29

Cn

3 S

31-6 ....

48-0 ....

2018

30-20

6 O

„ 48-0 ....

31-15

C*H«CuS»0«

156-6 ....

. 100-00 ...

100-00

BthyUrithioncUe of SUver. — Prepared by dissolving carbonate of
silver in the free acid. White crystalline body, very soluble in water
and highly deliquescent. It is not decomposed by exposure to light or by
a temperature of 1 00"^, but is entirely decomposed at a temperature a little
aboy«.

Dried over

4C

5 H

oil iff vitriol ts vacuo,

24 .... 10-30

5 .... 2-15

Hobson {mean).

10-24

2-23

Ag

3 S

6 0

108 .... 46-35

48 .... 20-60

48 .... 20-60

46-18

20-49

20-86

C«H»ZnS»0«..

233 .... 10000

100-00

JSthyiotrithionate of Ethyl, — Prepared by distilling the crystallised
bar3rta-salt with sulphovinate of potash in an oil- bath, washing the
distillate with water, drying it with chloride of calcium, and redistilling.
— Yellow oily liquid, slightly heavier than water and having a disagree-
able odoar. It is insoluble in water, but mixes in all proportions with
alcohol.

Hobson.

8 C

.. 48 .

... 81-17 ..

30-93

10^

.. 10 .

... 6-49 ...

6-60

3S

.. 48 .

... 31-17 ...

31-05

6 0

.. 48 .

... 31-17 ...

31-42

C*H»(C*H*)SH)« ..

.. 154 .

... 10000 ...

10000

Metbylobithionic acid .and ethylotrithionic add (anhydrous) are the first and

■econd terms of a series whose general formula is S**-! q2d.i ^ '^'^ ^"Q

being formed by replacing 1 M, oxygen in n-atoms of anhydrous sulphurous acid by
1 At. of the (m— l)th term of the series of alcohol-radicals. Tbe sixth term would be

2 L 2

6ie

ADDITIOB^S TO VOL, Vllf,

BisulphethoHc Acid.

BucKTON & HoPMANN. Afiu. Phafm. 100> 145^ CAaft, Sae. Qu. J,

Obtained hy the action of fuming aulpUuric acid on pn^piooitrtli
(cyanifle of ethyl), or propiooamida. The latter is preferable on account
of the greater facility of preparing^ it. The mode of preparation ia fiiuiiltf 1
lo that dei^eribed tor bisuFpbomethollc acid (p, 484). The proptoii-J
amide niiiBt be as dry a» possible, otherwise the only products oblala
are propionic acid and sulphate of ammonia. To ensure tints Gonditio%l
it must bo heatod in a retort, and only that portion collected whjok]
distils above 2I0\ The proportions required are 1 At, propioDatnidAJ
C^NH^O* to 6 At SO*H; but as the funimg sulpliuric acid of comiuen
ifi not of constant conipositioHj its strength must be determined by
flpeojal ejcperimentj because too large quantity of acid carbonises
mixture completely, and if too little li used, the chief pKKlac
sulpbopfopionic and propionic acEds. The heat must be so reKnIati
to produce a continuous evolution of carbonic acid, — The residue i
fetort le dissolved in water when cold, and treated, first with earbonM]
of baryta and then with carbonate of ammonia^ as in the preparaiioD of
biauljdiometbolic acid. The filtered liquid yields by evaporatiou a
mixture of bisulpbethotate and sulphopropionate of ammoDia, the latter
of wbicb is quite uucrystal Usable and miiy be removed by washing with
weak spirit. Blsulphetbolate of ammonia then remains on tlie IUt«r
and may be purified by two or three crystallisations from hot watar.

The free acid is obtained by decomposing the lead*^lt with m\*
phuretted hydrogen. By concentration it forms a thick syrup wbicb
ukitnately sodiHeg in a crystalline mass. It is decomposed by beat,
with deposition of charcoal and emission of white fumes.

Biml/Jidholat€ qf Ammonia. — Crystallises from the ftqaeoui aotnlion
in oolonrle^ regular cubes or square prisms. It is insoluble in aJeohol
and in ether, Resenibles the bisulphometbolaio, but is more floioble il
water, and leaves a Carbonaceous residue when strongly heated.

Bixidph^QhU of ^^r^fa.— C'H'Ba^S*^* + 2 A q. — Obtained by
heating a solution of the ammonia- salt with hydrate of bairyta^ ttU iJit
aomionia is completely eKpelled» and precipitating the exceis ^f bftfjrtft
by a stream of carbonic acid, — Crystallisei in r«giiUur nix-tfided pkt^t,
generally radiatini^ from centres. After drying at 100^ it jjivoa olf
5'M p, a water (2 At.; by calculation 5'24 p. c) at 220^^ Uie «]i«e»
perhaps arises from partial decomposition. Wlien strongly haftlad k
close vcasels, it blackens, gives off euipyreumiilic vajmnrs, and 1«av<« a
black residue, which burns with a sulphur- Hame* It m rery mAMM sa
water but insoluble in strong nitric acidj which doe* not decotn ^

from solution In tUe ^\aie add, \i aty&tallisas without appaxeitl

I

BISULPHETHOUC ACID, 517

4 1 1 70^. Backton & Hofmann.

4C 24 .... 7-38

4 H 4 .... 1-23

2 Ba. 137 .... 4215 4236

4 S 64 .... 19-69 19-68

12 O 96 .... 29-55

g*H^Ba»S*0>^ 325 ... IQQOQ

When the salt is fused with chlorate of potash and carbonate of soda,
and the fused mass is treated with water, the filtered solution is found
to contain sulphates, showing that the salt contains more sulphur than
is required to saturate the barinm. This reaction distinguishes the bisul-
phetholates from the sulphopropionates.

Bindphetholate of Lead. — Easily soluble in water. The solution
when evaporated over oil of yitriol, yields thin prisms and four-sided
lamiDfle; when quickly eyaporated, it thickens to a yiscid gummy mass.

BinUphetholcUe of Silver. — Obtained like the bisulphometholate.
Crystalline. In the dry state, it bears a tolerably high temperature
without decomposition, but the soli^tion blac]sens when boiled-

ADDITIONS TO VOL, IX,

Pago 2i.

I meid, — Kane, hy ttctinif upon metUm^ whh ^

■^ obluned two acid©, vU., meajijlo-sulphuric anJ pcmwatTV

^ ^U, Uie lime s^U of the first cootaitiitir C^H*Car*^^

m wmamd C*H'0* SiCaO^SO*). Acconiiog t*/HWi«uj
^•^, 11, its), i4^toiie tre&lod with rooaol^vdr^t^d i
dtlphorii: actd ia v&rioii^ proportions— the
Ut iiicraie the «ctioB— &Jw«7a jidds an

of tlM forater of these mclda. The

«M diJml^ whh water, ^turil^^ »i4

irhhfin^
H«Csi0UU

heTmB
m4 binif t

WtDg Ttmimd mm il sep&mted ^ aud th« iMih

wi^cfa ftinned mtmU ctjstak Vr » gamm^

_ iMf aplvtioQ in hot aJcohut bmI |mcipiUitioD with ether. If w

■r eUabed aa a g^latioons iwilpi, which dried up to s wbili w

'^ «ibw powder, ha? iDg nesrij tke 091x1 poet tioti of Uie hjot^iik

Z>fiW«l 100*,

CaO
6C «.

5 H .....
tS ....
5 O

36 ,_

5 ....

32 ....

40 ...,

19«

2B'4

2(l'3 to 2r7
4 0 ^ 41

C*HK:.C^,S2CM HI

tOOD
re^rd« tli« silt analjtcd si ititl Impure.

1^ 4ecomposiTi^ the lime-salt with carbuuate of ammotiia, efiMi-
^^ filtrate, e^fiaustiiig the residue with stropg alcobol, aii4 hmt
^ mlmiton to evaporate, a buttery dcliqueacent mmm wia fihtaM
■^^^"^ -jht^n leali*d with putash, gave off ammaBiaauidyieUltdadiftillitt

C*H'CuOlSW + 2Atj. was oh ta 1 n cd lij exactly ,
I of the limo-^ilt with sulpbtite of copp^^r. Iti

i>l in grceuish crystalline need lee.

ACETAL.

5!H

Page 3a.

AcetaL C«H»*0* = ^^,^,\ 0\
Tvmx. iV^. Ann, €him. Fkyi, 48^ 870*

Wurtz prepares this compound hj distill in g 2 pis. of alcohol with
'6 pU. of peroxide of manganese, 3 pta. of oil of vitriol and 2 pta. of water
} (the proportions recommended hy Liebig for the preparation of aldehyde).
An soon as the efferrescetice which at first takes place has subflided,
0 pts. of the liquid are distilled off] the distillate is rectified; and th«
portion A which distile beJow 60^ (the thermometer being immeraed
in the vapour) is separated from the portion B which pnesea over
hetweeu 80'' and 95^ The former portion is placed iu contact with

5 ul verified chloride of calcium and rectified- The portion which then
istils below 60'' coneiata ehielly of liquid containing aldehyde^ and
above (JO*^ a distillate is obtained from which, on addition of concentrated I
of ehloride of calcium, an ethereal layer separates. The portion B of
the former distillate (hoiJing between 80^ and 05*=^) in Hkewjae rectified ;
and from the portion which first passes over^ an ethereal layer is alst*

I separated by addition of chloride of calcium. The ethereal Irquida
thus aeparated, containing aldehyde, acetic ether, kc.^ and acetal, are
itmitedj and shaken up with caustic potash, whereby the aldehyde is
^T6sinised and the greater part of the compound ethers decomposed* The
|brown liquid which then floats upon the potash-solution, is separated
and distilled; the di^itillate again mixed with chloride of calcium; the
liquid thereby sjoparated is heated with twice its volume of potaah-ley to
100'^ in a sealed tube for 24 hours; the lighter stratum rectified ; the
distillate again shaken up with chloride of calcium; and the separated
layer digested with pulverised chloride of calcium and rectified alone.
Pure acetal then passes over between 100° and lOS"",

12 C

72

.. 61^02 ...
.. 11-85 ..„
.. 27a2 ....

.... 6061

14 H .......«^«.. 14 .,

4 0...... 3« -

.... 11 '84
... 2? 55

C'^B'^U^

its

100*00

10000

w

(ki 40) re»rtle4 ac«tal u a compc^nad of I At. aldehyde with 2 At. ether

+ 2C<H*0]'. Wuitz regard* it a« gljcol or hjdrnle of elliyleiie ^ J], V O*

liaviug the two Iwiaic jitom* of lijdrogen rcpUcad bjf 2 Kt* clh/1. Tlib view it con*

oicd b; tho fi^riDBtLoii of Ibe com pounds deacribcd Wlov^

Acetal ts diasolved by strong hydrochloric acid. The liquid if left
to ilaelf bbckens at the end of two day^^, and then holds in solution &J
considerable quantity of chloride of ethyl. — PeuLachloride 0^
fus acta upon it energetically, giving off a considerable (quantity

520 ADDITIONS TO VOL. IX. ^^^^^^^

of ethyK — Mixed with ecveral times its weight of glacial acetic acid
and heated in a sealed tube placed in the oil- bath, it vields aceiie etbef,
eskch atom of acetal yielding more than 1 At acetic ether-

MtUi^ktt of Etkylmc, C^^H^W = ^^tst \ 0*-—Ohtainw], logger

with the following eompotind, by mixing in a capacioui retort, 110 pta*
of aloohol and 90 pt9> of wood -.spirit with 300 pts. of oil of Titriol,
300 pts. of water and 200 pta, Qf peroxide of manganese. Ah »ood m
the first elferveecence has subsided, the mixture is distilled till a quantity
of liquid baa passed over efjual to that of the mixture of alcohol and
wood'Ppirit used, and this product is rectified, the portions which go over
above and below 68'' being collected separately, and the distillation
stopped at 85^, Theae two portions are rectified, as in the preparation of
aeetal, then shaken up with chloride of calcinni, and the liquid treated
eevenil times with caustic potiish. An ethereal product is thuia obtoained
having a peculiar odour and containing acctal and the intcrroediale
compounds, togctber with a trace of mcthylol. On subiecling this tiiixtum
to fiuctional distitUtiou, vk considerable portion of liquid paaai« ovtr
between 60° and 70", and anotber between 80^ and m\ These wh«n
purified by further fractional distillation, ultiniately yioUi a product
boiling at about 65% which is methylate of ethylene, and another hoiling
at about 85^

Mothylato of ethylene is a colourless mobile liquid having an etherml
odour, like the nietbyl-conipounds in general Sp. gr. 0 8555 at 0 '* li
burns with a bright white flame bordered with bine. DIssoIf^ io a laigp
quantity of water.

Wurti,

^^ 8 C 43 .... &a*S3 53*69

^H 10 H... 10 .. nil .., ii':u

^^V 4 O , ,.. 32 ... 35 5S 3500

^R CH^"0*..... 90 ... 100*00 .... ... 100*00

Acctal in which ihe ethyl i* eotii^ly replaced by methjl, or glycol. In which tin
2 At. basic hydrogen mtt thtw rapUcied.

Mi^th^UihifMenfEihtjhnt or Mfthf/lacdal, C**E^O« = c;iH*^H'l^'

— ^Thia is the product which boils at about 35*. It i? n very mobilo
liquid having a penetrating ethereal odour, like th^t of Acetal itself.
Sp* gr, 0 8535. Vapour-density, 3*475* It dissolves in about 15 timiA
its bulk of water and in all proportions of alcohol, Jt i^i prt^cipitAted
from its alcoholic solution by water and niore eep^dally by aqucioai .
chloride of calcium; if however the alcobpl is m excej&a, water doeci
separate any thing from the solutiop*

Worti, VoL

10 C m ..,. 57'fi9 ...... 5/7? C-ifapouF ..*..,,«*,...... 10 ^, .^ 4HliiJ

12 H 12 ... U 53 11 64 H-ft« ........... ^ |2 fH^II

4 O ....... 32 ... 30 78 .... 30 50 O.gM ....... „, % f^lH

V^H^O*.... 104 ... lOO'OO lOO'OO V*imurof C*^H»"Ur .. 2 T*«liiJ

1 s-Mit)

AeataJ in whirh I M. elU^l i* rt^lKeed by inelhyL

, TRlBTUVLPliOSrHl?SK. 621

Page 65.

TriHhylamine, — This coinpDiiml may bo prepared by dilating

cyanrtte of etliyl with pure Khylato of potaBsium or eodiiini (absolute
alcohol aatu rated as far as possible with potasfliuin or sodium) for several
hours ut a moderate heat^ and eubseqnently distilling on % sand-bath.
A strongly alkaline liquid is thiia obtaiuetl, which, when saturated with
hydrochloric acid, yields, on evapomtioti to dryness, a residue from which
a considerable quantity of triethylaniine is expelled on addition of
potaeh. The reaction, which lu expressed by the equation,

18 jireclaely analogoui to that by which ethylamine ia obtained in the
action of hydrate of potash on cyanato of ethyl ;

A qoantity of the biso prepared as abore yielded an ora n go-col oureil
platinum-eivlt, which gave by analysis 32*73 and 32 55 p. c. of platinum,
the formula requiring 32' 12 p.o. Tho slight excess of platinum is due
to admixture of ethylaniine, the formation of which ariMes from a trace
of moisture in the ethylate of potassium or the cyanate of ethyl. In fact,
I if g^reat care he not taken to dry the roaterials^ ethylamine is tho prin-
I cipal product formed. (Jfofmann, Chcm.Soc. Qtt. J. ltl,20S.)

^■^ Triethylphospbine,

HoPMANM k Cahoubs, PML Tram. 1857, 575; Ann^ Pkarm, 104, 110;

Mrmaiion By the action of ierchtoride of phosphorus on ^inc^etbyh
PC|3 + 3C*H*Zn = (C^H*)*P + 3EnCl.

^V Frepttratwn. A tubulated retort/, \s Joined to a receiver e, which, in
Its torn is connected wlih a wide glass tube ^/, bent at an angle of ah oat 130",
misd acting like a second receiver. The angle of this tube is filled with
terchlorideof pbosphorns^ and the tube is connected with a large cylinder d
which is supplied hy a suitable apparatus «, h, with dry carbonic acid.
As soon as the carbonic acid has expelled the air from the reservoir, tube,
receirerj and retort, an exit-tube from the reservoir, up to that time
closed by a caoutchouc cap^ is opened to let out the carbonic acid^ the
©volntion of which is maintained during the whole operation. Tho
iubukture of the retort is now connected with the cop|>er diget^ter in
which the sine ethyl has been prepared ; and as soon as the retort has
rec4?ivcd a charge of the ethereal solution of xinc-etbyl, there i^ fixed into
the same tubulature a little dropping apparatus t^^ consisting of a glass
globe, with a tubulature and stopper at the top, and terminating below
in a glass tube in which a stopcock is fitted. This apparatus is fill—*
with terchloride of phosphorus, and by appropriately adjusting

in

&n

AUDITIONS TO VOL. IX.

fttepcock and ope Ding or closing lb e stopper of th© gl3s« globe^ aoy de _.

IHow of tbe liquid caa be niaintain^ with the greatest nicety. Howerii
lalowly the action may be acconiplished, and bowerer well, nior«OTf

i ibe retort and receiver may be cooled by water or !oe, the action ifl
I nevertbeless po %*ialent, that all the etber, and with it a large quaAlitri
*^c{ the xinc-ethyl, parses over into the receiver. By tbe powerful cboU
J lltioD which periodically euauea, a portion of the vapour ifi driven eveal
liutu the benttubiij and a considerable lossof zinc-etbyl is iucurred, EttlMl
this tube is filled with terchloride of phosphorus* wbicb greedily abtorm
evtry trace of tbe former compoimcL This tiuid valve, aacenalng andl
deacon ding in the tube, in accordance wiib tbe progress of the reaction,]
regulates tbe function of the apparatus so perfectly^ that tbe operation,]
whicb alwaya takes several hours, continues by itself when once begun.]
Sometimes tbe absorptton is so violent that the terchloride of pbo^hont*!
in the tube is sucked back into the receiver; but oven then no lo^ is lof
be feared, since tbe tube is connected with tbe reaervotr filled witbi
carbonic acid. The first drops of tercbtoride of phosphorus wfalch fall]
into tbe ^olution of zinc-ethyb biss like water coming in contjifiti
with rod-bot iron. Tbe action becomes by and by lesa violent, iLud lui
s{}Oii a£ an evolution of heat is no longer pereoptible, the operatiijn i$j
terminated. Tbore remain in tbe retorc, in tbe reisciver, in the bent tub%4
and some times even in tbe carbonic acid reservoir, two liquid layers,-^]
tbe one a heavy pale straw-coloured thick Buidj the other a transparent I
colourless mobile fluid floating on tbe former.

The heavy fluid, a compound of tbe pbospborui-baae witb chloride
of zinc, nearly solidifies on cooling; but the viscid transparent mtmi
oxhibita no trace of crystalline structure. The light fluid i» a misiartj
of ether with an excess of the terchloride of phosjiborus; after di*coii* {
nectiug tbe apparatus, it is poured off* from tbe vi«scous fluid, and ptay I
he uscdj after di»tilbition, in a second operation. So jn© ether and tcr^j
chloride of phcjt^pUorus wbicb may still adbere are expelW bygratlyj
beating tlie retort upon a Mud bath* I

The phiispborus base is liberated from its oombi nation with tloc hf\
distillation wilb polasb. To prevent destruction of ibe retort, itnd loM.1
of mjAterhil, thin operation is conveniently performed in tbe folb»wti^|
manner. Solid hydrate c»f potash is placed on the bard rrisinoun oikf
attached to tbe butUmi of the retort, and a slow current of water aJk
to flow hi by the dropping apparatus, after the air in the retort htm]
carefully displaced b^1iyito^B\i\ \X\^\!i«^\. ft>rQlved duiing tbo

TBIETHYLPHOSPKINE,

523

' i» quite J3u(6cient to volatilise tKe Ti»se with tte vapour of the water; it
tnaj be condensed by ao ordiuary cooler. The base, whicb is now float-
ing on the water of the distillate, is reinoved by means of a eeparatinff
funnel ; it ii allowed to staud for a day over hydrate of potash, and
6nalJy rectified in a current of dry hydrogen gas.

Pj*opertm. Transparent, coloarlees, mobile lic|nid wliich etrongJy
refracts light. Sp, gr. U'812 at 15^, Boils at 127*5 under a barometrio
pressure of 0 '7 44 mni. Ila odonr is p>enetratiugj altno&i benumbing but
still not disagrees b I e, and in a dilated state, resembles that of the
hyacinth. The intolefiible odour which oiu*Ut attendt the prepatttjon of this and
the other phoaphotui-htstAf arises from the forioalion of other products. Long-
Con tinned working with this substance produces head-ache and eleep-
lessneaa. When recently prepared, it is without act»on on vegetable
eoloun, but if exposed to the air for a few seoondt, it shows ^ constantly
jocreaelng acid reaction.

19 C ......«., 72

1& H .,. 15

P _...„.._ 31

(C»H»)^P _ lift

HohiuinD k CiihoutB,

61-01 .„ 60-00

1271 ....... 12-68

100 00

The aiiKl^aiii exhibitA a im«U lat« of earboOr ariaiirg from ovidihon iii the prcviooi
tiipuktioDft.

^m J)e€ompo9iiiom^ 1. When brought iti contact with oxygen gaa, U

emits vapoursj and freq^nently takes fire, omitting douse white fumes of
phosphoric acid. If a strip of paper iDoisteued with triethylphogphiDe
bo introducod into a test-tube containing oxygen and immersed in hot
water, the vapour of the phosphorus-base forms with the oxygen an
explosive mixture which detonates violently after a few montents. —
2. When triethylphospbine is poured into a flask containing ckhrimj every

»iIrop takes fircj with formation of hydrochloric acid and peuttichloricfo
of pliosphorus^ and reparation of carbon. If however the action be
ni ode rated, crystalline compounds are prod u ted. — 3 In ei/anoi/en^gaJSf
triethylphosphine is converted into a rosinone mass,

^^ CtmihinalloTiB^ Triethylphosphine has a powerful aflinity for oxygen
and sulphur, loss for selenium. Its combinations with these bodies con*
I t&iu 2 At. of the electro-negative element to I At. triethylphosphine.
It is perfectly insoluble iu water,

I Omdt ^ Trkthplphotphim. — {C*H*)^POl — Obtained ; 1, By the
I direct oxidation of the phosphorus-base. This substance has bo strong an
I Attraction for oxyxen^ that it cannot be distilled without oxidation except
I in an atmo6[jhere of hydrogen or carbonic acid. In contact with pi^re oxygrn, it
. •uflFcrs dct-omijoiiition (nrf, tup.) When the larger quantity of the base \\m
\ distilled over, the boiling point suddenly rises, and the neck of the retort
' becomes covered with a beautiful network of crystals of the oxide. —

2. By gently heating triethylphosphine with oxide of morcury or oxide
of silver. Considerable evolutiou of heat then takes place, the metal is

I

reduced, and oxide of triethylphosphine separates in oily drops, or some-
times sublimes in radiated crystals. It also separates in oily dro^a wWo,

ADDITIOKS TO YOL. IX.

\ k boiled wtA ^trtmg mtfic moA, and pnlmh ^U Is
||iie Ui^lj owMtmed iMfaid, — a Bj ibe ae&iiifi of Wii «b ik
^jdimtad oijd€ ef leti«ilij!piio«fb9iiiBiii :

[Dta i«tjcc<aaf tim iMkdjr to SslMMimi, wmter psMe* 9f«r li int:
Mirbta iM liquid bM «tiaiiied & nttiuii dt^gree of fsooaostaiiiN^ ^
bjrdilde of etli jl is fXToa lA On ooatwui^ ihe best, tbe »vo4iilm •! pv
i; ttid ftt 20Q , a vifieid ncail/ iaodotm liquid dtstib orv , t^ t»>
^ tben abwij fin% till, mt sbooi f 40^, tii# boiling point bmwi
17 mmd tbe dietiUate tiieii fenenlly «oItdiie9 in m ewj^lim wm
I ibe iMk of ibe ffitttii.
Oxftde of trntb^plMflpbiifte fbrnw cokwrleA enstals^ wbliA ««ii
snt that m €Tj^al exposed to the wr Ijqtis^ cntti^lj io 1 lb«
In perCMLj drf nir, bowever tber are permanent. ' Oli Mif
[tike «]r8la]liae Ma« bj tbe beat of a ^'^i^^^'laiEip and ctollocii^ ill
]M|nad ta m receiTcr, it often iolidiies tmUuktmiBcoui^w m «»oliif« kt
jfcMttlmpw fcmaiBfi Li^aid for montbs. It wmf h^ ob^uii^ ptifiiti/ kj
'wmd «oiid br distiUMion wiib ao)ijdroiEs phosidK^rle neijrbBl a^m

[ijBiiial do«dipoiiiion at tb« am% time, — It k dooomponed hy poliww.
[«nA Mpritinn af tmtbjlpboqikine. — II ^molwem in all mjmi^tm
Lin vnlar and in aleobol, bat h less soluble m rtber. Tbe a^iteoai m^
J tiott k precipitated bj pola^, tbe oxide then Eepnraiing in cejovibn
I pity dro^ wbkb Temain Itquid eveo aiter niticb concentfatiaa^ ai
|«apidl|' dmolTe on diluting the potaab-eolalion wltb a «ftfffpiff!i»j*ffy
f iaall <|aintitf of water — The nxide dittdTn fcadJly 10 ] "

ai^jiifilr — pHyPS'. - Obtain^ , 1. By the dlroct cotobinte
[9i nMhjipboiiibine with snlpbiir. Flo wen of onlpbar are gndaif
nd into an ethereal solution of tnetbjipbo^bine till n piffM
t nndiisolTed, the liquid efferveeeing on eadi additjon. Tbe «tW
lildMB vnlalilked, and the residimrf mixtttf^ of tbe sulpbido mud im
lndpbnr treated with boiling water, wbicli dij^olrefl ibe €iilpfaidt and «i
ImlJnf depodla it tn ctyetals of perfect pnriij. — S. By dinaiM
[ trietbylpbo«^hiD€ with cini^abar, whicU is ihen r%>dtieed ta iabolphi^
\m to inelallio mercury, — The com^nmd w not fbn&fd by tn^Hn^ Ow «ti4»«il
■ — "^ifcttretted h;dro««n or sulphide of uiiinoiiittm^

By slowly cooUng the aqiieoaa ifobtion, tbn cotn pound b i^MiH*
in boantifal iiee«ile-slia[ieci crystals oft^n fire or sii: itirben law, k
melUs at 94% and rcdolidi6es at 88^. When heated beycmd JOT, tt a
volatilised and difftises a white vapour having a di«a^i«eable luMf

' " ~^ '*' ' ' '' "^^ t» ^ ^ wSi

traosparent otl, whidi i« **y^f -Birfj Tiiliiihrl

<»dour, which is but ^tightly perceptible at oonini0n **«■« f**^*^»TW, Wlni

L heated with a qnaptity of' water not aulficienl for iU nalinjott, it mm to

iba anrbion in tbe form of a traosparent oil, whidi i« ""T'f iirtj Tiililihrl

wiSSkJ^^g/pm^ vapour,

LIS „_ $2 21^33 „„_ fl.74

IC*H»?P lie ... 78-67

CC'E^^-PS* .„. ISO „. 10000

TRIGTtlYLPHOSPIIINE..

898

I

^

The sulphide la instabtaneouely decom posed bj potassium, witli

Heparation of tri ethyl [»baspliine*

It is xxiuth inure goluhle In bot tbati in cold water^ only a small
quantity remaining^ dissolved at onlitiary temfjei-atures. It is still lees
eolubJe in alkaline liquids. On adding un aikali to the cald aqueous
®olu ttOD J the mixture becoraes turbid and soon cicpesits small crystals*'
On adding potash to the boiling saturated aqueous solution^ tho sulpbide
Instantly separates lu oily drops, which, as the liquid cools, rapidly
Bolidify into spherical a^^^rt^gatea of crystals, — It dissiolves even more
readily tn alcohol and etlier, and in bisulnhide of carbun almost without
limit; from this solvent it does not crystal lisc perfectly.

The aqueous solotion la without action ou vegetable colours; the
compound nevertheless appears to possess faintly basic properties. It
dissolves more readily iu hydrochloric acid, especially when couceutratedj
than in water, and the solution fiirnlsbes with bichloride of phitinum ^.j
yellow preeinitate, which rapidly cakes into a resinous mass, giving i
indications of decomposition by the s^pamtion of bisulphide of platinum* I
The sulphur compound also dissolves in dilute sulpbune and nitric acidsj
concentrated nitric acid decomposes it j the fuming acid gives rise to n
flort of detonation. The aqueous solution is not aficeted by lieetiite of leiid,
nitrate of i^ilver, or protoxide of mercury, even at the boilmg temperature;
the alcoholic solution, on the other band, is instantaneously decomposed, J
with seimration of sulphide of lead, silver^ or mercury. The liquid Hi tared]
off from the precipitate now contains the oxide of tricthylphosphine, either
free or iu the form of acetate or nitrate^ and easily separable by the
addition of an alkali*

Seimide. — (C*H*)^PSe*. — Prepared, like the sulphide, hy the direct
combination of trietliyiphosphiuo with selenium; the reaction bowevor
ifi less powerful than with sulphur, — Crystallises from water as easily
&8 the sulphide* hut the solutitm is apt to undergo partial dccomposiliou
vheu exposed to the air. Even the dry crystals are slowly reddened
in the arr Melts at J12\ and is easily volatiliiicd with partial
I decomposition.

Hcifmann 8t Caboara.

(C'H*)>P tl8 ... 59'9

2Se.... 79 ..» -iO'l

3945

CMorkU, Bromide, and lodidt of Trteihyiplumiphine,— O^lde of triethyl-
phospbine, when treated with hydrochloric, hydrohromie or hydriodic
acidj is converted into the corresponding chloride, bromide, or iodide,
which closclv resemble the oxide in tlieir general prop^srties. They aro

also be obtained by the action of these elements m aqueous or yilcoholio I
solutions upon tho phosphorus-base itself. Both methods, however,

I furnish products which are difficult to purify. . , , , 1 1 *

^ Trietbylphosphine forms cry**talline compounds with hydrochlonc,

^hydrohromie, bsdriodic^ sulphuric and nitric acids; Imt they cau ha

obtained in the dry stat^ only by means of the exsiccator.

525

ADDITIONS TO VOL.

Chl&roplutim£t€ of Trinh^lphosphimB* — The lolatioii af the \mm in
hydrochloric acid afTfipiIs a crystUlUne piatiuutii-gak, which id inflolubk
in coJd waJ^Tj in aloobol and in ether, aud dccotupo^i at 100°.

2>fi^ ovtr oil {^fvitri&K If of mum & Cahonn*

13 C 720 ... 22 21

16 H ..«..„„, I6fl .... -I 94

P 3ia ,»* rS$

3 a ,..«««,^ 10€*5 »,. 32'8i ..„..„ mB6

Ft ..,.„. 98-7 >™ 30 44 ..._ 305^

(C*H*)>P.HCl,PtC!».,., 324-2 .... IMOO

Tfae f>1fttiniiiD in this und the correapanding talU oJ th« other pbotpliora
c&iiDOt be deUsrmiiied in the ordinary way by limple ignttionp becanae » eaati
{|uantUy of it is carried off with the ph'»*phorU9-TBpotirr however fllowlj and cm
th«^ procesji ma? be carried out i but by heating with a considermbte «ce9» of e»rh
of lodA in A porcelain cracible on a ftsnd-bsth, the tempera to re of which is
Twhtiy the determi nation iucceed« witbont dHBcalty. After retnoifml ©f th«
■oltthle in wBlerp the ploitinam-re^idnet which ii alwajt coiitiLmijiated vith ttlkrie I
ii dmoWed in nitrohydrtK^UloHc «eid, the lolotloii «ira|Hir<ited lo dryuen, jiad lb* '
rcitdiie again diiaolved in acid : the careAit eraporntioii of tht« sotution fumisliefr t
perfcfl^tlj accurate result. This methodt thodgh somewhat tedbm, hu the adTaotagQ
of affording a ■imnltaneoua determiiiatioii of the chlorine.

Tetretixylphosphomam,

HoFMANK A CAHoimfi. PhU. Tmm. 1867^ SS3«

OhtaiDed as an iodide by the actian of iodtde of ethyl on triethyU
[|ihoaph]iie :

Ci*H«P + C*H*I • C»H*PJ.

Not known In the separate itate^ U may he n»giirded a« amtnoiiiQin ni «hi«i thi
nitr^Ofcn i« r^iilaoed by phosphorus and the 4 AL H b; 4 At* C*H^

H}fd$^Ut! Ox«/<r. — fC<HVPO,HO-— Ohuined hy aie action rfl
oiide of SI her on the lodi Je. A strongly alkaline aolutioii m fom«d '
which retains a small quantity of si)yer iu solution,

Thia liquid, which is almost without odour, and hu a hitt«r tnA
^hosphonc ta«te, drie» up when placed over stilphuric acid, into a etjf-
^ialline eattremely deliquf^scetit mass, the silver sepan*ting at ihr wm^
I time in the form of a black powder, or aa a brilliant metallic nti^^BH
iThe njaas, when redi-ssolved in water, fumi^hee a colourless 1^<>^4^|^|
[from fiilver, bm generally containing carbonic aaid* Jt »tlf»nto £m^|
water and carbonic acid with avidity, ^|

In its deportment with other gubetanoes, this oiidi* r«eeiilUc9 Ibc
oxide of teLrethylium (ix, fiS), it^ solution exhibiting all the r«««tMi
of a eolation of |kotm£h; the precipitates, such »s aJumina and prutoxid*
of line, dissolve, however^ Icei r^dilj in excess of the phosph
compound.

TBTRETHYLPHOSPHONIUM. 527

The hjdrated oxide is resolved by beat into hydride of ethyl and
binoxide of triethylpbospbine (p. 524). If however it has been exposed
for some time to the air and has absorbed carbonic acid, a different
decomposition takes place, the carbonate of tetrethylphosphonium being
resolved into triethylphosphine and carbonate of ethyl, which passes over
in the form of an inflammable aromatic liquid, without any evolution of
permanent gas :

(C*H»)^P0,002 - (C*n^P + C*H»0,CO«.

Iodide, — (C*HYPI. — On mixing triethyl^osphioe with iodide of
ethyl, a violent action ensues after a few momenta, the liquid efferv«flcing
witii almost explosive violence and then solidifying in a white orystallino
mass. If an ethereal solution of triethylphosphine is used, the ctTstals
form more slowly. The iodide is very soluble in water, less soluble in
alcohol, insoluble in ether. The aqueous solution crystallises on addition
of potash-solution, in which this compound, like the iodides of tetrame-
thylinm and tetrethylium (vii, 320; ix, 66) is but slightly soluble.
From the alcoholic solution it is deposited, on addition of ether, as a
crystalline powder. If ether be added to a cold alcoholic solution, as
long as the precipitate first formed is dissolved by boiling, well-fonned
crystals of the iodide are deposited on cooling.

Hofmann & Cahours.

{Cm^y? 147 .... 53-65

1 127 .... 46-35 46-25

(OH»/PI 274 .... 10000

Tetrethylphosphonium produces crystallisable salts with hydrochloric,
nitric, and sulphuric acids. All these compounds exhibit the deliquescent
character of the oxide. Like the latter, they are also soluble in alcohol;
in ether they are for the most part insoluble. The hydrochloric solution
forms sparingly soluble precipitates with bichloride of platinum and
terchloride of gold.

Chlai'oplntinate, — The pale orange-yellow precipitate which falls on
addition of bichloride of platinum to a moderately dilute solution of the
chloride, dissolves with difficulty, but without decompositioUi in boiling
water; it is insoluble in alcohol and in ether.

Ai 100"*. HofBDann & Cahours.

C"H»P 1470 .... 41-75

3 CI 106-5 .... 30-23 30-13

Pt 987 .... 28-02 27-82

(C<H»)*PCl,PtCl« 352-2 .... 10000

Chloroaurate, — The crystalline precipitate obtained on mixing
hydrochlorate of tetrethylphosphonium with terchloride of gold, separates
from boiling water in brilliant yellow needles.

At 100*". Hofmaon & Cahours.

C>«H»P 147 .... 30-25

4 CI 142 .... 29-22

Au 197 .... 40-53 4022

(C»H»)^PCl,AuCl» 436 .... 100-00

6S8

ADDITIONS TO VOL. IX,

Methyltriethylphosphonium.
O'W^F = (C'H^)(C*H*yK

HoFMANK & Cauouhs, FhiL 2-mn#. 1857, 590.

lodidi!. (C'H»)(C*H»)'PI.— ObUined by the lusiioD of iodide
tnelhyl on triethyljiLoaphme. Tlie iiction U etiU mora iriolent than \n
the caae of ioclido of ethyl (p. 527), and uiilesa ether is ailded> a p^jrlioa
of the prod net is very apt to ba lost. The coinpouDd aeparaU*s iWm
cryatiiila, which, when dried at 100% contain 48 T? p. c. iodine, tbe formu
reqiiiriiig 4885 p, c.

The aulutioii of the iodide treated with oxide of silver, yields
strongly alkaline soluttun of the kydrattd Qtlde.

C^ioroplaUnai^. — The alkaline eolutioa saturated with hydrochloric
aeid arid mixed with bichloride of platlniim^ yiehb a bestuiiful oraQ£^e»ye]lo«
platinum salt, crystallising in well defined cubei truncated by the pbnffl
of the octohedron» It b insoluble in alcohol and ether, and nmy
recryt^talHscd from boiling water without decompoeition.

C«H»F .», .,...„ 533*0

$01 106-5

K m^7

(C*li*)(C*Hfi)^PCI,PtCl* ,.. 338-2

31*49 __ ai-ji

29-31 29 h^

100 00

TrimethylethylphosphonimEt
CioH"p = {CH»/(C*1I»}P.

HalPMAXH & Cauours. PhU. Tr&m. 1857, 5B5^

l6diJe. (CH»)'(C*H»)P,~ Obtained by the action of iodide ofetbj

on an ethereal solutiuii of trinielhylphosphine (p. 491)- Ci^nti
ra<lily from boiling water. It yielded by aualysia 53'6Tp. c. k
(Cakulationj 54'76 p. a)

C^or^phtmaU. — Yellow salt insoluble tn alcohol and ethers boll
r&tlier aoluble in water, aud cry !>ial lilies from the boiling «aluti«»ii ii
tnagnifioent octohedrons*

C^il"P ,.„. 105 0 .,., 35 86

SUl .....».«.,..„,« ^„» 106-6 .... 34-33

Pt ..,.,„...., .......... 987 ,. 31*81

HofmiiQu at C^onfi.
33-t^

((?H^)Hc*H»)rcuPicp .„. 3Soa „., loooo

TRIETHYLAMYLPHOSPHONIUM. 529

Trimethylamylphosphoninm.

HoFMANN & Cahours. FhtX, Trans. 1857, 596.

Iodide. C^H'^PI. — Deposited slowly from an ethereal mixtnre of
iodide of amyl and trimethjlpbosphiiie. Extremely solable in water,
so that if the ethereal solution of iodide of amyl contains only a trace
of water, the salt separates in the form of a syrap which only gra-
dually solidifies. From absolute alcohol it crystallises, though with
diffionlty, in needles. It gare by analysis 46*22 p. c. iodine, the formula
requiring 46*35 p. c.

CfkhrovlatincUe. — The oxide liberated from the iodide by means of
oxide of silver, yields, with hydrochloric acid and bichloride of platinum,
a very soluble platinum-salt, which crystallises from boiling water in
splendid needles aggregated in spherules.

Hofmann & Cahours.

C»«H»P 147-0 .... 41-74

3 CI 106-5 .... 30-24 80-24

Ft 98-7 .... 28*02 27-91

(C^HV(<^^"H»»)PCI,PtCl«.... 352'2 .... 100-00

Triethylamylphosphonium.
C«H«P = (C*H»)»(C»*H")P.

Hofmann & Cahours. FhiL Trans. 1857, 591.

Iodide. C"H*PT. — Todide of amyl acts but dowly on triethylphos-

5 bine. An ethereal mixture of the two substances deposits in a few
ays beautiful crystals, which may be puri6ed by solution in alcohol and
precipitation by ether. They contain 40*45 p. c. iodine (by calculation
40-20 p. c).

Hydrated oxide. — Obtained by treating the iodide with oxide of
silyer. Resembles the oxide of tetrethylphosphoninm. When heated,
it gives off a small quantity of inflammable gas, probably hydride of
ethyl, a liquid being also formed which boils at about 280°, and appears
to be the bmoxido of biethylamylphosphine:

(C<H»)»(C»«H")PO,HO « (C<H*)2(C»0H")O» + C*H«,H.

Chlorophtinate. — The solution of the hydrated oxide in hydrochloric
acid deposits, on addition of bichloride of platinum, a beautiful platinum-
salt, which crystallises in prisms with flat terminal planes. It is inso-
luble in alcohol and ether but rather soluble in water.

VOL. XT I. 2 m

530

ADDITIONS TO VOL. IX-

C?»H=«P 190-0

3 CI , 106 S

Ft ii8-r

2702 27-42

2504 .... 2518

lf>0*00

Cadmmm-ethyL

J. A, Wanklyn, Chi^. JSoc. Qtu J. 3, 193.

Obtained hy the action of cadmimn on iodide of ethyl. Thin on
miuiri foil wx\& enclosed, togetlier witb half its welglit of iodide of eik
dissolved in an equal vol nine of etlier, in a scaled tube, and heated » a* ii
Fmnklanda prejmrntJon of stinc-ethyl (x, 530)^ at first to 130'=' for
hour and afterwards to 100'^ for 30 or 40 hour^. Oa opening the vc
a larj^e qnautity of gaa escaped, and when the con ten U of the tube wei
distilled in an atmosphere of carbonic acid, ether and excesa of iodide
etlijl passed nrer at firsts and between 18 0"^ and 220^^ acolonrles® lic|u
which giive off wliite and afterwards brown vapouri on exposure to i
air, and at length took fire, emitting a brown smoke. It bad an mlo
like that of Kincethyl, and was decomposed hy water, with ©ffervc^cen*
and fornnation of a white preciipitate. It contained 36 8 p, «-
cadmium, whereas the formula C*H*Cd requires 06 jj©r cent, Tbij
wonid show that the distillate contained about Tjfi per cent of cadmiuia'
ethyl, the remainder consisting of ether} iodide of etbyh ^nd perhapa
certnin hydrocarbons.

In another experiment, in w^bich cadminm w.is heated with iodide of
ethyl and ether to 125", for two or three days, the portion which distdli
above ITO^ yielded on rectification between 05"^ and 165'' (no con^t*
boiling point was observed), a Jiquid whtch famed bat slightly in tl
air and did not take lire spontaneously; tlie ri^idue contained m^tjUli
cadmium.

When c:idmium, iodide of ethyl and ether were heat<^d togather fori
considerable time to 100' in a aealed tube, the action began after devei
boura only, a crystalline powder then separating; wben the tul^»0 i
o|jened, the contents did not fume, the crystalline powd«r Ij^came bf*l
exposure to the air, and effervesced with waiter- It appears proWi
that, in the action of cadmium on iodide of ethyl » a et>inp<jund
cadnHum-ethyl and iotlldo of cadmium is formed, and that the ^tral
part of the cadniiuin -ethyl is decomposed at the temperiLture reaiiire^t lo
liberate it from this compound, a small portion only beinji^ carried oTer
undecompoyed, together with the hydrooarbon<* resultjsig from ibe doooid^
position. (Wanklyn.)

Sonnenschein (J. /?r. Qh^i, 67, 1G9,) by heating ati aUoy of cadmiui
and sodium with iodide of ethyl in a sealed tube, obtained »
crystn-lline mass, which w*iis insoluhle in wittor, sulublo in iodide of
and had an extremely penetrattng unpleasant odonr^ like thai of tiM
The hptija of e^dmiuii] an ioditle of t^thyl w*g trictt bf Sf baler in ii&3^ {Amm, Pi>
tt7, 3I«) buiwitbaut jtnjr ile^tute reftult^)

of

lODrOE OF ACETYI.

531

Iodide of Acetyl. on'0\h

. CAnotJRs. CompL rend. 44, 1252; Ann. Phaiyn. lOi, 109.
Guthrie. Ann. Pharm, 103, 335,

lGdid€ qf OihyL

Formation By tlie act ion of iodide of phosphorus on aniiydroue
etic acid (Gutbrie), or anbydroiii acetate of polash. (Call ours.)

Prepamtton. I. An hjilro lis acetic acid (1 At.) is xioured upon moro
LU I At, of dry phosphonis in & loDg-neckcd flask^ and riitlier more
than 1 At, dry iodine gradually added by small portions* The flask is
then heated till the action is complete, and the liquid gtill CQDtaintng
free iodine, is poured into a retort contain it>g a few pieces of dry phos-
phorus^, and having its neck turned upwards and connected with a con-
densing apparatus. After the li<]uid has been boiled in this manner for
aonie minutes^ the neck of the retort is turned downwanls and the liquid
distilled off. The bnillng point remains almost constant at 108^ but
towards the end, when there is but little liquid remaining, it rises to
120^ The distillate la well shaken with mercury till it becomes trans-
parent, then qnitkly poured ciff and rectified, the portion which distils at
308^ being collected apart llowcfcr onrefnlW the dbtilliition may be conducted,
part of the iodide of ncetyl is decompo^pd, hydriodic ftdd e»captn^, iuuJ a solid siibftance
coritjihiiiig iodine, prabAbty a inbatitution-product* remaining. 3| oi. of aiihydrotia
Acrtie acid treated a a above with 9^ o^. of iodine &Qd about 1 02. of pboaphonis, jtetded
! about b oz. of iodide of acetyl, (Guthrie,)

^B Froprrties. Transpareut colourless liquid. (Cahours,) When fir«t pre-
^^nsrrd it baa a brownifb colour, wliieht according to Gotbriet ii pecuJiar to it, and c:»nnot
^^Re rumored hy a citation with iivfictirj; Cabourcs however states that the colour 19

^«tr-
■ ta-

^^ The excess of curbon and bydrogeo
»nbydrons acetic acld»

ompletely removed by agitation wirh mercury. Sp. i^; 1 '08 at 17^ (Guthrie.)

\mU at lOS"" (Oathrie); between 104'' and 105\ (Cahours.) It fumes
strongly in the air, has a very pungent odour, and Intensely aour caustic
taste (Guthrie.)

4 0 ...,.

3 U

..... 24
3

.... H 12 ...
... 176 ...
... 7471 -.
.... 941 ...

Guthrie.

233

1

2 0 ...,

.... 16

n-m

.... sao

c^H*on ,

.... 1?0

.. 100 00 ...

... 100^00

in the anaiysii &rose from adinliture of

Decontpos tt iu n$* 1 . I od ide 0 f aoo ty lis pa r t i al ly d eco m posed by distl I-
lation (p'rf. f*fp V — f . Waaler deconipoees it inatantly and with violencO|
forming bydriodlo and acetic acids. (Guthrie^ Cahours.) — 3, It actfl
violently on alcohol, fornaiug acetate of ethyi. (Caboura.) — 4* It is
decompoaed by kjuc a id by aodiuin at ordinary teniperiiture** also by

2 h

fiB2

ADDITIOKS TO VOL. IX.

mfiroarj in direct sunsbijie, loiiide of mercury being formed and little *
na permaDewt gajs given off'. The product* formed hy the action of ih^
thrm metals on iotiide of ethyl are t^imilar^ and consist of on© or of m
number of bodies, which are soluble in ether, and in contact with tli«r^
qnicklj absorb oxjrgen and become hardened, (Guthrie/)

Page 187.

Bromacetic Acid. C*H>BrO^

W. H. Perkim k B, F» Ditppa* Chem. S^, Qt/. J. xl, 22.

Fof'mation. By the action of bromine on acetic acid :
C<HW + 2Br = C'H^tJrO^ + HBr,

A «mall qomulity of bibromncetic »cid is fortned ml the sime time.

Prepamtion, A inirture of glacial acetic acid and bromine in
abers of alonia (an excess of acetic acid being used to ab^or^'tf
tydtubromic acid and thereby di mi nidi the pressure) U id trod need int
' 8. strong sealed tubo^ and heatrd in an oil-bath to I SO**, and the bath
then left to cool gradnally. When the tempeTature hm fallen to about H6% 1
mhturi* 9ud(]enlir becomet neurly poloarless or light amber brown, juid at the tatni* tin
the ti}bps are apt to bur?it. thouj^h the terriperature of the bath mRj have th^n it hi^
*al5i^ The tube when quite cold u opened, torrents of bydrobromii
acid gas lh@n escaping j the contenta are transferred to a retort provid©
with proper apparatus for condensing the hydrobromic acid, and heat
to 200^ ; and the tetort is left to cool The whole contents th«
solidify after a while into fl^ beauilfully erystalliue mass cotis^stim;
bronmcetlc and bibroniaceiic acids, mixed with hydrobroniic »cid,
remove which the mixture ia heated to 130^ and carbonic acid iriis [
throngh it till the presence of hvdrobromio acid is no longer indlcai
nitrjte of silver Carbonate of lead is then added in excess, to
with a volume of water about ten times as great aa that of th#1
and the whole is heated to 100'', and allowed to stand for some hour
Bromacetate of lead then crystallites out, while the bibroniacetutc remaiiW
in solution; the cryj^tala may be freed from the last portions of ihi? «ih
by washing with a little cold water. Lastly, the crystals of bronmceUlftj
of lead are suspended in water and decompossed by sulphnrelted bydr^i^i
and the filtered liquid is evaporated till tt crystal Haes,

Prapetti*'$, Bromacetic acid forms rhombohediHl crystaU wfaicli
very deliquescent. Melts below 100', and boib at 208^ Attacks th
skin powerfully, raising a blister like a burn; when the aeid h dilDi
this effect takes place after eight or ten hours only,

Dt*:omposiiif>ns. 1, The acid strongly heated in a sealed tnbt,
resolved into bi bromacetic aciif, carbonic oxide^ and apparently iiiar»h

\%\y as repr«

together with water and hydrobromic acid, probably

the equation :

pr«i€nt«d

BROMACETIC ACID. ' ^ 633

r 2. On distilling it with acetate of potaab, acetic acid is evolved. —
3. Heated with metallid zxuCf h jielda acetate and bromide of zinc. —
I 4. Heated with ammouia^ it foruis bromide of ammouiimi and glycoeol:

Chmbinalionx. The at;jd di^^olves very readity In tmtet\
With most bases it forms cry stall isablo salts^ many of which decom-
pose rapidly,

Bromacetale of Ammonin. — Nearly un crystal Usables very soluble
lia water; decomposes when boated, yieldiag bromide of ammonium.

Bromacetute of FiMsh. — Obtained by neutralising a solntioa of
foirbonate or hydi-ate **( potash with broiiiacetic acLd> and evaporating
rthe solution iu a water- bulb. It is a crysUilline salt very soluble ju water
land alcohol .

Broinacciaie of Soda is very soluble in water, but inscluble, or nearly
f«o in alcoboL

BromacHatt of Baryta cryst^dlises with difficulty in small stars, con-
! taining water of crystallisation; it is tolerably soluble in alcobol.

Bromacdaie of Lime is a very difficult crystallisable taltj very soluble
[in water.

BromQ€etat€ of Copjyer is a green crystalline salt, very soluble in

rater. A solution of it appears to decompose when boiled, as the colour

ecomes paler. The solution, after jitandiug for some days^ deposits

ueedle-shaped crystals and small malacbitc-green tufts of great beauty,

L which appear to contain a large quantity of water of crystullisation*

Bromacehite of Lmd, — Obtained, either by neutralising bromacetic
ttcid with oxide of lead and recrystaili^ing the product froni water, or by
adding a solution of bromacetic acid to a solution of acetate of lead,
washing tbe resulting crystalline precipitate with cold water, and
recrystallising from water. Crystallises iu needles sparingly soluble \xi
cold, but moderately soluble in hot water.

^B Bf^miMixte of Silver, — 0*BrH*AgO*, — Obtained by treating brom-
acetic acid with carbonate of silver, or bv adding a solntiou of broma-
cetic acid to a solution of nitrate of sifver. In tbe latter oai^e, it is
thrown down as a beautiful cry stall lue precipitate, which may be washed
with culd water, and dried over sulphuric acid iu vacuo. Contains
43"62 p. c. silver (by calculation, 43'0),

It is very unstable. The dry salt heated to about ^O'*, decomposes
with a sort of an explosion* It is ra(>idly acletl upcin by light when moist
Boiled with water^ it yields bromide of silver and glycolic acid i

C^BrUUgO* + 2HO - AgBi + Q*WOK

Ai im\

P«rkin At Ouppa,

4 C „.,

............... 24-0 ..

..„_ 10*25

2tt

2-0 ..

0*9

Br .,.

^....„, 80*0 ..

.. 331

..,».. 33 1

Fb

lOS-fi ..

,. 42-9

_.... 42-8

4 0

.,„ 32-0 ..

. 13*3

C*Brll2PbO* 241-6 .... lOO'O

2.2^ iWitlMHil lO ^OL. IX.

— CmkO' = C*IPO,C»IPBK)». — ObtiiMd
i4aI aad linMHicetie meid in & snM
•f l«a^, vaflkiBg the prodict ^itk
if ciiHw, and rectifying.

Bf«i^ kmYing* aa mromatk odov
lai iW cj«i. It is liearier tkan witer;
^ fadBaOjr ererj time it iB difdlM.

-u :^ fKWKfia^ It is a dear eolonrieai liomi
loe^r TTTTtMJag to ike ejes and noae. It Uk

*C 4S — »-r J8-0

rX 7 — 4-« 3-5

*• «• — 47-7 47-5

«0 58 — lS-4 21-0

c-ffmo- i<7 — im-9 100-0

r«emnweef larailj *c«rT toK it is distilled, with erolatMi rf
xymQcvBJH mssmL Ii x nffdlj acfeed oa bj ammonia.

J>-wM«w ^r ^fa^— C'«='BcO» = C»H»«0,OIPBrO».— OUiW
W MT'nc ftBj^r ajM&il vick exems of liromaeetic acid, wiahiof (Im
iriicm -9^ wer. a:ai i^^^ •^^'^ chloride of calciom. It is ib oily

I*£XL*£ vxitrs 2:^ & vusftsis: t!«k«r whtn cold^ bat if heated, wets opoo tM
e]pf* ia*£ T»iee Lk* ue precedi^. It boils at 207', and decomjH'Bes
warzu^j iT^cT ^zBit is if i^fcilled. Ammonia acts bat slowly upon i: ii

Perkin & Dapp*.

14 C S4 — 4#-19 4002

II a 13 -. 6->2 ^ 6-28

Br .. >0 _ 3S -22

4 O S2 U-S7

C-H^»BK)» -- 2W — 100-00

Ti« VroQiaKiaies of methvL ethjU and amjl boil at tcmpeniurci
aU;LS S:r so S<'. ki^er than the aoeutce. Thos —

BoCinf Boiling r, ^

P^^- point. * •

Vu MJicnrf of V-rfnl U4* Acetate of Methyl 58* H!>

Erbyl _ ._ 159* „ Ethyl 74* * «

^ Amjl ^ 207' „ Amyl 126*

A similar difference exists between the boiling points of bromace^f
acid \2v:^' }, and acetic acid (120^).

ACTION OF CHLORINE ON ALDEHYDE,

585

Bil^romacetic Acid, c*H*Br*0^

Pbrkim k DupPA* Chem. Soc, Qu. J. xi, 28.

This acid ia funned when a mixture of bromine ami acetic acid is
heated in presence of light; also in emaH quantities whea bvoniacetio
[mcid is heated* It ie difficult to obtain in large qnaniitiee,

Blbromacetie aeid ia a very heavy liquid, boiling at about 240"; it

I ia decomposed partially every time it i« distilled, evolving liydrobromic

ffcrid. It does not aolidify at L^^. It is possible that by the contimiod

I action of heat it might bo transfumied into terbroniJicctic acid. Its

i|>ecific gravity is very jy;reat.

BrQiuacetic acid forms salts with most bases^ which are in general
BmcrystalHfiable*

BihromaceUiU of Baryta la deliqueicenti drying up to a gum-like
Fflticky ma^B.

Bibi'^macdMte of Lead is nncrystallisahle, drying up to a highly
afractive transparent substance, which attracts moisture t^d becomes
Dpaque. It is very soluble in water.

Bibrottiacfiate of Silver is obtained as a crystalline precipitate by
ruddling nitrate of silver to a solution of bibrouuicetio acid. By boiling
with water it ia resolved into bromide of silver and a soluble acid>

Per km k Dupp*.

4C .„..„.„... 24 .... 7-4

H »,., I .... 0*2

As 108 ,... a3*2 BZl

2 Br ..._............. 160 .... 49 S .^.. .. 49 1

4 0 32 ..,. 9-9

C^Br^HAgO* ..... 325 .... 1000

Bihrfmmcd4iU of Mthyl ifl obtained by heating alcohol with bibroni-
cetic acid to 1 00° in a sealed tube^ washing the product with water,
land drying over sulphate of copjier*

Page 19L

Action of CMorine on Aldehyde.

|A. WoRTZ. N. Ann. Chim. PhyM. 40, 5%,

Perfectly dry aldehyde Introduced into a large vessel filled with dry
chlorine, is immediately attacked and begins to boil, and in a few hours
the colour of the chlorine disappears entirely. The product begins to
boil at 50^ and the boiling point ultimately reaches 200^. The more
volatile portion consists chiefly of chloride of acetyl C'H'O'CI, and IP
decompoaed by water into hydrochloric and acettc acids*

^^ aecon

536 ADDITIONS TO VOL. IX.

Monachlonmutaldehydey C*H^C10*. — On collecting apart the liquid
which passes over at 1 20', and washing it repeatedly with water, a dense
oil is obtained, which when dehydrated bj chloride of calcium, distils
between 120' and 130^ and appears to consist of a doable molecule of
aldehyde, in which 1 At. H. is replaced by chlorine.

8 C

... 480 .
.. 70 .
.. 355 ..
.. 320 .

... 39-17 .-
... 5-71 -
.. 28-97 ...
... 26-15 ..

Warts.
39-00

7 H

6-04

CI

4 O

26-87

.. 2809

C»H7ClO« .

^ 122-5 .

.. 10000 ...

..^ 100 00

Chloral is not foand among the prododB of the resctioor

Monochlorinated Chloride of Acetyl OH«ClK)«.

WuBTZ. N. Ann. Chim. Pkys. 49, 60.

When chloride of acetyl is introduced into large flasks filled with dry
chlorine, the colour of the gas disappears rapidly in sunshine, and after
24 hours in diffused daylight. On opening the vesseU acid vapoora are
idven off in considerable quantity and with great force, indicating the
formation of gaseous or very volatile products. The resulting liquid
begins to boil at 55>^, the boiling point ultisuUely rising to 200® ; and
by repeated fractional distillation, monochlorinated chloride of acetyl is
obtained, boiling between 100° and 105''.

Colourless liquid, having an irritating odour, and diffusing a small
quantity of white acid vapours in the air. 6p. gr. 1*495 atO^ Boib at
about 105^

Wurtx.

4C 24 .. 21-23 2107

2 H 2 .... l/G 1-71

2 CI 71 .... 62 83 63 70 .... 62-77

2 O 16 .... 1418 13-52

C<U«CI"0- 113 .... 10000 100-00

The compound is decomposed by water, yielding hydrochloric and
monocbloracetic acids:

c<H-ci202 + 2HO = HCi + c*hh:io*.

It absorbs dry ammonia with avidity, yielding sal-ammoniac and mono-
cbloracetamide. Alcubol converts it, with evolution of heat, into hydro-
chloric acid and monochloracetate of ethyl.

>N0CHL0RACETIC ACID-

637

Fago 192.

Monochloracetic Acid.

t Hoffmann. A^m. Fhai^m. 102, L

Kobta

DutkiAi observed that in tbe preparatton of ten'hloraeetlc «cld by the artiou of
chlorine un KC«tic acid iti si]ti»hiiie» a Lowtrr fiubistitution produci;: is al«4ya obtained,
cat»ccUUy if the Hcctic aeid is iu excesA, in the form of an oncryaUltieable acid, which
howevfr he did not aurci^ed in prepfirin|^ in the separate sCHtitei F* LebUtic afterwards
btaincd this acid» the nionocblorai.^tic acid, in ihe form of a ootourltis liquid, by
iin^ chlorine tbroiigb gUciuL ac^-tic acid in the shade ; his product howt^ver wajs
nut qoiTe pure. Mure recently Hoffmann baa showti that the chief product of the
Action of cUorine on a^:etic acid in sunMbintj, b not terchluracetic but moaochbmeetic
MfMi and thaX thb acid wheti pure is Boiid and cry^Udliue At ordinury temperature*.

PreparaiUm. 1. A tubukteil retort of about 1 litre capacity and
coataitnug from Lalf a pomiU to a pound of gkclal acetio tie id, ia placed
in a batb contalniu^ a saturated solution of nitrate of eoda (boiJtag at
1 20^) J and dry cblorine ^^aa is pa^se^i into the retort by a tube pasaiug
througb the tubulurts and terminating just above tbe liquid, »o that tbe
gas may mix iui mediately with the vapour of the acid, '^l be neck of tbo
retort, having a wble ^duss tube attached to it, h liirected up\¥ftrds, eothat
any acetic acid which evaporates undecomposed may be condensed and
fluw back agB^iu, while the hydrochloric acid and excess of chlorine
escape- Tbe whole apparatus t» placed in the sunshine, and the evotu*
lion of chlorine is so regulated that the ripper part of the retort always
appears coloured b^ it. Tbe stronger the light, the more rapid is the
absorption of chlorine; hut the action takes place, though slowly, even
under a cHuded sky, A very alow aubittituUoti of chlorine for hydrogen hkewise
tAkew place in the d*rk and at ordinary tern pt^ratu res. A ^ the formation of chloracetto
acid goes en, tbe actiou i^lackenE, so that it is best, after about 15 hours^
exputiure to sun«bine, or twice as long to difTiified daylight, to txpel the
excess oi chlorine from the apparatus by a stream of dry air, and rectify
thtj product in a gmalUr retort. The portion wliich distils below 180^,
c^onsiiils almost wholly of unaltered acetic acid, and may be used in a
eulsequent preparation. That which passes over betwten 130' and IdQ^^
is easily separated by repeated rectidc&tiou into acetic acid atid a thick
liquid which boils between 1 85"" and 187^ and either solidilieH inimedmtely
into a mass of while needle-shaped crystals, or yields after some time,
large, isolated, tran»parent, colourless, rhombic tables, while the greater
portion remains liqald, but if shaken up or stirred with a glass rod,
aobdillea suddenly and with considemble rise of temperature, the crystaU
previously fonued becon»ing opaque and white like porcelain. The
crystalline mass, which nick«s between 45"' and 47 , consists of nearly puio
monocldoraoetic acid, mixed however with a certain quantity of liquid^
which may be removed by dccantatien and rapid pressure, and used,
together with the portion of tbe original liquid which distilled below 130^
in a subsequent preparation. The expressed crystals are placed on
bibulous paper and completely dried in vacuo over oil of vitriol and a
few lumps of hydrate of potash, and then redistilled, the first and la^t
j portions of tbe distillate being rejected. As they are very deliquescen
^^tbey should be kept aa much aa possible from tbe air. (Holfmann.)

^ ■

638 **■' -^ ADDITIONS TO VOL. IX. ^^^^^^^^

In the first dUlillation, a^d in the subfleqaent rectifications, there b obtaltieii d
small quantity of a liquid which boib above 19Q'» and appears to contain an acetkadil]
with mote thnit 1 At. hydrogen rrplacfd by chlorine. It yielded ia diScrent exp«rt-«J
ments, from 48 to SO per cent, of chlorine, which doea not agree with the forniulu
either of bichloracetic (reqairing 55*04 ) or of terchlorncetic ftcid (requiriQf S5'l^ p. owl
of chlorine) » In one esperlment^ thii liqnid, on being »atnrat«d wttb baryu, yidded,!
be^idea monochlora estate of baryta, a small quantity of small opaqac warty crystali, J
the composition of which aeemed to show Ihut they contained a higher chlorinated acid f I
bu£ in no instance ^ even when the purest cry$talliaed acetic acid wag. need and the ab^l
florptioti took plitoe in the brightesit stinshine, was any definite bichloracetic orl
terchloracetic obtained^ the chief product being invariably monochtoracetic add,]
Neither was any ostalic ar:id formed, as stated bf DnmKi (ixt 209). f Hoffmann.) |

2. Wonochloracetic acid is also obtaint-d in a state of purity bjr llial
actioD of water on luonocbloriiiated clUorida af acetyl. On distil liag I
the licjuid, the tbormoineter rl^ee from 100" to 180"» and the H*iiii3 J
whicli paases over at that temperature solidiSee iu a cry stall ioe niaas dd J
cooHog. (WurtK, p. 536). I

Properties. Crystallises from fueioE m rboniUic tablea, tavipg' acute 1
angles of 77^ or 78 ; from solution in acetic acid — •€. ff., from tbe Hqatdi
obtained in the £rst distillation between 180° and 1S6^ and betweeo
166^ and lOO"*, — in cryetala having a prismatic cbaraoter^ and very niueb j
reaembling tboac of tercbloracetic acid. Melting point 62\ When thtl
melted add was left tt» coinl, the thermometer at the comiuenc«ttient of rry atallitatiea I
generally marked 60*, then rose rapidly to S3* or 64% and ultimately sank to G2% iCl
which point it remained constant. It contracts fltroDgly in soltdtfjin^, aljl
generally gives off numerous air- bubbles. The specific gravity of th* I
melted acid at 73^ is 1 366 as compared with water at l& , and r3947
compared with water at 73°. Boiling point from 185"^ to 187*8^ It
distils undecomposed, and when pure solidifies in the neck of the retort;
but if mixed witb acetic acid, remains liquid below itA ordioaij
point of solidification, Wben kept for some time at a temperatuivi
Its melting pointj it sublimes in long spieular cryiitals. It ia iT^
inodoroiia at ordinary tempera tureSj but ita vapour has a pungent \
eating odour. It has a strong acid taste, attacks the cuticle, iind
blisters if kept on it for some time.

Boffmano.

iC ....„»» 24 0 ..., 2S'40 ,...,. 25 27

3 H ., 3*0 ..„ 3*17 ...... 3-29

CI .....^, 3&-5 ... 37 57 ..«»» 37-64 to 396

4Q 33-0 ■„■ 33-96

C*iFClO* Uh .... 100^)0

Dec&rnpo^Uums. 1. Tbe a'^id is decomposed hy pen taehlo ride
pboj^pborus, with formation of chlorophospboric acid and monochlortnated]
ehloride of acetyl; but the two chlorides <^nnot be separated by dittillatiQi^l
as tbey both boil at about 110''* When the product wa^s repcalc^lj
distilled with small portions of acid monocbloracetate of potafih, tbv
reeidues of the l&cit distillations yielded at high tempcmtures a Imrgv
proportion of nmnoeblonicetic acid, the last port ions of which boiletl
bi:;h as toa"", and had a more penetrating odour, prob«.bif mowing I
the presence of a small quantity of the anhydrous add. — %^ Tbe l
heated with potiisb-ley, ammonia, baryta- water, or litue*wmt6r» boi
diately yields a chloride of tbe a I kali- metal without muj OAriHmifi^ fiitmi%1
oxalic, or acetic acid. In this respect, it diSen remarkftUy fMn
ftoetic and from terchlorace tic acid (viii, 2$5i is, ill); lifter hanilumim

3RACBTrC Acm.

639

I

I

eome time the wbole of the monochbracetiite ia decomposed. A similar
but les9 coJuplete decomposition takes place when a neutml solution of a
monocbloracetate^ or even the free add, is boiled for a cotisideralle time.
The crystallised potash -salt also is decomposed id like luanner at 110^,
becoming dull and yellowish, and acquiring an acid reaction; cold water
then extracts from it chloride of potassium, and leiives a white powder,
which has an acid reaction, dissolves in hot water, and separates on
cooling. Poaaibly the reaction may coneist in thefomiatlon of a metallic
chloride and the assumption of the elements of ^ater by the organic
reaidue, the result of which will be the forraation of a compound having
the compofciition of glycolic acid:

Cm^CIMO^ + 2HO = C^H^O* + MCI. J

3. Monocbloracctlc acid is reduced hy potassium or aodium-amalgam, to
I acetic acid, in the same manner ae teruhlo race tic acid (ix, 2U); the
' decomposition is however incomplete^ and is attended with eYolution of

hydrogen. (Hoffmann.)

Combinatimis, The acid deliqtjesces in the air, and dissolves very
I easily in wata\ producing considerahle fall of temperature.

The MoiwMiractiateA^ C*Cl*MOS are obtained hy digesting tbecstidee
I €r carbonates in the aqueous acid ; tbey are £or the most part easily
I soluble and crystallisahle,

Mouockloi-aMtiU of Ammonta decomposes by evaporation like the

potash'Sak. It is more soluble than that salt, and solidifies only fronk a

' perfectly viscid 6olution> in tUe form of a crystalline cake, which quickly

deJiqiicBces on exposure to the air. The &dt was not obtaiDcd free from mI-

MonochlotYtC€tat€ of Poiash.—a. Neutral, C*C1H*K0* + 3Aq.—
Obtained by saturating the acid with carbonate of potash and evaporating
to a syrup in vacuo over oil of vitrioL It then separates in thin colour-
less laroiuie, which may be obtained pur© by draining on bibulous paper.
It is not deliquescent, and does not give up its water of crystallisation
at lOO"", but la decomposed at a higher temperature, yielding chloride of
potassium (p. 538), also when its solution is evaporated at a gentle heat
It is very soluble in water. After drying in vacuo^ it yielded 24 63 p. o»
potassium (hy calculation, 24 55).

h. Acid. C*CIH'K0*,C*C1H>0*. —When a solution of the neutral
ealt is mixed -with as much acid as it already contains, the whole solidifies
to a thick pulp of small white pearly crystals, which may be purified by
draining on bibulous pnper or by drying over oil of vitriol. Sparingly
soluble in water. Contains 1723 p. c. potassium (by calculation, 17*25).

Monoehi*tra<^eta(e of B<^ryi<i, C*ClH'BaO* + 2Aq. — Maybe obtained,
eveti with very small quantities of material, in distinct prismatic crystals,
apparently belonging to the rhombic system^ and containing 39*J>J> p. o-
barium (by calcnliition 40'0(j). Decomposes hut little during evapora-
tion, and separates out almost completely on cooling from a hot saturated
solution. (Hoffmann.)

M&HOchhraCi'iaU of Silver, — ^A bet solution of the acid saturated
with exide of silver, yields the salt on cooling in splendid rhouiboidaL
iridescent la mi me* (Wurtz*) — Anhydrous. Dissolves sparingly in e<

^lO ADDITIONS TO TOL. IX.

m£Ij ia Imc vmtcr, aad k easiljr obtained by oooling in sbiO
■■ft iBiM«i vkkk Uai^ea oa expoMire to light and yield diloride of
■£v«r. Bccvccn 110' aad liO' h decompooea with a kind of explosos,
fiiijag tW aae odaar mm the acid whai it eTaporates, mod Ifiariif
«/ flilTvr Mixed with a Terj small qoantitj of metallic olTer.

AT -fi-a

— 11-91

— 099
__ 17 61
_ 53-59

- 15 90

Wwtz.

11-91

1-07

17-48

-. 53-41 ..

- 16-13

Hofinan.

* H *-#

a 35-5

Ag _ 109-0

4 0 3*9

^ 52-03

oae=A£0»_ joi-o

^ 100-00

100-00

MomochloTacetate of EthyL
CH^lffO* = C*HH),OClHH)*.

K. WnuL jr. A mm. Ckim. Phyt. 49, 97.

Obtained bj the action of mleohol on monochlorinated chloride of
aeecrl:

CHHy + CKHn^KV » CX1H70« + HCl.

The action, wbidi is rerr violent, most be moderated by cooliof tbe
T«s$^ exienuillT. mod, x< soon as it is finished, the product may be it'^ea
wlih wa:er, dehydnited by chloride of calcium and rectified.

Coloariess liquid, having an ethereal odour and burning taste, heavier
than waier and in.<o)nble in that liquid Boils at 143*5^ when the
bai»meier stands at 758' mm. Vapour-density 4-46.

sc

: H

Cl

4 O

.. 480

70

.. 35-5

.. 320

.... 3919 ...
.... 5 72 ...
. .. 28-95 ...
... 26-14 ..

waiin.

38-87

5-87

2903

26-20

OH'CIO* ..
C>v&pottr

.. 122-5

.... 100-00 ...

Vol.
.. 8

lOo-QO

Density .
... 3*3280

H-cas

.. 7

.. 1

... 0*4851

Cl-eas

... 24543

%.i 5»a

Q.ras

.. 2

.. 2*2186

^' 5"*'

Vapour of C^H'CIO*..

.. 2

... 8*4860

I

... 42430

The ether bums with a bright flame, green at the ed^s. It is dertn-
»M>sed bv piitash, into alcohol and monochloracetic acid, which then suiTf^
her ' decomposition, yielding chloride of potassium and aceute y.'i
ih.
t is mso\u\Ae \vi ^aXftt,

ACETYLAMINE. 54 I

Monochloracetamide.
C*H*C1N0» = C*ClAdH»,0» = N.H«,C«C1H»0».

E. WiLLM. iT. Ann. Chim. Phy$, 49, 99.

Obtained : 1. By the action of ammonia on monochloracetate of
ethyl :

C8H7CnO* + NH» « C<H*ClNO« + C<H«0«.

2. By bringing perfectly dry ammoniacal gas in contact with monochlo-
rinated chloride of acetyl:

C^H2C1202 + 2NH« «« C*H*ClNO« -i- NH*a.

The product is a white amorphous mass, from which absolate alcohol
extracts the monochloracetamide and leaves sal-ammoniac. On evaporat-
ing the alcoholic solution, the amide is obtained in large shining laminae.
It dissolves in 10 parts of water at 24^, and in \0\ pts. of alcohol at the
same temperature, but is very sparingly soluble m ether. From the
aqueous solution it crystallises by evaporation in small mammellated
masses.

4 C

240 ..
40 ..
35-5 ..
140 ..
16-0 ..

.. 25-67 ....
.. 4-30 ....
.. 37-95 ...
.. 14-88
.. 17-20

Wniro.
.... 25-75

4 H

4-70

CI

N

2 O

38-29

C^H*ClNO»...

. 98-5 .

... 10000

It is decomposed by potash, with evolution of ammonia, and forma-
tion of chloride of potassium and acetate of potash.

Page 247.

Acetosylamine.
C*H»N = C*H>,H»N.

J. Natanson. Awn. PJuxivn. 98, 291.

Acctylamine,

Produced by the distillation of hydrated oxide of acetosylium (or ace-
tjlium, X, 588) :

C*H»

1nO,HO = CnP.H'N + 2H0.

Preparation. The yellow liquid obtained by the action of amtnooia
on chloride of ethylene is evaporated till the sal-ammoniac crystalliff^

sirwi

0»<»^: il« «?j iwR- ttu9 MC BioAf a2 2I$=. Tif i liiiiu 1'5S1

4C M

— »^1 —

-> iiiC

5H - 5

-- ll^O «-

— 11-31

S U

-. tm ..

„ »-»

C«H'X_ 43 — l»MPi l»inl« Tj^Mr^CH^N ^ S «•!!

1 l-dft

liBvlbe^l At, H M iiilirri W MBfcwri C*H»,

Aeeto^iamise ii not deeospoeed W wjdiwm, WWa kealfd will
iodide of etliTU it jidds appanatlT tke kjdriodale of etkrlacelanrluuM.
(OH')(CyH*',HS. The pnidnct dcoMipoeed bj poCaslT jidds i biovi
oil poftsew'mg basic properties.

C<^mbin/xiwnt. Ac^to^laniice mixes in all proportions with waifr.

It combines with acid4, forming salts whicb exhibit all the cbaractcn
of the saltA of acetosjliam. It absorbs water mod cmrbonic aeid wbei
exposed to the air. A glass rod moistened with it, fames when beli
OTer hydr>chione acid. The salts of acetosjlamine when decomposed bj
potash, do not give off the characteristic odonr of the base, because it is
then converted into the inodorous oxide of acetosjlinm; the aqaeons »oU-
tion however, retains the odonr for a long time. Heated with chloride
of lime, or with chroniate of potash and snlphuric acid, thej gite off i
considerable quantity of aldehyde.

Acetosylamine forms precipitates with most metallic solutions.

The Phtinum-saU, C*H*NCl,PtCi', is an orange-yellow amorpb^w
powder sparingly soluble in cold, easily in Lot water. It gave bj
analysis 39 29. 3934 and 39*86 p. c. platinam, (compare x, 540).

Acetosylamine mixes in all proportions with alcohol, bat is insoIaUe
in ether.

r reparation of Acetamide and AceUmitriU, — Acetamide is reaJilj

obtained by heating a mixture of equal volumes of acetate of ethyl ud

aqueous ammonia to a temperature between 120° and' li^'

<wl vessel for six hours. On subsequently distilling the prodort,

ich passes over above 260° is pure acetaraidc. (Bnckton t

^ Chm. Soc. Qr. J. 9, 242).

ACETAMrBE.

54.^

When acatamide is mixed with about an etjual volume of anKydrmm
pboapliorie acid, a violent action takes pUcej and acetonitrile pasf^es over,
contaminated Low ever witlj hydrocyanic and acetic acids. Thi9 dietillate
ia wiisLed with potash, and the ac^tonitril© is decanted and rectified over
anhydrous pLoaphoric acid. Thus prepared it has an ethereal odour,
somewhat like that of cyanogen, and a rather pungent, aronmtic taste;
it boils at TT"' nr 7B\ and burns with a bright flame reddi«h at the
edgei. ffi nekton &^ Hofnionnj

Preparation of Acetamide ffom Acetate of Ammonin^ — It la generally

apposed that the aninionia-salts of monobasic acids do not yield amides

tj deliydnitioo. Kiindig has however shown (Arm. Pharm. 105, 277)

Itbat when acetate of ammonia is distiHed, a portion of it is convertetl

into acctaniide. At the beginning of the tliiti Nation, a larije quantity

of ammonia Is ^^iven off; afterwards at 100% at which point tlie ihermo-

tieter remains constant for a long time, an acid distillate, prolmbly con-
Iviijting of acid acetate of ammonia; above IGQ^ a distillate eontaininj^

eetaniidei which at a temperature a little higher^ crystallises in
Ihe condensing tube; and above IDO^ nearly pure acetamide. The
quantity of that substance is not increases! by adilition of alcohol.
The largest product is obtained by passing dry amnioniacai gns for some
hitarA throagh glacial aeetic acid, which is at fir^t kept cool in an appa*

atus provided with a condensing tube directed upwards^ but afterwards
Ilea ted to commenciiag ebullition. By subsequent distillation, a quantity
of ace t amide was obtained equal to ^ that of the glucial acetic acid

In the distillations above described, the thermometer was never
""dbserved to rise above 218"*; neither, accorrling to Kiindig does it ever
Tise above that point, in the prepamtion of acctamide by the action of
ammonia on acetic ether^ whereas Buck ton A flofmanu state that the
portion which distils above 260** is to be regjirded as pure ncetainide.
The boiling point of pure acetandde way ftiuud by Kiindig to be 222"',
attention being paid to the corrections pointed out by Kopp {Ann*
Fharm. 94, 250)-

Compounds of Aeetamide.

E. Ami. Pharm. 100, 32h

Ihjdrod^hrfttt, — (Cni*NOy,HCl — Obtained : 1 . By the action of
ehlorophosjihoric acid on acetaniide. When chlorophosphoric acid is
added to acetamide fused at a gentle heat, the two liquids mix, pre*
ducing rise of temperature, and soon solidify into a compact mass^
without evolution of hydrochloric add or any other gas. This mass is
insoluble in anhydrous ether, but nbeolute nlcohol dissolves itj especial I3'
with the aid of heat; and the solution on cooling, or better on arhlition
of ether, deposits colourless crystalline needles of hydruchloratc of
acetamide. Tlae cryatDlLine mnas at fint ubtained ajip«Ari to be a c^nspouat! of
icetamide n^Lth chloropbnBptiorir: acid, whk'b, on addition of alcc^boL \% resolved ittto
phosphoric etber atid bydrochlotic ucid, th*t lutter imiting wUb the afetamlde :

[2C*H*N0» + PCTO* + 3(^'^V) - (C*H*NO*)5HCl + PfC<U*)so« + 2aaX

544

ABBtXrONS TO VOL. IX»

2. By the actif>n of hvUrochlorit! airul gas on a snlulfon of acet,imhlo in
ether-alcohol, the liquid heino- cooled from without arid the gas directedij
on its surface. The g^rettler part of ihe liquid then aididifios in a crT$«|
talline masa, which ia washed with aohjdrotis etlier aiid dis^lvod iq
warm alcohol ; the eohufon on cooling, or more quickly on additiofl
of ether, yields the hydrochlomte in the crystalline form. TUi* nnxic i
prepare tjon n preferable to the furm^r*

Pr^ertits. Long ?peaT-sh5ipe<l crystals, which
water and alcohol, hut »re io^oluhle in ether. '^'
taste and an acid reaction.

dissolve readily
They have a very bo

Streelci^r.

B C

12 H .»* .. .^ ,

4H^a ,.
no .

35-5 .
520 ,

... 3M
.. 7 1
.. 18-1 ....
.., 230 ....
., 20-7

2N ^. ....„^.

.,„ 1«*2

CI ,..., „,,

.... 22-9

4 0 „„.™„ ,...

(C*H>NO*/HCL„ ..

l&4a .

.„ looa

The alcoholic eolation of th© crystals does not form any precipil
with hichloride of j>laiinum, hut after ataoding- for s^mie time in ll
cold, and qinrkly when heated, it deposits chloroplatioate of ammoi '
giving off at the same time an odour of a^^etic ether.

Perfectly dry hydroohlomte of acetamide heated in a aeale^ fcoh
melts at first without decomposition, but hetween 180'" and 200%
E^nffers complete decomposittrm, bein«f converteil into a pasty mixture
solid and liquid matter, which, when distilled in the oil-lwith, ySelde
first a strongly acid liquid (a), and afterwards a liquid which golidififl
in colourless crystals {h] in liie receiver, while a slijgjhtly brown residu
(c) remained in the retort, Tho ganie products are obtitined wbe
Bcetamide Is heated in a stream of dry hydrochloric ^as. — a. The Gf
distillate when rectified begins to boil at (tO\ at which temperatufi
chfon <h f / ficffffl a ri d a ppa re ii 1 1 y al so aceton i I r i 1 e p ass o v e r , t h e bo i 1 iii^
|K)int afterwards rising to 120'', and conceutmted nrefk fjeid pa*«in
over. — 6. The crystalline di&tillate dissolves partly in ether, th^ undii
solved portion consisting of unaltered hydrochlorate of acclamidc. aod tha"
ethereal solutifin yielding on evaporation over snlphnrjc acid, tTysluUine
gmniiles of a compound of acetamide and biacetanrid^s, C**H^*XH>* =
C*H*XO* + CH'NO*. — The non-volatile residue in the retort is par-
tially soluble in alcohol, the undissolved portion consiatini; of sal-
ammoniac, and the alcoholic solution depositing by RfMintancons evapor*-
tion crystals of hifdrockhraU of acfdmmhie C*H*N^HCL

The dcrom position of bydrochlorate of acetnmr-le by b«lt^ 6r of aeetft-
miilf? under the in Alienee ot heat and dry hydrochloric acid, may l>e repre-
sented by the following equations :

2C^H*NO» + HCl

biAcetiimitle.

2r^H*Nn* + HCl = r*H NMKI ^ e*M*o*

hydro* lilorwte »cttic m^i^,

of iicedi«TYiJne,

ACETAMIDfi. 545

C<H»N03 + 2HC1 =- C^HWCl + NH^Cl.

chloride of
acetyl.

OH«N0« = C<H8N + 2H0.
acetonitrile.

I^itraie of Acetamide. — C*H»NO«,HNO«. —When acetamide is dis-
solyed in cold strong nitric acid, and the solution is left exposed to the
air in shallow vessels, colourless crystals separate, which have a very
sour taste and reaction, even after being dried between bibulous paper.
They melt at a moderate heat, and detonate when more strongly heated
in a test-tube, leaving scarcely any residue. They gave by analysis
45*2 p. c. nitric acid, the formula requiring 44*2. The excess arose
from adhering nitric acid.

Acetamidate of Mercury, C*H*HgNO'. — Yellow mercuric oxide
added to a solution of acetamide disappears very quickly at first; but
for complete saturation, it is necessary, towards the end of the process,
to heat the liquid with excess of mercuric oxide. The filtered solution
evaporated in vacuo leaves colourless crystalline crusts, easily soluble in
water, sparingly in alcohol. The crystals, after drying in the air, did
not lose so much as 1 p. c. at 100°. They gave by analysis 62*8 p. c.
mercury (calculation 63'3).

The aaueous solution of the crystals does not form any precipitate
with potash at ordinary temperatures, but deposits white flakes on boil-
ing. Ammonia, on the other hand, immediately produces a yellowish
turbidity, which increases considerably on boiling. Metallic zinc im-
mersed in the aqueous solution becomes covered with a grey film of
mercnry, white flakes of oxide of zinc floating in the liquid. The liquid
after a while contains neither mercury nor zinc in solution, but when
evaporated in vacuo leaves pure acetamide. Cadmium acts in a similar
manner to zinc Copper does not precipitate the mercury till the solution
10 acidulated.

Acetamid<Ue ef Silver, — Recently precipitated oxide of silver dis-
solves readily in aqueous acetamide, and the solution when evaporated
leaves crystalline scales of acetamidate of silver. (Strecker.)

Biacetamide.
C^H'NO* = (C*H»0«)',HN.

STRECKfiit. Am. Pkarm. 103, 327.

The ethereal solution of the compound of acetamide and biaceia-
mide (p. 544) deposits, when hydrochloric acid gas is passed through
it, spicular crystals of hydrochlorate of acetamide, and the liquid
filtei^ therefrom, yields by evaporation over sulphuric acid, needle-
shaped crystals of biacetamide, easily soluble in water, alcohol and
ether.

VOL. XII. ^ '^

543

ADDITIONS TO VOL. IX.

8 C .,

SIrecker. H
48 .... 47*5 ,.„,... 477 ^|

7 n

7 _ 0-9 6't ^1

N „.

14 .... 139 ^^1

4 0

%\'j H

"*'"

yslale boiled

witli

101 ... 1 00-0 H
acids are resolycd into acetic acid aai

ammonia, but not so readily as acetaiulde,

Tbe alcoholic solution is not decomposed by blcUlorido of pi at In ua

nt ordinary temperature 3, but after boiling for some timB it depositi
cliloroplatinato of ammonium*

BiacHamide with Acdamidt, C*ffNOSC*H*NO*, — Depoaiied from
tbe ethereal solution (p. 544), by evaporation over sulphuno acid, in ban"
cryBtalline grainsj which are at first contaminated with acetic acid, bu
lose their acid reaction by standing over aulphuric acid or lime m vacu<Kl
They fuse readily and volatiliae gradually in vacuo at ordinary tem|
turea* They dissolve readiJy in water, alcohol and ether.

12 C

12 Fi,.... .„,

.-.. 72 .

.... li .

., 45*0 .
.. 7-5 ..
.. 17*S „

.. 30-0 ..

Strecker.

45*0

...... 7'&

4g IN mm**nm**iwwm*

6 0 _.......

«n 2B .
... 4S .

17-3

2fl*B

CiSH^KO'........

... 100 ,

.. 100-0 ..

«.... 100 a

Acadiamiiie. C*H*K*.

Streckef. Ann, Fharm. 103, 32a.

Fofmniion (p, 544), The prismatic crystals of hydro^htfiratD
acediamine which separate from the alcoholic solution of the residue le
on dbtilUng the product of the decomposition of hydrocbbmte
aeetamide^ are freed from adhering sa1*animoniae by solution in
mixture of alcohol and ether; and on evapomting this solution in vacua,
tbe puro hydrochlorate of acediamine separates in cryetak of tbe originit
form.

SttlphatCf C*HW,HSO*, — Obtained by mixing the aqueous golntJon i
of tbe hydrochlorate with sulphate of silver, aa long as any precipilal^H
of chloride of silver is produced, cont5entmting the EUrate nvtit ^ki^H
water-balb, and recrystallisini^ from boiling alcoboL Tbe salt t« tliereby
obtained in colourless nacreous laminae, easily soluble in water^ spanaglr
in alcohol, even at the boiling heat, and neutral to vcgeUble coIouib. ft
gave by analysis 37 '3 p. c- sulphuric acid (by oaleuUtioi]| 37'2).

Vhlorophthudt. — The aqucoua solution of the hvdrocblomte ii
precipitated by chloride of platinum j but the Uqaia when 6Ta|

yiclda ratlier largo bafd yellowish rod prisms of the platintim-eiUt,
aro easily freed from adllcmg cUloroplatinatc of ammonium by soki

ACEDIAMINE*

647

in aJcobol* The crystals, afteif being dried in the air, do not give off any
"00°. Tbey dissolTe readily in

. mixture of alcoliol and ether.

thin^ at 100 . Th^y dissolve readily in water, less in alcohuJ, aud uot
at all in a : ■

4 C
7H

Pfe
3 CI

24 0

280
106^5

9-1

10*6
37*4
40-2

Strecker*

.. 2-9
.. 10-5
., 371S

C^B^NSHCUPtCR... 264-5 ... lOO-O

Acediamine may be regarded aa ammonia in whicU 1 At* H. is replaced

by tbe monatomio radical C*H^N, its rational formubj beinff then
C*H^N|

H^N; or as a doable molecule of ammonia N*H*, having 3 At H

replaced by the triatomie radical C^H^^ its formula being UaJNl It

bears the same relation to acetamide tliat ethyLamine bears to alcobo!:

Cm«0* + NR^' = cm'N + 2 HO.
And I

C^H^NO^ + NH« = C*HWf + 2HO.

It is very unstable, and cannot be obtained in tlie free state. When
the sulphate or hjdrochlorato is heated with a stronger base, such as
potash or baryt% ammonia is given off and acetic acid remains in combi-
nation with the base :

Z^WW + 4HO = C*H*0 + 2NH5,

The salts likewise undergo a similar decomposition when boiled with
acids in excess. Thus the residue obtained by evaporating the hydro-
cbl orate with excess of hydrochloric acid, consists chiefly of sal-ammoniac,
only a small quantity of the original salt being extracted by alcohol*

Page Sa5.

Temitracetonitrile.

L. ScRiscnKOFP. ^, Ann, CMm. Ph^. 40, 323; abstr* Ompt rend.
45, 277; Ann. Fharm. 101, 215,

Produced by the action of a mixture of nitric ami sulphuric acids en
fulminurio acid (x, 550) ;

L

C*I>F>ii>0« + -2K0*I1 » C*N'0» + SCO* ■*■ >U0 + NH\

2n 2

4C sft n-«

ITS

a&m&L'ifccL Whh wun and
C=X»XH* (p. 4W).-

A:t HmniiiQei^ niLtiQai. «£ secBBCn0e«;.Mitnle wxed with nitrite d
sl*>:'£!i ims & vbIii<«- fc«ci9c2Be^ w^jdk ^asoires readilj in but water,

4 C U — 3-§f 4-&3

l4 5 14 — 5-3S 2-i2

:•! 3t !«• — 2S-25 24-^5

i A- „ ♦!< _ 3i-?83 35-39

if :• _ i-fc? — 34-53 _ , 32-61

e>"*5^-A-^3* ,. €.:» -. 10O^M> 100 00

BimLraiwin^HYi,
OH*NH)* = OX\XH*)X.

SS2SCSXI7F 1 KoscK. Amm, Pkarau 104, 250.

run i—iijC—Agcoaar:^ a vkick 2 At. H are replaced bj N0« aa^ -^

P:r>r2>aii tj XAd icdoa of calphiiretted hydrogen on temitnoetc-

C»-0:^- ^ SHS -.C<N(MA'N*H^N ^. 4HO h 8S.

Crjnillls^w :- boictifal colooriess shining needles, very soloble ia
w^ifr. If<5« 5«:*.i:'e in a:«vhoL and nearly insoluble iu ether. ^^'^
saii«ilT keii«o« :t t&kes fire andhama away. At 100"* it rolatilieei J
|*rv>rr-: lie ^:iAz:*n-. emiitingan extremely pangent odour.

I; :? p-:r:\x':Ij ceainl to test-paper^ but nevertheless exhibits ^
0{<nl<» t?C t:. va^'ws Viyarof^ Wng partially replmceable by mcUli

BINITJIAMMONYL*

549

ft dom not giro off ammonia even T^hen boyod with moiloraiely strong
poUsslirlej (1 pi. hydrate of potash to 2 pts. water), hut the liqyjd
solid ifiea on cooling into a maas, which is probably the potash-fiaJt

Hf _ Siiver-$alt, C*X'(KH^Ag)N. — The aqueons Boktion of hinitramraonyl
boiled with oxide of silverj yields, when liltered and cooled, a beautifnlly
crystaJlieed silver-salt, which explodes very readily and dissolves sparingly
Id cold, but abundantly in hot water.

4C _ 24

3 R ..„^ ., 3

4 N , _ 56

Ag ..„ .., 108

8 0 _.„ 64

C^HWAgO*. 255

9*4X - 9-40

117 MS

21-96 ....... 21*35

42-35 41-91

25*11 2G'I6

100-00 ». 100-00

IOC

5N

8 0

00

1

70

64

195

30-77
0-51

35-90
32-fl2

100-00

SchkchkofT & Rowing.
. 29-73 .... 28-96
. 0-51 .... 0-67
.... 360

Action of strong Sulphuric acid on .Bmi^rammo jtyL—Binitrammonyl

slowly deooinposeil by sulphuric acid at ordinary teriiperaturca. On

heating the mixture over tho water-bath, tho action is accelerated,

aiphate of ammonia is formed, and an oily layer collects on the surface;

nd this, when separated from the lower liquid and cooled by a mixture
tf ice and gait, crystal Hses in large fine prism e, which soon melt when
leraoFed from the freezing mixture* They explode violently when
beated, are iDBoluhle In watcfj and dissolve very sparingly in aqueous
ammonia, forming a dark yellow Bolutiou, which leaves a brown resinous
iuhstunco when evaporated. The composition of the crystals is as
follows:

^^ The cryeUla were diflicuU to free from tUe motUcr. liquor, tUe tolution bc<;ommg^

I The ratiotULl fomiulii of the <^anipoynd h perliaps Cy^C^(NO^)=H.

The mlphuric acid retamed in solution » b^aidea aulpUatc of oinOTonia, a body
I apparently idetttlf«t witli Ihe preceding ; it wna separated from the at^id liquid bj
afiutioa mlth ether, but wai not obtained in quantity luifitileDt for analjiif.

Action of Potash on Bmitmmmmiyl . — Whew binitrammonyl is boiled
with a very strong, nearly syrupy solution o{ potash, a large qnantity of
ammonia u given off,and a salt gradually sepai a tei in prismatic crystals,
which are but sparingly soluble in the caustic potivsh-ley. An additional
qnantity of this salt separates when the liquid is left to cool after the
evolntion of ammonia has ceased. This salt dissolves very sparingly in
cold water or alcohol, but very abundantly in those liquids at the boiling
heat, and is deposited from tho eolutiont oa cooling, in sbiniog liglS
yellow laminie, somewhat like those of picric acid- Tho salt is perfectly

L

SC^MK -h l^OFK + 5H0,

Tlie pofftaow «( tk

oil, whtclt^ afler itenfjf k

oj Oc MiMM of bromuie on oqoeoat

p<HkiL PokctlriM]
ll ■■Ill.AJMIfcWtt

, , , fc»Tllig «i mkv Sk

Ii m mfmrn^f irabtO^ i$fii«4
iw vkkh otteeka tko i^w 117

form M oooll&f. BifiMii

>• ftt UlO «MU llM^ iMff

» mifc bmm Tvpooii wket

liM wiik poUyA MHi & fi

4^

FULMimC ACID.

551

4G .

2K ,

4 0 .

84

2B

160

32

9d4

11^47
65*58
13*11

Keku]£,
10*20 .,.. 9-73

63*01

65-90

CHXBr^N ..., 244 .... 100*00
The formula k that of ftibnraatmg Mtircmr m which the 2H^ are repJa^d by 2Er,

BibromonitmcGtonUrile treated with cLlorine or brorain©^ yields an
oily product whicL is doubtless cMoropicrin or hromopicrm* Also when
fulminating mcrcary is treated with excess ef bromine, tire crjstiils
abtainod arc emaller in i[(irintity in proportion to the oily liquid, than
when the fulminating mercury is in excess »

IBiniodamiracetonitrile^ — When iodine is added to fulmiuatlug mer-
CQty suspended m alcohol, and the alcoboJio solution evapomted, colour^
less crystals are formed, which eontam iodine and emeli like ehloropierin;
they have net yet been obtained in the pure state*
K

Page 295.

GoDBtitution of Fulminio Acid.

^Keedle^ Amu Phm*m, 101,200; 105,270.
ScmscnKOFF, Ann, Fhurm. 101, 218.

That the fntminates contain a nitro-componnd (NO*, NO", &o,) h rcn*
dered highly probable, both by their mode of formation, and by their
explosive prqperties (ix, 29G). This view receives strong confirmation j
from the recent experiments of Keknl6 and SehischkofT, which have
shown: 1, That fulminating racrcury, treated with chlorijie, or with |
hypochlorite of lime, yields chloropicnn^ a compound certainly containing
ifO* (xi, 216) ; and with bromine, it yields bibromonitracetonitrile
C'XBr'N, or bromoplcrin C^XBr', accordimij na tho fulminating' mercury
or the bromine is in excess. ^ — 2. Fulminoric or ir?ocyaniiric acitC
C'N*H*0', a compound produced by tho action of alkaline chlorides or
Jodidea on fulminating mercury (x, 556) also yields chloropicrin when
treated vyith bypoclilorite of lime, and tern i trace ton itrile, C^X^N, when
trt^ted mih strong nitric acid. Scbischkoff has also observed that when
the same acid is decomposed by jtinc in presence of a mineral acid, tho
hydrogen eliminated from tho latter is almost wholly absorbed. This
reaction, together with the explosive ehamctcr of the fulminurates, also
points to the exiJ^tence of an oxide of nitrogen in these compounds; and this
being the ca^e, lite mode of formitticn of falminnric acid shows that the
nitrO'Compound must also exist in fuimiuic acid*

Kekule assigns to fnlniinic acid the formula C^(NO^}(C-N)H' or
C'XCyH^ which amounts to supposing (L) That half th<? carbon and
Iialf the nitrogen in fulminic acid are so armngad aa to yield cyano«^^en-
compoirnda under the influence of certain reagents. (2.) That tho remain-
ing half of the nitrogen exists in fnlmiuic acid in the fame form us in
the so-called citro- compounds, (3;) That the remaining half of the carbon

552

ADDITIONS TO VOL IX,

is io disposed aa to jSeld in certain rfaetions, a body belongiDg to tlid
metliyl-series or a product of the decompasitioii tliereof. — Thk Tiew k
ellppo^t^*d by tbe follow iug facta :

Fulminating mercury trcarted witb clilorine gasj yields chloropicrin^
gaseous clilorido of cjanogenj a.nd chloride of mercury^ without any
evolution of carbonic acid, according to tbo equation ;

CTXCjHg^ + GCl ^ aXCP + CyCl + SHgCJ.

When chlonoe ia passed into water in wUicb fnlminating mercoiy h
immersed, tbo gas Is rapidly absorbedj the fulminating mercury dissolves,
and a yellow or £ometSmes bhiieb greca oil is formed in coeaiderable
quantity. The liquid decanted from this oil gave off chloride of cyanogen
wlien beatedj and on further evaporation yielded yiure chloride of mer*
cury. The oil, when purified by washing witb potasb and with water,
and subsequent diattllatiou with water, exhibited the properties of cbloro-
picrin; it was however impure and j^ieldcd by analysts 69 per cent of
chloriDe, whereas the formula C*XC1* requires only* 64'75. The exoeai
IS attributed by Kekul^ to the admixture of a chloride of carbon pro*
dnccd by the action of cblorin© in excess ou the chloride of cyanogen.—
A similar reaction of chlorine qn fulEniiiati[i|r glKer waa obienred by Liebi|t tmt not
tnitmtdy invf^stigatcd (ix^ 306). Fulminating mercury distiUed with cblorido
of lime yields pure clxloropicrinj boiling between 112'' and 116^, and
giviug by analysis 64*93 p. c. chlorine,

Fulminating mercury treated with sulphuretted hydrogen yields
fiulphocyanido of ammonium and carbonic acid :

a(KO*)CyHg' + 4HS ^ 2Hg9 + Cj(NH*jS' 4 2COJ.

The liquid produced by this reaction, after being filtered and freed from
excess of sulpliurettcd hjdrogcn by exposure to the air, is perfectly
neutral J reddens ferric salts, gives oil' ammonia when treated with fixeit
alkalis, and when evaporated yields deltquescent gulpHoi^aEtide of am-
monium. With citrate of silver, it yields sulphocyanide of silver can-
tainiug 65*84 p* c. silver (calculation 65 €6), The formatiott of a sulpho-
cyanide ia this reaction had been previously observed (ix, 302). Gay*
Lussac & Li'ebig, by decomposing 2'2C8 grm, of fulminating silver witfi
sulphuretted hydrogen, obtained a sulphur-acid which yielded VSQ grm.
f>( sulpbate of baryta* Now, if all the carbon in the silver-salt had
psfieed into the form of sulphocyanogen, the quantity of salphato of
baryta obtained should have been 3- 70 grnu; hence tt niay be infertod
that only half the carbon was thus disposed ol^ — ^The formation of c«r»
bonre acid in tbis decomposition had not been previously obsei vml; but
Kekule finds that when sulphuretted hydrogen is passed through boiling
water in which fulminating mercury is suspended, the gas which escapes
contains a considerable quantity of carbonic acid; and wheo ib# emiod
compound ia decomposed b^ sulphide of barium^ a large (taantity of
carbonate of baryta ia precipitated,

SchiscbkolF doubles the formula of fulminic acid and regards il &« n
compound of 2 At. cyanic acid with 1 At. nitracetonitrile ;

In like manner, he regards fulminuric acid C*N*H'0* as C^NHO* NC^IPX,
and supposes it to be derived from fulminic acid by abstrmcitoa of
1 At* cyanic acid (x, 55Q). When the yellow precipitate farmed hy
the action of chloride or iodide of potassum ou fulminating

i

mcrcurj J

ruLMmic ACID.

55S

(x, 542) is treated with lodido of |>oia8smni, animonia is evolved and tbo
filtered liqiiid contains a cy at) ate, or at all events a carbonatej arising frnm
tbe decomposition of Ibc cjanate if the action has been carried too far.

Kekule, on tho otLer hand, maintains tbat fnlminiiric acid ino^t have
a more camples: constitution than fulminie acid, because fulminating
mercury treated with bromine yields bibromonitracetoaitnlc without
evolution of oaHrbonlc acid, whereas the formation of tbe same compound
by tho action of bromine on fulininnrate of potash is attended with
evolution of carbonic acid* He represents tho fonttaiioa of fulminurio
from fulminie acid by the ei^nation :

2ON5H=0^ + 2HO = CWJFO* + 2C0^ + KH'.

According to Schiebkoff's formula of fulminie acid, only | of the
nitrogen le in tlio form of NO*, whereas according to Kekule s formula^
one-half of the nitrogen is in tbat form. Now, as the nitrogen of nitro-
oomponndg is ne%^er completely converted into ammonia by burning wiih
Boda-linie, it follows that if Kekule's view be correct, fulminating mer-
cury burnt with soda-lime should yield only half its nitrogen, that is to
Fay 4*9 p^r cent, in tho form of ammonia, whereas, according to Schisb-
koff's formula, J of the nitrogen, or 7 '4 per cent,, should bo thus given ofT,
Now Kekule obtained in two experiments 6-29 and 6*21 p, c. nitrogen,
a result which Is not easily explained on SchiachkoS"9 view, tnasmuch as
the nitrogen oven of nitro-compounda is always partly converted into
Rmmonia by combustion with floda-lime, and therefore th© error should
be rather in excess thau in defect.

According to Kckule*s formula, fulminie acid belonga to tlio same
type as marsh -gas, and exhibits a very close analogy with tho bodies in
tne following series :

Mftmh^aa. O* H H H U,

CUloride of Mcthjl ».., C= H H H CL

Chloroform „, „„_„.. » C? H €l CI CI.

Kiu-oform... CHX X X,

CbloTopicrin.,,..... „» C^ X CI CI CI

MiHgnoc's Oil (tii, 360) _ C^XX CI CL

AcfUjuitrilo C3UH H Cj - CH^N/

TerchlormiNjtooitrile CHnCl Cl Cy ^ CTPIf.

Ternitrncctomtrilis CX X X Vj ^ C*X*N.

IJibromonilmoetoiiilrilo C^X Br Br Cy = C*X Br^N.

Fulmiriitinjc Mercury C^X Hg Hg Cy ^ C^XHr'N.

Fulminie idd (%/i.) _ C^ X 11 H Cy = C^XIl^PP.

According to these formulrc, tho compounds to isvhich fulminie acid i^
most intimately related are chloropicrin and acetonitrite; its formnla is in
Jaci the same as that of niononitmcetonitrile*

TIjo formatioE of fnlminio acid by tbo action of nitric acid upon
alcohol may be explained it& follows. On the one hand, cyanic acid U
formed ;

C^H'O^ + 2N0* - 2C^HO» + IHOi

the other, nitro-aeetic acid; and these two compounds by their mutual
action produce fulminie actd ;

C^U^XO* + C*NM05 « C^E^N + 2COa + 2H0 ;

', a<JCording to Sebi^hkoff :

cm^Q + ac^Naos = (c^niio^.nc^h^ + aco* + iiio.

m flBb|Dii to

alevhol is soljeeted to tib sailtt*

M*n '» »M^ agBEts; m ^ odcr, Ae

aoiiLwUeattk

li m^ to tibtW

dke ^TongBitiie add

O^. Ik BCXr ^JaBBKttEMg JIMiUlJ BB^

qriiriffir'iu 3t wiue& 2 Ai. CI sre replieed bj

Tlsr ■Drip reeeiies we conobonlMi

CBLuiu|PiuiBy ■ pndiBfv

314.

r c«^!rap^c«HTL

i W, Hirstmsy Cfac 5kL ^ J^ W^ I93L

^S"iKSi -TT^'if^itig s iuaugygii at ift&is •£ Betkjl mixed with its ovi
loJi: i£ fciifT 1 siiiii !T75a.-:ai5 3xss i 5:rmeii sfter 12 hoars, consisiif

£ 1- jr- «Li--.i i£ iitf^^j-''! :i-''Li«f. wiiVii car l^ h^^d from aiLtri:
u..:^ ^.f :^ irLi£i_2:r ▼^^ *ci*;r iJi»i crjr?tAllLiIii^ from alcvboi. Tie

H-^^xrn.

:t : ~ >*

— ^*5 J

- -. 26-92

:i - — *i

— 3 i3 «

— yu

V „ :*

4-} 5

t > -?-*

. i»J~J^

. 4:-5o

: £ >v h: .-... y-^

-. I .'.*-: >

:? «.:li'!'> ii Trx»r jad akcicl. b^t in^c»!al»le in etber. wair^
;: jz. \ht crrizi'-'Jf^ itite froa th* aJ^^hclic sohitioa. Th?
. — - -..: :i ^i*J i^ **^'- ?«^--- **d when xxiixe«l with fotuk :=
: ^ . L .>r:T»r.::?ii-» fait :• :» orri^al «t*ie. The^e ckirmcters rwfoWf
•sf :' ili ..«i-ii:j •: ^-^ i3i=::--i3i-ba?e?, such a* iifJi«!e of tetn-
Ht .izi. T'lT r:-3Lpc^ri is however sosewhat less s^Juble in wat<'
^ - ji: >: riT-K-tei if :: wer^ c:n5:::atied in that manner, an*! m- rf-
IT i-itrj n- omr'ece .if«>arc«?i;k« when boiled with i canfi'f
a1-: - 1^ :u ! •: : - : rf:rLz:e:hvI:;iia icaj be reerjstalli^ed ondiiDST^
1 a f:r rj x.lirj 5^ l-ixi of p::aib.

»B a^ii:::, x: > vt silver to a friction of the hrdrioJate or ioJi'i*'
thTiiLiiiii-c, :.»i:ie of silrer > IvrmeJ. and th« lipoid acqain? »
f BkkxJLSc^ wacuoTi, v^rha^ from separation of a fixed base; but *
t decooiwssiuoii Sbsu»?^^ »aM»\ n^^dft of silrer is fo^n^i;

METHYL-THIALDIKE*

al<l©lijtl© is evolved In considerable quantity; and the liqiiM is fonnd tn
contain ammonia, oxide of tetmmethylium and acetate of silver:

4C"HJ*NSH ^^ 20AgO + &HO-;C«U'=NO + 12Cni^0« -i- SNU^ + ICAgS h 4AgU

oxide of alJeliydc.

tetrapoctUylium*

nt aeetle add ift a further produdt of the oxidation of tlie ddelt^rde.

As tliialdlne ha^ been stated to be converted into leucine C**H'*NO*
by tbe action of oxklo of stiver (ix, 314), it appeared probable that a '
Lomologoua compound, namely, nietbyl4eucine, would be found among j
tbe products of tho deconiposition of methyl tbialdjne by oxide of eilver. ]
No such compound wm however observed. Moreover, Hofmann baa shown I
bv direct experiment that when tbialdine is decorapoaed by oxido of ]
Buverj the tv/ioie of tha nitrogen ia eliminated in the form of ammonia, and
not a trace of leuciae or any other nitrogenous organic compound is pro-
duced. 2^065 grm* of thialJiDc were deaulpburised bj oxide of silver; and tLi9
liquid freed from eilrer hy hydrochloric add, wa& mixed with btchloHde of p]atiatmi|
cMoroplatlEiate of nmmomwin ^aa ihua. obtained, w^lghmg2'792; by calenlatioo, suppoi- i
ing all Ibe nitrogen to be cotiTerted into ammoniji, it fihould hare been 2'S28, In: '
another expenoieQt, 0^17 grnii tbialdine yielded 0-430 gnn. chloroplatinitte of
ammonia I the qnantity required bj calculfitiou beitig C"436 grm* Henoe it appears
that the original statement of Liebig & Wohler (ix, 313) reerpeoting tho

S decomposition of thialdine by oxide (or nitrate) of silver^ is correct.
Iodide of eth^fl acts on tbialdine in the same manner as iodide of
methyl, but tlic crystalline iodide forms more slowly. Tbe formation of
tbe corresponding awj^^compound requires several weekn.

Binitro-ethyUc Acid. c*H«N'0*.

FAAnKiAHD. PhiL Tmui. 1857| 59; -^ni*. Fharm. m^ 342; €hm, Soc,
DmitraHh^Uc add.

Fonaaiion and Preparation. If a small quantity of lincethyl, either
pure or dissolved in ether, be passed up into dry bin oxido of nitrogen
confined over mercury, the biuoxido is very slowly hut completely
absorbed in large quantity, without the productiou of any other gan. I
The solution m^y be accelerated by agitation, but even then it is exceed-
ingly slow. At the expiration of from ono to four dny^j rbomboidal '
crystals begin to be deposited, and iucreaso in number until tba liquid
Bnalty solidiftcs.

1*0 prepare these crystals in larger quantity^ about an ounce of zinc-
ethyl, dissolved in an equal bulk of dry ether, is placed in a flat-
bottomed llask and supplied with binoxide of nitrog^en fnini a gas-holder^
the gas being thoroughly dried by passing through a long scries of bulbs
filled with concentrated sulpbtiric acid, which also serves to absorb any
traces of nitrous gas that nu|,dit be formed by atmospheric oxygen gain-
ing access to the iiitorior of tho appnratus. The gus is conducted into the
flask by a tube which terminates just below tho cork, a provision being
' made iqt its exit by another tube continued to within a short distauco
e surface of tbe liquid^ and terminating outside the cork ia a capil

sm

ABDITIONS TO VOL. IX.

kiy extrenjity, wliicli cau be readily sealed up by tlio blowplpo «j<l
reopened at pleasure. As binoxide of nitrogen prepared fiom copprr
turnings and nitric acid, always contains a considerable perceotage t»f
protoxide, it is neccsi&ary occasicmaJly to allow a stream of the gas U>
flow Ibrough the flask, fto na to prevent tbe absorption being hiodfr^d
or stopped by the aceumulation of protoxide of nitrogen i at oilier tiioii
ilio exit tube U hermetically sealed^ and the gag supplied only as h U
absorbed. TLe absorption is however extremely filotr, requiring serf nl
iTceks to complete itj. even when the operation is con tinned d:iy aot!
night, and a ibrtnightj even when the action is accelerated hy violent
agitation for several hours each day. It may however be greatly tnw-
lerated by introdncing the zine-ethy! into a strong copper eylraikr
furujshed with a condenalng syringe, by which the binoxitie of nltrogfjia
may be compressed to about 20 atmospheres.* By thia condoDsati&Df
mdmi by agitation of the li^juid, the proeeea may do completed withia
a day.

The cryetalUue compound obtained by ttis prooess la a eompoinid cl
binitro-ethjlate of zinc with zinc-ethyl^ its form^tieti being refrmMkisi
by the equation :

2C*IPZn + 2N0» *- C*H^Znl^^Q*,Q*n^Zn.

It is decomposed by water, with evolntion of hydf id© of etbyl sad
formation of basic bioitroethylate of line, which remains dis^olrea in tlio
watcFj forming a milky solution;

CqPZiiN O^.CWZii + HO = C*IISH + aH*ZQNS0^,Zii0,

and on passing carbonic acid through this litjuid, carbonate of xiac ii
precipitated, and a solution is obtained which when crapomted to
dryness yields neutral biuitroctbylnte of sine in the form of a ndial^d
crystalline mats composed of 2C*H*ZnN'0* + Aq.; tliia when hmM
to 100", yields tho anhydrous salt C*H*Zn2!C*0*.

Binitroeth^lk acitL — When dry binitreethylate of xinc U tttaS^i
with concentrated sulphuric acid^ and the vessel containing thoee iagff*
dfcuts is placed in a free^inc^ mixture, binitroethylio acid is libeimlti];
but it is so unstable, that when the temperature rises a few di|^1iti,
it begins to effervejsco violently, and is rapidly decompoficd witl
evolution of gases and white vapours. A dilute solution lafotBtwhal
more stable; it may be prepared either by decomposing % diltite Bolntki
of bini tree thy late of xlne with dilute eulphurie acid, and iken dUtillkf
in vacuo, or by adding to a dilute solution of the baryta-E-.r * riit-
eient sulphuric acid to precipitate the base. Dilute biniti ^mi

thus prepared possesses a pungent odour, somewhat reaombUi^g ikud
the nitro-fatty acids, and an acid taste. It reddens litmus paper 9ti>oiig[lyt
and gradually deeoinpoaee, even at ordinary temperatnres,

I'he hypothcticiil itabfdroas acid C'^H^N'^O^, m«j be nsgvrdcd m* MiMifii^ b
the tviie of tiitrlc oKidc coitUinin^ a doable atooi of nilrogen (NHj^y uii haimt

] AL oiygen replaceJ by ethyl thus i N'{ qj or us niiroui add (NO*) h«TtDf 1 AL
oiygeu rpplAced by ethyl and another hy Bltrk oxide; K(N0*

* For tt figure and ilen^ription of the
eilhtr of the JottruftVi ibo^t Ttk\te4 M)«

apparatnt, §ee the otigiaal

BINITHO-ETHYLIC ACID,

55

57

The salts of binitroethylic acid are all soluLle in water and mIcoIioI,
and most ef thorn cryatalUee with more or less difticu It j. They arc all
violently acted upon by concentrated nitric acid, the binitroethylic acid
being entirely decomposed and a nitrate of the constituent base pro-
duced. Dilute nitric acid acta in the same mannerj but more slowly.
They all fuse at a. temperature a little above 100'- The potash, soda,
lime, and baryta-salts deflagrate explosivelyj like loose gunpowder, at a
temperature considerably below redness.

BmiirodhplaU f>f Soda. — Prepared by precipitating biuitrocLhylate
of lime with carhoDate of soda, and evaporating the filtrate in a water-
batli. The residue being treated with strong alcohol, the bin itroethy late
of soda dbsolTCa, and ia thus separated from the excess of ca,rhonate of
soda. The alcehollc solution evaporated to dryness in a water-batb,
yielded minute scaly crystals, which were anhydrona.

Frankltiid.

4C „.

24 .

,.. 21-43

5 H ,.

6 ..

.. 4'4G

2N

28 ,.

,., 25^00 .„.

... 25 4 G

NtO „„.„._

31 ..

.. 27 -m ..„

.„. 27*G0

3 0 ,.

24 .

,. 21-43

C*H^N*NW...

. 112 ,

... 100-00

Bmitroeth^laU of Bur t/ta. '^^ This salt is produced by adding caustic
baryta in excels to a solution of binltroethylate of jcinc, carbonic acid
beiog passed through the solution until the excess of baryta is preci-
pitated. It is then treated with sulphuretted hydrogen to remoyea trace
of oxide of zinc, which is still held in solution. After heiug heated to
boiting for a few minutes, and then filtered, the solution is concentrated
by evaporation^ and finally dried down to a gummy niass, which does
not crystallise on cooling* This is anhydrous biuitroethylato of baryta.
It is uncrystallisahlOj very deliquescent^ and very soluble in water* Its
iolution U perfectly neutral to test-paper.

Franltland.

4C .„.. 240 .... 15-23 ........ H-65

BH..„......* 5-e »» SI? ,. 32S

2N 280 .... 1777

B* .,..„ <J8'6 .... 43-52 „ 43-82

4 0„ ,. 32-e .... 20-31

C<H*BaN»0* ....... 157-0 .... 100-00

SinUrodhylate of llnte, C*H'*CaN'0* + 3Aq. — This salt is readily
pre|*ared by treating a solution of binitroethylate of zinc with excess
of hydrate of lime, parsing carbonic acid through the solution, and
tbett boiling for a few minutes. The filtered solution deposits, ou
evaporation, beautiful ailky needles of hinitroethylate of lime, which
contain three atoms of water, two of which are expelled at 100" C, An
estimation of Itme in this salt gave 2070 per cent.^ the above formula
requires 20*59 per cent.

When this salt in the state of coarse powder is e^cposed to the gradual
action of strong sulphuric acid, in a vessel externally cooled, a quantity
of gas is evolved, equal in weight to 30'6 per cent* of the salt, that is to
iay, almost exactly half that of the antydroaa acid contained in it

558 ^^^ ADDITIONS TO VOI^ IX,

(59 6 p. c). Tbo gaseous mi^ciuTe ihm evolved had a sp, jpri"* ©^^ l*3€0l
anU contained Iti ]00 pte. 8'PO pts. of ultnc oxide^ 24^24 of olefianl ^
60 65 of nitroua oxidoj and 6 '2 1 of nitrogen. The liquid and mM
products of the dccompogittoQ contained eulphate of lime^ enlpbovuiala of
lim^i and B(il[)hato of ammonia or etbjkmine;*

Mniifoethi/Uu^ of Mcg/usia, — Prepare*! by treating tba solaitoa of
binitroGtlijlato of ainc witk excesa of caustic magnesia^ boiling tad
filtering. The filtered Eolution, concentrated in a watcr-batb, yiddi
granukr crystals, which fuse afe lOO', and dry op to a 6olid amorpliirtii
mass consisting of the anhydrous salt*

4C ..,..„.MM,.,., 24 >,,, 23-76

5H ^ „ 5 .„. 4S&

2N ..«.„ 23 ... 2-'72 29'37

MgO „. .., 20 ,,.. iy»80 ., iy-^2

3 O „ 21 .... 23'77

C^H»MgN^O< ....,„. 101 .„, lOO'OO

BlnUroHliylate of Einc. — a. Bmie. — C*H»ZnN*O^ZoO. — Pio-
duced by the actioa of water on binlttoethylato of line and tinc-
cthyl (p. 556); also by exposing that compound to a stream of dry air,
wlioreby neutral bin it roe thy kto of zinc and e thy late of sifl€ are f oi
and trealitig the product with water :

C*H6ZtilW<,C^M*Zn + 20 = eH^ZiiN^O* + C*H«ZnCK.
and:

C*H*2nK^0* ^ C*H'ZnO^ + 110 = C^lPZnN^OVZnO + C*H*0^*

K Feutral — C*H^ZnN*0*. — Prepi^Htm (p, 5i6). — Cryst&Uiaw ii
niinnte colourless needles containing half an equivalent of w^ter^ wiidi
tliey retain when exposed over sulphuric acid i» vacuo. Tbey tneh
Ifclow 100" J and gradually become anhydrous at tbia temperatare.
They are very solnhle in water and in alcohol ♦ The ccmeciitraled
aqueous solution solidifies on cooling to a white fibrous crystalline
Heated suddenly in air to a tciuperatnre of about 300% this salt
not deflagrate, but inflames, burning rapidly with a bf^ntifui bluish gnm
flame.

Dried ai 1 00**. Fnnklmia.

4 C 240 «„ IS75 ,.,.._ Li-g?

5H .- 5 0 .... 4 11 .„ 4-41

2If _.„..,^ „ 2Si> .... 23*04

Sa „ «... 32*5 .... 26 7a ........ 2?-2S

4 0 „.,..^ 32'0 .,„ 2W4

Q»H^iiN«0* 121'5 100 00

BQ.^.^^. .......... . 48 ,«. 19-04 It-yt

nU.. II «« 473$ 4-^

4N.^., *^«*.-, , M ^ 22'tt ^ 25 78

2Zii «. 65 .... r^n .....^ 24 4et«i

9 O . ,. »..„„„..- n .... 2S-57

SC^tt'^aN^-O* 4 A%. mi -,* 100 on

DINITKO-ETHTLIC ACID. 569

BinUroethylaie of Zinc wUh Zincethyl. — (?H'«Zn»N«0* =
C*H»ZnK»0* -f C*H»Zii. — Pr«|»arfl/ioii(p. 556)._It is also obtained by
adding aa ethereal eolation of zincethyl to anhydrous binitroethylato
of zinc. — Corresponding conrpouncU appear to be formed in like manner with other
salts of binitroethylic acid : these compoands are analogoas to the compound of sine-
ethyl with iodide of zinc, which is formed so abundantly daring the preparation of
zincethyl.

Binitroethylato of zinc and zincethyl is deposited from its ethereal
solution in large colourless and transparent rliomboidal crystals, which
instantly become opaque on exposure to the air, owing to the formation
of an oxidised product.

8 C

48 ..

.. 26-22 .
.. 5-46 .
.. 15-30 .
.. 35-53 .
.. 17-49 .

Frankland.*
25-61

10 H

10 ..

5-48

2 N

28 ..

14-89

2 Zn

65 ..

35-36

4 O

32 ..

18-46

C^H*ZnN20^Cn^»Zn .... 183 .... lOO'OO 100*00

The simplest expression of the analytical resolts is C^H'ZnKO^, which represents
the salt as composed of 1 At. zinc-ethyl and 1 At. nitric oxide ; but the decomposition
of the salt by oxidation and by the action of water (p. 556), seem to show that its tme
formula is that above given.

The crystals dissolve with tolerable facility and without decomposi-
tion in anhydrous ether, but are instantly decomposed by anhydroas
alcohol and by water. The compound exposed to the gradually increas-
ing heat of an oil-bath, melts at 100°, then froths up and begins slowly
to evolre gas. At 180^ the colour darkens, and a small quantity of a
yellowish liquid of penetrating odour, free from zincethyl, and possessing
a very powerful alkaline reaction, distils over. This liquid, neutralised
with hydrochloric acid and treated with bichloride of platinum, yielded
a splendidly crystalline platinum salt, which was obtained, however, in
too small quantity to allow of its composition being determined. From
180° to 190°, binitroethylato of zinc and zincethyl rapidly evolves gas
consisting of 18*4 per cent, carbonic acid, 23*66 per cent, defiant gas,
and 57*94 per cent of a mixture of hydride of ethyl, nitrogen^ and
protoxide of nitrogen.

Binitroethylate of Copper, — This salt is prepared by mixing solutions
of binitroethylate of baryta and sulphate of copper. The filtered
solution is of a magnificent purple colour; on evaporation in vacuo, it
yields splendid purple needles, which contain half an equivalent of water,
and may bo obtained several inches in length; they are four-sided
prisms.

Frankland.

8 C 48-0 .... 19*18 19*60

11 H 11-0 .... 4-39 3-93

4 N 56-0 .... 22-37 21-82

2CaO 79-3 .... 31-68 31-12

7 O 56-0 .... 22-38 23-53

2C^II*CuN20^ + Aq... 250*3 .... 100*00 10000

* In this and in the analysis of the other salts, the mean of the eiperimental
numbers is given.

r

ADDrriONS TO VOL, It,

it ^ Siiwer is prD^uced bj doable decomposition feom
if 1)kijta aad ^Iph&le of ell ver. It ts very 8oli»l>t* ia
m in very li^t soUes, mud is so fi|>eedily decomposed,
expo^are to Ught^ that no Batisfactory aoaljaia couI4 bv

a/€ amd BmitroetA^iate of Siltfer. — Thia salt i* Twy
» in water ^ it ia precipitated in a crystalline ^dulir
sntrated solutions of Viaitroetbylate of £jdc and nitimte of

4C_- .»„„»».......,« Si „.* 654 „. 6'67

5H ..™^ 5 ^^ 1-36 ,.-„„, l-4€

3N_, .«.,«. .. 42 ... H'45

2 Af .„ ^.,„ 210 ..« 58 8« 5S-iS

laO,. ^„.»,.^>. BO ,... 2179

OH*Af N=0* + NO"Aj 567 ... 100*00

Bmitrodhylk Efh^r, — Several attempta Tvero made to prepare tliii
touud by the nsnal methods of etheri fixation, but with oolj reiy

il saccess. When crystallised bioitmeUiylat© of lime is diftallel

ButpboTtQate of potash, alcohol comes over mixed with an etbtfital
id, which dissolves io water^ but separates agaia ou the addittoti of

le of calciuni. in the form of oUy drops of a pccnliar elh«fr»J
The quantity ^a^ howeror eo small as to preclude the posiihihtj

.ng Its compo^itioa.

END OP VOL. Xn.

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