Organic Chemistry.25Constitution of Mercuric Fulminate. By A. F. HOLLEMAK'N(Rec. Trav. Chirn., 10,65-84 ; compare Abstr., 189 I , 64) .-In order todetermine whethcr mci*curic fu!minate contained the same empirica26 ABSTRACTS OF CEEMICAL PAPEHF.group, C2K20?, as the ‘‘ diriitrosacyls” (Abstr., 1889, 49), the authorstudi d the action of benzoic chloride on dry mercuric fulminate, andfound that a dibenzoylcnrbamide was formed. I n the course offurther experimental work, which is here described a t some length, hehas determined this to be symmetrical and t o be identical in meltin:point (19i” j and physical characters with the dibenzoylcnrbamideobtained by the actioii of guauidine carbonate on anhydrous benzoicacid (Creath, Beis., 7, 1739), and with that described by Riidd&ns(Abstr., 1890, 12:3).Schmidt’s s’atement that dibenzoylcarbamideyields benzamide when boiled with pot rssium hydroxide solution(this Journal, 1872, p. 718) is incorrect. The author has preriviifil~~-pointed ouh the alialogy which this formation of a substituted carb-arnid(a presents to the conversion of isocynnic acid into an analogoussnbstaiicc, whilst Scholl (Abstr., 1891, 282) obtained acctylisocyanicacid by the action of acetic chloride on mercuric fulminate. Fromthis it would seem that the formation of dibenzoylcarbamide is alsodue to the formation of a n isocyanic derivative. Kekulb’s formula,CNCH,.NO,, neither explains these results nor the fact tbat carb-amitle is formed on the decomposition of coppcr ammonium fulminateby hycli-ogen sulphide (Gladstoile, Quart.Journ. C‘henz. Soc., 1, 228),nor Steiner’s observation (this Journal, 1875, p. 1382), that urea Rndguanidine result from the action of ammonia on mercuric fulminate.Steiner’s formula, OH*N:C:U:N*OH, explaiiis these reactions, but notthe formation of chloropicrin and of cyanogen chloride by the actionof chlorine water on mercuric fulminate. Regarding fulminic acid asa desrnotropic compound, the author suggests the following tautomericfoi.innla, which he thinks Divers’ results (Trans., 1884, 13) support :To demonstrate the preseixe of the nitro-group in the molecule, anattempt was made to sycthesise mercuric fulminate by the actionof monobromonitroethane (1 mol.) on a solution of mwcuric oxide( I mol.) and mercuric cyanide (1 mol.), but R red precipitate ofthe compound CHgBr,N02 was alone obtained, wbich neither deton-ated on percussion nor on heating, and yielded with potanaium cyanidethe salt RBr,HgCg, + 2H20.-4 further attempt to prove thepresence of a nitro-group by the action of chlorine-water led to nodefinite result, a very complicated reaction ensuing.Mercuric fulminate (1 niol.) absorbs dry chlorine (4 atoms) withoutevolntioii of anygrtseous product, and i s converted into a yellow massof pungent odour which is soluble in cold water, and is probablydichloronitroncetonitrile. Bromine vapour is absorbed by the fnlmin-ate in the same rz,tio, and steam distillation of the resulting yellowmass affords a liquid of irritating odour, which soon solidities toyield crystals of dibromacetonitrile melting a t 60”; the latter canalso be separated from a slight residue of mercuric bromide byexhausting the crude product of the reaction with light petroleum.Scholl and the auth-w consider dinitroacet,onitrile to be a nitro-derivntive.Provided no oxidation occnrred in the action of drORGAXIC CBEMISTRT. 27chlorine on mercuric fulminate, the study o€ dinit~oacetotliCIeshould determine the validity or otherwise of Kekuld's fornau1;c.T. G. W.Constitution of Ally1 Cyanide. By F. LIPPMAKN (iMonafsh., 12,402--409).--The sn-called R l l v l cyanide was prepared according tothe directions of Riiine and Tollens (Annalen, 159, lO5), exceptingthat ally1 brornidc was substituted for ally1 iodide in the process;$0 per cent.of the tlieorcticnl yield of cjanide boiling at 118"was obtained. In o ~ d e r to prepare the dibromo-additive product,a quantity of the cyanidf. u-as cooled in ice, and gradually treatedwith a molecular proportion of bronline. After 1-2 days, the pro-duct, which no longer hnd the odour of bromine, was mixed withfuming hydrochloric acid, arid allowed to remain for 2-3 days, untilthe liquid assumed it reddish-brown colour. It wits then decomposedwith water, and the crystalline precipitate thus formed recrystallised,first from ether atid afterwards from. hot chlorofoi-m, when silkyscales of ap-dihrornob?Lt7JI.nmir7e, CHMeBr-C H BrC O N B?, were ob-tained. It melts at 147-148", is readily soluble in cold ether and inhot alcohol and chloroform, but loses hydrogen bromide whm heatedwith water.The acid solution from which the rtmide was separated by waterwas shaken with ether. The ethereal extract, on evaporation, gave Bcrystalline residue, p r t of which was insoluble in water, and con-sisted of a further quantity of the amide, whilst the rem:iinder wasreRdily soluble.The aqueous solution, on evaporation i n a vncunm,gave white, needle-shaped crjwtals of ap-diLromoh?dyric arid,C EIMeBr*CHBr*COOH. This acid may be recrystallised from etherand water, in both of which it is readily soluble; it melts a t88-89", and differs considerably in physical properties from norrnrildibromobutyric acid, CH,Me*CBr2*C00H, wliich is liquid at ordin-ary temperatures.The amide. melting at 147-148", is readily con-verted into a@-dibromobutyric acid when heated with fuming hydro-chloric acid for five hours a t 120".The formation of ap-dibromobutyyic acid from the so-called alljlcyanide shows that the constitpution of the latter must beCHMe:CH*CN. This is in harmony with the view of Kekule and ofRinne (Ber., 6, :38t;), bvt does not agree with that of Pinner (Ber.,12, 2053). G. T. M.Direct Synthesis of Primary Alcohols. By P. HENRY (C~n?pt.ven,d., 113, 368--370).-Monochloromethyi ether, CH,Cl*OMe, and thecorresponding ethyl compnund CH.,CI*O E t, react energetically withthe organo-zinc compounds. Zinc chloride separates, and, on treatingt h e product with water and distilling, the primayy alkyl oxide can beis0 1 at ed .The following ethers were prepared :-Primary methyl props1ether boiling at 41" under a pressure of 761 mm.; sp. gr. = 0.7381a t 20", by the action of zinc ethyl on inoriochloroniethyl ether.Normal primary butyl methjl ether, by the action of zinc propF1 onmonochloiwmethyl ether; i t is a colourless liquid with an agrzeabl28 ARSTRXCTS OF CBENICAL PAPERS.odour, insoluble in water, and boiling at 71" under a pressure of7.59 mm. ; sp. gr. nt20" = 0.7593. Normal ethyl propyl ether, by theaction of monochloromethyl ethyl ether ; it boils a t 63-64' ; sp. gr.a t 20" = 0.7474. l4t,kiyl butyl ether, by the action of zinc propylon monochloromethyl ethyl ether; it boils at 9d0 under a pressureof 753 mm.Zinc prcpyl is produced as easily as zinc ethyl by means ofGladstone and Tribe's zinc-copper couple, biit the yield is only 90t o 75 per cent., propylene and propane being liberated.Oxidation of Tertiary Almhols. By G.WAGXER ( J . p ~ . C'hem.[2], 44, 308--312).--TL\e oxidation of the tertiary alcohols has here-tofore always been eflectcd by chromic acid mixture, which, however,is acknowledged to convert them, by denydration, into correspondingolefines, so that the products of t h e oxidation have been those derivedfrom the olefines, ratlier than true oxidation products of the tertiaryalcohols (compme Abstr., 1883, 566 ; 1886, 4:{7). E'or this reasonthe author lias experimented with a neutral solution of potassiumpermanganate as an oxidising agent for tertiary alcoliols.He findsthat trimethylcarbinol is scarcely ;ittacked by an alkaline 4 per cent.solution of potasssiurn permanganate even when warmed ; and thattertiary amyl alcohol is oxidised by the same solution at the ordinarytemperature, but even after a month, the reaction is not complete.Dimethylisopropylcarbinol (b. p. 117-118"), howevey, is readilgoxidised to pinacone by a neutral aqueous solutim of potassium per-mangauate, aud the process adopted is fully described in the paper.This is the first case in which a saturated monhydric alcohol hasbeen directly converted into the corresponding dihydric alcohol.From this result, the author concludes that the oxidation of tertiaryalcohols results in the hydroxpli+iug of oiie of the carbon atoms whichare directly linked to ttie C(0H) graup, a reaction similar to thatobserved in the oxidation of the ketones, and probably conforming t othe same rules (compare this vol., p.35).c. H. R.A. G. B.Xylose. By G. BERTRAKD (Bull. SOC. Chim. [ S ] , 5 , 554--557).-Xylose may be obtained from wheat or oat straw by the followingpi*ocess, which is stated t o be less laborious than that used byWheeler and Tollens (Abstr., 1889, 847) in preparing i t from pinewood. The straw is extracted witli tepid water, and is then boiledfor several hours witli dilute (1-2 per cent.) siilphuric acid. Theliquor, after removal of the sulptiuiic acid by barium hydroxide, is con-centrated on the water-bath, and treated witti nlcoliol, thus yielding anextract from which xylose is obtained as a yellow syrup on removingthe solvent.The syi*up crptallises oil the addition oF a crystal ofxylose, arid the product is recrjstallised from hut alcohol. Ttie yieldfrom wheat< btr<tw is 2 per cent., from oitt straw 4 per cent.When xylose is treated with sodium amalgam, xylitol is obtainedas a syrup, whiclt, like sorbitol and perse'itol, and unlike arabitol,gives, with benzaldehgde iu the presence of sulphuric acid anabnndaiit precipitate, which appeilrs to have the compositionC5H80,(CHPh),. The xglitol mty be recovered fmm the compounORG ASIC CHEW ST RY. 29by hydrolysis, and, as thus obtained, is a rather sweet, faintly dextro-rotatory syrup. PentacetyExyZitoZ is obtained as a syrup, whenanhrdrous sylitol is treated with acetic anhydride in the presence ofzinc chloride.Xylose is farther distinguished from nrabinose by the fact that thecadmium salt of it's first.oxidation product, xylonic acid, forms well-defined, crystalline, double salts with cadmium bromide and chloride ;the react-ion is very sensitive, as it is visible when only a few milli-grams of the sugni. is present. The xylose (1 part) dissolved inwater (5 parts) is treated with brom.;ne (1 part), and, after 24 hours,the excess of bromine is evaporated oft'. If the bromine compound isrequired, the residue is now saturated with cadmium carbonate, con-centrated, and precipitated with alcohol ; whilst, if the chlorine com-pound is wanted, the hydi-ogen bromide i~ removed by means of leadcarbonate.cadmium carbonate and chloride are ndded to the imDurexybonic uckd thus obtained, and the operation is completed as befire.JN. W.Constitution of Xylitol and Xylose. By G. BERTitAh'D (7l1dZ.Soc. Chim [3], 5, 740-742 ; compare preceding abstract).-Whenxylitol is treated with a mixture of nitric imd sulphuric acids, it yieldsa pentanitrate, C,H,( NOg)5, as a colourless, irisoluble syrup, which i8lieitvier. t'han water, cati he exploded by percussion, and burns rapidlywithout leaving auy residue.By hentirig xylitol with amorphous phosphorus and iodine in astteam of nai*bonic anhydride, i t is converted into a secotidary amyliodide, which boils at 146', and yields, on prolonged heating withlead hydroxide and water, methylpropjlcarbinol, boiling a t 116O.Xylitol is thus an open-chain pentabjdric alcohol, of which xylnseis the aldehyde; the two substances being represented by the forffiuls0 H*C H2.[ C H-OH],*C H:,.O H and OH*CH2.[ C H-OH] ,.C 110.Js, W.Epichlorminel By R. SCHIFF (Gazxettc, 21, ii, 1-ti).-Equiva-lent weights of epichlorhydrin and ethyl acetoacetate are mixed withexcess ot' alcoholic ammonia solution and left for some houi*s ; there isa slight development of heat, and the reaction is completed by heat.ing on the water-bath for 15 minutes ; on the addition of water,colourless oil is obtained, which soon solidifies to aciculnr crjstals.When recrystallised from dilute alcohol, the new compound has thecomposition C,H,,NO,Cl, melts a t 95" without decomposition, mid isnot altered by beating for some time at 100-110".It dissolves inacids to form salts, and is precipitated unchanged from the solutionby alkalis; it is moderately soluble in absolute alcohol, less so iuether, and very sparingly in cold water; it separates from its hotaqueous solution in long needles. The solution is not precipitated bysilver salts or by picric acid and sodium carbonate, arid does notyield a platinochloride.If, in the preparation of this substance, the heating on the water-bath be too prolonged, a whitish, slightlg crjstailine substance isdeposited, wliich is insoluble in all ordinary solvents, aud has theNo ncetyl derivative could be prepared30 ABSTRACTS OF OHE3lICAL PAPERS.composition C12H1'IN3CILOP ; it appears to be identical with the chlor-hydrinimide of Claus (Abstr., 1875, 1121).When the eubstance C'9H16N03C1, is dissolved in hot alcohol, andtreated with oxalic acid in alcoholic solution, Ppichloramine oxalate,( C,H,NOCl)2,H2C201, is obtained as a voluminous.white precipitate,and is puritied by solution in water and precipitation by absolutealcohol. I t melts a t 193-184" with evolution of carbonic anhydride,is moderately soluble in warm water, and almost insoluhle in alcohol.I n a similar manncr. epich/ommiwe l ~ ~ ~ ~ ~ ~ o c h Z o ~ ~ i t Z e , C..H,NOCI,HCI, isobtained by treating the coiidet:satdun product with hot dilute hydro-chloric acid; on evaporating the solution in a vacuum, the salt isobtained colourlesd atid well crystallised ; it is very soluble in water.Free epichlorsrnine is verv soluble in water, atid is decomposed bysteam distillation with evolution of ammonia ; it seems to be veryrendily converted info condensation products.The a n tlior regards itas formed hy tile condensation of a niolecnle each of ammotiia, epi-clilor~hjdriii, arid ethyl nceto;wet:tle M it11 eliiiiination of wiLter, aud cou-d e r s that it has p i ohably the conhtitutionC H,CI-CH( OH).CI€,.N:CMe*CH,.CO~~~t.W. J. P.Unsaturated Fatty Amines. Hy C. PAAL and A. HELPEI, (Be]..,24, 3035-3048 ; con~pare Abstr., 1889, 116, and 1890, 399).-Dihromopropy Zctu L t r I I I idp, NH**CO*NH*CH2-CH Br*CH,Br, is preparedby mixing a conccntricted aqueous solution of the hyd~ocliloride ofdibrornopropylsmiiie (compare Henry, Ber., 8, 39!1) with potassiumcyanate.It melts a.t lt;3", and dissdves easily in alcohol and hotwater, sparingly in ether and cold wnter. An attempt t o prepare theartalogous thiocat*haniide from the hydi olnmide of the base andpo t,assium t hiocpnate was unsuccessf'u 1.By acting on an alcoholic: solution of free propargylamine wit11e t h j l iodide, and allowing th mixturw to evaporate i t 1 the absence oflight, ti crystalline wsidue is obtained, which is separated by treat-ment with alcohol into propurgy1arrz;ne hydr-ioditle, C.,H,*NH,,HI,which forms lustrow, large, white plates, melting a t 205" andsparingly so1 uble in alcohol, and diet Izylp1.opa,.~u?llcL~~i~~~ hydriod ide,C,+,H,*NNt,,HI, which is easily soluble in alcohol.The silvei- com-pound of propargylamine previously prepared was found tt) have avariable constitution, but undoubtedly contains oxygen. PI opargyl-amine itself, when boiled with sodium nitrite atld a little hyclrocliloricacid, jieldv propargyl alcohol ; Chis can be distilled with Btea~n, a n di f the distillate is collected in an ammoniacal silver solution, a white,explosive silver compound, C,H,Ag*OH, is formed.Propa,.~?/l~Zithiocar.Damic acid, C3H3.NH*CSSH, is obtained by boil-ing ail alcoholic so1utio:i of free propargyiamine with excew of carboubisulphid: in a reflux apparatus. J t melts a t 115", has a feeble, un-pleasant odour, and, when heated, smells like a thiocarbimide. Itdissolves eaily in aqueous alkalis, mineral acids, hot water, ether,alcohol, and benzene, sparingly in light petroleum and cold water.Piom dilute alcohol, it crysfallisc s in white needles ; from a mixtwORQAKlC CKKXISTHT.31of benzene and ligbt petroleum in long plates. Acetic acid and dilutemineral acids precipitate it from solutions of its alkali salts. Thebarium salt forms a white, flocculent, the stannic B white, gelatinous,the copper a preen, flocculent, the lead a white, granular, and thesilver salt R white, flocculent precipitate. The silver salt yields silversulphide wheu boiled with water. The acid itself is completelyoxidised by silver or mercuric oxide.Propargy lpheny Zcnrbumide, NHPh*CO*NH*C,H,, is prepared bymixing an aqueous solution of propargylamiiie oxalnte with ratherless than the theoretical amount of phenyl cjanate, mid adding to thecooled mixture a slight excess of a concentrated solution of potassiumcarbonate.After shaking for a time, a crystalline product is obtainedcontaining a small quantity of symmetrical diphenylcarbarnide, whichis easily soluble in hot water, mixed with very spzringly soluble proy-ai.gylphenSlcai.bamide ; the lntt,er crystallises from water in radiatinggroups of needles, melts at 133". and dissolves easily in ether, alc;ohol,and benzene, sparing1.y in light petrolenm and cold water.Isobuty ZalZylamine, CsH5*KH*CH2.CHMez, is prepared by digestingequivalent quantities of allylamine and isobutyl bromide for two o rthree days at first a gentle heat, finally on the water-bath.The pro-duct is diluted with water, acidified, separated from unattackedisobutyl bromide, and treated with caustic soda, and the bases thusliberated are dried with d i d potakh and fractionally distilled.Some diisobutyZaZl!/Zanziiir, C,H,.N (C,H,)?, boiling a t about lti5", wasisolated, but the main product is isobutylallylaiuine, a coloui~lees, vola-tile liquid boiling at 123" (uncorr.), and having a penetmting odourresembling that of allylamine. The hydro-chloride, C,HlaN,HC1, crystallises i n white, lustrous, hygxmopicplates whichmelt a t 216", and are fatty to the touch. The aiirocltloride,C,Hl,N,HAuC14, cryst allises from hot water ill splendid, yellowneedks which ue!t at 140", and slowly decompose wiien boiled withwater. '1' 11 a plat hr oc: hloride, (C,H,,N) 0,H2 P t C: 1.1, crys t allises fromalcohod in splendid, red needles, melts at 18Y, and dissolveseasily in alcohol and water.The AydroLromzde, C7H,5N,HBr, crystal-lises from a mixture of alcohol and ether in white plates whichhave a silky Instie ; it melts at 222" and dissolves rt adily in waterand alcohol. The acid oxalate, C7Hl5N,CZHZO4, crystallises from alcoholin small, white plates, inelts at 221", and dissolves fairly easily inwater, sparingly i i i alcohol.Isu but y la1 l p lp heny Zcarbanzide, C4H9*N (CJ&)*C 0 *NHPh, is formed bythe nriioii of isobut~lallylarnine with phenyl cyauate at the ordinarytemperature. A viscid, colourless oil i s obtained, which very slowlybecomes crystalline. It is insoluble iu water, but soluble in alcohol,benzene, and light; petroleum, and crystallises from the last solventis aggregates with a radial structure which melt at 37-39".I~oh~tylallylphtn~lthiocarbamide, CdH ?ON( CsH5).CS*NH Ph, is ob-tained by mixing equivalent quantities of isobutylallylamine andphengltliiocarbimide. It forms a viscid colourless oil which slowlycrystallises in long, colourlem needles grouped like ice- flowers.I tmelts at 41-43', and dissolves readily in ether, ethyl acetate, alcohol,md benzene, sparingly in light petroleum and not at all in water.It is soluble in water32 ABSTRACTS OF CHEXICXL PAPERS.lsobut?/Zpropargylanzine, CrH9-NH*C3B3, was prepared bv gradual I yadding isobutyldi bromopropylamine hydrobromide, CaH,*NH*C3B,Br,,to a well-cooled alcoholic solution of sodium ethoxide, and finallyheating the mixture in well-corked bottles in the water-bath.Thecontents were then diluted with water md distilled with steam untilan oily base tjhat w-as also forrned began to come over. The distil-late was concentrated, treated with a large excess of potassiumcarbonate, and the bases extracted wihh ether. The ethereal solutionwas dried with solid potash and fractionally distilled ; by thismeans, isobutylpropargylamine was isolated AS ~1 colourless, volatileliquid, boiling a t 134-136" (uncorr.), miscible in all proportionswith water and having an odour which recalls that of ammoilia, and atthe same trime tha&of camphor. Its aqueous solution precipitatesiron hydroxide from a solution of the chloride, has no effect on anammoniacal copper solution, and with an ammoniacal silver solutionyields a silver compound as a white precipitate which is fairlystable while moist, but explodes easily when dry.The oxulate,C7H,3N,C2HZOd, forms lustrous, white needles or plates melting at210" ; i t can be crystallised from alcohol or from water. It reducesa solution of gold chloride only very slowly (ullylamine oxalateitself, C3Ks.NH2,CzHzO4, which forms radiating groups of whiteneedles melting a t 120", effects this reduction even more slowly).The hydrochloride, C7H13N,HCI, crystallises from a mixture of alcoholand ether in large, lustrous, white plates melting a t 148" anddissolving readily in water and alcohol.The platiiiochloride,(CiH,,N)2,H,PtC16, separates from alcohol in ill-defined, red, crystal-line aggregates which iiielt a t 172", and are decomposed when keptfok a short time at 100".Isobut!/ZproljyZcrmine, C4H,*NHPp, is obtained by reducing isobutyl-propargylamine in alcoholic solution with metallic sodium, tbemixture being heated on the water-bath. The product formed wasdiliited with water and distilled with steam ; the distillate acidifiedwith hydrochloric acid, evaporated to a small bulk, and treated withpotash; the oily layer was removed, dried with solid potash, andfractionally distilled, finally over metallic sodium. The base is a.colourless, volatile liquid boiling at 123-125", miscible with water i nall proportions, and very similar to isobutylallylamine. The hydro-chloride, C,H,,N,HC'l, dissolves easily in water and alcohol, andcrystallises from a mixture of alcohol and ether in Rmall plates whichmelt at 135".The oxalate, C7H1,N,C2H2O4, crystallises from alcoholin small, white needles melting a t 224". c. I?. B.Crotonaldoxime. By T. SCHINDLER (Illonatsh., 12, 410-418). -This componnd is obtained when 2 mols. of crotonaldehyde (compareLieben and Zeisel, Monntsh., 1, 20) is slowly added during continuedagitation to a cold solution of 3 mob. of hydroxylamine hydrochlor-ide which has betm carefully neutralised with sodium carbonate, andthe resulting carbonic anhydride conipletely removed by shaking.The product is extracted with ether, and the ethereal solution dis-tilled until the greater portion of the cther is removed.The con-centrated solution is allowed t o evaporate spontaneously, when an oiORGANIC CHEMISTRY. 33having a characteristic odonr separates, and in this oil a number ofstout, closely striated prisms of crotorraldoxime, CJH,ON, slowly form.The compound is insoluhle in water, but readily dissolves in ether,alcohol, chloroform, and hot benzene, and may be best recrystallisedfrom the last-nariied solvent, when it forms colourless, odourless,volatile crystals which melt at 119-120". On heating mith aceticanhydride for two hours in a ~eflnx apparatus, the aldoxime isconverted into crotononitrile, C,H,N, a product which boils at117*4-118*4"; has a sp. gr. of 0.8468 a t 0" cornpiired with water a t4", and is apparcntly identical with that, obtained by Rinne anctTollens (A~znaletz, 159, 105) from ally1 iodide and potusiiim cyanide.Tollens (loc.cit.) and Pinner (Ber., 12, 2053) have erroneouslyatti ibuted the formula CHz:CH*CHz*CN to this compound, which, asshown by its prridiiction from crotonaldoxime, CHMe:CH*CH:NOH,must really be CHMe:CH*CN (compare KekulB, Ber., 6, 386). Onthe additlion of bromine and subsequerit digestion with concentratedhydrochloric acid, the nitrile is converted into a mixture of dibromo-butyramide, CHMeBr:CHBr*CONH,, which melts a t 148-149", anda/3-d;bromobutyric acid, CHMeBr.CHBr,*COOH, which melts a t87-90" (compare Lippman, this vol., p. 27). When the aldoximeis reduced by Goldschmidt's method (Abstr., 1887, 568), crotylamine,CiH,NHz, which boils a t 81-85', i s obtained.The oil from which the crotonnldoximc separates is a very inactivesubstance, and does not readily lend itself to purification. Since, O I Lelernen tar7 analysis, it gives numbers which w r y ciosely correspondwith tliose required for the formula of crotonsldoxime itself, the authorsuggests thnt it may possibly be the stereoisomeride of the formulaC,d,*CH:N.OH (compare Hantzsch, Abstr., 1891, 439).G.T. M.The Oximes of Chloral and Butyl Chloral. By R SCH~FF andN. TARU(;T (Gazzetta, 21, ii, 6--12).-Nageli (Abstr., 1883, 728) pre-pared a dichloroglyoxime, OH.N:CCl-CCl:NOH, in small quantities bythe action of free hydroxylamine on chloral hydrate. The autborsfiticl t h a t chZwaldosinze is easily prepared by boiling an aqueous solu-tion of equivalent proportions ot' chloral hydrate and hydroxylaminehydrochloride (compare V.Meyer, ,Qbstr., 1891, 1181). On cooling,a yellowish or greenish oil separates, having an odour closely re-semiding that of free chlorine. It could not be obtained in a statesutiiciently pure for analjsis; if left to itself, or treated with hotwater, it decomposes with evolution of hydroyen chloride andhydrogen cyanide, probably in accordance with the following equa-tion:--CCl,*CH:NOH = HCN + COC1, + HCl.BufyZchlornZdoxime, CHMeCl-CCl,*CH:NOH, is readily prepared bypouring boiling water on a dry mixture of equivalent proportions ofbntyl chloral hydrate and hydrox~lamine hydrochloride ; the oximeseparates as an oil which solidifies on cooling.A still better methodof preparation is to pour the cold solution of the hydroxyln-minehydrochloride on the i r y butyl chloral hydrate, and allow i t t oremain for some days; the theoretical yield of pure oxime is thusobtained. Butyl chloraldoxirne is fairly soluble in all the usualsolvents excepting water ; it crystnllises from light petroleum in veryFOL. LXII. 34 ABSTRACTS OP CBEMICAL PAPERS.largr, opaque odahedm, and melts at 65' without drcomposit,ion. It.dissolves in cold. concentrated sulphuric acid, and is precipih tedunaltered by water ; on heatinc the solntion, however, hpdroyenchloride is evolved. Tt i8 extremely sensitive towards aIkalis, andeven when washed with ordinary tap-maim.rapidly turns yellow andgreen. AcetyZbiityE ahZoraMoxhne, C6HSC1:302, is obt,ained bv Cent.1-yheating the oxime in wetic a.nhvdride snlution ; it is a whit8e sub-stance melting at 63-64". If the heating be too prolonged, decom-pnsition occurs with evoIution of hydrogen chloride and hydrogencyan i de.On henting with alkalis or alkali carbonates. hutvI chloraldoximebecomes first green Rnd findly bright ycllov, hypoahlorous acid beingformed. If the reactinn is arrested a t the preen stage, R yellowpowder is obtained having tJhe covpnsition C,H,,Cl,N,O,.When a few drops of glacid ncet,ic acid a m added to an alcnholicsolution of the oxime (1 mol.) containing Iit,hnr(re (2 mols.), leadchloride is formed, and a CoIourless, well crpstallised subst,nnce isobtained which melts wit,h dwnmposition at 158".This is probablyd.i~:hZo?.ncrotonaZdlnxime, CMeCl:CCI*CH:NOR.The study of butyl chloraldoxime is being continued.Sulph inic Derivatives and their Analogies to Compoundsof Organic Amines. By R. NAPIXI and T. COSTA (Gnzzetta. 21,554--565).-1t WRS previously shown hy t,he aut,hors (Ahstr., 1891,1305) that the mnlecnlar refractive energv of sulphur in t,he deriva-tives of triethylsulphine is extremely high. and especial attentionwas drawn to the iodide, the molecular refractive energy of whichremains const,ant when the concent'ration is varied, but varies whenthe solvent is chmged. Similarly, aqnenns snlntions of trimethyl-sulphine bromide and iodide give very high results for the molecnlarrefrwtive energy of sulphur.The authors consider that the theoryoE electric dissociation affords a simple explanation of these facts.I)et>erminations of the molecular weights of the above-med%medcompounds by the crposcopic method yield approximately normalnumbers in aqueous soluticms, but the acetic solut,ions of the chlorideand bromide of t,riethylsulphine yield abnormal results. It is, how-ever, noticenhle that the hydrak, chloride, and iodide, which yieldsuccessivcly incressing values for the molerular refractive energy ofsulphur. also appear to be successively less dissociated in their solu-trions. Similarly the iodide of trimethylsulpbine appears t o he lessdissociated than that of triethglsalpbine, and the sulphiir in theformer compound a.ccordingly appears t.0 have a smaller molecularrefractive energy. The alcoholic solution of triethylsulphine iodide,in which electrical dissociation cannot.take place. in like manner yieldsthe highest value for the molecular refractive energy of sulphur. I nacetic acid solutions, the molecule of triethplsulphine iodide appearsto be more complex. The moleculnr weight of triethylsulphinebromide calculated from the rise of the boiling point of an alcoholicsolution gave approximately normal resul ts.The molecula~r depression of tetrethylammonium iodide in aqueoussolution is almost equal to that of the corresponding sulphinic de-W. J. PnRQANIC CHEMISTRY. 35rivative. The refractive enerpy of tetrethylnmmonium iodide is greaterthan the sum of the refractive energies of triethylamine and ethT.1iodide, exactly as the refractive energy of triethylsulphine iodideexceds that of its constituents. The determination of t>he molecularweight of tetrethylammonium iodide from the rise of the boilingpoint of an alcoholic solution also yields a normal result.S .B. A. A.Oxidation of Mixed Ketones of the Fatty Series. By G.WAGNER (J. pr. Chem. [2], 44, 257--308).-0f Popoff's seven rulescwcerning the oxidation of ketones (Annulen, 161, 299-301 : J. ETLSS.Chpm. Soc.. 4, 67), the fourth, or that which is commonly knowh as" Popoff's rule," asserts thah when a ketone whose alcohol radiclesare of t'he mme series, bnt not isomeric, is oxidised, the carbony1remains linked to the alcohol radicle which is lowest in the series;the fifth states that in a ketone whose alcohol radicles are of the sameseries and are isomoric, that alcohol radicle in which the leasthydrogenised carbon atom is attached to the carboiiyl will be thefirst oxidised.In this paper, the author details several experiments which are notin accordance with the above rules, and disciisses them hy'the lightof t'he work which has been done on the subject by various chemists.The experiments, some of which have already hem puhlished in.J.Russ. Chem,. rcCoc., 16, 645 and 695 (compare Abstr., 1885,1197),b u t have not been copied into other journais, may be summarisedbere.Ethyl propyl ketone (b. p. 122-123" a t 745 mm.), from the actionof zinc ethyl on butyric chloride (b.p. 98--102"j, yields butyric.propionic. and acetic acids when oxidised by potassium dichromateand sulphuric acid. The formation of butyric and acetic acidsappears to be the pyimary reaction, the propionic acid resulting froma secondary one; two distinct reactions take place in this way inthe oxidation of most mixed ketones, and the proportion of theprimary to the secondary reaction approaches 2 : 1, as in this case.Popoff (AunaZen, 161, 289) and Volker (Wien. Acad. [el, 73, 335)found that propionic acid was the only product of the oxidation ofethyl propyl ketone ; the author can only conclude that they workedwith too small quantities of the ketone, and failed to separate theacids.EthyZ hexyl ketonp, obtained by the oxidation of tbe correspondingsecondary alcohol, itself obtained from the action of zinc ethyl oncenanthaldehydc, is a clear, refractive liquid with a sharp, aromaticodour; it crystallises at -8" i n long prisms, and boils st 190"(752 mm.) ; its sp.gr. at 0" = 0.840, a t 20°/00 = 0,825. The pro-ducts of the oxidation of this ketone are mnanthylic and acetic acidsfrom the primary reaction, and caproic and propionic acids from thesecondary, the proportion between the two reactions being nearly 3 : 1.Propyl hexyl ketone, obtained by the oxidation of the correspondingalcohol (b. p. 210-211" at, 759 mm.), boils a t 206-207" (753 rnm.),and solidifies in a freezing mixture to clusters of needles which melta t -9.5" to -9"'. Its odour is similar to that of ethyl hexvl ketone ;d 8 6 ABSTRACTS OF CHEMICAL PAPEHS.its sp, gr.at 0' = 0.839, a t 20*5"/0" = 0.8'24. Only cenanthplic andpropionic acids could be separated from the product of the oxidationof this ketone.The above experiments disprove Popoff's fourth rule ; the followingconcern the fifth rule :-3 i h y 7 isobafyl lrafone is formed by the action of zinc ethyl on iso-propplacetic chloride (b. p. 116-116*.5"). It i s a reFr;wtive liquidwith an odonr like peppermint ; i t boils a t 134.5-135" (735 mm.) ;its sp. gr. a t 0" = 0.829, at 17"jO" = 0.815. Isopropylacetic acidboils a t 175" (749 mm.). When oxidised, the ketone yields, from theprim8ry reaction, isopropy1;icetic acid and acetic acid ; and from thesecondory reaction, isobutyric acid and propionic acid, the pyimaryreaction exceediiig the secondary ; acetone and dimethacrylic acid(?) are also obtained, probably R S secondary oxidation products of theacids.This behaviour shows that the fifth rule is fallacious.Propyl isobutyl ketone (b. p. 154-156" at 755 mm.) yields iso-propylacetic acid, propionic acid, ncetone, and acetic acid, when oxi-dised.Ethyl isopropyl ketone is prepared from isobutyric chloride (I). p.92-93") and zinc ethyl ; it boils at 11375-114" (745 mm.), not117-119" (Pawloff, J. Buss. Chem. Soc., 8, 242) ; its sp. gr. at, 0" L=0.S30, a t 18"/0" = 0.814. It yields on oxidation acetone, propionicacid, isobutyric acid, and acetic acid (compare PawlofY, Zoc. cit.).Methyl isobutyl ketone boils a t 115.5" (745 mm.; Frankland,Aniialen, 145, 8 3 , gives 114" at $58"), and has a sp.gr. at 0" = 0.8195(Frankland gives 0-81892), a t 19"/0" = 0.8034. When oxidised, ityields isobutyric and acetic acids from the primary reaction, and iso-propylacetic acid and formic acid from the secondary.Methyl isoamyl ketone (b. p. 144-144.5" a t 752 mm.) yields iso-propylacetic acid and isobutylacetic acid on oxidation ; PopoE obtainedvaleric and acetic acids.Methyl butgl ketone yields butyric acid and normal valeric acid onoxidation,The author deduces the following generalisations From the resultsof hisand of other experimenters' work on this subject :-1. When a ketone of the fatty series is oxidised, the hydrogenatom attached to one of the carbon atoms linked to the carbonyl ishjdroxylised : the molecule of hytlroxyl compound thus formed issplit u p by further oxidation, 2 mols.of fatty acids, or 1 mol. of afatty acid and 1 mol. of a ketone, being formed.2. If only onr of t h e carbon atoms linked to the carbon71 behydrogenised, only this will be oxidised .and detached. If, however,both be hydrogenised, chromic acid mixture at 100" will generallycrluse oxidation in two directions, so that in some molecules of theketone the one, arid in others the other, of these carbon atoms will beoxidised, and theye will rewlt a primary and a secondary reactionregulated by the following conditions. 7;3. If the carbon atoms linked to the carbonyl be unequallyhydrogenised, the one which has less hydrogen will be oxidised andeliruinated in the primary reaction, and the one which is more hydro-genised, in the secondary reactionORGANIC CHEMISTRY, 374.If tbe carbon atoms be equally hydrogenised but combined,t h e one with a secondary (or tertiary ?), the other with a primary,alcohol radicle, the latter will be oxidised and eliminated.5. If the carbon atoms linked to the carbongl be eqnally hydrogen-.ised and combined with radicles of the same series, but of diffprentmolecular weight, that which is combined with the radicle haviirg lesscarbon will be preferably oxidised and eliminated.These generalisations allude to the oxidation of ketones a t 100"with chromic acid mixture. Experiments made w i t h methyl butylketone showed that (1) the course of the oxidation of methyl butylketone is influenced by the temperature ; (2) a t low temperatures, theoxidation proceeds in one direction only, and the less hydrogeuisedcarbon atom attached to the carbonyl is oxidised and eliminated ; (3)at higher temperatures, the oxidation extends to both these carbonntonls ; (4) it is thus probable that a t vei-y high temperatures, if theketone could withstand such, the coiirse of the oxidation mould be inone direction only, and that would be the reverse of (2).A.G. R.Determination of the Affinity of Organic Acids by means ofLacmoid. By F. ROHMANN and W. SPITZRR ( B e y . , 24, 3010-301.5).-During the titration of organic avids with soda, the authors haveobserved that a drop of the liqnid brought into contach with redlacmo'id paper produces a blue colour before sufficient soda has beenadded to form the norrrinl salt; the solution will turn blue Iacmoi'dpaper red, but t,his red colour disappears before the acid is cntirelyneutralised. This reaction depends on the fact that the alkali isdivided between the Iacmoid arid the organic acid in a definite pro-portion, which varies according to the nature of the acid ; a methodis thus afforded of determining the relat'ive affinities of acids for alkali.Experiments have shown that the coefficient of neutrality s/s' of twoacids is in inverse proportion to their affinity for alkali: s = thequantity of acid which is necessary to bring about the change incolour of the lavmoid paper, and s' represents the amount of normalsalt present.For the full details of calculation the original papershould be consulted.The affinities of the following nionobasic acids, compared withformic acid, agree closely with the values given in Ostwald's tables :-Acetic, propionic, butyric, isobu tjric, valeric, hydmxypropionic, andIiydroxyisobutyric. The method is also applicable to the bibasicacids, a similar agreement i n the results, as compared with othermethods, beinc obtained.It is desirable t o always deterniine the quantity of alkali which isrequired to be added to the acid in order to produce a blue colour onred lacmo'id paper, since the inverse procedure is more liable toexperimental error. J. B. T.Behaviour on Dry Distillation of the Silver Salts of OrganicAcids. By J.KACHLER (Monafsh., 12, 3 3 8 4 4 9 ) .-Silver acetate, CIILdry distillation. is decomposed according to the equation 4AgC,H,O,= 4Ag + 3C,H,02 + C + C02, the reaction being complete a t a tem-perature of 220-240'. The compound furnishes the same products38 ABSTRACTS OF OHEMICAL PAPERS.and in practically the same proportions, when it is heated to a hightemperature with water in sealed tubes.Silver formate decomposes in accordance with the equationSAgCHO, = CH,02 + CO, + 2Ag, when heated with water in sealedtubes.The silver salts of isovaleric, normal caproic, and oenanthylic acids,on dry disdlation, are approximately decomposed according t o theequation 2n(AgC,H2,-102) = (an - 1)(C,,H2,0,) + (n - l ) C + C 0 2 + 2nAg; in fact, this equatioti appears to indicate tlhe manner inwhich the silver salts of fatty acids are generally resolved under suchconditions.Silver palmitate, on distillation under reduced pressure (430 mm.),gives a considerable quantity of palmitic acid, aud, similarly, thesilver salts of lactic:, 01- hydroxy iso bu tyric, phenylacetic, and beuzoicacids decompose with formation of the respective free acids.The author confirms the statement of Klirnenko (J.Rus.s. Chem.SUC., 12, 97), that silver lactate, when air-dried, crystallises with 8 4101. H,O (compare Engelhardr, and hladdrell, Amalen, 63, 90).G. T. ill.Action of Hydriodic Aoid On Amido-auids. By A. KW~SDA(-Monatsh., 12, 4 1 9 4 3 0 ) .- l'lie author finds that the readiness withwhich .hydrogen is substituted for amidogen, on treatiug the amido-i~olcls with hydsiodic acid, varies considerably with the constitutionof the acid (see original).In his investigations, the acids utlderexamination, namelj, glyc;ociiie, u- and p-alauine, leucine, asparticacid, glutamic acid, aud oi*tho-, meta-, and para-amidobenzoic acids,were heated in sealed tubes with excess of Iiydriodic acid of sp. gr..1.96. Monobasic, Eattj acids, ot' the formula NH2.C,H2,z*COOH, arethereby decomposed, accordiiig to the equation NH2*CnH2rl*CO0 H -+-3HI = C,H2H+lCOOH + NklJ + 12, whilst such bibasic acids asaspartic and glutaniic acids are converted into monobasic acids,NH,I + 1,; ortho-, nieta-, and pal-d-amidobenzoic acids are llotdeconiposed in the ssme way as the monobasic acids of the fattyseries, for, in addition to the chief product, benzoic acid, smadyuautities of carbonic anhydride and of free hydrocarbons are ob-tained.The author has not been able to confirm the observation ofRosenstiehl ( Z e d . fiir Chem., lb69, 471) that toluidines are formedon heating amidobenzoic acids with hydriodic acid.6- Trimekhyle thylidenelactic Acid. By C . G L ij c KSM ANK (Monatsh. ,12, 356-361 ; compare Abstr., 1890, 237). - A more convenientmethod of preparing trimethyllactic acid than that previously de-bcribed is as follows :-20 grams of pinacone is suspended in 100 C . C .of 20 per cent. sodium hydroxide solution, and 63 grams of potassiulnpermauganate in a 4-5 per cent. aqueous solution is slowly addedt o the well-cooled mixture. When the oxidation is complete, theproduct is filtered, neutralised with sulpliuric acid, and evaporated todryness on the water-bath.The residue is dissolved in the leastpossible quantity of water, and treated with 250 grams of 4 per cent.sodium amalgam, added a little at a time. 'l'h solution ib filtered,thus:--NH,.C,H,,-,(COOH), + 3HI = C,B2,+1*COOH + COZ +G. T. MORGANIC CHEMISTRY. 39acidified with sulphuric acid, extracted with ether, the ethereal solu-tion evaporated, and the residue steam distilled, until the distillateceases to be acid. The residue, dried in a vacuum over sulphuricacid, consists of trimethyllac t ie acid.On heating the acid (1 part) with 98 per cent. snlphuric acid( 3 - 4 parts) in a reflux apparatiis at SO", it is resolved into carbonmonoxide, water, and tri.methylacetaIdehyde, CMe3*COH (yield 80 percent.).The new aldehyde boils ah 92-94', reduces a solution ofsilver, restores the colour to magenta, which has previously beentreated with sulphurous anhydride ; and, on oxidation with chromicacid, appears to be converted into acetic acid.By M. CONRAD andC. BK~;'CKNEK. (Ber., 24, 2993---3005). - h'thyl clichloromalonate,CCl,(COOEt),, is prepared by treating ethyl chloromalonate withchlorine a t 12U", removing t'he excess of the latter and the hydrogenchloride, first by heating on the water-bath, and subsequently byallowing the product to remain over soda-lime in n vacuum, and dis-tilling, when the compound passes over at 231-234" with only slightdecomposition as a colourless liquid, having a sp.gr. 1.268 at 17"compared with water at 15". Treated with an excess of cold alcoholicpotash, a niixt ure of potassium dichloromalouate and meaoxalateappears to be formed; whilst on mixing it with 6-10 times itsvolume of concentrated alcoholic ammonia, dichloromalonamide,melting at WiY (see Zincke an3 Kegel, Abstr., 1890, 49Oj, separatesafter two days, arid dichloracetamide (m. p. 98") is obtained fromthe filtrake.Ethyl chlorobromomalonate, CClBr( COOEt),, is obtained by bromin-ating ctliyl chloroniaionate ; it distils at 1.36-139" under a pressureof 35 mm., and boils a t the ordinary pressure af, 239--241" witlipa~tisl.deconiposition ; its sp.gr- is 1.467 a t 16" compared with watera t 13". Treated with four times its volume of concentrated alcoholicammonia, a compouud melting ah lC;O--ltj5" separates, which ie,perhaps, a mixture of chlorobromomalonaniide and amidochloro-malonnmide ; whilst chlorobromacetawide melting at 117" is obtainedfrom the filtrate. Chlorobromacetauiide has already been preparedby Cech and Steiner (this Journal, 1876, 1, 373), and as i t differs inmeltiug yoiiit from the authors' compound, they have repeated Cechand Steiner's experiments, and find that neither chlorobromaceticwid nor the amide described by these chemists are homogeneous sub-stances, but are contaminated with the dibromo-derivatives. Xthylbromornalomte, CHBr(COOMt), (Knoevenagel, Abstr., 1888, 707),lias A sp.gr. of 1.426 a t 15" cornpared with watein a t the same tem-perature.&thy1 acetyltwtronate, OAc-CH(COOEt),, is produced togetherwith the cowzpound C(COOEt),:C(COOEt),, by heating ethyl bromo-ma1on:tte (88 grams) arid potassium acetate (40 grams) dissolved in;tbsolute alcohol, a t 40-50' ; tlie formek is zlr bright yellow oil, boilingat 1S8--163' (60 min.), and has a sp. gr. la1;3l at 1.95" comparedwith water a t 15", whilst the latter is a solid compound melting a t 56".LVLcu etlrgl u c e t ~ Itartrunate i:, dissulved iu e t k i aid treated withG. T. M.Halogen Derivatives of Malonic Acid40 ABSTRACTS OF CHEMlCAL YAPEltS.sodium (1 eq.j,and then heated for 10 seconds on the wntein-bathwith ethyl iodide, the ethyl derivatice, OAc*CEt(COOEt),, boiling a t151-153" (30 mm.) is formed.Ethyl mesoxalate, C(OH),(COOEt),, described by Petrieff as anoil, is obtained by treating ethyl acetyltartronate w i t h somewhat morethan one molecular proportion of bromine a t 110" : i t boils at 140-145"(50 min.), solidifies after a time, and when crystallised from ethermelts atl 57".Ethyl phenyltartronate, OPh-CH(COOEt),, is prepared by dissolvingsodium (2.3 grams) in alcohol (35 c c.), adding phenol (9.4 grams)and ethyl bromomalonatr~ (24 grams), heating, distilling off thegreater portion of the alcohol, adding water, and extracting the pre-cipitated oil with ether ; it distils under a pressure of 60 mm.at,'2:30--'240". The acid obtained on hydrolysis with hydrochloric acidyields phenglglycollic acid (ni.p. 96') when heated a t 180".Ethyl dibromomalonate, CBr,( COOEt), (J. W isliceiius, Abstr.,1888, 151), is obtained by brominating ethyl mnlonate in direct sun-light ; it distils a t 145-155" under a pressure of 25 mm. ; when dis-solved in half i t s volume of cooled, concentrated, alcoholic ammonia,crystals separate, after a time, of a compound which probahly consistsof dinmidomalonarnide, C (NH2)2( CONH,), ; t h i s darkens at 150",dissolves in water with decomposition, and loses ammonia when care-fully heated a t 90-100",. yielding i?)zidoma!onarnide, NHI:C(CONH,),,a compound dissolving in water t o a neutral solution, from whichammonia is evolved on heating. When ethyl di bromomalona te i.;Iieated with benzene and sodium in the form of wire, i t yields thecornpowad C(COOEt),:C(COOEt), (see above) ; if digested with analcoholic solution of potassium acetate, ethyl mcsoxalate is formed ;whilst whcn heated with a mixture of plienol and sodium ethoxide,ethyl diphenoxymalonate, C(OPh,) (COOEt),, is obtained distilling a t250-260" under a pressure of 60 mm., and this, on boi1in.g withalcoholic potash, yields the corresponding acid, which, after beingcrgstnllised from water, melts a t 173".Brornethylrrialonic neid, Cfi;tBr(COOH),, is obtained in theoreticalyield when ethylmalonic acid is heated on the water-bath with a11excess of bromine ; i t melts a$ 104" with the evolution of carbonicanhydride and the formation of bromobutyric acid.A.R L.Action of Zinc on Ethyl Dibromosucciiiate. By A. MICHAEL(J. pr. Chem. [el, 44, 399403).-In this paper t.he author repliest o the criticisms of Claus (Abstr., 1891, 1338) on the work whichMichael and Schulthess published on the subject (Abstr., 1891,1184).The discussion is now closed as far as the author is concerned.A. ti. l5.Decomposition of Glutaric Acid at a High Temperature.By A. CLAUS (Annalen, 265, 247--253).-1n reply t o Wisbar (Abstr.,1891, l o l l ) , the author states that a careful repetition of his previou.;experiments has proved conclnsively t h a t carbonic anhydride isevolved on heating glutaric acid under the conditions already de-scribed. When the acid is kept for a long time a t 180-210°, it isconverted into i t s anhydride ; this compound is then cornpletelORGASIC CHEMtSTRS.41decomposed 'with evolution of carbonic anhydride, and there rcmainsa pornus, carbonaceous mass; the liquid distillate contains a con-siderable quantity of a n acid, which is not butyric acid, as was firststated ; the investigation of this product will be continued.Synthesis of Polybasic Fatty Acids. By K. AUWERS, E.K~~BKER, and F. V. MKYENBURG (Ber., 24, 2887--2901).--Tn a previouspaper (Abstr., 1891, 307), Auwers has published a preliminaryaccount of the synthesis of polybasic acids ; the present commuiiica-tion gives a detailed account of the acids already prepared. Theprocess employed is the same in all cases, and consists in warming amixture of a solution or emulsion of the sodium compound of ethylnialonate or one of its nlkyl derivatives with the ethyl salt of anunsaturated acid.The product is mixed with water and dilutesiilphuric acid, and the oily, ethereal salt which separates washed,dried, fractionated under reduced pressure, and hydrolysed by boilingwith a niixture of equal volumes of concentrated hydrochloric acidand water.The preparation of symmetrical ax-dimethylglutaric acid hasalready been described (luc. cit.).F. S. K./3-2l.;Crdhylgluturic acid,CO OH*C]H,*CHMe*CH,* C OOH,is formed by the action of ethyl crotonate on ethyl sodiomalonate,a~id hydrolysis of the crude ethyl salt, first obtained ; after crjstallisa-tion from ether and benzene, it nielhs a t 86". Ethyl sodiorrialoriate andethyl fumarate yield as t,he first product ethyl pro~nnetefracarboxylate,CH(COOEt),.CH(COOEt).CH,.COOEt, which boils a t 200--220"under a pressure of 25 mm., and on hydrolysis yields tricarballplicacid, COOH*CH2*CH(COOHj*CH2.COOB, melting a t 162 -164".The authors confirm Emery's statement that this acid, on treatmentwith acetic acid, yields an CLil7Lydrot).icai,ballylic acid, c;j6HG05, meltingat 131" (Abstr., 1891, 689).The product of the reaction of ethyl fumarate and ethyl sodio-niethylmalonate is an ethyl salt which boils a t 196-198O under apressure of 'LO mm., and has a sp.gr. of 1.1158 a t 38"/4". On hydro-lysis, i t yields two acids of the composition C7Hln06, which must,from t heiv mode oE formation, both be a-metl~yltI.icrzrball!/lic acid,COOH*CHMeCH(COOH)*CHL*COOH, and represent stereometrici>omerides, an acid of this formula having two asymmetrical cilrbonatoms. The acids are separated by crystallisation from water ; theless soluble compound crjstallises in compact, lustrous prisms, meltsa t 180", is readily soluble i n alcohol and acetone, but alrnost insolubleiii benzene and light petroleum ; its siluer salt, C7H7Ag3O6, is a heavy,white precipitate.The more soluble pcid is contained in the motherliqaor of the previons acid, and is separated by repeated crystallisa-t,ion from water ; it still, however, contains ammonium chloridederived from the ethyl cyanacetate present in commercial ethylmalonate, and may be separated from it by treatment with anhydr-ous ether.It then melts a t 134", and in its other properties closelyrcsembles the isomeric acid, into which it is partially converted byheating with hjdrochloric acid at 200"42 ABSTRACTS OF CHEMICAL PAPERS.The action of ethyl sodiomalonate on ethyl cit,raconate mightFroceed in two different ways, giring rise either to an a- or a /3-methyl-tricarballylic acid. The intermediate ethereal salt boils a t 226" undera pressure of 39 mm., and on hydrolysis yields i n small quantity anacid which has the composition C7HidOs, forms beautiful, transpareid,Crystals, and ruelts at 164". It is not identical with either of the fore-going acids, and mu.& therefore be ~-methyltricsrbccElylic &,id,COOHCH,-CMS( COOH).CH2*C00 H. If ethyl itaconat,e be substi-tuted for ethyl citracorinte, two reactions are also possible.leadingto the formation of either P-methyltricarballylic acid or butanetri-carboxylic acid. The iuterutediate ethyl salt was found t o boil at200-240" under 37 mm. pressure, whilst the acid formed from itcrystallises in rosette-shaped aggregates of prisms, and melts at116-120". It differs, therefore, csrripletely from /3-mehliyltricarb-allylic acid, and must be bzLtanet~i.'carbox~lic acid,C OOH-C H2*C H,.CH( COO H) *CH2C OOH.The two stereoisomeric a-eth~ltricarballylic acids,COOH*CHEt*CH( COOH)-CH,*COOH,may be prepared in a manner exactly similar to the correspondingmethyl compounds, TI be. intermediate ethyl ethylpropnnetetracarb-oxylate boils at 207-212" under a pressure of 25 nirri.The lemsoluble acid forms spherical aggregates of thin, lustrous obliqueprisms, and riielts a t 147-148"; its silver salt, CdH9Ag306, is a volu-minous, white precipitate, very susceptible to bhe action of light.The more soluble acid was not obtained in auffiicieut quantiky for COLU-plete purification.Yropy Ztricarhally Zic acid, CO OH-CH Pra* CH (C 0 OH) *ClH,*C OOH,and isvyropy ltricarballylic acid,C 0 OH- C H Prp* C H ( C 0 0 H j - C H,. C 0 0 H,are readily obtained by heating ethyl fumarate with ethyl propyl- orisopropyl-sodiomalonate. The former crystallises from water onspontaneous evaporntion in cumpact, lustrous prisms which containwater of crystmallisation and melt below 100" ; when rapidly crystal-lised, however, i t forms nodules consist,ing of anhydrous plates,melts at 151-152", and is soluble in alcohol and ether, but alnio,stinsoluble in benzene and light petroleum.The mother liquors con-tain lower melting products which could not be isolated. Isoprupyltri-carballylic acid crystallises in anhydrous nodules formed of platesor compact prisms, meits a t 161-162", and behaves towards solventsin the same manner. as the previous acid.Determinations of the conductivities of these acids have been madeby Walden, and it appears that, as j11 the case of succiriic acid, theilltrod uction of alkyl groups into t,ricarhallylic acid raises the toll-ductivity t o a cousideruble extent.An attempt W H S made to bring about the combination of ethylsodiomalonate and t h e ethyl salt of A'-tetrnhydroplithxlic acid, HYthe lat,tor beh;~vea in many rospects its an uus'tturilted fatty acidORGANIC CHEIIISTRI'.43No reaction, however, was found to take place on digesting the mix-ture for six hours at 100". H. G. C .Furfurylamine. By A. DEUTZMANN (Chew. Centr., 1591, ii, 295-296 ; from Dim. BerZiiL).-The following compounds are described :-Furfurylamine furfury~ditlai~arbamate,C40 &* C H2.NH.C SSH,NH2* CH2*CaOH3,is prepared from 6.8 grams of carbon bisulphide dissolved in dryether and 18 gmms of furfurylamine; i t is soluble in alcohol, ether,benzene, and light petroleum; when exposed to the air, it becomesyellow. ~urfiec9.ylthiocarbimide, CS:N.CH2-C40H3 is prepared fromthe last-named salt by the action of mercnric chloride, which mustnot be in excess.D~iL.1.fu?.ydthioca1.barrLide, CS (KH-CH2*C40H,),, prc-pared by heating the dithiocarbamate at loo", melts a t 85-86".MethyIfurfurllZthio~rEamide, prepared from methylthiocarbimide andfurfurylamine, melts at 85". Etl~ylfur~ury7thiocarbnmide melts at 67".AllyQurfuryIthiocarbamide melts a t 42-43'. Y?~eny~u~fui.?Jlthioccxrb-amidc! melts at 128" ; the paratolglmrbarnide melts at 165" ; the metu-z y iy lcarbamide at 12 1-3".f~brfur~lcarhnnzide, NHz0CO*NH-CH2-C@H,, prepared from f u r -furylamine and potassium cyanate, melts a t 110-111" ; difurfuryl-carbantide, prepared from furfurylamine, potassium h-j-droxide, andcarbouyl chloride dissolved in benzene, melts at 128". E'thyI;fiir-u~yl-carbaniide melts at 95 -96" ; a~~lj~L1j:u?.y1cal.lramide at 120-1.'1".These were prepared by the aid of ethyl- and aniyl-carbimide respec-tively.PhenylfurfurylcarEa~aide melts at 124" ; the orthotolylcarh-amidP at ltjS-16t3*5° ; the metnxylyQluarbamide a t 178". From di-fur~~ryltl~iocarbarnide, by the action of mercuric oxide, cyanamide andfurfurylamine are obtained, but not the corresponding guanidine.The hydrochloi-ide of jurfurylguanidine, C( NH,)2:N*CH2*C40H,, maybe prepared by heating cyanamide and furfurylamine hydrochlorideat 100" in a sealed tube. Both it and the platinum salt were analyseti.Dipheng Vurf u ~ ! / lguanidine, C (NH Ph) , X * C H ,.C,OH 3, is preparedfrom the last-named compound by heating i t with aniline a t 80-81".By treating the aniine with methyl iodide, t l .i m e t h y ~ u ? f u r y l a n ~ ~ ~ o ~ ' i u iodide, C,0H,*CH2*NMe31, is obtained,By distilling f urfurylamine hydrochloride, a liquid was obtainedwhich probably contained furfuryl chloride. Nitroj"urfu,ylami?/e isprepared by acting with nitric acid on acetylfurfusylauiine in glacialacetic acid, and then distilling with steam. J. W. 11.Intramolecular Change of the Propyl Group. By 0. WID-MAN ( J . pr. Chew.. [ a ] , 44, 414-415; compare Abstr., 1891, 686,1344).--Fileti (Abstr., 1891, 1,344) quotes Widman as having pointedout that the nitration of cumenylacrylic acid produces paranitrociii-namic acid, orthonitroparisopropylcinnamic acid, and an isonieride oftile latter which he called orthonitroparapropylcinnamic acid.Wid-man now points out that Fileti has missed the publications (Abstr-.,1891, 69, 45) i n which i t is shown that this " orthonitroparapropyl-cinuamic;" acid is really a mixture of about one-third ruetanitlo32 ARSTRACTS OF GHEMIOAL PAPERS.cumenylacrylic acid and two-thirds orthonitrocumcnylacrylic acid,the mixture having a constant melting point and crystnllisinq in adefinite form. A. G. B.Isomeric Change in the Synthesis of Aromatic Amines andPhenols. By M. SET~KOWSKI (Ber., 24, 2974--3977).-It is wellknown t,hat the higher homologues of aniline, produced by heating itsalkjl derivat,ives or the corresponding alcohols with its hydrochlorideor stannochloride, invariably belong to the para-series ; the sameapplies to the homolopes of phenol obtained by the action of zincchloride on a mixture of phenol and the alcohol.The experimentsto he descrihed were instituted to ascertain whether in these casesintramolecular changes occur similar to those observed in the syn-thesis of aromatic hydrocarbons by means of aluminium chloride.Paratertiarybutylplienol (Abstr., 1890, 1296) is obtained by theaction of zinc chloride and isobutyl alcohol on phenol in the mannerdescribed by A. Liebmann (Abstr., 1882, lil, 72'7).Paramidophenyltrimethylmethane (7oc. cit., 1890j is formed byheating auiliiie hydrochloride with isobutyl alcohol in a sealed t,ubea t 230"; it yields trimethylphenylmethane (Zoc. cit., 189U) by thediazo-reac tion.The so-called isobutylbenzene boiling a t 165-1'70" (Goldschmidt,Ab$tr., 1882,952) is a mixture.When treated with bromine in directsunlight until the colour of the bromine persists for several minutes,and, after wasliing the product with potash and drying, it is distilledover sodium, a small quantity of a bydrocarbon passes over at167-168", apparently identical w i t h trimethylphenylrnethane.1soam.ylnniline (Hofmann, this Journal, 1874,807 ; Merz and Weith,Abstr., 1882, 179), when treated with one molecular proportion ofbromine in sunlight, and with a second, in the dark, at the temyera-ture of the water-bath, yields Schramm's isoainylbenzene dibromidemelting a t 129" (Abstr., 1883, 977), and is, therefore, a normalproduct. A. R. L.Action of Nitrous Acid on Resorcinol Diethyl Ether and onTriethylresorcinol.By A. KRAUS ( M o ~ L u ~ s ~ . , 12, 368-378) .-When a solution of resorcinol dietliyl ether (1 part) in acetic acid(10 parts) is saturated with hydvogen chloridc, and treated in thecold with a large excess of alkaline nitrite, a very considerable quan-tity of a dark-green precipitate separates. The product is dilutedwith water and filtered, and the solid thus obtained treated with cold,dilute potash, whereby the greater portion dissolves, forming a dark-red solution, f rorn which hydrochloric acid separates nitrosoreso~-c.inoZethyl, sthey, NO*C,H,(OH)*OEt, in the form of a voluminous, light-yellow precipitate. The ether may be readily recrystallised from hotwater and from hot alcohol (compare Aronheim, Ber., 12, 30).when it forms thiu, pale-yellow scales which decompose at 150"without having previously melted.That part of the above-mentiouedproduct which is insoluble in cold dilute potash is washed with coldalcohol, and dried in a vacuum. On elementary analpsis, it giveORGANIC CHEMISTRY. 45numbers correspondirtg with t h e formula for nitrosoreso&noZ diet7,yzether, NO*CaH,(O13t)2. It melts at 122--123", is soluble in cold chloro-form, benzene, and ether, but is decomposed when warmed with thosesolvents ; i t has a pale-rose colonr, and givcs a n intense blue colorationwith concentrated sulphuric arid hydrochloric acids. The benzoyZderivative of nitrosoresorcinol et h j 1 ether, NO.C,H,( OEt)*OBz, isobtained i n the form of yellow flocks on sbaking a solution of theether i n soda with an excess of benzoic chloride.When recrystal-lised from alcohol, i t forms beautiful, jellow crystals which melt at155".Xitrosoethy Zresorcinol ethyl ether, KO*C,H2Et (OH)*OEt, is obtninedwhen triethylresorcinol (compare Herzig and Z ( isel, Abstr., 18!& j,1404) is dissolved in ten titnes its weight of absolute alcohol, aild thesolution mixed with slightly more than the molecular equivalent ofsodium nitrite, and decomposed with concentrated hydrochloric aciduntil the whole assumes a brownish-yellow colour. On the additioilof v\ ater, a green, flocculent pi-ecipitate is formed, the colour of whichgradually changes t o reddish-yellow. The precipitate is dissolved inpotash, and the solution exhausted with ether; the ethereal extrac.tis acidified, and the yellow precipitate thus obtained crystallisedfrom hot benzene, which furnishes the compound in the form ofheautif'ul, yellow prisms.I t dissolves when warmed with ordiuaryFolvertts, and decomposes a t 150', without having previously melted ;it gives a stable base on treatment with reducing agents, is oxidised bynitric acid, first to a nitro-compound, and eveiitually to oxalic acid,and forms a well chara eterised hrnzoyl drricatice,NO*C,H,Et( OEt)*OBz,which is insoluble in potash, and melts at 141-142'. G. T. M.Hydroxyquinones. By KOWALSKI (Chem. Cenfr., 1891, ii, 377 ;from Schweiz. Wochewsc7ir. Yhurin., 29, 265).-The author hasobserved the formatioil of hydroxyquinones from quinones, when thelatter are left exposed to the action of aqueous alkali and air.Fronla-naphthaquinone and from thyruoquiiione the corresponding hydl--oxy q ui n ones were obtained .Isoeugenol, Diisoeugenol, and their Derivatives. By E.TTEM.4SN (bey., 24, 2870---2877).-1n his researches 011 the productsof oxidatiori of acetyleugenol (tliis vol., p. 59), the author was ledto suppose that t h e eugenol enipIoyed might contain a hithertounknown isomeride, or that such a cornpound might be formed as a11intermediate product during its oxidation. H e therefore examinedthe action of various reagents on eugenol, but only succeeded in con-vertiiig it into the already known isotneride, isoeugenol,CHMe:CH*C6H3(OMe)*OH [l : 3 : 41.This molecular interchange proceeds best when carried out asfo1lows:--12-5 parts of potash a r e dissolved in 18 parts of amylalcohol, 5 parts of eugenol added, the mixture heated for 16-20J-. W.L46 ARSTRACTS OF CHEJITCAL PAPERS.hours at 140", and the nmyl alcohol removed by distillation in acnrrent of steam. Snlphiiric acid is then added, the isoeugenolseparated, washed with Podiiim carhnnnte solution, and distilled ina current, of steam. It then boils at 261" (uncorr.), and hfis all theproperties assigned to it by Kmaz and Tiemann (Abstr., 1583, 201) ;in alcoholic solution, it is coloured olive-green bv ferric chloride, andif left it becomes yellow, bnt mnch less rapidly than engenol. Itscoefficient of refraction is 1.5728, that of en pen01 being 1.5438.The substance described by Kraaz and Tiemann as Inenzopliso-eiigenol is in reality a derivative of diisoeugenol, and not of iso-euyenol.The monomolecular acetyl and benzoyl componnds can onlybs obtained under certain conditions. Acetylisoeugenol, Cl,,H,,02Ac, isprepared by boiling the phenol with acetic anhydride, and separates inlustrous, white needles on the addition of l i g h t petroleum to its benzenesolution; it melts a t 79-40", boils at 282-283" (uncorr.), and isreconverted in to isoeugenol hy alkalis. Benzoylisoevgenol, CloHI1O2Bz,is formed by the action of benzoic chloride on a solution of isoeugenolin dilute soda, provided the liquid never becomes acid ; it crystallisesfrom alcohol in white prisms melting at 103-104".Dia,cety ZdiisoeugenoI, C~~HZ,O~AC~, is obtained by adding acetylchloride to isoeugenol previously warmed to 54", and raising thetemperature to 80°, heating as long as hydrogen chloride is evolved.The product solidifies on coolinq, and may be separated from adheringoil by means of ether ; the rcsidue is crystallised from boiling alcoliol,and then forms white needles which melt at 150-151", and arealmost, insolnhle in water and ether.Dihenzoy ZdiisoeugenoZ, CzoHZOdBZ2,is the compound previously described by Kraaz and Tiemann (Zoc. cit.)as beneoylisoeugenol. Both these substances on hydrolysis yielddiisoeugenol, which may also be obtained by the action of mineralacids or acid Halts on isoeugenol; it crystallises from 50 per cent.alcohol in slender needles, melts at 180-181°, is readily soluble inether and chloroform, less easily in alcohol, and almost insoluble inwater and light petroleum.Its alcoholic solution is coloured olive-green by ferric chloride.The molecula~ weight of diisoeugenol, as found by Rnoult'smethod, agrees with the above formula, but no evidence as to i t sconstitution has yet been obtained. It might possibly be a tetra-methylene derivative of a formula such as~HMe*~H*C6H3(OMe)-OHCHMe*CH*C6H3( OMe)*OH'or it may be a diphenyl derivative. Further investigation of thiscompound is in progress.Oxidation Products of Safrole. By F. TIEMANN (Ber., 24,2'379-2886).-The results given in the preceding abstract and on p S 9show that acetyleugenol and acetylisoeugenol are compounds whichreadily undergo decomposition.and that in their oxidation several pro-cesses occur simultaneously ; the exact investigation of these processeshas been rendered still more difficult by the fact that in thesecondaryreactions the benzene nucleus itself has been attacked. The authorH. G. CORQANIC CHEMISTRP. 47therefore wished to follow out the oxidation pi'ocwses in a phenyl-allylene derivative, i n which the action of the oxidising agent wouldbe confined to the carbon side chnJn. Such a derivative has heenfound in sifrole, which has been shown by Eykman (Abstr., 1886,95) and Poleck (Abstr., 18E4, 1339 ; 1886, 697) t o have the constitu-(3)tion CH2<o>C,H,.CH,*CN:C12 0 (1).(4)On carefully oxidising safrole wit'h 14 per cent,.prmanganate solu-tion at 70--80", it takes up two hydroxyl groups, forminq mefhylene-3 : 4-dihydroxybenz?/ 1 glycol, CH2< o> C6H3*CH2*CH(OH) *C H2*OH,which crystdlises from henzene in white needles, melts at, 82-83',and is readily soluble in boiling water and ether, less eRsily in alcohol.Its diacetate. ClnHlo04Ac2, is a pale-vellow oil boiling at 240" undera pressure of 15-20 mm. ; and the diphenylcarbarnate,obtained by the action of phenyl isocyanate on the glycol, crystallisesin plates, and melts a t 127".If 5 parts of safrole be warmed at 70-80" with 12.5 parts of per-manganate, 5 parts of acetic acid, and 1000 parts of water. piperonal,piperonic acid, and a-homopipwonic acid are obtained. The f i i a s t isremoved hy extracting the alkaline solntion with ether, and the alkalinesolution is then concentrated.acidified, amd exfracted with ether.The residue obtained from this extract, which contains piperonic and01- homopiperonic acids, is boiled with ma,gne&-im carbonate, resinousmatters being removed by ether, the solution again acidified and takenup with etrher, the latter evaporated, and the residual mixture of thet w o acids separated by fractional crystallisation from hot water,0Cl~H~oO~ (CO*NH Ph) 2,2-Homopiperonic acid, CH2<O>CJ13*CH2*COOH, 0 c~ystallises inwliite needles, melts a t 127--128", and dissolves readily in boiling water,alcohol, ether, and hot benzene, scarcely a t all in light petroleum.The calciuriz salt contains 2 mols. H?O, which are given off sit 100"; thecopper salt, (CgH,04)2Cu, forms a pale-green, crystalline powder ; thesilver salt, C9H,04Ac, a white, crystalline powder, which may becrystallised from hot water ; the zinc salt, (C,H704)2Zn, is also whiteand crystalline.The methyl salt, C4H704Me, and ethyl salt, C9H7O4Et,are yellow oils boiling at 278-280" and 291" respectivelg, and thearnidr, C,H,O,.CON H2, crystallises in needles melting at 172-173".On treatment with nitric acid, a-homopiperonic acid yields a, nitro-cninpouv.d, CgH,04*N02, which ~rysta~llises in yellow plates, andmelts a t 188". Further oxidation converts the acid into piperoaicacid and piperonal.From these remlts, it appears that the allenyl group of safroleundergoes oxidation in a normal manner ; the intermediate homo-0 piperonal, CH2< > CsH3*CH2*CH0, has not been isolated, owing 0probably to its instability; so far also no indication of a compoundcorresponding with acetovanillone has been observed.H. G. C45 ABSTRACTS OF CHEMICAL PAPERS.Action of Benzyl Chloride on Orthotoluidine. By C.R,ARAUT (Bull. Xoc. Chim. [$I, 5, 742--743).-Benzylnrthotoluidine,C,H,Me*NHPh, is formed when benzjl chloride (1 mol.) is heated wit,liorthotoluidine (2 mols.) in a n open vessel for 4U hours at 175". Thecrystalline product of the reaction is treated with aqueous sodiumcarbonate. and gieltls a dark, chestnut-coloured oil, which, on puri-fication, becomes almost colourl~ss. Benzylorthotoluidine boils a t210' under a pressure of 25 mm., cryst'alliees from alcohol in tuft+,melts a t 56-57", and is soluble in the ordinary menstrua.Thehydrochloride forms white crystals, is soluble i n alcohol and hotwater, and unites with platinum chloride to form a jellow, crystal-line platinochloride. The acetate, sulphate, nitrate, and oxalute arewhite.When henzylorthotoluidine is treated with ethyl iodide, henzyl-ethylorthotoluidine, C,H,Me*NEt*CH,Ph, is obtained as a yellowislr,neutral oil boiling at 230" under 25 HIM. pressure.AcelyZbenzllZorthot(,luidine is solid z t ordinary temperatures, andboils at 289-285" under a pressure of 20 mm. JN. W.Oxidation of Azo-compounds. By C. LAUTH (Compt. rend., 112,1 512-1514) .-Azo-compounds, when oxidised by various reagents inthe cold, yield diazo-compounds together with quinones.Acid andalkaline reagents give similar results; the author has chiefly eni-ployed lead dioxide in the presence of sulphuric acid.The sodium salt of henzeneazo-/3-napht~holdisulphonic acid is dis-Folved i n 30 parts of water ; to the solution, 2 parts of sulphuric acid(66") and 1 part of the lead dioxide are added; the red-orange solu-tion rapidly becomes lemon-yellow, and there i s no evolution of gasi n the cold. Kitrogen is rapidly evolved on heating, and, when dis-tilled, phenol comes over in tlhe first portions of the distillate. Thediazo-solution, on treatment with a n alkaline solution of phenol,yhenolsulphonates, o r amines, gives azo-colouring matters ; foroxnmple, the addition of ~-naphtholdisulphonic acid regeneratesl~enzene-azo-~~-naphtholdisulplionic acid.Conipounds substituted int h e diazo-group react equally well: Orange I (the sodium salt ofsulphobenzeneazo- a-iiaphthol) yields, similarly, a diazo-solutiou ,giving, on distillation, phenylparasulphonic acid. Again, snlpho-henzenenzo-phenol, by oxidation, yields a diazo-solution, u hich, ont h e addition of an alkaline solution of a-naphthol, gives Orange I.The reaction has been applied to a large number of azo-compounds,including unsubstituted compounds, such as azobenzene, as well ascompounds containing amido-, hydroxg-, or carboxyl-groups. Noexception has been found to the general course of the reaction in-dicated above. The reaction may be considered to be characteristicof the azo-compounds.When the liqnid, after oxidation, is filtered from t h e lead sulphateformed, it yields a yuinone in the case of sulphobenzeneazo-phenol ;in other cases the residue contains most of t h e oxidation products.The general reaction for the oxidation is of the type ofC6$&,.Nz*CJ€G*OH + H2SO4 + 0, = C,III,.N,*SO,H + CIUHGO, + H2OORQANLU C KEXISTR Y.4)intermediate products may be obtained at tohe same time, if thooxidising agent is noto present in sufficient quantity, as well as tetrazo-compounds. W. T.Action of Phenylhydrasine on Phenols. By A. SEYEWETZ(Compt. retad., 113, 264--267).--Phetiol, the cresols, and thenaphthols do noh yield compounds with phenylhydrazine in presenceof various solvents, and under various conditions.Dihrdric phenols behave differently, and readily combine withphenylhydrazine, the reaction being so distinct in the case oforcinol that it would almost seem to indicate the presence of a ketonicor aldehydic group in this compound.A concentrated aqueous solution of the phenol is mixed with asolution of phenylhydrazine in water slightly aciditied with aceticacid.After agitating for some minutes, the compound separates, iswashed with water containing a little acetic acid, and then recrystal-lised from benzene.Q uinol yields the compound C,H,( OH),, 2NHP h*NH?, which crystal-lises from boiling benzene in small, white, nacreous plates melting a t70-71". It gradually alters when exposed to the air, and becomesyellow, is slightly soluble in cold water, somewhat soluble in warmwater, alcohol, chloroform, ether, and benzene, very slightly soliiblein light petroleum.Alkalis liberate phenylhydrazine, even in thecold ; acids liberate the phenol.Resorcinol yields the compound described by Baeyer and Kochen-doerfer.Orcinol readily yields the compound C,H3Me(0H),,2NHPh-NB,,which forms white crystals melting at 61-62", and similar in generalproperties to the yuinol derivative.Catechol seems not to form a corresponding compound, and this istrue also of pyrogallol.Salicylic acid, in presence of toluene, yields R compound crystal-lisiug in slender, white needles, and melting a t 122-123". In manycases, however, the finding of a suitable solvent constitutes a greatdifficulty.C. H. B.Combination of Phenylhydrazine with Ethyl Oxalacetate.By W. WISLICENUS and M. SCHEIVT (Bsr., 24, ~~006--3010).-0nmixing together ethereal solutions of phenylhydrnzine and ethyloxalacetate in molecular proportion, and cooling, an additive corn-pouiid is deposited in coloiirless, lustrous plates ; it may be crystal-Jised from absolute alcohol, and melts at 105-106". This substanceis distinguished from the hydrazone (m. p. 76-78') by its colour,and by its insolubility i n ether arid in light petroleum. The adclitivecompound is readily converted into the hydrazone by filsion, or byheating it in solution ; a t ordinary temperatures the change is moregradual. The constitution of this compound may be represented bythe formula CoOEtC(3H)(NH*NHPh)CH2.CO0 Et, which wouldreadily exp'lain its conversion into the hydrazone ; from the generalproperties of the substance, however, as well as from tho fact thatall efforts hitherto made to prepare similar substances from ot,herVOL.LXII. 50 ABJTRACTS' OF OHEMCCAL PAPERS.less acid, ketonic, etheraal salts have failed, t,he authors consider i tt o be an analogue of the ammonium salts, with the formulaCOOEt-CO-C H(NH,.NHPh)*COOE t orC0OEt.C ( O*NH3*N HP h) :C: H*COOEt.The same substance is alsn formed bv the action of phenplhydr-azine hydrochloride on ethyl sodoxalacetate in cold, concentrated,aq 11 eou 8 solution.Mrthyl oxalacetate and ethyl et,hoxyoxnlacetate yield additive com-pounds with phenylhydrasine similar to the one described above,whilst et(hp1 methyloxnlacets,te, et'hgl oxalsnccinate, ethyl acetoacetate,ethyl benzoylacetate, and ethyl levulinate do not react in this manner.J.B. T.Oximes and so-called Stereochemistry. By A. CLAUS (J. pr.Chem. [2], 44, 312--385).-This paper deals with the isomerism ofthe hgdroxylamine derivatives of benzile. and esp~cially with theI-ecent work of Anwers and Meyer on ths subject (Abstr., 1889, 403,609, 611, 713). The author concludes by claiming that he has in-c mtrovertibly proved that all mnnifesta tions of isomeri,sm amongthe products of the reaction of hpdroxylnmine with benzile can beefficiently and easily explained as caqes of isnmerism in Rtructure,without having recourse to any stereochemical hypothesis.A. G. B.Intramolecular Change of some Isoaldoxime Derivatives.Ry R.BEHREND (Annmlen., 265, 238-246).- When pure benzpliso-1)aranitrohenzaldoxime (m. p. 118") is dissolved in alcohol (9-10parts), and the solution warmed with a few drops of a dilutealcoholic solution of sodium ethoxide, it is partially converted intolwranitrobenzy lisobenxaldoxime ; this change is expressed by theeq urttionand is, to st certain extent, reversible, as when para,nitrobenzyliso-benzaldoxime is treated with sodium ethoxide under the sameconditions, it is in part transformed into beneylisoparanitrobenzald-oxime.When benzylisometmit rohenzaldoxime, prepared by the con densa.tion of metanitrohenzaldehyde with B benzylbydroxrlan~ine, is warmedwith a dilute alcoholic solution of sodium ethoxide, it is partiallyconverted into the isomeric metanitrobenzylisobenzaldoxime, and onevaporating the solution, amixture of the two isonierides is left ; this isdissolved in alcohol (about 10 parts), and on keeping the solution forabout 24 hours, the greater part of the unchanged benzylisonitro-benzaldoxime is deposited in crystals, whilst most of the isomerideremains in solution; the latter is obtained i n a pure condition byrepeated fractional crystnllisation from alcohol.Metanitrobenzylisobenzaldoxime, C,J€12N203, purified in the mannerjust described, crystallises from hot alcohol and benzene, in both oORGANIC CHEMISTRT.51which i t i s readily soluble, in lustrous, pale-yellow needles, melts at114-115", aiid is only sparingly soluble in ether, and almost insolp-hle in light petroleum.It seems t o he unchanged by a warm solutiono€ sodium ethoxide, but when heated with hydrochloric acid, it isdecomposed into benzaldehyde and p-me~anitrobenzylhydrox:ylamineh~d?-ochlo~ide; the latter is readily soluble in water, but moresparingly in alcohol, from which it is precipitated OR the addition ofetlikr, as a colourlesa, crystalline powder, melting at 145-146",with previous softening; the melting point of the salt which hagonce been melted is much higher. The free base crystallises fromhot water in needles, melts at 79*5-80*5", and reduces Fehling'ssolution,Renzylisoanisaldoxime is not acted on by sodium ethoxide underthe conditions described above. F. S. I(.Amidines. By W.LOSSEN (Annalen, 265, 129--178).-Theinteresting results obtained on treating benzeaylamidine and otherItmidines with nitrous acid (Abstr., 1891, 103%-1042) have Ied t h eauthor and his pupils (Mierau, Kobbert, Neubert, C. Lossen, Kiimh-nick, and Umbowski) to subject the amidines to a somewhat ex-tended investigation, in order to determine (1) which of thesecompounds form dioxytetrazotic acids and stable nitrites, and (2) howthe properties of the amidines compare with those of the amid-o xi rfi es .Benzmylamidine sidphafe, (C7H8Na),H2SOa + H,O, is easily ob-tained by evaporating a solution of the nitrite with the theoreticalquantity of sulphuric acid, and extracting the residue with aicoholland ether successively; the insoluble sulphate is then dissolved inwater and reprecipitated by the addition of alcohol ; it loses its watera t 80--81", and decomposes into benzonitrile and ammonium sulphateon further heating.The formate, C,H8N2,CH20a + H70, prepared bydecomposing the sulphate with barium formate, orystallises well, isreadily solnble in alcohol and water, and loses its water over sulph-uric acid. The acetate, C7H8N2,C2H,0a, forins monoclinic crystah,a : b : c = 1.099 : 1 : ?, p = 120" lS', and is readily soluble in waterand alcohol. The n.itrite, C7HsN2,HNO2 + HzO, can be obtained byevaporating a solution of equivalent quantities of benzenylamidinehydrochloride and sodium nitrite ; it crystallises from alcohol innionoclinic (01- rhombic ?) plates, a : b : c = 3.467 : 1 : 3.425, /3 =94" 32'.and decomposes below 70" with formation of benzonitrile ; itis readily soluble in water and alcohol, but insoluble in ether.Pbenylbenzenylaniidine can be prepared by triturating benzimido-ethyl ether hydrochloride (1 mol.) with warm aniline (1 mol.), andalso by treating benzanilide imidochloride with aiihjdrou; ammonia inlight petroleum solution ; i t melts at 112", and is identical with thecompouud obtained by Bernthsen (Annulen, 184, 348; 192, 29)by treating aniline hydrochloride with tbiobenzamide, or withbenzonitrile ; its constitution is probably exprewed by the formnlaNH,*CPh:NPh. When thifi amidine is treated with nitrous acidunder various conditions, it yields benzanilide a8 the sole product, afact which shows that the nitrite of the base is very unstable.e 52 ABSTRAC l'S OF CHEMICAL PAPERY.Phenylbenzin~idoethyl ether, NPh:CPh.OEt, is formed in preparing~,henylbenzenylanidine by the action of aniline on benziniidoethylether hydrochloride ; it is an oily liquid, the hydrochloride of whichdecomposes at about 60" into henzanilide and ethyl chloride.Whenthe oil is heated ato about 70" with phosphorus pentachloride, i tundergoes decomposition into eth-jl chloride and Lenzxnilideimidochloride, CC 1 P h:N P h.Metanitrobenzimidocthy3 ether hvdrochloride, identical with thecompound described by Tafel and Enocli (Abstr., 1890, 973), can beprepared by passing hydrogen chloride into a well-cooled, alcoholicbenzene solution of metanitrobenzonitrile ; the pZatJnochloi.ide,is a reddish-yellow compound.When met:mitrobenzimidoetbyl ether hydrochloride is treated withalcoholic ammonia, it is converted into nietani trobenzetiylamidinehydrochloride (compare Tafel and Enoch, Zoc.cit.). The correspond-ing sulphate, [NO,C,H,*C (NH >):NH],,H,SO,, prepared from thenitrite, is soluble in water and alcohol.N0,*C6H,*C (N H,) : NH,HN O,,is obtained when a concentrated solution of the hydrochloride istreated with d y e r nitrite, and the filtrate evaporated a t 30-40" ; i tcrystallises in prisms. and decomposes when heated, yielding meta-nit robenzoni trile, water, R TI d nitrogen.Metanitrobenzo y Zbenzamide, N 02*CsH4* C O*N H *CO P h, is formedwhen metmitrobenzenylamidine is treated with bcnzoic chloride andpotash ; it crystallises from alcohol i n plates, and nielts at 133--134O.An ethyl derivative of metanitrohenzenylamidiiie can be obtained bytreating the amidine with ethyl iodide in ethereal solution; itsplutiizochloride has the compo-ition ( NO,G H,-N,H,Et),,H ,PtCI,.When iiretatiitrobenzenylamidine is treated with hydroxplamine, it isconverted into the corresporiditig amicloxirne.PheTrylmetanitroherLzimiclo ether, N0,.C6H,*C( :NPh)*OH, is formed,together with phenylmetanitrobenzenylamid~ne, when metanitro-benzirriido ether.hydrochloride is warmed with aniline ; i t crystallisesi n yellow prisms, melts a t 55-56", and is readily soluble in colcihydrochloric acid ; when heated with alcoholic ammonia a t 100°, it isdecomposed into aniline and metanitrobenzonitrile.Yhen~lm~tanitrohenzen!~lumidine, rc'0,-C6H4C(:NPh).NH, + HzO,can also be obtained by heating metanitrobenzonitrile w i t h anilineliydrochloride ; it crystallises from ether in yellow prisms, melts a ti2-73", and deconiposes a t 100".nielts a t about 251".When an ethereal solution of the amidine isheated a t 100" with ethyl iodide, :: yellow, crystalline salt ot' thccomposition N 02*C6H4*CN2 HPhEt,HT is formed.Symmetrical diuhenylbenzenylamidine is not acted on by nitronsacid ; when anhydrous asymmetrical di phenylbenzenylanlidine iswarmed with amy1 nitrite, or treated with nitrous ncid in aqueoussolution, it is couvcited into diphenylbenzamide (m. p. 175").(C,H,UN?O,)Z,H!2PtC16,The nitrite,The hydrochloride,NOzoC6H4*CN2H2P h ,HCIORGANIC CHEMISTRY.53EthyZhenzenyEamifli//e, CN,K2PhEt, is for tied when b3tizimido etherhydrochloride is treated with a 25 Fer cent. solution of ethylatnine,but it, cannot be obtained i n a pure condition. The hydrochEoride.CN,H,PhEt,HCI, crystallises from alcoholic ether in needles, melts rtt161", and decomposes above 200" with formation of beneonitrile andethylamine hydrochloride; i t is very readily soluble in water andalcohol. The platinochloride, ( CN2H2PhEt),,H2PtC16, crystallises fromalcohol in microscopic, reddish-yellow prismg. The nitrate,CN,H,P h E t ,HN03,is deposited in long needles when a. solution of the nitrite in fuminqnitric acid is evaporated at the ordinary temperatuve; i t is veryreadily soluble in water.The nitrite, CN2H2PhEt,HN0,, prepared bytreating an aqueous solution of the hydrochloride with silver nitrite,crystallises from alcohol in slender needles, melts tit 12T, and is veryrertdily soliible in wRter and alcohol, but almost insoluble in ether ; it isonly slowly decomposed by boiling water, and it, is stable in pre-sence of tiitrous acid. The henzoyE derivative, C,,H,,N20, crystallisesfrom dilute alcohol in needles, melts at 88", and is only moderatelyeasily soluble in ether. The diethyl derivative is formed when theamidine is heated at 100-110" with an ethereal solution of ethyliodide ; its hydriodde, C,,H,,N,,HT, is a coloudess, crystalliiie com-pound, but turns yellow on keeping.Acetarnidine nitrite, CN,H,Me,HNO,I prepared by treating a con -centrated aqueous solution of acetamidiiie h i drochloride with silvernitrite, melts a t 148" with decomposition, and is soluble in water andalcohol, but insoluble in ether.Propioimnzidine nit?.de, CN2HJEt,HN02, obtained in like manner,separates from alcohol in crystals, melts a t lit?, and is readily solu-ble in water and alcohol.PaTatoleny lamidine nitrite, CsH,MeCN,H,,HNOZ, cr.ystallises inneedles, melts at 133", and is readily soluble in alcohol and wafer,but insoluble in ether.Imp h t hulamidine nitrite, C,H, ( CN2 H ,3) z , 2 H N Oz, cry s t a1 1 i ses f roniwater in lustrous needles.Succinimidine nitrite, C2H4<C C ( N H ) > ~ ~ , ~ ~ ~ , (NH) + +H,Q, ic;formed when a solution of a mixture of the hydrochlorides of snccin-amidine and succinimidine is treated with silver nitrite ; i t crystallisesin small, yellow plates.Guunidine nitrite, CH5N3,HN02, can be obtained by evaporating asolution of guanidine sulpbate with sodium nitrite, and extracting theresidue with alcohol, from which the nitrite is deposited in crystals ;it melts a t 76-78.5", decomposes at about 120", and is readily solublein water and alcohol, but insoluble in ether.Froin the results of the experiments described above, the authorconcludes that the substituted amidines cannot be converted intodioxytetrazotic acids.The sti*ongly basic amidines combine mi-changcd with nitrous acid, but when. b.7' the substitution of a phenylgroup for hydrogen, they are converted into feeble bases, they becomeless stable towards nitrous acid.F. S. K54 ABSTRACTS OF CHEMIOAL PAPERS.Thio-derivatives of Orthamidobenaamide. By A. STEWART<,J. pr. Chem. [2], 44, 415-416) -The compound CIIR~oNzSO isbtained by beating oi*tjhamidobenzamide with allylthiocarbsmide(equivalent proportions) in benzene for several hours. It crys-tallises from hot alcohol, ether, or benzene in colourless needlesNnd tables, and niclts with decomposition a t 198-199". It dissolvesin alkalis, and is reprecipitated by acids unchanged ; its solution inbenzene has a blue fluorescence.A compound which ci-jstallises i n colourless, silky tables is formedwhen phenylthiocarbimide is substituted for the ally1 compound inthe above reaction.By heating orthamidobenzamide with thiocarbamide i n an oil-bathat 180-200", until no more ammonium sulphide is given off, thecompound C,H,N,SO is formed; it crystal!ises from alcohol increamy-white nodules, dissolves in ether and benzene, and melts at280--281".It dissolves in alkalis, and is reprecipitated by acids.When heated for 2-3 hours with methyl iodide (2 mols.) and sodium(2 mols.) in a tube a t about 130°, a, smell of mercaptan is perceived,and beautiful, colourless, six-sided priems crystttllise out ; they containsulphur, dissolve in alkalis, nild are unchanged at 300'.A colourless, crystalline substance is obtained when thiocarbamideis heated with anthranilic acid.The author suggests constitutional formulm for some of the abovecompounds, but does not support them.The investigation is pro-ceeding. A. G. B.Condensation of hilpyruvic Acid. By C. BOTT~KGER(Annulen, 265, 253-256).--ln hhe conversion of anilpyruvic acidinto aniluvitonic acid by treatment with concentrated sulphnric acid,a very small quantity of a compound, which is insoluble in alkalis, isdormed; t h i s substance has the composition C17H16N20, melts a t194-195", and is identical with t.he compound obtained by LaznrusFy t,renting aniline with pyruvic acid a t a high temperature. Thecondensation product of paratohidine and pyruvic acid has con-sequently the composition C19HZONZ0, and not ClaHz0N20, as given byLazams. F. 8. K."tranilide. By H. POLIKTER (Rer., 24, 2959-296.2) .-Tnrtr-aailide is obtained in almost theoretical yield by gradually addingtartaric acid (1 part) to boiling aniline ( 5 parts), and after a timedistilling off the excess of aniline from the solution, waslling the solidresidue successively with dilute hydrochloric acid, boiling water, anda little alcohol, and finally crystallising from alcohol ; it melts above250" with decomposition.C2H2(0Ac),(CO*NHPh),,is formed when tartranilide is boiled in a reflux apparatus with aceticanhydride until the solution commences to darken ; i t cryetallises inlieedles, melts a t 227", and is more soluble in alcohol, ether.andchloroform than tartranilide. The triucetyl derkntive, CnHZ20;Ns, isThe diacetyl deriratiseORGANIC CHEYISTRY. 55produced by heating tartranilide with acetic anhydride in a sealedtube at 150" for two hours ; i t forms delicate, liistrous, white needles,melts a t 216", and is readily soluble in alcohol, ether, and &.cia1acetic acid. The tetracetyl derivative, C2H2(OAc),( CO*NAcPh)2, isobtained when tartranilide (3 grams) is heated with acetic chloride( 5 grams) in a sealed tube a t 140" tor two hours, the product beirigwashed with a little glacial acetic acid, and repeatedly crystallisedfrom alcohol ; it forms colourless needles, melts at 137", and is moreeasily soluble in all solvents than the di- and tri-derivatives.When tartranilide is submitted to dry distillation, 01' better, when amixture of tartaric acid (1 part) and aniline (4 parts) is heated forhalf an hour a t the boiling point of aailine, then distilled over n freeflame until nothing but a carbonaceous mass remains, the distillateagain treated with tartaric acid, and the same operation repeatedseveral times, on adding dilute hydrochloric acid to the last distillate,dianilidosuccinaiiilide, GHZ( NHPh),(CO*NHPh),, melting at 220", isprecipitated, the yield being at most 20 per cent.It is very stable,beirlg attacked neither by acids nor alkalis, and boiling at about 300".The acetyl derivative,NPhAc*C EI( CO*NHPh)*CH(NHPh) GO*NHPh,is prepared by boiling dianilidosuccinanilide with acetic anhydride in a1.etlux apparakus for two hours ; it crystallises in large, yellow leaves,arid melts at 252". A. R. L.Aromatic Dithiocarbarnates. By S. M. LOSANITSCH (Ber., 24,3021--3028).-Ammonium phenylditbiocarbamate, NHPh*CS*SNH,,is prepared by the interaction of aniline, carbon bisulphide, andammonia o r ammonium sulphide, in dilute alcoholic solution a t ordi-nary temperatures ; it crystallises in large, yellow, transparent prisms,and is soluble in aqueous ammonia or ,zmuionium sulphide, but de-composes when dissolved in alcohol or water.Ammonium sulphide,ammonium thiocarbonate, carbon bisulphide, thiocarbanilide, andaniline are formed on heating the compound a t 100". Ammoniumphenyldithiocarbamate appears t o be identical with the " phenyl-ammonium thiouramate " of Hlasiwetz and Kachler.Yhenyl~i~hiocLIrbamic thioanhydride, ( CS*NHP'h)2S, is obtained bythe action of iodine in excess on animonium phenyldithiocarbamate ;i t crystallises from benzene in yellow, lustrous needles, melts1:36-138", and i s not affected by acids, but is converted into thiocn.:b-rtnilide on treatment with potash.Barium phenyldithiocarbamate,(LVHPh-CSS),Ba, is insoluble in alcohol 01' water at ordinary tem-peratures, and crgstallises in yellow plates. The pntussium salf,NHPh*CSSK, is deposited in long, t h i n , colourless needles ; the nickelstdt forms yellow, lustrons plates. The remaining salts are sparinglysoluble, and on heating are decomposed qudntitatively into themetallic sulyhide and phenylthiocarbimide.Methyl phenyldithiocarbamnte, NHPh*CSSRle, prepared frommethyl iodide and ammonium phenyldithiocnrbamate, crystallisesfrom alcohol in large, white needles ; it melts a t 93*5", not at 87-88",as stated by Will, The ethyl salt melts a t 59.5"5 1; ABSTRACTS OF CHEMICAL PAPERS.By the iutemction of carbon bisulyhide, aniline, and tetmmethyl-ammonium hydroxide in dcoholic solulion, a compound is obtainedwhich crystallises in yellow needles and melts a t 152-1.53" ; this ~111)-stance is not a phenyldithiocarbamate, and is being further invest; -gated.Ammonium pnratoluyldithiocarbamate, C,H4Me-PU'H*CS*SNH4, isprepared in a similar manner to the phenyl derivative, and crystal-lises in large, yellow prisms.The harium salt is deposited i n colour-less needles ; the nickel salt forms brown needles. The observationsof Will and Rilschowski on the methyl and ethyl salts of the abovecompound are confirmed.Barium rrzetatol7Lyldithiocarbamlnte resembles the para-compound ; i tis soluble in wafer, h u t not in alcohol.The wickel salt crystallisesin yellowish-brown, lusti*oiis plates. The methyl salt,C6H, Me-NH-CSSMe,crystallises from alcohol in colourless needles, and melts a t 89".Barium orthotolisyldithioca6amate is obtained i n colourless plates,which are insoluble in water or alcohol ; the nickel salt forms browiineedles. The methyl salt crystallises from alcohol in colourlessneedles, and melts a t 132".Ruriurn cc-naphth?yldithiocnrbamate is prepared in a manner similart,o the preceding compounds, and is deposited in colourless, insolubleneedles ; the nickel slrlt crystallises in yellowish-brown needles.Bayiurn /J-naph thyli7ithiocarb~imate forms yellow, crystalline plates ;the nickel salt resembles that of the a-derivative.The difference in behaviour between aliphatic and aromatic aminestowards carbon bisulphide appears t o be due t o the extremely feeblebasic properties of the aromatic ammonium gronp (NH,X), since, i i ipresence of a base, the aromatic amines react i n a manner similar tothe aliphatic amines, yielding dithiocarbaruates.J. B. T.Ethyl Acetoacetate Aldehydeuramides. By P. BIGINELLI (Ber.,24, 2962-2967 ; compare Abstr., 1801, YOS).-When salicyldiurelde(Xchiff, Annulen., 151, 199) which has been previously dehydrated,first in a vacuum, and then by heating a t 90-100", is boiled withabfiolute alcohol and ethyl acetoacetate ('2 mols.), ethyl /j-ui-amido-crotonat,e, and a subdance having tlie composition CilH16N20i, areobtained ; the lattcr is also formed when carbamide, salicylaldehyde,avd ethyl acetoacetate are boiled together, in molecular proportion,with a little alcohol ; it appears to be a mixttiire of two isomerides,aiid separates from alcohol in small needles melting at 199-200",and large prisms melting at 203-201", these having probably theconstitutions OH-C,H,*CHE:N*CO*N:CMe~CH,*COOEt andOH*C,H,.CH: N*CO.NHCMe*CH.COOEt 'respectively.If the prisms are dissolved in hot alcohol. the needlesseparate out on cooling, whereas if the latter are allowed tto remain incontact with this solvent they change by degrees into thc former. Thcsubstance is insoluble in water, and decomposes when boiled with it ; itORGANICJ CEEhlISTKY.57however, dissolves in dilute potassium hydroxide, but, the solution be-conies yellow after ;t time, o w i n g to decomposition. When a currentof carbonic anliydride is passed through the alkaline solution until thesubstance commeiiceo to separate out, hydrochloric acid precipitatesthe compound Ci,H,,N,02, which crystallises from alcehol in whiteiieedles,' decomposes a t 260-270" without niclting, and is insolubleNH*CO*PU':$IH , in alkalis ; it probably has the constitution CHMe< CH2---0- C6H, 'it is formed more readily from the iqomeride of lower melting point.Cumiiidiurei'de, CsH4Pr13*CH (NH-CO-NH,),, is prepared by addingsuficient alcohol to a concentrated aqueous solution of carbamideto enable i t to dissolve cumaldehyde, allowing the mixture to remainl o r two days, collecting the precipitated compouiid, drying, and wash-ing with ether; it is a colourless, crystalline powder, insoluble inwater, only slightly soluble in boiling alcohol, and melts att175-176".The compound C,,H,:N,03 is obtained when a solutionof ciimindiureide and ethjl acetoacetate in absolute alcohol, or one ofcarbamide, cuniilldehyde, and ethyl acetoacetate in the same solvenl,is boiled ; it crystallises from alcohol in delicate needles, and melts at161-162"; if left for some days in contact with the solvent, or ifrepeatedly fused, it changes its form to octahedra, and then melts a tCi.rinnmdizcreide, CHPh:CH*CH(NH-CO.NH,),,'separates as a white,crystalline substance, when a concentrated aqueous solution of carb-amide is shaken with cinnamaldehyde ; it melts a t 172" with decom-position.TricirLnanztet?.aurei'de, C,H,(NH-CO*NH*C,H,.NH.CO.NH,),, isobtained by gently heating a solntion of carbamide and cinnnm-aldehyde in alcohol ; i t is a yellowish powder, and melts at 183-184"with decomposition. Both urei'des are decomposed on boiling withwater, or more quickly by dilute acids ; nitrous acid occasions com-plete decomposition, and when suspended in ether they absorbbromine.When cinnamaldellyde is shaken with a very dilute solu-tion of carbamide at a moderate temperature for a long time, a urejidemelting at 212" is formed; but if an excess of cinuamitldehgdeis digested mith a concentrated solution of carbamide a t 50-60" foi-an hour, a urei'de meltirg a t 115-116" is produced.When either ofthe cintiamure'ides is heated with ethyl acetoacetate, the coinpountlC16H18NZ03, crystallisirig from alcohol in needles, and melting a t243-244", is obtained; this appears also to exist in two forms, theinelting points of which are very close. Althongh, as- Schiff hasshown, fiirfurnldehyde does not yield a urei'de, when this aldehyde isheated with carbamide and ethyl acetoacetate, ethyl P-furfwainido-crotoiiate, C40H3*CH:N.CO*NH*CMe:CH*COOEt, is formed. Whenthe benzurzmide derivative (m. p. 207-208" ; Abstr., 1891, 908) iscrystallised from hot alcohol, needles are obtained having the meltingpoint 206-206.5". A. R. L.164-165".Ethylation of Salicylaldehyde.By M. Liiw (Monatsh., 12,39S-4Ol).-T he author has ethylated salicylaldehyde by slowl55 ABSTRACTS Ol!' CHEMICAL PAPERS.adding a mixture of it (1 mol.) with ethyl iodide (3 mols.) to a boilingsolution of alcoholic potash (3 mols.), exhausting the product w i t h ether,and distilling the residue from the ethereal extract under a pressurrof 25 mm. The ethyl compound t h u s obtained (yield 54 per cent. oftheory) boiled at 143-147" (25 mm.), and melted a t 20-22".OrthethoxyEenzaZdoxime, OE t*C6H,*CH:NOH, is formed when ethyl-salicylaldehyde is heated w i t h hydrox~lamine hydrochloride andexcess of soda, It is readily soluble i n alcohol, ether, aud benzene,sparingly so in water, slightly volatile in a current of steam, hasa, characteristic odour, and crystallises from light petroleum in colour-less, compact prisms which melt at 57-59'.The hydrochloride, OEt.C6H4*CH:NOH,HCI, separates in the formof small, yellow needles, when the base is dissolved i n ether and thesolution treated with dry hydrogen chloride. I t melts a t 123-125",and is reconverted into orthethoxybenzaldoxime on warming withwater .Orthethoayb~nz!/Zamine, OEt-C6H4.CH2.NH2, is obtained on dissolvingthe aldoxime in a little alcohol, and reducing with 4 per cent.sodium amalgam, keeping the solution always slightly acid withacetic acid. The ylatinochloride, OE t*C,H,.CH,*NH,,H,PtC16, is acrystalline, yellow precipitate, and melts at 182".Orthethoxybenzonifrile, OEt.C,H,*CN, is formed on Heaking i n areflux apparatus a mixture of orthethoxybenzaldoxime (1 mol.) andacetic anhydride (4 mols.).The product is neutralised with soda,extracted with ether, and the ethereal solution distilled, when thecompound separates as a colourless oil which boils at 252-254"(260.7" corr.). On heating 4 t h alcoholic potash in sealed tubes, it isconverted into a mixture of orhhethoxybenzoic acid, OE t*C6H4*COOH,and orthethoxybenzamide, OEt*C,H,*CONH,. The latter crystttlliaesfrom hot water in flat, silky needles, and melts at 132-135".With phenylhydrazine, ethylsalicylaldehjde forms a ver-y unstablecompound, which is readily oxidised, even by atmospheric oxygen.The formation of the above-described compounds confirms Perkin'sview ( A n d e n , 1868, 306) t h a t the product of ethylation ofsalicylaldehyde is really orthetboxybeiizaldehyde, a n d shows that theeth)l is not directly attached to a, carbon atom (compare Hersig andZeisel, Abstr., 1888, 882 ; 1889, 247 and 966). G.T.,M.P ~ O I l O l . B y W. N. NAGAt (Bw., 24, 2847--2853),-Paeonol wasfirst obtained by Martin and Yagi ( d ~ c h . I'?xzrm., lo), from thebark of the root of Ptaonia rnoutan, a drug frequently used i n Japanand China. In order to prepare it, the finely-powdered bark isextracted with ether, the extract shaken with sodium carbonate solu-tion to remove impurities, and then with aqueous soda, which takesup the psonol : the alkaline solut,ion is acidified with sulp'huric acid,again extracted with ether, and the residue obtained on evaporatingthe latter is recrystallised from alcohol.Peon01 is thus obtainedin colourless, lustrous needles, having the composition C9HloOs, andmelting a t 50" ; it bas an aromatic odour and burning taste, is spar-ingly soluble in cold water, readily in alcohol, ether, and benzene.It gives a reddish-violet coloration with ferric chloride, but dissolveORGANIC OHE3fISTRY. 59in sulphuric acid without alteration of colonr ; i t rllso dissolvesreadily in caustic alkalis, but not in ammonia or solutions ofalkRli carbonates, which agrees with the supposition that it is aphenol.When fused with potash, it yields 1 : 2 : 4-dihydroxracetophenonejresacetophenone), CsH3Ac( OH),, a-resorcyl ic acid, COOH*C,H,( OH),[l : 2 : 41, and resorcinol ; tbe first is probably the primary product,the other compounds being formed from i t by the further action ofalkali.Hydriodic acid converts i t into methyl iodide and resrtceto-pbenone, of which it must therefore be the methyl ether. To ascer-tain which of t.he hydroxyl groups is methylnted, the acetyl derivativewas prepared by boiling pmnol with acetic anhydride for 30 honrs,extracting any unaltered paeonol with light petroleum (b. p. 55-57"),and recrystallking the residue from alcohol. AcetyZpceot/oZ, C9H9O3Ac,is thus obtained in flat, lustrous needles melting a t 46.5". If insteadof acetic anhydride a mixture of this compound with anhydroussodium acetate is employed, two condensation products are obtained,melting at 180" and 160" respectively; these are being furtherexamined.By oxidation with alkaline potassium permanganate, acetylptzonolyields parame thoxyace ty lsalicylic acid, COOH*C,H., (0 Ac).OMe[1 : 2 : 41, which, on treatment with strong aqueous potash, is con-verted into paramethoxysalicylic acid, COOH-(:,H,(OH)*OMe[l : 2 : 41, the properties of which were found to agree with previousstatements (Abstr., 1881, 270; Ber., 14, 847), except as regards themelting point, which the author finds to be 156".The formation ofthis acid shows conclusively that the methoxyl group occupies thepara-position with respect to the acetyl group, and hence pseonolmay be termedparumet h o q o r t h 07~ydrmyacetopheno ite, OH* CsH3Ac*0 Me[ = 2 : 1 : 4 ] . H. G. C.Pzeonol Phenylhydrazone and Oxirne. Bp F. TIEMANN (Bey., 24,2854-2853).-Although paeonol, according to Nagai, does not form ;Idouble compound with sodium hydrogen sulphite, i t readily combineswith pheny lhydrazine atid hydroxy lamine.Pworwl phenylhydrazone,C9H,002:N2HPh, is prepared by the addition of phenylhydrazinehydrochloride and sodium acetate t o an aqueous s o h tion of p8eono1,a.nd crystallises from alcohol in pale-yellow needles, melts at 107", isreadily soluble in ether and benzene, sparingly in alcohol and1 ight petroleum, and almost insoluble in water. PceonoZoxinw,CgHloO2:N*0H, separates in needles when its dcoholic solution ispoured into water; it is almost insoluble iri cold, readily solublein hot water, and in akohol, ether, &c.Paeonol itself may be readily purified by distillation in a curroit ofsteam and recrvstsllisation from hot water. It then melts at 48".and not at 50°, is stated by Nagai (see preceding abstract).H. G.C.Acetovanillone. By F. TIEMANN (Ber., 24, 2855--2862).-Inthe course of his researches on the members of the protocstechuicseries, the author, in conjunction with Nagai (this journal, 1877, itGO ABSTRACTS OF GEIEMICAL PAPERS.3W), showed that acetylengenol, on oxidation and subsequent. hydro-lysiq, gives a product from which a-homovanillic acid, vanillic acidand vanillin, may be isolated ; in addition to these, a large quantityof a i*esinous maw is obtained, which, on dry distillation, givesguaiacol aq tlie sole recognisable product. Further investigation ofthis resin in larger quantity has shown that a crystalline compoundmag he obtained from it, by neutralking the free acid present withcalcium or magnesium carbonate, repeatedly Pxtracting with boilingwater, and shaking the extract with ether.The ethereal solution isthen treated with sodium hydrogen sulphite to removevanillin, the etberevaporated, and the oily residue repeatedly washed with water, anddistilled under a pressure of 50 mm. The distillate solidifies on cooling,and may be purified by dissolving it in aqueous soda, reprecipitatingwith carbonic anhydride, extracting again with ether, evaporatingtho latter, and recrystallising the residue from boiling water, alcohol,or benzene. The new compound then forms long prisms, melts at115", boils a t 295--300", and may be readily sublimed.The analysisand molecular weight determinations lead t o the formula C9HI0OJ,and it is termed metovanilbone for the reasons stated below.Acetovanillone has the properties of a phenol, yields protocatechuicacid wlien fused with potash, and contains one methoxyl group, asfound by Zeisel's method. It therefore contains the residueiC*C6H3( OMe)*OH. The remniniiig atoms, CzH30, must be present asan met71 group, for acetovanillone yields an oxime and phenyl-hydrazone, and is also formed, although only in small qumtity, bydistilling a mixture of calcium acetate and vanillate. On boilingwith acetic anhydride, it yields an acetyl compound, which may bereadily oxidised to acetovanillic acid and vanillic acid, showing thattile hydroxyl and methoxyl groups occupy the same positions as inthe last-named compound.Hence, acetovanillone has the constitutionCsH3Ac(OMe)*OH [l : 2 : 41, aud stands in the same relation tovanillin as acetophenone does to benzaldehyde. Acetovanillone givep,with an excess of ferric chloride, exactly the same reaction as vanilliii(Abstr., 1886, 238); tlie liquid assumes first a deep, bluish-violetcolour, and on warming gives a precipitate of insoluble dehydrodi-ace tovani llone.The presence of acetovamillone among the products of oxidation ofacetlyleugenol, CHz~CH~CH,CsH,(OMe)-OAc, is not capable of readyexplanation. The simplest way of explaining it would be to supposet h a t it is present ready formed in the eugenol, or that it isobtained by the oxidation of an isomeride of eugenol, of the formulaCH,:CMe*C,H,(OMe).OH, either present i n the liquid or formedduring the reaction ; no evidence has, however, been found in favourof these views.To explain its formation from acetoeugenol, ono mightsuppose that the latter first takes up the elements of water, formingthe compound OH-CH2-C;H2*CH2*C,H3( OMe).OAc, and then undergoesoxidation in the w- and /&carbon atoms of the side chain, FieldingCOOH*CH2*COoC6H,(OMe).0Ac, which loses carbonic anhydride,forming acetovanillone.The properties of the substances obbained in this research are givenin the following abstract. H. G. CORQANIC CHEMISTRY. t; 1Derivatives of Acetovanillone. By E. NETTZEL (Rer., 24,2863--2868).-Acet~ovanillone yields a series of phenol salts wit,h theirietals of the alkalis and alkaline earths, the former having :in:Ilkaline reaction, and all readily undergoing decomposition.Thecopper salt is a yellowish-green, amorphous powder.By the action of an alcoholic solutirm of methyl iodide on analkali salt of acetovanillone, t h e methyl ether, or acdoveratrone.C,H,AC(OM~)~, is obtained ; i t forms rhomboidal crystals, melts at48-49", boils a t 2 ~ 7 ' under 15 mm. pressure, is soluble in hotwater, alcohol, ether, and benzene, and is converted by 1 otasFiuiiiIwrrnRnganate int,o veratric acid. The corresponding eth?/Zaceto-yaniZEone forms radial groups of needles, and melts at 78". Acetyl-acetovanillone, OMe*C6H2Ac*OAc, prepared bay boiling acetovanillonewith acetic anhydride, crystallises from alcohol, on the addition ofwater, in long needles melting a t 58O, and yields vrtriillic acid on oxid-ation.Henzoylucefovanillone, OMe*C&&'O~Z, obtained frl jm analkaline solution of acetovanillorie by the action of benzoic chloride,melts at 106".Acetoprotocatechone. CsH3Ac( OH),, is formed in small quantity bpthe action of hydrochloric acid on acetornnillone a t 140-1 Xi", andseparrtt es from chloroform solution, on t.he addition of light petroleum,in crystals which melt a t 96-98'. The same compound appears to beformed by the action of zinc chloride on a mixture of catecbol andacetic acid, but could not be separated from the excess of catechol.zlcetovaniZEoneplien?/Zl~ y d rami e, N? H Ph: CMe*C6H3 ( 0 Me) *OH, form swell-developed crystals, melts a t 125", and is soluble in alcohol aridether ; the oxime, OHoN:CMe.(=,H,(OMe~*0H, melts a t 95", is fairlysoluble in water, and cryntallises best from henzene.Ethylaceto-.ca~zillor:oxiirre, NOH:CMe*C,H,(OM~)-OEt, c-rystallises fi om alcohol inlustrous prisms melting a t 116-118". As already mentioned in thepi-eveding abstract, ferric: chloride converts acetovanillone into dehydw-diacetocanillone, C18H which is almost insuluble in the usualsolvents, and melts above W O " .When a mixture of calcium acetate and vanillate in rnoleculiu. pro-portions is distilled, acetovanillone passes over in small quantitytogether with acetone, guniacol, &c. These are removed by distillingi n n cutarent of steam, and the residue purified by repeatediy Iirecipi-tating the benzene solution with light petroleum.Synthesis of Acetovanillone from Guaiacol and Acetic Acid.By T.Owo ( B e T . , 24, 2869-2S70).-Acetovanillone may be oh-tained synthetically by dissolving 60 parts of guaiacol in 120 parts ot';Lcetic acid, and gradually adding 30-40 parts of a niixtrire of zincand aluminium chlorides i n equal proportions ; the whole is warmed onthe water-bath after the frotliing has moderated, and finally heilted a t14&-150" until hydrogen chloride is no ioriger evolved. The productis then poured into water, the unaltered guaiavol renioved by distilla-tion i n a current of steam, the solution filtered from resinous matters,;\nd extracted with ether; the residue from the ethereal sulutioii istreated with fioda, the aqueous solution saturated with carbonicanhydride and again extracted with ether, the latter distilled off,H.G. Cti 2 ABSTRACTS OF CHEXICAL PAPERS.the residue fractionated, and finally recrgskallised from boiling water.The acetovanillone thus obtained crystallihes in white needles, meltsat 115", and hns all the properties ascribed to it in the previousabstracts ; the yield of the pure compound is, however, verv small.H. G. C.Aromatic Hydroxyketones. Ry P. CRlhEux (Chem. Centr., 1891,ii, 377 ; from Schweiz. Woc7masclw. Pharm., 29, 255-256).-AppIy-ing the same method as Nencki used to produce hgdroxyketones, theauthor has obtained from resacetophenone, a substance of the formulrCaHzAc2(OH)2, and from gallacetophenone, a compound,C6HA~( OH),*OAc.The latter is hydrolysed by potash, one acetyl group beinqeliminated, and the compmud C,HAcz(OH), formed.By the actionof glacial acetic acid and fused sodium acetate on propionyl-p benol, resacetop henone, gallacetoph en one, the acetyl derivativesA cetyl propioph enone, diacetylgal lace to-phenone are formed. Where more than one hydroxyl group waspresent, one remained intact, the others becoming acetjlated.Constitutents of Paracoto Bark. By G. CrmIcIm and P.STLBER ( n e r . , 24. 2977- 2990).-The authors find that hydrocotoin,to which they assigned the formula OH*C,H,(OMe),*COPh (Ber., 24,299; Ahstr., 1891, 578), yields neither an oxime nor a hydrazone:many ketonic compounds are, however, indifferent towards h~droxyl-amine and phenylhydrazine (compare Hantzsch, Abstr., 1891, 36),arid in the case under discussion, this behaviour is perhaps explained bythe position of the methoxyl groups in the molecule.The compoundis not attacked by aqueous alkalis, but when hekted with alcoholicpotash under pressure, benzoxc acid and a phenolic compound, appa-rently a mixture, are formed. When hydrocotoln (10 grams) isintimately mixed with phosphorus pentachloride (60 grams), and themixture slowly distilled uiitil all the phosphorus trichloride and oxy-chloride hat*e passedover, the residue and the distillate being then mixedwith water, united, and steam distilled, benzotrichloride first passesover, and then very slowly a solid compound, C,H,CI,O, ; this crystal-lises from alcohol i n colourless needles, melts at 174".and is imolublein alkalis : it yields methyl chloride when heated with\ hydrochloricacid at 140", and i8 probably a dimethoxy-derivative. When methyl-hydrocotoh (2oc. cit.) is treated in a similar manner with phosphoruspentachloride, benzotrichloride, together with a compound, C9H9ClJ03,probably a trimethoxg-derivative, is obtained : the latter formxdelicate, white needles, and melts at 130-131"; benzo'ic acid isfound in the aqueous portion of the Tesidue from the steam distilla-tion, whilst by treating the solid portion of the latter with glacialacetic acid and adding water to the solution, a compound, C16H14C1204,separates, which crystnllises from alcohol in colourless prisms, meltsat @1--82", and is perhaps dichloroniethylhydroco~~n.Protocotozn, ClsHldOs, is another constitnent of prrracoto bark, andoccurs AB an impurity in crude hydrocotoh, from which, by reason of itsmuch smaller solubility in alcohol.i t may be separated by fractionalcrystallisation from that liquid. It forms bright-yellow, monoclinicm onacety lresaceto phenone,J. W. LORGANIC OHEMISTHY. 68prisms, a : b : c = 2'930.3 : 1 : 2.0558; p = '79" 06', melts a t 141-142",iq soluble in most solvents, hut insoluble in water; it dissolves inalkalis, and is reprecipitated by carbonic anhydride : its solutioIl indilute alcohol gives a reddish-brown colour with ferric chloride ;whilst on treating it with dilute nitric arid, a bluish-green cnlour isproduced.and on heatinv the solution a reddish-brown precipitat,e isformed. When its solution in alkali., is reduced with sodium amalgamand acidified, ether extracts a compound cryshllising from alcohol inwhite. amorphous flocks, and melting a t 215-220". A determinationbv Zeisel's method showed that protocotoin contains two methoxplgroups. The acetyl derivative, C,,H,,O,, p,repnred by heating it withan equal weight of anhydrous sodium acetate and four time8 itsweight of acetic anhydride i n R reflux apparatus for six hours, formscolourless crystals, melts at 10:-3", and is insoluble in water andalkalis, but readily soluble in ether, hot alcohol, and chloroform: itdiwolves in cold nitric acid to a yellow solution. which.on heatinp,becomes bluish-green, and finally red ; its solution in dilute alcoholgives no coloration with ferric chloride ; on hoiliiig with alkalis,protocoto5n is regenerated ; i t contains one methoxyl group.MethyZprotiIcotoin, C14H703(OMe)3, is obtained by heating togetheri n n sealed tube, protocotoin (10 grams), a little methyl alcohol. potash(3 grams), and methyl iodide (15 grams), evaporating the alcohol,washing with water, and crvstallising from dcnhol ; i t forms colonrlessprisms, melts at 134-135", and is insoluble in water and in alkalis.Protocoto'in does not react with hydroxylarnine.The hydrazone, C22H20N206, is obtained by heating protwotoynwith an excess of pheny!hy?razine, dissolving the melt inglacial acetic acid, pouring I t into water, and crystallising tl:eprecipitated compound from alcohol ; i t forms small, colourlesnprisms, melts at 211".m d is sparingly soluble in rtlcohol andglacial acetic acid. Dihromoprdocotoin, CI6Hl2Br2O6, is preparedby treating protocotoyn dissolved in chloroform with m excem ofbromine, evaporating the sdvmt, and crystallising from dcohol ; i tcrystallises in silky scales, melts R t 170°, and dissolves in alkalifc, inh4)t dilute nitric acid, and in d p h u r i c acid with a yellow colou1-.BromacetyZ~rotr,cotoi'n, CI6Hl5BrO,,, is obtained in a similar mannerfrom acetrlprotocotoh ; it forms smdl, delicate, white needles, meltsat 175", and is insoluble in water and cold alkalis, b u t dissolves inhot alkalis with a yellow colour. Protocatechuic acid is producedwhen protocotoin is fused with potash or heated with concentratedhydrochloric acid in a, sealed tube at 130"; whilst the compoundCRH7C1302, melting a t 174", and identical with that obtained fromhydrocotoin (see above) is produced by treating protocotoh withphosphorus pentachloride in the manner already described underhydrocotoin.Methylprotocotoln, treated in a similar manner, yieldsthe compound melting at 131° identical with that obtRined frommethylhydrocotoin. Taking all these facts into consideration, it isprobable that protocotoh has the constitution3CH2<~>CaH3*CO*G,EI,( OMe),*OH,4: 4 ABSTRACTS OF CHEMICAL PAPERS.which is, however, given under reservation, as the presence of n,inethylene group has notl yet been demonstrated.When protocotoin is oxidised in alkaline solution with potasqiumpermanganate, a11 acid, which is being investigated, together with Jobst;~nd Hesse's paracouniarhydrin (Abstr., 1880, 3271, is formcd ; ittaontains a carboxyl group, as it yields a, hydrazone, C,,H,,N,O,,melting at 114".A. R. L.Vanilloylcarboxylic Acid (Parahydroxymetamethoxybensoyl-carboxylic Acid). By F. TIEMANN (Her., 24, 287$--28i9).--Tbeclimethoxyphenylglyoxylic 'acid [I : 3 : 41 recently obtained byCiarnician and Silber by the oxidation of methyleugenol (Abstr.,189 1, 966) has already been described by the author and Matsmotounder the nume veratroylcarboxylic acid (hbstr., 1878, 503). Thecorresponding ketonic acid of the vanillin series, or vaniZloyZcarboxylicmid, COOH.CO*C6H,(OMe)-OH [l : 3 : 41, has been found in certainvanillin preparations obtained by the oxidation of acetyleugenol, andacecylisoeugenol, and distinguished by their yellow colour.I t may bebeparated from vanillin by shaking with water containing magnesium(.arbonate in suspensioii, the vanilloylcarboxylic acid passing into theaqueous solrition as a magnesium salt. This is aciditied with snlph-uric acid, extracted with ether, the latter distilled off, the residue heatedat 50-60" in R vacuum and crystitllised from benzene. It then formsprisms containing benzene of crystallisation, which is rapidly givenoff on exposure to the a i r ; after dryingat loo", it meltsat 233-134 ,and dissolves readily in waitel., alcohol, ether, and benzene, sparinglyi n light petroleum.When heated above its melting point, i t isresolved into vanillin and carbonic anhydride. H. G. C.Benzenesulphamides and Mixed Secondary Amines. By 0.HINSBERG ( A ~ w l e n , 265, 178--192).-1n a previous paper (Abstr.,1891, 491, i t has been stated that phcnylsulphoiiic chloride reactsvery readily both with secondary and with primary amines; thecompounds obtained from the primary amines are soluble iu potash,yielding stable salts, which react .readily with fatty and (sotlie)aromatic halogen derivatives, being thereby converted into trisub-stituted amines (or disubstituted alliides). Various new compoundsobtained in this manner are described below.l'enzerLesulphonernethylethylcLmide, SO,Ph*NMeEt, is easily obtainedby warming a solntioir of benzenesulphonemethylamide in excess ofpotash with a, little alcohol and excesb of ethyl iodide; the yield isquantitative. It is a thick oil, distils under reduced pressure(50 mm.) with only slight decomposition, and is only sparingly solublein water, acids, and alkalis, but readily in alcohol and ether.Ethylmethyluniine, NHMeEt, is produced when the preceding corn-pound is heated with conceritrated hydrochloric acid a t 150-160" ; itboils a t 33-34.", and has properties similar to those of its nexthomologues.The hydrochloride, C3HqN,HCI, separates from a mix-ture of chloroform and ether i n coXourless, hygroscopic crystals, andis very readily soluble in alcvliol ; d l the other salts are very readilsoluhle in water and alcohol, hut the platinochloride crystallises fromthe former in moderately large plates.Renzene.szilphonepiperidine, SO,Ph.C,NH,,, mii be prepared by re-peatedly adding stiiall quantities of a mixture of phenylsulphonicchloride and coiicentrnted potash to an aqueous solution of piperidine,and shaking vigorously until the reaction is complete.It crystallisesin colourless prisms, melts a t 93-94", and is readily soluble in alc I -hol and ether, but only sparingly in water ; it is decomposed into itscomponents by concentrated hydrochloric acid a t 150".Re~~zenesul-phoneben~ylamide, SO,Ph*NH*CH,Ph, prepared fromben zylamine and phe ny lsulphonic chloride, crptall ises from dilutealcohol in colourless needles, melts a t 88", and is readily soluble inalcohol and ether, but only sparingly in water.The methyl deriva-tive, SO,Ph-NMe*CH,Ph, is obtained when the aniide is warmed withmethyl iodide and alcoholic soda; i t is a colourless, crystallinecompound, melts at !)4", and is decompo:,ed into benzenesulphonicacid and methrlbenzylamine by concentrated hydrochloric acid at160-1 go".ill'ethylbenzylamine, CH2Ph*NHMe, is a colourless liquid, boils at184", and has a slight amine-like odour ; i t is more readily soluble incold than in hot water. The sulphnte and the hydrochloride are veryreadily soluble in watei-. The platinochloride, (C,H,,N),,H,PtCl,,crystallises in long, yellowish-red needles, melts a t about 199, and ismoderately easily soluble in water.Benzenesulp honeortho to1 uid ide, S 02P h* N H*Cs H4Me, crystal 1 i ses fromdilute alcohol in colourless needles, melts at 125--126', and is readilysoluble in alcohol and ether, but only sparingly in water: i t is in-soluble in mineral acids, but it forms stable, readily soluble salts withalkalis.Brtrzenesulp honeparaphenetidin e, S 0,P h*NH.C6H4.0Eh, cry stsllisesfrom alcohol in coloui*less needles melting at 142" ; its methyl deriva-tive, C,5H1,NSOJ, crystallises from ether in large plates, and melts a t79".nibeiizenesulphonediphenetidine, CzsHz8F2S2O6, can be obtained bygradually adding it Concentrated solution of iodine in potassiumiodide to a hot, concentrated solution of benzenesulphonephenetidinein sodium carbonate.It crystnllises from alcohol i n colourlessneedles, melts a t 168", and is more sparingly soluble in alcohol, ether,and glacis1 acetic acid than the simple sulphone from which i t isobtaiued ; i t gives a blue coloration with hot, concentrated sidphuricacid, and forms a crystalline potctssiurn derivative of the compositionC,,H,,N,S,C),K, which is only sparingly soluble in water, but itrorereadily in alcohol. When heated with concentrated hydrochloric acidat 170", it yields ethyl chloride, benzenesulphonic acid, and a bluesubstance which is soluble in alkalis; its constitution is probablyexpressed by the formula S02Ph*NH*CsH,(OEt).N( d02Ph)*C,H*.0 Et.A bertzyl derivative of the composition C35Y34N,S2O, is formed whenthe potassium derivative just referred to is treated with benzylchloride ; it crystallises from alcohol in slender, colourless needlee,and melts a t 158".Dibenzrnesulphonepnraphenylenediamine, C,H1(NH*S02Ph),, crystal-The nitrnsamirie is a n oil.VOL.LXII. 66 ARSTR ACTS OF Cki EMICAL PAPERS.lises in colourless, 1ust8i*ous plates, melts a t 247', and is re:idily soluhlein alkalis, but only nioclerntrly easily in hot alcohol, and almost i i r -soluble in water. The diethgl derivative, C22H21N2S20,, crystallisesfrom dilute alcohol, in which it is moderately easily soluble, incolourless needles melting a t 197" ; on hydrolysis, i t yields diethyl-phenylenediamine, the diacetyl derivn tive of which crystallises fi-omhot water or dilute alcohol in colourless needles, melts a t 186-18i0,and has the composition C,,H,,N,O,.Di benzenesulp ho ti eort hot0 iw y lenediamine, C, H,Me ( N H* S 0,Ph) 2, cr7s-tallises from alcohol in plates, melts a t 178--1i9", and is readilysoluble in alkalis ; its solution in ammonia gives a blue, amorphousprecipitate on the addition of copper sulpbate.The diethyl deriva-tive, C-,H&N2S,04, crystallises f rowL alcohol in coloui~less needles tion-taining 4 mol. C,H,O, and melting at ahout 117" with previoussoftenirig; it loses its iilcohol at about 120", and solidifies on cooliiigt o a vitreous mass, which melts at 62-70".DiethyZtuZuyle?,ec?iu~~n~, C,B,Me(NHEt),. is obtained v hen thepreceding componnd is hydrolysed with concentrated hydrochloricacid ; it isa colourless oil, boils at 265" (uncorr.), and rapidly darkenson exposure to the air.I t gives a reddish-brown coloration withplatinic chloride aud also with ferric chloride i n presence of hydro-chloric acid ; in its concentrated aqueous solution, potassinni ferro-cyanide produces a colourless precipitate. Its salts are readily solublein water, and seem not to cr.1 stallise ; when tlle diamine is warmedwith phenanthraquinonc and acetic acid, it yields a reddish-yellowsolntion, from which, on evaporation, only amorphous substances areobtained. I?. S. K.Synthesis of Indole from Tartaric Acid and Aniline. By H.POLIKIER (Bw., 24, 2954-295!)).-- 'l'artrai\ilide (30 grams) is fusedi n a retort, and, after heating a t 260-270" for t w o hours, slowlydistilled over a tree flame, until nothing more passes over ; the productis then redistilled in ;I current of steam, when a mixtiire of aiiilineand indole passes over, fibom which the 1att8cr Ciin be isolated as picrate,0.74 pram being obtaiued ; whilst a yellowish residue weighing 4.8grams remains.which, on crystallisation from alcohol, melts a t 220",;tiid proves to be dianilidosuccinanilide (compare t h i s vol., p. 5,5). Byhclating tnrtranilide (20 grams) with an equal weight of zinc chloride at270-280" for an hour, diaiiilidosiiccii~anilide (1.32 grams) and indole( ~ 2 2 gram) may be isolated ; whilst, if a mixture of tartaric acid,aniline, and zinc chloride is heated in a sealed tube at 280°, theproduct extracted with alcohol, and the solution distilled, indole isobtained from the portion of the distillate pausiQg over last, and ispurified as described above.When tartaric acid is added b? degrees to boiling orthotoluidine i tdissolves after a time, and, on now distilling, the tempwature quicklyrises to 300", carbonic anhydride is eyolved, and orthotoluidine, nietlyl-indole, and a white, crystalline compound melting at 247" pass over ;the methylindole is formed in much larger quantity than is indole bythe methods described above.When dianilidosuccinanilide is heated in a sealed tube with a littlORG .%SIC UHEMISTEZT.(i iw.nfer at 200", R isesinous mass, tozether with aniline and traces ofindole is obtained ; whilst, if etliyldianilidosnccinic acid (Abstr.,1888, 951) is heated with zinc chloride, a compound melting a t about62", and giving all the reactions of indole, is produced. It wonldappear, therefore, that bv the action of aniline on tartiaanilide, di-anilidosuccinanilide is initially formed, and this, by the action of water,yields indole, aniline, carbonic anhydride, and carbonic oxide.Furtherexperiments are promised. A. R. L.Molecular Weight of Nitrosoindole. By C. ZATTI and A.FERRATINI (Gazzettn, 21, ii, 19--25).--The authors have already notedtbe comparatively hiEli melting point of the nitrosoindole describedby them (Abstr., lt390, lag?), and suggested that its empiricalformula might, have t o be doubled to give the tru2 inoleoular weight.'1'11~ moleanlar nreicht could not be determined by the cryoscopiomethod, owing t o the very sparing solubility of the substttnce i n thecold, but by observing the elevation of the bailing point of its solu-tion in acetone, numbers were obtained showing that the moleculavformula of nitrosoindole is C,,HI2N,O2.Nitrosodimethylindole behaves normally in i t s solution in acetone,the formula of the molecule being C,,,HloN20.When nitrosoindole is treated with nitric acid, i t dissolves, yieldingail intensely red solution, and on pouring thin into water, a flocculent,blood-red substance wparates, which agrees in properties with the so-called nitrosoindole nitrate prepared by Nencki (Abstr., 1875, l.LO.j),W. J.P.Indazole Derivatives. By C. PAAL (Ber., 24, 3058-3065;compare Abstr., 1891,723).-Phenylindazole, C,H,< 1- >NPh [l : 21,was dissolved in glacial acetic acid, treated with rather more thanthe theoretical amount of chromic acid, and boiled in a reflux appa-ratus until the solution acquired a pure green tint.On diluting themass with water, azobe?izeneorthoi.ar.Eozylic: acid, N2Ph*CGH4*COOH,separates out, the yield being 70 per oeut. of the theoretical. It dis-solves easily in ether, alcohol, glacial acetic acid, ethyl acetate, andbeuzene, very sparinqly i n hot light petroleum, and riot a t all in water.It crystallises from alcohol slowly in large, dark-red crj stals, or quicklyin small needles of the colour of azobenzene. It melts a t 9S0, and ata higher temperature decomposes with evoliition of red fumes, azo-benzene being formed.The alkali salfs and thc barium salt are easilysoluble i n water ; the lead salt forms a n orange-coloured, granular,amorphous precipitate which melts in hot water ; the silver salt formsan unstable, yellowish precipitate, which decomposes when heated,yielding azo ben zene, carbonic anhydride, s i 1 v er, and carbonaceousproducts. The acid itself is converted into h2/drazobsnzenerll.thocarb-ozylic acid, NHPh:NH-C,H,*COOH, when it is dissolved in alcoholand treated with zinc-dust and a few drops of acetic acid. The newacid separates on pouring the mixture into water. It dissolveseasily in mineral acids, ether, alcohol, glacial acetic acid, and ethylacetate, sparingly in benzene and light petroleum, scarcely at all inN-LHf 68 ABSTRACTS OF CHEJITCAI.PAPERS.w,atpr, It crptallises in yellowish, ill-defined pi isms which melt at.16,?-1B6 , aud, in the air, quickly darken in colour, hec*oming oxidisedto t h e azo-acid. The white sodiu,m. salt dissolves readily in water ;the barium salt, (Ci3HllNzOz)2Ba, forms lorig, white, hair-like crystnlsgrouped as in wavellite ; i t oxidises 1'ea.dil.y in the air.BenziJiltemetacarbozy Eic acid, N Ht2*CcHt.C6H3( NHz)*COOH, is formedto the extent of 60 per cent. of the t,h(,oreticalyield, whet1 ambenzene-orthocarboxplic acid is reduced by dissolving i t in absolute alcohol,excess of tin added, and then IiTdrochloric acid in snccessive smn.11proportions, the niixture being heated. On cooling the solution, theI-lihydrochlovide, C18H12N'L02,2HClr crjstnllises out in white, lustrousneedles which melt at a very high temperature, and do not dissol\.ei n alcohol, but do so in water, iindergoing dissociation and forminqthe rnonohy~lrochloride, C1:,H12N202,HC1, which separates in short, dull-white needltbs ; this melts i j t a very high temperature, and is only spar-ingly soluble even in hot, water.This salt; may also be obtained hy boil-i rig a hydrochloric acid sol u t ion of h y drazobenzen eorthoc.nrboxylic acid.The acid itself is ohtained by dissolving either of the hydrochloridesin aqueous ammoiiia and adding acetic acid. I t dissolves sparinglyin I ot wat,er, hard!y a t all in absolute alcohol; from dilute alcoliol, it,crystallises in crusts formed of white needles which melt at 210",decomposing into carbonic anhydride and benzidine.The allcLzZi saZt,<are soluble in water, but insoluble in concentrated alkalis. T h abarium salt forms short,, white prisms, almost insoluble in cold waterThe silrer salt, C&TlIN2OzAg~ is a white, amorphous substance, fairlysfable in the light, aiid almost insoluble in hot water.Pa,.nchZoi.~rzobenzeneorthocarb/,zyZic m i d , C6H4Cl0N2*C6H4-COOH, isobtained by midising parachlorophenylindazole in acetic acid snlrl-tion with chromic acid, cooling the solution, and diluting i t withwater. It dissolvcs readily in hot, alcohol, glacial acetic acid, ant1benzene, scarcely a t all in light petroleurn. It forms small, 0i.ang.e-coloured, dendritic needles, mid melts at, 166".Reduced w i t h zinc-dust and acetic aci(1, it yields p~rrachl~~rhydraa~~benzeneol.thocarhoxyl~icacid, C6H,CI*NH*NH.C6H,.COoH~ which is precipitated in whiteflakes on the addition of water. 'J'ht: yellow sodium sdZt of t h e azo-acid is soluble in water, but insoluble in concentrated alkalis. Thebariiim salt forms lustrous, orange-coloured needles illsoluble in watey.The copper salt forms a briglit,-green, amorphous, the silcer salt, areddish, amorphous, granular, and t,he ferric salt, a bulky, reddish,precipitate.YarlLbrornnzobenzeneol.thocarboxylic acid, C6H4Br.Nz.C6H4.COOH, isprepared by oxidising par,zbromophenylindazole with chromic acid inacetic acid solution. It crjstallises from alcohol in small, lust,rous,orange-red needles, melts at 176", and dissolves readily in glaciaiacetic acid, ethyl acetate, and benzene, b u t not i n light, petroleum.It,is redneed by zinc-dust 2nd acetic acid to parabromh~jilrazoben2ene-carboxy lir: acid, C,H,Br*NH*NH*C,H,*COOH. which forms white,crystalline flakes insoluble in water. The salts of the bromazo-acidresemble those of the chlorazo-acid, except that. they are redder, andthat t h e cnpper and ferric salts are, respectively, bright-green a,n(1rusty coloured . C. F. BORGANIC CHEMISTRY. 69Synthesis of Indigodisulphonic Asid. By B. HEY.II~YN(Bey., 24, 3066--3070).-A reply t,o Kuiet,sch (Abstr., 1891, 1231). 1tis sliown t h a t when indigocarmine is obtained from phenylglycocint!by dissolving the latter i n funiing sulphuric acid (containiug 80 percent.of t h e anhydride) and removing the excess of anhydride by t h eaddition of concentrated sulphuric acid, the oxygen of the a i r plays nooxidising part in the reaction, for in an experiment, during whicha i r was carefullv excluded, as good a yield was obtained as i n otherexperimeuts. The author is of opinion that the 1euco.compound atfirst formed has a constitution similar to HSO~*C,H,<~~so3H)~CH,and that, when t h e concentrated sulphuric acid is added, this com-pound either splits u p into indigo-carmine, sulphurous acid, and water,the sulphuric acid residue furnisbing the necessary oxygen, or, as ismore probable, breaks u p into the sulphonic acid and the leuco-com-pound, which is then oxidised to indigo-carmine by sulphuric niihydr-ide still present in the solution.C. 17. B.Diphenyltetraketone. By P. W. ABENIGS and H. G. SODELRAUU(ljer,, 24, 3033--3034).-The yellow substance melt.ing at 170"(Abstr., 1891, 1043) obtained when the acetyl derivative of w-isonitro-soacetophenone (benzoylformoxime) is dissolved i n a dilute soIution ofsodium carbonate is shown to be in reality diphenylhydroxytriketone(phenylglyoxalbenzoh), OLI-CHBz-COBz, for i t is identical with thesubstance obhained by treating ben~oylformaldehyde~ COPh-CHO,with potassium cyanide in alcoholic solution. When treated withstrong nitric acid, i t is oxidised t o a tetraketone, COPh*CO*CO*COPh,a red substance which easily takes up 1 mol. of water, formkg ayellow hydrate which melts at 86- 88"-and crystallises weil.C.F. B.Constitution of Naphthalene. By G. ClawcrAN (Gnzzetta, 21,ii, 101--108).-The author considers Bamberger's hypothesis of theconstitution of naphthalene to be erroneous, and believes that the in-ternal structnre of the molecule is better represented by employingBaeper's conception of five double bonds of mean solidity 01- resistaim.The author is of opinion that the internal structureof thenaphtha-lene iiiolecule is well represented by considering the carbon atomsplaced at, the ceritree of the sides of two intersecting equilateral b u tnot equiangular hexagons, the two ceritral carbon atoms being commont o both hexagons. I n the orthogonal projection of such a system asthis, six of the straight lilies joining pairs of carbon atoms will belonger than the remaining five ; these latter represent the f i v e doublebonds in Bweyei*'s conception of tlie ring, whilst t h e longer ones repre-sent the single bonds.The hydrogen atoms are disposed in two])lanes parallel to that of the carbon atoms, the plane of the hydrogenatoms belonqing to one hex:igon being above, that of the other.hexagon below, the carbon plane. Such a, s.vstem as this is perfectlysgrnmetrical and may be considered to explain t h e seeming proximityof the peri-h~drogen atoms i n the naphthalene molecule.W. J. P70 ABSTRACTS OF CHEMICATA PAPER,!?.Azines of the Uric Acid Group. By 0. K ~ H L I S G (Ber., 24.alloxantin with a-naphthylenedinmine hydrochloride in aqueous solu-tion ; i t crystallises from a mixture of glnciat acetic acid and alcoholin small, slender, yellow needles, melts a t 285", and is insoluble in sodaor in sodium carbonate solution.N:C*NMe.COIlIethyZal2oznzine, C6H4<N:b.co. kH, is obtained from ortho-phenylenediimine hydrochloride and dimethylalloxantin, arid crys-tallises from a mixture of alcohol and glacial acetic acid in small,pale-yellow needles, melting att 250". The conipoulici is soluble insodium carbdnate solution at the ordinary temperature, and is reprc-diuitated anchanged bv acids.1 : 3 : 4-ortliotolnylencdiamine hydrochloride and dimethylalloxantin ;i t resembles thepreceding compound in properties, and blackens when-heated above 250".N:C.N.Me-COilIethylnay7~thaZloxazi~ze, C,oHs<N:A .co *.&H, is deposited onheating a-naphthylenedi~mine hvdrochluride with dimethylalloxantinin aqueous solution; i t is iriaoluble i n water, very spariugly so inalcoliol, and ciystallises from glacid acetic acid in sletider, yellowneedles. The azine dissolves in scjdaor in sodium carbonate solutionon gently warming, and is piwci~tatecl unchanged by acids ; i t is uri-altered by heating atgabout ROO". On boiling aqueous solutions oforthodiamine .hydrochlorides witli parabanic acid, spwingly solulllecompounds are obtaivrd, which proved on analysis to be dihydi-oxy-quinoxalines ; thesejcoqounds are formed h 7 t h e resolution of theparabanic acid into cvlibamide arid oxalic acid, and the condensationof the latter cornpovrncl with the orthodiamine.Nnphthndih!/droxy/-:s prepared by heating parabanic acid N :COO H' q ctinozaZine, >C,,H,.<Lvith a-naph~~ylenedinmine hydrochloi-ide f o r several hours in aqueoussolution ; i t is,purified by dissolving in dilute potash and pwcipitatitlgwith hydrochloric acid, and forms slender, coloui.less needles whicllmelt above NO". l l i e compound dissolves iu glacial acetic acid, and+paringJy in aicohol, but is in>olublc: in water. The Larium salt is+isoluble in water a n d is decomposed by acids.The substituted pai*abnnic acids appear to be morc stable towardsorthodiamines ; cholestrophane is unaffected by orthotoluylerledi-aniine hydrochloride, and allantoin does not rcact at all witli ortho-diamines.J. B. T.N:y'oHA Volatile Oil from Aristolochia reticulata. By J. C.PEACOCK (C'htm. Ctwtr., 1891, ii, 379 ; from Amw. .I. Yhawn., J u n e ,l890).--From the rhizomes of this plant, a s they are obtained COIUORGANIC C HEMISTltS'. 51.mercially, the author separated 0 61-0.94 per cent. of a golden-yellow oil. It has a camphor-like odour and taste, dries slowly whenexposed to the air, does not solidify a t -17", and has a sp. gr. of0*9i45-0-9785 at 15*5", and 0*971+-0*9758 at 20". I t is misciblewith alcohol, et,her, chloroform, benzene, and light petroleum ; i texhibits no a!dehyde readion, and rotates the polarised ray -4 in100-mm. tube. By fractional distillation, 10 per cent. passed over at74-75' under a pressure of 43 mm., 60 per cent.between 122-124",under a pressure of 43 mm., and 20 per cent. between 147-150" undera pressure of 47.7 mm. ; the residue in t h e retort possessed a blue andgreen fluorescence, and contained tawy matters.This first distillate boiled at 157" under a pressure of 769.6 mm. ; i t ssp. gr. was 0.865 a t 13.5" ; its formula is C,,H,,, wihh which its vapoiirdensity corresponded ; it absorbs bromine very readily, and is charac-terised as a member of Wallach's pinene group.The secoud fraction boils a t 211" under 763.6 mm. pressure; itsformula is CI5Hz5O2, wit,h which the vapour density corresponds. Onhydrolysis with potash, a camphor, CloHi80, is produced, which is verysimilar to borneol ; it boils a t 199*5-200". A n acid is also sept-rated of tlie probable formula C,H,O, ; melting point about 65" ; itforms a red precipitate with ferric chloride ; its odour is unpleasant.The third fraction, boiliiig a t 239-240", under 762.1 mm.pressure,is a greenish-yellow oil; sp. gr. 0.938d at 15-5"; its formula isCl9HZ90, with wliich the vapour density corresponds; i t is a n e u t r ~ ~ l ,indifferent substance. J. W. L.Bergapten, the Stearoptene of Bergamot OiL By C. 'POMERANZ(JIorLatslL., 12, 379--396).--Tliis subsharice separates as a crystalliiiemagma when the ethereal oil obtained from the rind of the fruit oECitrus Zlergamia is kepc for some time. It may be purified by s ~ h -limation 01- by recry stallisation from alcohol, when i t forms hard,white, silky needles, whitah are tasteless and odourless at ordinarytemperatures, but evolve aromatic vnpours when heated.It issliglitlg soluble in cold alcohol and in hot water; dissolves in hotalcohol, acetic acid, chloroform, benzene, and phenol, and melts at188', with partial sublimation. Elementary analysis and a determina-tion of its molecular weight by observing the depression of thefreezing point of a solution in phenol show t h a t i t has the moiecularformula C,zH,O,. Aqueoiis and alcoholic potash, acetic anhydride,pheiiylhydrazine, and boiling hydrochloric acid are all without actionon the compound, which, however, as shown by the action of hyclriodicacid and acetic arihydride (compare Herzig, Xonatsh., 9, 544), con-t<iins three rnettioxyl groups.On heating bergapten with potash, methyl alcohol, and methyliodide in a reflux app3ratus €or five hours, two new compounds areobtained.One of these has the formula C,,H,,O,; crystsllises fromalcohol in microscopic prisms, which are far more soluble in alcohol,chloroform, arid ether than i s bergapten, and melts a t Y,iL". Theother, which the authw has named iriethylberqaptic acid, contains CHless than tlie precediug cunipound, which is prohably its rnethjl sali 2 ABS I'HACTM OF UHEMICAL PAPERS.since, on hjdrolysis with potash, it furnishes the lree acid. Itcrystallises from dilute alcohol in small, rhombic plates, dis-solves readily in alkaline hydroxides and carbonates, and melts at138'. When, in the above described operation, ethyl iodide is sub-stituted for methyl iodide, ethylberguptic acid is ohtained ; this crys-tallises in acute-angled prisms or in twinned or clustered needles, andmelts at 142".From its behaviour with methyl and ethjl iodides,nbergapten must be regarded as the anhydride, C1,H,O,<Y and it,CO'tlierefore, closely resembles coumarin in constitution.Wlien fused with potash, bergapten gives rise to phluroglucinol,and on treiit,u\ent with two moledi~l* proportions of bromine, the an-hydride is converted into monobromobeygapten dihroriride, Cl2H,O4Br,,formed froni bergapten, whicbh has two double linkages in the sidecI\ains, by the addition of four atoms of bromine, one of which isafterwards eliminated in the form of EydroLrornic acid.On reduction wit,h sodium amalgam, methylbergaptic acid is con-verted i n to methy Ihy dmbergaptic acid, C,,H,,O,, which crystallisesfrotn dilute alcohol in small, white needles, and melts at 122".Thisproduct is analogous to the hydro-acids obtained on the reduction ofmethyl- and ethyl-coumaric acids.The above-described reactions of bergapten point to its having oneO F the following constitutions :-$H--y:C(OMe)*g*C'H:yH, ~ H . O . ~ . C H : C ( G M e ) . ~ * C ~ : ~ H ; orCH*O.CH --- C-0-CO ' CH-C--C-0-GO$ €I - C 0-0 $ *CHIC( OMe)$ -- 9 HCH----C ---C*O.CHG. T. M.Action of Sodium Alkyloxides on Caxnphor. Preparation ofAlkylcamphors. By A. HALLEK (Compt. rend., 112, 1490-1494).-Action Oj'Sodium a'thoxide o n C!untphor.-At 100" there is no reaction.5 grams oE camphor and 30 c'c.of absolute alcohol to which 0.75gram of sodium has been added are heated in sealed tubes for 24hours a t 200". A great pressure is observed on openirig the tubes, dueto the disengagement of large quantities of bydrogen. The productis treated with water, and the separated, coloured, viscous mass dis-solved in ether, from which it separates on spontaneous evaporat.ionof the solveut. Repeatedly crystallised from a mixture of ether andlight petroleum, it forms white, hexagonal crystals. melting a t208-210". This substance i s a niixture of dextro- and hvo-borneol,the proportions varying with the preparation. The rotatory powel-sof t w o preparations were [.In = +125" and [ a ] D == +16".15 grams of camphor yield 8-10 grams of pure borneol.Thejield is better than with Berthelot's method ; the product is riot mixedwith camphor, and only contains traces of campbic acid, small quan-tities of a liquid produut insoluble in water and alkalis, and sodiumacetateORGANIC CHEBILS'L'HY. 73Sodium propoxide, isobutoxide, and amyloxide yieid borneol, thequctiitity decreasiug with the rise in the molecular weight of thealcobol employed. Secoudary liquid products intermediate i n com-position between alk-jlcampliors and alkylborneols increase in the sameyatio.Bemylcnvip7)oT.-Dry dextrocamphor (1 mol.) is heated with sodium henzyloxide(1 mol.), dissolved in excess of benzyl alcohol, a t 220-225" for 24liours. There is no disengagement of gas. L)ist,illation of the etherealextract at 220-225" (H = 70 mm.) yields SL s*yrupy, very I-efractivesubstance, which, a t first, has a slight empyreumatic odour, becomingsimilar to the odour of benzaldehyde on exposure to the air.Boilingalcoholic potash, glacial acetic acid, 01' hydrochloric acid does notattack t h i s substance. It ct-ystallises on cooling, after the addition ofa crystal of benzylcamphor, in small crystals which, when recrystal-lised from alcohol, yield fine, large crystals melting a t 51-52', solublei n alcohol, ether, benzene, and toluene, aiid insoluble in water and thealkalis. The formation of benzylca~nphor is accompanied by the pro-duction of an equivalent amount of sodium benzoate and the libera-tion of hydrogen, which, doubtless, acts on a part of the benzyl-camphor yielding reduction products which remain in the uncrystal-lisable oil.Benzylcamphor may also be obtained by the action of benzyl chlorideon sodiumcamphor when heated.l'he reaction is finished when aportion of the material, diluted with water, does not give an alkalinereaction. When distilled a t 110 mm. prcssiire, a mixture of camphorand oily products passes over below 'LOO' ; from 2L5-22Oo, benzyl-borneol passes over; whilst from 220--250", a fraction distils as at liick oil, crystallising on cooling. The crystals, purified by recrys-t:illisation from alcohol, correspond in properties with the benzyl-camphor prepared from sodium benzyloxide.Benzalcamphor also yields benzylcamphor on reduction with sodiumaiualgnm.Action of Sodium Benxytoxide .o n Dextrocarn.phor.aBenzylcamphoroxime, C,H,,< I is obtained by heating forCH*CH,Ph'two days benzylcnmphor, mixed with the theoretical amount of thedouble chloride of ziric and hjdroxylamine and a little alcohol. l'hepiboduct crystallises from alcohol in long, flat prkms melting at12';-128", soluble in ether, benzene, and light petroleum, insolublein alkalis. The oily liquid separated from the oxime solidifies intime ; it has not been examined, but is, doubtless, an isomeride.Lrlevobenzylcamphor may be prepared fi*om Iaxocawphor by themethods given above. The crystals melt a t 50-52". Benzplb, rneolsare formed, together with benzylcnmpbors, when t h e camphor iodidesare treated with benzpl chloride. They are separated from the benzyl-camphors with some dificulty, owing to the approximation of theboiling points. They are oily liquids, having the odour of bitteralmonds, and distillinq a t 215-216" under a pressure of 80 mm.The oily products obtained by treating camphor a t R high tempera-t u r e with sodium propoxide, butoxide, and amyloxide are held tocontain the propjl-, butyl-, and amyl-camphors.W. Ti 4 ABSTRACTS OF CEEJlICAL PAPERS.Action of Sodium Benzyloxide on Ethyl Camphocarboxyl-ate. By J. MINGU~N (Compt. rend., 112, 1454-1455).-20-30 C.C.of benzyl alcohol to which has been added 0.5 gram of sodium ishetited with 10 grams of ethyl camphocarboxylate a t 1.50" for24 hours. The resulting pasty mass yields an oil on treatment withwater. On evaporating the ethereal solution, the residne yielclsbcnzyl alcohol and a viscous liquid distilling a t 260-290" under10 mm.pressure. This is benzyZ hydroxlycamphocarboxylate,The yield is about 30 grams from 40 grams of ethyl camphocarh-oxylate. Hydrolysis with alcoholic potash in sealed tubes givesbenzyl alcohol and hydroxycamphocarbox3lic acid. Tbe rotatorypower in alcohol is [ a ] D = +35.5".The wash waters, on nentralisation with an acid, yield an oil whichdistils at, 250-275" a t a pressure of 10 mni. This acid is veryviscons a t the ordinary temperature, On hydrolysiy it gives benzj Zalcoliol and hydroxjcamphocarboxylic acid. It may be considered tobe beti zy 1 hydroxycnm ph ocarboxylic acid, C 0 OH.C,H,,.(=H,*COOC?H,.Its rotatory power in alcoholic solution is [aID = 52-62'.New Method for Determining the Constitution of Homo-logues of Pyrroline. By C.U. Z A N w r r (Gaxzerta, 21, ii, 25-32).-Cismician arid Zanetti (Abstr., 1890, 1155) showed that hydroxyl-amine reacts with members of the pyrroline series, yielding dioximes,which are oximes either of dikrtones or of ketoalclehydes, accordingt o the constitution of the pyrroline. By boiling the resnlting oxinlewith 30 per cent. potash, the author finds that the correspondingbibasic o r keto-acid is obtained. This reaction furnishes a means ofdetermining the constitutioii of the pyrrolino homologue employed.Hydroxj laniine and pyrroline react to form succindialdoxime ;when this is boiled with 30 per cent. caustic potash there is ariabuiiclant evolution of nmmonia, and succinic acid, amounting to70 per cent.by weight of the oxitne employed, may be extractedfromthe solution.2 : 4-lXmethylpyr~oline, on treatment with hydroxylamine, yieldsa-methjllevulindioxime, which, when boiled f o r 2+ hours with causticpotash, gives the /3-acetoisobutyric acid prepared by Bischoff (Abstr..1881, 4Lc)). The hydm,-.o?ie of this acid crystallises from alcoholin splendid, yellowish scales melting at 122O, with evolution of gas,to a yellow liquid ; it is solnble in glacial acetic acid, alcohol, ether,benzene, and ethyl acetate, sparingly so in cold dilute alcohol, aridirisoluble i n water or light petroleum. It dissolves in solutions oftlie alkaline carbonetes with effervescence, and is precipitated un-altered by acids.On exposnre to air wid light, i t is converted into aheavy, reddish. brown liquid. &thy 1 /3-acetoitsobutyrafe is obtained asa liquid of fruity odour. on passing dry hydrogen chloride through astrongly cooled sollition of the acid in absolute alcohol. I t s hydrazonr,which heparates from dilute alcohol in yellowish scales, riielts a t 105",arid is soluble in alcohol, ether, etlijl acetate, and acetic acid, spiir-ingly so it1 cold, dilute alcohol, ant1 insolnble iu water and alkaliueW. TOHQANlC CHEIJIETRY. 75cmbonntes.exposure to air and light.Methyldipyridyls. By A. HEUSER and C. STOEHR ( J . pr. Chem.[Z], 44, 404-410).--aa-Dimethyldipyridyl (Abstr., 1891, 80) isbetter isolated by extracting the base, which separates from theaqueous solution of the reaction mass, with ether, drying the ethercia1solution over pot,assium hydroxide, distilling off the ether, re-dissolv-in$ in absolute alcohol, and converting the base into hydrochlorideby a stream of dry hydrogen chloride.When aa-dimethj ldipyridj 1 is oxidised with permanganate, threeacids are obtained, namely, a-methyldipyridyl-a-carboxylic acid, di-pSridyl-aa-dicar~oxylic acid, and lutidinic acid, in the proportion of10, %, and 2 grams respectively, from 20 grams of the base.Five gramsof the base are introduced into a solution of 32 grams of potahsiumperniang:inate in 1200 grams of water, and the solution is kept a t40" for about 14 days. The manganese dioxide is then filtered off,the filtrate evapoiwated in a stream of carbonic anhydride, andiieutralised with nitric acid.By evaporation with alcohol, most ofthe potassium nitrate is separated, and the acids are then precipitatedwith silver nitrate; the silver salts are decomposed by hydrogensulphide, when a jellow precipitate separates as the hot filtrate coolr ;this contains the mono- and di-carboxylic acids, which can be separ-ated by the greater solubility of the former in hot water; tlrelutidinic acid is extracted from the filtrate from the yellow precipitateby evaporation with animonia and extraction with ether.a-Methy Idipyri yl-z-carboxylic acid has been already described(Abstr., 189L, $1). When heated with glaci~l acetic acid at 180",it, is converted i n b methyldipyridyl with evolution of carbonic:anhydrideD ~ ~ y r i t l y I-rxa-dicarboxylic acid, C,,,H,N,(C@OH), + H,O, crystallisesin colonrless needles, melts at 247*j", decomposes a t a slightly highertemperatnm, and dissolves sparingly in water and glacial acetic: acid.It is colourecl retidish-yellow by ferrous snlphate when in aqueoussolution, and violet when crystalline.The silver and bariuob saits wereobtained, and also an easily soluble plafirmhlorids. When this acid isheated with glacial acetic acid in a sealed tube at 180", it yields+/-/-dipyritiyl, which melt,s a t ~ l ~ - - I l ~ * (Weidel gives 114", Abstr.,18K3, 483) ; the ylcttiaoc,hlnride of this base was obtained, and it, isnoted t h a t potassium ferrocvanide gives a red-brown solution withthe base, from which tramparent, six-sided tables gradually separate(compare Abstr., 1891, SO).L?itidinic acid, C,H,N(COOH), + H,O [(COOH), = a : -11, c y s t n l -lises in aggregates of mlourless needles, melts a t 232-233" withrapid evolution of gas, and dissolves easily in hot water.Like the hydrazone of tlre free acid, it liquefies onW.J. P.A. G. B.Preparation of g- and p- Pyridyllactic Acid from a-Picoline.By A. EINHORY (Airden, 265, ZO8-23tS).-Pj-ridyl-w-trichloro-=r-hJdroxypropane (Abstr., 1887, 845) is best prepared by heating asolution of a-picoline (50 c.c.) and cliloral (45 c.c.) in amyi acetate(175 c.c.) for 10 t o 1 2 hours a t 140-1.50"; the product is extracteARSTRSCTS OF CHEMICAL PAPERS. n a4from the solution by shaking with dilute hydrochloric acid.Theyield of the hydroclrloride is a t least 125 grams from 100 g r a m sof picoline ; this salt crystallises from alcohol i n lotig, prismaticneedles, and melts at '201-202". The free base crystallises fromdilute alcohol in hexagonal plates melting at 86-87". The hydro-bromide, C8H9NOC13,HBr, forms well-defined crystals, and melts at20i-206".P!/ridyl-w-trirhZoro~~o~~Ze~~e, C5NH,*C H:CH*CCl,, can be obtainedby gradually aciding phosphorus pen tnchloride to a boiling mixtureo f py~~idyltrichloroliydroxypropane hydi-uchloride and chloroform, anddeconiposing the salt thus produced w i t h sodium carbonate ; i tcrystallises from alcohol in prismatic iiedlee, melts at 97", andpadually decom ~ O S W on keeping.a-PyTidylZaclic acid, C,NH,*C H,~CH(OHj*COOH, is formed whenNn aqueous solution of pyridy Itrichlorotiydrox-~ propane hydrochlorideis gradually added to boiling sodium carbonate, and the heating con-tinued until the reaction is a t an end ; it is isolated by means of itsbasic copper salt.It ct*ystallises from alcohol in transparent, seem-i n g l y iriotloclinic prisms, melts a t 124 -125", and is only sparinglysoluble in ethyl acetate, but more readily in cliloroform. The basiccoppier salt, ( CRH,N03)2Cu,Cu0. crystallises from hot water and am-monia in slender, green needles. The silver salt, CHHsNOJAg, crys-tallises from dilii te ammonia in colourless needles. The hydrochloride,C'8H9NC)3,HC1, separates from alcohol i n crystalline aggregates, andmelts a t 85-86'.The hydrobromide, CsHgNOJ, H Br, crystallises fromglacial acetic acid and alcohol in large, well-defined needles meltinga t 125-126". The ylatinochloi-id?, ( C6H9NO,),,H2PtCI6, is moderatelyeasil7 soluble, and inelta a t 202-204". The aiwocldoride forms com-))act, yellow prisms, and melts a t 177". When pyridyllnctic acid isheated at 130-140" under reduced pressure, i t is converted intopyridglacrylic acid with elimination of 1 mol. H20 ; on oxidation withexcess of very dilute potassiurn permanganate, it yields picolinic acid.BeiLzoyZ-31-pyI.idyZZactic acid, C:,NH[,.CH,*CH( OBz)*Ci>OH, is bestprepared by gradually adding bmzoic anhydride (4 grams) in smallportions a t a time to a solution of a-pyridyliactic acid (2 grams) inwater (4 grams), heated a t a temperature just below 90" ; it crystal-lises from hot water in lustrous needles, and melts at 145" withd ecom position. The platinochlr ir ide, (C ,5H ,,NO,) 2, H,PtC 16, crystal -lises from water or dilute alcohol i n yellow, transparent, prismaticneedles melting at 179" with decomposition.The barium salt is acoloiirless, crgstalline compound, readily soluble i n water and alcohol ;tlie silcsr salt crystallises in cdourless needles. The methyl salt, pre-pared by treating the silver salt with methjl iodide, is an oil, but itsp!atinoctiloride, ( C16H1,N0,),,H,PtC16, crystallises from hot water anddilnte alcohol in yellow needles melting a t 193" with decomposition.Methyl a-pyyidyliactate, C5NH,*C:H2*CH( 0 H)*COOMe, prepared bytreating a methyl alcoholic solution of the acid with hydrogen chloride,is a colourless, crystalline compound melting at about 34O ; its aura-chloride, C9HI1XO3,HAuCl4, separates from water in crystals, and meltsat about 119" ; its benzoyl derivative crystnllises in transparent needles,iiielts a t 41°, and is identical with the methjl benzoylpj ridyl-cc lactatOR OhNIC CHEJIISTRT.77just described (as an oil), as was proved by converting it into thecrystalline platinocliloride (m. p. 193-194").Pyridylacrylic acid, C5NH4-CH:CH*COOH (Zoc. cit.), is best prc-pared by adding pyridyltrichloropropane hydrochloride (60 grams),in Rmall portions (3 to 4 grains) a t a time, to a boiling solution ofpotassium hydroxide (132 prams) in alcohol (400 grams), air heiilgexcluded fts much as possible.After boiling for six hours, the filteredsolution is evaporated with hydrochloric acid, tho residue extractedwith alcohol, the extract decolorised with animal cbarcoal and con-centrated ; on cooling, pyridylacrjlic acid hydrochloride is depositedi n crystals, and the mother liquors contain pyridyllactic acid hydro-chloride, which can be isolated by means of its copper salt ; the yieltlof the former is 20 grams, and of the copper salt, 5 grams. Pyritlyl-acrylic acid crystallises from hoiling water in small, transparentneedles, melts at 202-203' with decomposition, and is almost in-eoluble in cold water, butl readily soluble in alcohol. The hydrochlor-ide crystallises from alcohol in colourless needles melting a t 220" withdecomposition.The hydrohromide, C8H,N02,HBr, forms spear-shapedcrystals, and melts a t 222-223". The aurocbloi-ids, C8H7N 02,HAuC11,crystallises from hot watey in small, light-yellow needles, and meltsa t 194-195". The plntinochloride, (C, H,NO2),,H,PtCl6, is moderatelyeasily soluble in water, from which it crystallises in reddish-yellowprisms melting a t 209-210". The barium salt and the salts of theaikalis do not crystnllise, but the cczlciiim salt, (C8H6N0,),Ca, separatesfrom dilute alcohol in slender needles ; the silver salt, C,H,NO,Ag,. isalso crystalline. Tbe methyl salt, prepared by treating the acid wlthhydrogen chloride in methyl alcoholic solution, is a solid, very hygro-scopic substance ; its hydrrch Zoride, CgH9NOz,HC1, sepiwates frommethyl alcohol in small, colourless crystals melting at 185-1 86".The Pthyl salt crystallises in lonp, transparent needles.The meth-iodid.-, C8HiN02,MeI, separates from dilute :tlcohol in amber-yellow,prismatic needles, and melts at 219-220" with decomposition. Themethobromide, C,H7N02,MeBr, separates from water in colourlesscrystals, melts at 242" with decomposition, and is almost insoluble inalcohol, and only sparingly soluble in glacial acetic acid.Yyricly Mibromoproioionic acid, C5NHEI*C HBr-CHBrGOOH, preparedby warming pyridglacrylic acid (1 part) with a glacial acetic acidsolution of bromine (1.3 parts), separates from water ill yellowishcrystals melting at 127", and from glacial acetic acid in grey crystals,which retain some of the solvent, and melt at 146.5".p- Pyricly 1 bromcpropionic acid lqdro byomide,C5NH,*C HBrC H,.CO 0 H, HBr,is formed when pyridylacrylic acid is heated a t 100" with a solutionof hydrogen bromide in glacial acetic acid, saturated a t 0" ; it crys-tallises i n colourlcss needles or plates, and melts a t 163-164".Pyridyler hylene is produced, together with pyridylacrylic acid andp-pyridyllactic acid, when an aqueous solution of the preceding corn-pound is warmcd with a slight excess of sodium carbonate; it isa colourless oil, boils a t 159-160" with partial decomposition, andis identical wi t,h Lad enburg's viny Ipyridine.The platinochloride78 ARSTRACTS OF CHEllICAL PAPERS.(C,H,N),,H2PtCl,, separates from W R ter in crvstals, and melts at 174"with decomnosit,ion.The nwrochloride, C,H,N, A.uC13, crystallises inyellow needles, and melts at 244".fl-.PyridyZZnctic u.cid, C,NH,.CH(OH).CH,.COOH, is isolated fromthe red solut.ion which remains after distilling the pyridylethjlcnewith steam, by first acidifyinr wit,h dilute hvdrochloric acid to pre-cipitate the pyridylacrylic acid, and thon adding an ammoniacal solu-tion of conper sulphate to the filtrate ; after a time, the bwic coppersalt, (CRH,N0,),Cu.CnO, is deposited i n blue crpstals. and can bepurified by recrystallisation from dilute ammonia. Thp free acid is acrystalline compound meltinq at 86". The hy&ocl/~loride, CsHnNO3,HC1,crpstnllises from alcnhol in colourless prisms, and melts a t 147".ThepZat;nochloride, ( C,E,NO:,),,H2PtC16. separates from dilute alcohol insmall, yellow crvstals meltin,q a t 191". The methyl salt, prepared bytreating a methyl alcoholic solution of the acid with hydrogenchloride, is a light. yellow oil ; its pZntinochZoridz, (C,KllNO3),,H2PtC1,,crystallises from dilute alcohol in lustrous, yellow plates, and meltsa t 178.5". The ethyl salt is also a pale-,vellow oil, but its hydro-chloride crvstallises from alcnholic ether in lustrous plates.Renzo?lZ-~-p~ridyZlacfl:c acid. C ,,H13NOC, is formed when ethyl B-pvridyllactate is warmed with benzoic chloride on the water-bath ;the benzoic acid is separated in the nsual wa.7, the product theti dis-solved in hydrochloric acid.the solution kept for some days, and thecrvAt8alline hydrochloride thus obtained decomposed with water : thefree a,cid crystallives from hot water in lustrous prisms, and melts a t135.5". The silver salt is a colonrless, crystlalline compound. ThemethyZ salt, C,,H,,NO,. prepared from the silver salt, crystallises intrmsparent prisms, and melts a t 79".The relationship between some of the compounds described zboveand certain derivatives of coca'ine is shown with the aid of graphicformulae. F. S. K.Synthesis of Quinoline Derivatives by means of Alkyl Aceto-acetates. By M. CONRAD and L. LIMPACH (Ber., 24, 2990-2992).--An extension of the method previously described by the authors(Abstr., 1888, 593) to the synthesis of other quinoline derivatives.Methyl phenylamidomethylcrotonate is obtained by mixing methylmethylacetoacetate and aniline in equivalent proportions, and allowingthe mixhure to remain for some days, or by dissolving methyl phenyl-amidocrotonate in benzene, and treating it first with sodium and thenwit.h mc thy1 iodide.nim,efhyZhydro~~yquinoZine, C9NHiMe2*OH [Me2 : OH = 2' : 3' : 4'1,is obtained by quickly heating methyl phenylamidomethylcrotonate(30 grams) to 240°, withdrawing the source of heat as soon as thetemperature reaches 260", dissolving in dilute hydrochloric acid,treating the solution with animal charcoal, and rendering it faintlydkaline with ammonia or soda, when it separates as a white, crystal-line mass ; the yield is 10 grams.It crystallines from boiling waterin lustrons prisms containing 1 mol.H20, sublimes at 300", meltsabove 305", and is only sliglitly soluble in alcohol ; it has not a bittetaLste. The platinorh7oride, (C,,H~lNO)21)-12PtC16 + 2H,O, forms long,orange-yellow needles.Methylethylhyclroxyquil70;ine, C,NH4'iLIeEt.0H, is prod {iced in xsiniilar manner to the dimethyl derivative, 1)y lieatinq uicithyl phenyl-smidoethylcrotonate ; it melts a t 290", and is only sparingly solublei n boiling water and alcohol. A. R. L.Action of Hydroxvlamine on Ketonic Nitriles. By HANRIOT(null. 15'oc. C71im. [ 3 ] , 5, 773-779).-When ethyl sc-cynnet.hy1 ketone,COEt-CHMe.CN (Abst'r., 1889, 841) (100 grams) is dissolved in con-centrated potash (200 c.c.), a potassium compound is formed, whichmay be crystnllised in brilliant, plates ; but if the solution is heatedon the water-bath for half an hour with a solution of hvdroxvlaminehydrochloride (100 grams) in the minimum quantity of baterr amido-?net lay 1 e t h y lisox az o 1 e , >0, separates as an oily liquid,FMe:C( NH?)CEt=Nwhich, on purification, becomes crystalline.It forms highly refrac-t i v e prisms, melts a t 44", and boils a t 180' under a pwssure of20 nlm. ; a t a higher temperature, it changes into an isonieric sub-stance melting at 280". It is soluble in the usual menstrua, with theexception of petroleum, and is not affected by alkalis. The hydro-chloride, CsH,,N,O,HC1, crystallises i n long needles, and is soluble inwater and alcohol, but insoluble in ethw.The acefyl derivative,C,H,N20Ac, crystallises in colourless plates, melts a t 16L", and isSOl-able in alcohol and acetone, sparingly soluble in water, and in-soluble in ether.When an et)hereal solution of the isoxazole is saturated withbromine, a yellow, viscous mass is obtained, which is decomposed bywater into ammonium chloride and rnethyZethylbromazolone,YMeBt-COCEt E N > 0 ,a crystRlline substance which melts a t 41", and dissolves in the usualmprtstrua. If, however, the bromination is effected in chloroformsolution, a substance melting a t 92" is obtained.When t,he isoxazole is oxidised with nitrous acid (sodium nitriteand hydrochloric acid), yellow crystals of the corresponiiing azoxy-compound are obtained. Azoxyrnet hyleth ylisoxneole,melts at 65-66", and explodes at a somewhat higher temperature.Itis soluble in al(:ohol, ether, and alkalis ; the alkaline solution is red,and is decolorised by acids, the compound being reprecipitated. Itdoes not unite with bromine.When hydrogen sulphide is passed through an ammoniacal alcoholicsolution of the azoxg-compound, the colour disappears, and on eva-poration crystal B of h!ldrazornet?L y 1 eth y 1 isoxy azoleFO ABSTRACTS OF CHRJIICAL PAPERS.are deposited. When pure, it foi*ms felted needles, melts a t 150", anddissolves in the usual menstrua. It is easily oxidised to the aizoxy-compound, and f o r m an oily compound with bromine.When ethyl a-cyanisopropyl ketone, COKt.CMe,*CN (Zoc. cit.),IS treated with hydroxylaniine hydrochloride, the ring conderisatioiican no longer take place, as tho hydrogen previously available forthat purpose is replaced hy metliyl.Consrquciltly, ethyl a-cyan-isopropyl hetoxiwe, OH*S :C Et*CMe,.CN, is obtained, instead of anisoxazole. I t crystallises it1 plates, melts a t 61-62', and is soluble in theusual menstrua with tlie exception of petroleum. It differs from thei,soxazole in t h a t it forms a cryshallhe potassium derivative whentreated with potash, that it does not unite with bromine, and that it isnot oxidised with nitrous acid. JN. W.Methylphenyldihydroquinazoline and its Derivatives. ByC. PAAL Nncl P. KKECKE (Ber., 24, 3049-3058; compare Absti..,1890, 144:3).-After orthoniti.obenzylacetanilide,has been reduced with tin and hydrochloric acid, and the stanno-chloride of methylphenyldihydroquinazoline, c61i4< hasbeen removed by crystallisation, there remains in the mother liquor avarying qnantity, never exceeding one-third of the theoretical, ofo rthamido benz?jlacetanilide, N H2* C6H ,*NP h Ac.This subs tan ce is . notforn~ed when the reduction is carried out with zinc-dust and aceticacid. It can be obtained from the mother liquor by removing the tinwith sulphuret ted hydrogen, and extracting the filtered solution withether, after previously making i t alkaline. It crystallises fronlalcohol or water in Iustroiis, white prisms melting at, 126-127", anddissolving easily in alcohol, benzene, carbon bisulphide, ethyl acetate,and glacqial acetic acid, moderately in ether, arid sparingly in IigIitpetroleum and hot water.When oxidised with alkaline permangall-ate at loo", it yields, besides a small quantity of azobenzene, a, sub-stance of undetermined constitution which crystallises irom water illbvoad, yellowish needles melting at 178", and from ethyl acetate incrossed crystals ; this dissolves sparingly in benzene, easily in alcohol,ethyl acetate, glacial acetic acid, concentrated hydrochloric acid,alk;jlis, and alkaline carbonates.Ort hanaido benzy Zacetan ilide hy drnchlcrid e, c 1,H,6'N,0, H C1, is bcs tobtained by adding a little concentrated sulphuric acid and ethcr toiin alcoholic solution of the base. It crystallises in white needles,melts at 170", and is readily soluble in water and alcohol.The,~tannochluride, C15H,6N20,HSnC13. does not crystallise readily; it meltsbetween 110-115", and dissolves easily in water and alcohol. Theacid subhate, C,5H16E20,H,SO*, crgstallises in stellate groups ofcolourless needles, which become green on the surface when kept,melts at 163", and dissolves readily in water. The oxalate and thepicrate are both easily solnble in water and alcohol.When the base is boiled for a short time with excess of aceticanhydride, arid the product treated with a dilute solution of sodiumNO,*C~H~*CH~*NP~AC (1 : 2),N= ?MeCH,*NP hOHQANIC OHEMISTRY. 81cerbonate, orthmetnrnidobenrylacetanilide, NHAc*C,H,NPhAc, sepa-rates. It crystallises from alcohol in four-sided plates, melts at 1 2 1 O ,and dissolves readily in most organic solvents and in dilute mineralacids, but very sparingly in w;i ter.Met h y l p hen y I d i hydro g n i v ~ azoline, pre v io us1 y obtained by red 11 cingorthonitrobenzylacetanilide with tin and hydrochloric acid, is betterobtained by using zinc-dust and acetic acid, the solution being keptcool.The solntion is then filtered from excess of zinc, and treatedwith excess of soda ; the base is extracted wihh ether, and convertedinto the sparingly soluble hydrochloride, which is purified by crystal-Iisation from water. It may also be obtained by distillinq orth-amidobenzylacetanilide, which loses water and gives almost a quanti-tative yield of methylphenyldihydroquinazoline. The arid sulphateC,,H,,N,,H,SO, + H,O, obtained by adding sulphuric acid in slightexcess and then some ether to an alcoholic solution of the base,crvqtallises from water in colourless, interwoven needles.It melts a t78" ; when anhydrous, at 201". When methylphenyldihydroquin-azolitie is oxidised with alkaline permanganate, the filtered solutioncontains pI~eny1l;etodihycEropuinazolinecurboaylic acid,This can be seprlrated as a crystalline precipitate by adding hydro-chloric acid to the solution ; when fresh, i t is soluble in hydrochloricacid, alkalis, and alkaline carbonates, but it readily loses carbonicN:CHanhydride, yielding phenyll;etodih2ld?.opui?zaxoline, C6&<C0.&ph.The manganese precipitate contains rnetiLylphe.rLylTcstodihydropuin-azoline, C6H,< which may be extracted with alcohol; it crys-tallises from that, solvent in long, yellowish prisms, melts at 143", anddissolves readily in ether, alcohol, benzene, and light petroleum, ye1-ysparingly in hot water.The hydyochlorids forms bunches of whiteneedles, melts a t a, very high temperature, and dissociates in water., was obt,ainedby reducing a hot concentrated alcoholic solution of the dihydlmo-compound with sodium in large excess, and then diluting the mixturewith water. It crystallises from dilute alcohol in broad ncedlep,melts a t 94-95", and dissolves easily in most organic solvents and i nmineral acids, but not in water. The hjdrochloride and oxalate wereN C;MeC 0 -N P h 'NH-YHMeMet hy lp hen y 7 tet rahy dropuinazoline, CGH, < CH,*NPhprepared.NAc-Y HMephenyltetrahydroquii~azoline, C6H4<CH,.NPh ,When heated with acetic anhydride, it yields acetylnzethyl-which crystallisesfrom dilute alcohol in colourless, rhbmlboidal plates, melts a t 120.5",and dissolves readily in the usual organic solvents. C. F. B.Action of Hydriodic Acid on Quinine. Isoquinine. By E.LIPPMANN and F. PLEISSNER (Monatsh., 12, 327-337 ; compare Zorn,9 VOL. LXII82 ABSTRACTS OF CHEMICAL PAPERS.Amden, 8, 201; Skraup, ,T. pr. ChPm. [a], 8: and Comstock andKoenigs, Abstr., 1887, 1122, and 1888, 7 1) .-Hydyiodoquiiiinc hydr-iodide, HZC2,,HzrN2O2,2H1, is obtained a s a heavy, yellow, crystallinepowder on warming quinine with hydriotlic acid of sp. gr. 1.7--.7 -8.T t is sparingly soluble in cold water; dissolves in hot water withpartial decomposition ; crystallises from hot alcohol in bright-yellowprisms, melts at 2 15-2SO" with decomposition, and, on treatmelitwith dilute ammonia, gives the compound hydyiodnquitrine,C,,H2,N,Oz,HI.This snbstance crystallises in slender needles, softens a t 95' andcommences to melt a t a higher temperature : gives silver iodide onheating with silver nitrate solution ; is insoliible in wntm, dissolves inalcohol and in ether, and forms solulile salts with acids.ffydy;ndo-quinine platinochloride, HI,C2,H2,N,0,,HzPt C1, + 2H20, is nb+aiiiedas a light-brown, crystalline precipitate on adding platinum chlorideto a cold solution of hydriodoquinine hjdrioilide in hydi*ochloricacid.Hydrindo-upoqitinine is prepared hy heating liydriodoqninine hydr-iodide with a solution of hydriorlic acid, saturated at, 0" for severalhours under pressure ?t 100".Methyl iodide is evolved, and, oncnoling, the new compound, HIC1YH22N202rZH'I, separates as a yellow,crystalline mass, which, after recrystallisation from alcohol, com-mences to darken in colour a t 120", and melts with decomposition at237". On the addition of ammonia, 2 mols. of hydriodic acid meremoved with formation of hydriodo-apoqninine, of which the platino-chloride, C19H22N20,,H1 ,H,PtC16 + H20, is a heavy, brown, crjsfallinepowder.Iso-upoquinine, C1RHZ2N202, is formed on warming hydriodo-apo-quinine in alcoholic solution with potash. It melts at 176" (Hessestates that the compound decomposes at lSOo), and dissolves readilyi n dilute potash ; the plafinochloride, C,,H?2N2c~2,H2PtC& + H20, isa crystalline powder, only sparingly soluble in water.Isoqitinine.--This base is obtained when hpdriodoqninine is boilcdwith alcoholic potash.After repeated crystallisations from ether anddilute alcohol, i t melts a t 186" (uncorr.). Hesse and Lenz have giventhe melting point as 174.4-175' and 170*4-174*4" respectively.The base is levorotatory, [aID = -186.75" being the rotation of analcoholic solution containing 0.9644 gram in 100 c c . , and [aIn =-1180.8" for a solution containing 3.9936 grams i n 100 C.C. Jso-quiiiine crystallises in small needles containing 2 mols. H,O ; thesulphacte, [C2,,H24N202]2,H2S04 + 10H20, forms characteristic groupsof slender needles readily soluble in water, giving a ready means of dis-tinguishing between the base and quinine.The no?-mal hydrochloride,CdLNzOZ,BC1 + 2H20, crystallises in needles, and is readily solublein water ; the acid hydi*uchZoride, C2nH20NzOz,2HC1, is not so easilysoluble ; the platinochloride may be obtained as a crystalline, yellowprscipitate ; and the compound with silver nitrate, C2,1H24KZ02,AgN03,precipitated a s a gelatinous mass on addiilg an alcoholic solutionof the ba,ge to a solution of silver nitrate. G. T. 31ORQANIC CHEMISTRY. 83Compounds of the Cinchona Alkalo'ids with Hydriodic Acid.Ry Z. H. SKRAUP (Moiiatslt , 12, 431-434) -Quinine, quiaidine,einchonidine, and cinchonine are all dissolved slowly by cold, andmore quickly by warm, hydriodic acid, with the formation of yellowor orange-red coloured compounds, which contain 1 mol.of the base to:$ mols. of the acid ; the quinine and yuinidine solutions, if kept, furtrherexchange methyl for hpdrogen, giving compounds of the formula,C19H,,N,0,(HI),, which are readily solub!e in caustic potash. Alithese substances crystallise well ; they are alrllost insoluble in water,slightly soluble in absolute alcohol, and dissolve to) a moderateextent in dilute alcohol, from which, with care, they may be recrys-tallised (compare Lippmann and Fleissnnr, preceding abstract), Thecompounds from isomeric alkaloids differ in appearance, solubility,and melting point, and are analogous in comlposition to the corre-s pondiiig compounds with hydrochloric and hgd robromic acids (com-p r e Comstock and Koenigs, Abstr., 1887, 11122 ;.and Zorn, AniiaEen,When the compounds CzoHziN20a,3 H I and C,,H,N,O,S HI whichare fortned from quinine and cinchonidine respectively, are gent'lywarmed with caustic alkalis, they lose 2 mols. of hydrogen iodide,and furnish the compounds C?,H,NzOzI and CigHJTZOI respec*-tively. These are analogous in composition to the couipounds withhydrochloric acid, which are obtained in a similar way (Corn-stock and Koenivs, Znc. cit.). The compounds C20H2,NzOz.SHIand C19H,N,0,3HI. formed from quinidine and cinchonine respec-tively, lose only 1 niol. of hydrogen iodide when treated with excess ofalkali, the bases Cz,, B26N202T2 and C1, H2AN2012, respectively, beingproduced.The mono- and di-iodine compounds are almost colonrlesF.and must not be regarded as periodid-s, the hydrogen iodide evidentlybeing held within the molecule. The compounds of the formulnC,9Hz2Nz02,3HI, obtained from quiuine and quinidiue, and which aresoluble in potash, behave in a preciselysimilar way when treated withalkalis, the compound from the former bme losing 2 mols. of hydriod cacid, whilst tliat from the latter loses only I mol. This differentliehaviour of the products of the action of hydriodic acid with potashforms a convenient means of distinguishing betweeri the isomericcinchona alkaloi'ds ; and it is also remarkable t liat those alkaloidswhich are decomposed in the same way hiive a similar effect on cir-cularly polarised light.Attempts to displace the iodine of the mono- and di-iodine com-pounds with alkyl groups or other radicles by heatiiig with sodiumt thoxide, potash, silver nitraite, &c., invariably led to the eliminationof hydrogen iodide.The base C ,9Hz~Nz012, obtained from cinchonine,Iiomever, gave, with sodium etlzoxide, in addition t o cinchonine, asmall quantity of a base which was readily soluble i n ether, refused tocrystallise, and was probably isocinchoninc. The quinidine compoundC20H26NZ0212, on similar treatment? did not give the original base, but,an isomeride, which is only slightly soluble, and gives salts whichcrystallise badly. The isomeric quinine compound behaves in anaudogous way, biit also gives some quinine; whilst the quinine8,20)84 ABSTRACTS OF CHEMICAL PAPERS.compound that is soluble in potash does not give rise to cuprejine,but forms an isomeride.The compounds with hydriodic acid are easily reduced with zinc-dust, and the products appear to be different from those obtained by thereduction of the cinchona alkaloids.They are semi-liquid, volatile insteam, and very rich in hydrogen.Quinoliiie, paramethoxyquinoline, chit enine, and cinchotenine do notcombine with hydriodic acid. The author therefore supposes that itis the C,H,J'TO porticn of the quinine molecule that attaches thebydriodic acid, but cannot explain the absorption of 2 rnols. of hydro-gen iodide, as, even if the oxygen were originally held to a carbonatom by a double bond, only one of the two molecules is accountedfor To explain the addition bg assuming a molecular ~earmngernentof the qainoline nucleus is unsatisfactory, as the hydriodic acid istaken y~p G t ordinary temperatnres.Full particulars of the compounds of the cinchonla alkalo'ids withhjdriodic acid will be giveu in a future paper.A new Alkaloi'd from Chrysanthemum Fbwers. By F.MARINO Zuco (Gazzetta, 21, 516--554).--'l'kie author has previouslyextracted from chi*ysanthemum flowers a new cholesterol (Abstr.,1890, 757), a glucoside, arid an aikalo'id (fiend.Acad. Lincei, 6, ii, 572 ;7, i, 121). The latter is prepared in quantity by boiling about10 kilos. of the flowers in distilled water (:3 parts) for 2 or 3 hours,filtering through cloth, pressing the residue, and trpatihg it again inthe same msnuer.The extracts are evaporated down to 30 litres,treated with.neutra1 lead acetate and basic acetate of lend, nentralisedwith soda, filtered, and the excess of lead removed'by passing sulphur-etted hydrogen. After filtration, the liquid is concentrated to about2 litres, boiled for some t'me with dillate sulphnric acid, filtered, andagain boiled until no more resinous matters are formed. The liquid isthen decdlorised withanimal black and an excesq of the double iodideof potassium and bismuth added, when a heavy, bright-red, crystallinepowder containing the whole of the alkaloi'd is deposited.The pure alkalo'id chrysmtthemine, C,*HnaN2Oj, is a colourless syrupwhich, when kept in a vacuum, partially crystalhes 'in tufts of silkyneedles, and may be heated without decomposition to 1 0 0 " ~ but notbeyond that temperature.It dissolves i n water forming alkaline solu-tions whichabsorb cal-bonic anhydride from the air ; it is also soluble inethyl and methyl alf,ohuls, b u t not in ether, chloroform, or benzene.Salts of chrysantheinine yield, wlth the double iodide of potassiumand bismuth, orange-red, flocculent precipitates which become crystal-line and bright-red on agitation ; with the double iodide oi' mercuryand potassium, a yellowish-white precipitate ; with the iodide ofplatinum and sodium,#& brown precipitate ; with auric trichloride, ayellow, crystalline precipitate which dissolves 011 heating and is re-deposited on cooling ; no pi-ecipitate is formed with platinic chloride,picric acid, tannin, or mercuiic chloride. The base is optically in-active and physiologically innocuous. Its salts are for the most partsoluble i n water and even deliquescent; the aurochloride and thedouble iodide of bismuth and chrysanthemine are insoluble, It is ilG. T. MORGAKIC CHEMISTRY. 85biacid base, but in dilute solutions it behaves towards acids as if i twere monacid. Both the hydrochlorides crjst:illise in small, colour-less, deliquescent needles, very readily soluble in water and alcohol,but only moderately in hot water. The azwochloride,crjstallises in minute, golden-yellow prisms T pry readiIy soluble inhot water and in absolute alcohol ; M hen pure, it is not much affectedby light. The platinochloride, Claf€?aN,03,HtPtC16, crystallises inorange-coloured prisms, and is extremely soluble i n water.On heating chrysiinthemine with an excess of methyl iodide for twodays a t 100". trio mcxtliyl groups are taken: up. and it is partly con-verted into a new base in which both nitrogen atoms are combinedwith hydrogen. The two baseq can be separated by taking advantage ofthe great difference in the solubility of their platinochlorides inwater. l h e pZutinochZol-ide o€ the new base, C16H,,N20,,H2P tCl,,crystallises in small, orange-coloured needles, dissolves very sparinglyin water, but moderately in hot water slightly acidified with hydro-chloric atilt ; i t is insolnble in absolute alcohol. The hydrochloride isa deliquescent compound which crystallises in a vacuum in tufts ofsmall needles. It is freely soluble in water and in hot absolutealcohol. The free base is a syrupy liquid which becomes partiallycrystalline after being kept for a long tinie in a vacuum.Oxychrysanthcmine, C1J32fiN201, prepared by oxidising chrysanth-emine with sodinm hypobromite, yields a doiible iodide with bismuth,crjsta11is;ng in orange-colourcd needles readily soluble in hot water.The alkaloid is a syrupy liquid which, if kept in a vacuum, isslowly con\-erted into a very deliquescent, crystalline mass. It hasan acid rcnction, but combines with both acids and alkalis. It formstwo hydrochlorides : the dihydrorhloyide is a deliquescent, crystallinemass very soluble in absolute alcohol ; the ?,ro,iuhydl.ochlorid~, is ;Icolourless, crystalline mass composed of very slender, brilliant needle-,very soloble in tiater, but only spmingly in absolute alcohol. Theaul-ochlwide, C,,H2,N20,Au,CI,, crptallises in brilliant, golden-yellow,Iiexagonal laminae freely soluble in hot water. Chrysantheminestrongly resists the 'action of oxidising agents ; on heating a sutph-uric acid solution of the base with potassium dichromate andsulphuric acid, it is almost quantitatively converted into oxychrys-antheinine ; a solution of potassiurri permanganate, on the other hand,only part idly converts i t into oxyclirysanthemine, carbonic anhydride,ammonia, and traces of trimethy lamine being evolved, whilst a portionof the base is conipletely broLen up. Oxychrysanthemine is completelydisintegrated by a hot solution of potassium permanganate. Dilutesolutions of alkalis have no action on chrysantheniine even after pro-longed boiling : very concentrated solutlions decompose it into tri-methylamiue, y-hydroxybutyric acid, and hexahydropiperidinecarb-oxylic acid with evolution of hydrogen according to the equationK2C03 + 4H2. The hexahydropiperidinecarboxylic acid obtained in thisway yields a very stable aurochloride, crystallising in golden-yellowscales very soluble i n hot water, but only very sparingly in cold, hiC1,H,,N2O, + 4KOH + HZO = C6H,,NO2K + (>~HTO~K + NMea 86 ABSTRACTS OF CHEMICAL PAPERS.melts at 150-1.51" without decomposition. The hydrochZo?.ide crystal-lises in plates, and melts a t 184-185". The acid corresponds, there-fore, neither with Ost's pipecolinic acid (Abstr., 1883, 791) nor withLadenburg's nipecotitiic acid (Abstr., 1891, 735) but is probably ar,-pjperidinecarboxy lic acid (hexahydroisonicothic acid). If chrysan th-cmine is tzeatcd with a- moderately concentrated solution o€ potash,the decomposition takes place more slowly and a small quantity of aproduct intermediate between chrysanthcmine and hexahydropyr-idinecarboxylic acid is obtained. This cornpound yields an a~~7-9-chloride, CllH,I0.,NAuC13, crjstallising in tufts of reddish-yellowneedles. Oxychrysanthcmine is deco I t 1 posed by very Concentratedsolutions of potash into EvexFthydroppridinecarboxylic and snccinic:acids, carbonic anhydride, trimethylatnine, and hydrogen. Fuminghjdrochloric acid has no action on chrysanthemine even after pro-longed heating ; concentrated sulphui.ic acid merely resinities a verysmall proportion on boiling. A glac'al acetic acid solution ofchrpanthemine (1 mol.) dissolves iodine (10 atoms), and on distillingoff the solvelit in a vacuum, a brown oil is lefb which does not loseiodine on heating a t 150". Chrysanthemine may be boiled with waterfor days wiihoiit change; if, however, a solution of the base i n anequal weight of water is fract,ionally distilled, water alone passes overuntil the temperature exceeds 150" ; trimethylnmine then begins tocome off, and continucs to do so until the temperature reaches ZOO",when an oily product accornpanies it. If the apparatus is nowexhausted, the residue distils over between 200" arid 230", the dis-tillate consisting of a mixture of aqneous solntions of hexahydro-pyridinecarboxy lic acid , amyl glycol, dihpdroxyarnylpiperidin e, tri-methylamine, and traces of pyridine bases. The amyl glycol isseparated from the mixture in the form of benrocr.te, C,Hl,(OBz),, acolourless, crystalline powder melting a t 40" ; the hexahydropJ-ridine-carboxylic acid is then removed a s aurochloride, and the residue cou-tains dihydroxyum ylpiperidine auroclzloi*ide, CloH,,O2NAuCl3, a yellow,crystalline salt which 1-eadily loses a molecule of hydrogen chloi*ideand decomposes at 100".From a consideration of all the above reactions, the author arrivesa t the conclusion that the structure of chrysanthemine is best re-presented by the formularMe,*CH,*y A1 e.CH,-C HI,.OH0- CO -CSNHg8. B. A. A.A new AIbumin from Protoplasm. By W. DEMME (Cltem.Cen.fr., 1891, ii, 257 ; from Centr. med. Wiss., 1891, 483).-Cyto3Eobii,,obtained from the lymphatics, liver, spleen, &c., by pressing, extract-ing the deposit with alcohol, dissolving the residue in water, andreprecipita ting with absolute alcohol, is readily soluble in water, isreprecipitated without coagulation from this solution by absolutealcohol, and may be again dissolved in water. I t decomposeshydrogen peroxide. Addition of a mineral acid to the nqueous soln-tion converts it into a n albuniin, prceglobulin, which is insoluble inwater, and into a substance soluble in water. ; the same change beingeffected by ljeatiilg to boiling. Cytoglohili and prceglobulin are buPHYSIOLOGICAL CHE3fISTRT. 87little soluble in the gastzic juice, and still less so i n the pancreaticjuice. Cytoglobiri contains : carbon, 52.4 ; hydrogen, 6.9 ; nitrogen,16.7 ; sulphur, 3.5 ; and phosphorus, 4.5 per cent. ; preeglobulin :carbon, 51.4 ; hydrogen, 7.6 ; nitrogen, 23.9 ; sulphur, 3.4 ; phos-phorus, 3.7 per cent. J. W. L