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i^A-^' 





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,M • m , ' 'n /'jiai r ci 




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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* _. _ _ 

r T mt^ 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 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 Jf i j y yia g 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 p ujpfa - 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 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 * ^! m jTtrm«» 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.: ca jisM ue 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 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 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 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 .,... 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 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 


,„......*«... 


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 p rBper tiei 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 fexT ih^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 
.»!•»•!»»: 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 . 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<*" ■ h i iiii oil in 5 vol ether, mixed irith 1 tqI 
^ wmmmk^ i iMiii i ii 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 

( hm h i n at iom* 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 .......^..... 


.., 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 


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. (FelJ goL) 
— 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 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» mi mam i mmh \» 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 . 



£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 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 

3 ... 24 

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 hmk m k 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 p n erirti f«t the BIO0I pari d 
_jtdi(rid(* T I 1 ' - '« I T1in »fci rtfci «f lUf li^aid lUitib oror al 194* or 
III tkwfij of tfckf Mt af baaaioyl; Am portmi vbkk 

mj>eratare hm m e o a ataa t 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 


.. 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 li PWiei thitk M sea 



Wten fliivie acid 



Willi «trDDc «^i09aB V^^*^ li PWiei 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 


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 





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 fBcra ted to '^rfmam, j mAaam 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 : »7€a 
1*1605 (Dauber) i = 1 : 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 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 .... 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 ....... 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 

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 .... 0-31 

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 .... 63-72 

5 HO ■■„..„.. ..„,... 45 „„ 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 

N * 14-0 

8H » «. e^o 

h O 40 



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 .». 


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 


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 






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 








C»NM«A80* .. 


.. 286 .... 10000 







lie. 108 .... 86-61 86-44 

N 14 .... 4-75 

Af 108 .... 86-61 86-40 .... 86'.12 

OH .... 8-08 8-10 

7 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 
t e p e al edly 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 


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 %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 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 



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 -« — M ,^.,. 


. 6631 

. 2i-&8 
11*66 


Otleuiatim f . 

26 C . IH ....,.» 43*82 

«H ...^.». i ...... 2-23 

2 Br ..., , tm ,. iiU 

4 ..,,..,„. . 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 


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 „„. 




. 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 ... 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 «.. 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 ,.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 gre tlci 
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 

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 


.,. 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 


t. 








a. 


». 


t. 


d. 


20 C ........ 


.. 120 ., 


., 61*2 .„ &98 . 


... fil'O 


.... 61 « 


^ 617 


nu .... 


,. 12 . 


.. 6^1 ... 


61 . 


... 5-7 


.... 6-2 ., 


. «-y 


2 


.. 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 

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 . 


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 . 



$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! 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 .... 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 
fm w $m m 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 32 ™. 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 .... 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. 

Ai i w ii tf t s , 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 .., 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 , 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%)i i b i b K 6fDr' 



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 , ..„ &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 



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 

?H ». 7 

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 .... 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 .. 


...... 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 -.,......„»... 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 % 

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 .. 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 ..„ 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 






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 . ,... 


... 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 





.... SBO 



NmO^.SO^H + 2Aq .... 204 .... 100 .„.»., 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 ,. 


.... 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 „ 


. 2^93 .... 


.... 3 51 


6 H „. 


60 „ 


.. 3350 .... 


„„ 3^20 


B» 


68^5 ,. 


6-04 




4 ..,...,. 


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 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 . 16-0 .... 10 3 

C"NH«C10> ,..p 145-4 .... 100 

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 Ai iliiii 
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 



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 



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. <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 tJi erefo fg 

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 A wia g 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 _ 7S25 .. 

...„„ no . . &-13 . 


Luitreiil. 
?J 



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 . 
... 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 . 

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 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 


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 


... 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 


.. 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 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 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 .,». 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 al eohoiic 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 fc jdiy, 
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 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 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 >e Mg re 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 Trmi tmmMrw . — 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 am muaij 
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 .. 

17 U . 
6 . 



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 .... 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 
jjihSa i U iii 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 96 .... 2110 


12 


.... 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 

16 128 .... 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 



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; P Jmm' 

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 u rleas, m i croscopi c, re ctan g ul ar pria m s w i th t w < 
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 


,.. £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 

5 6 


4 


.. 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 ........... 


... 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 peJ a c t 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* ( 

$«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 


.,.««...-.. 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 , ..... 


... 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 rit cp rfin ii 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 
• g fc gtf gd 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 b etw e en 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 

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 :: :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 

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 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 . 



.,*.„.. 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 . 

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 .,., ...„...» 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 .. 



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 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 aa hj J n w 

Freparaiicn. WhfB Tspoor of anh jJmi 
•▼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 d iwulrrf 
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 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 


,,... 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 

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 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 



^ 



TOUJ R Kg : 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 


... 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 . 
. 

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 .. 


.. 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 

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 pcecifi U t c d 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 


u 

32 

9S 


..... irs 

35-3 


Cs^Hsso^ 


...» 274 


.... 100 ». 


..... 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 ... 






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 .. 



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 , 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^ a py e^ 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 bo comei 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 . 


.. 44*02 


,. 39'fl4 


4 H ....... 


. 40 . 


,. 2 09 


289 


2 CI 


. ?0'8 . 


„ 3711 


37-06 


4 .. 


. 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 ,.. 


. 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 ..,,,.. 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 ....... 


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 deoolo riied 
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 ., 


.... 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 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' i i < 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 


..,. 


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 





■^*.,,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 








■■- 


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 ..»». 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 

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 

, c rjstdliaatioD 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 .... %-m .„..,.. 9*05 

3H_„_ ..„,.._ 3 ... 95 ...,,.,. 1-Ofi 

13 Q 304 ... 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 , , 


... 104 . 




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 

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 ... .,.. «-» 

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 .... mi 

N « UO .... B3 ., 8-3 

6H 6 .... 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 , 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 .». 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 — *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 ,„. 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 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<«» > *i w nm jg^WB^ai WHi ii 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 calo ag, 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 ».,,.. 

3 N 

18 H .» 

8 .... 



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 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 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 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 . 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 i t auMw^ 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 .. 



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 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 aom eadc d 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 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 
t mf^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 
^ihito fcbUic 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^ l i KWn -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» 

17 136 ..« 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 


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 .... 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 ... 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 



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 Il l 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 

Hw f iJ CTi ■■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 ; 
ffc rw a pfc 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- — 
Tb