3s ABSTRACTS OF CHEhlICAL PAPERS. Organic Chemistry. Melting and Boiling Points of Cyanogen Bromide. By E. 3fULDER (Rec. Trav. Chim. 4 151-152).-Cyanogen bromide be- comes somewhat transparent a t 16" but melts a t about 52' it boils a t 61.3" (corr.). A. P. Normal Cyanuric Acid. By E. MULDER (Rec. Tmv. C'him. 4 91-1Ol).-In continuation of his researches on the derivatives of normal cyanic acid (Abstr. 1883 304 and Rec. Tmv. Crlziliz. 2 133) the author finds that both normal ethyl cyanurate and the crude prodact a(CN*OEt*C,H,O) (Abstr. Zoc. cit.) when saponified with aqueous soda at the ordinary temperature and then neutralised with ltydrochloric acid yield a white crystalline deposit haring the compo- sition C3N303HEtZ and probably the constitution C.3N3(OEt)2*OH or C,N,(OEt);CONH. Normal ethyl cyanurate yields isoqanuric acid on acidification with hydrochloric acid normal cy;innric aqid seeming t o be incapable of existing in the free state.The author considers that Wurtz's diethglcyanuric acid is most probably identical with that obtained by Habich and Limpricht and has the constitution c:,O,(NE!t), KK. A. P. * Additive Compounds of Normal Ethyl Cyanurate with 'Cyanogen Bromide. By E. MULDER (Eec. Trac. Claim. 4 147- 150) .-On treating normal ethyl cyanurate with excess of cyanogeii bromide an additive compound C,N30,Et,2CNBr is formed. I t I S liquid a t the ordinary temperature crystallising a few degrees lower. The author considers that i t has the constitution CBr(0Et)N C(0 Et) NC'N< CBr( OEt) --N (CN ) > When heated for several hours a t 125" until no further pressure is developed a yellow liquid is formed which by continued heating a t the same temperature in an open tube is converted into a hard and vitreous niass.On treating cyanogen bromide with excess of norms1 ethyl cyanurate a second additive compound seems to be formed having the composi- tion C3N3O3Et,CNBr. A. P. Action of Ammonia and Amines on Methyl Thiocyanurate and Cyanuric Chloride. Normal Alkyl Melamines. By A. W. H.OFMANX (Ber. 18 2755-2781).-The final product of the action of ammonia on methyl thiocyanurate is melamine but by modifying the conditions of the experiment either of the intermediate products may be produced. To obtain the primary aqnido-base C,N,( SMe)2.NH the methyl tliiocjanurate is digested with a moderate excess of strong alcoholic ammonia for about five hours a t 100".The purified base cq-stallises from boiling alcohol in rhombic plates melting at 200; it is readily soluble in hot more sparingly in cold alcohol and is not cluite insoluble in wat8er. I t s solutions give no reaction with vegetable colours and no sulphur reaction with alkaline lead salts. The base dissolves sparingly in hydrochloric acid and is reprecipitated on the addition of water. On boiling i t for a. long time with hydrochloric acid it is decomposed with production of mercaptan ammonia arid cyanuric acid. The platinochloride and aurochloride are described. The secondary amido-base C3N,(NH2),.SMe is obtained on digesting methyl thiocyanurate with alcoholic ammonia for about five hours at 160". It differs from the primary basc by its ready solubility in water and more sparing solubility i n alcohol ; it melts a t 268" dissolves readily in hydrochloric acid and yields a platino- chloride (C,H,N5S)2,H2PtC16.When boiled with hydrochloric acid it gives the same decomposition-products as the monamido-compound. The tertiary amido-buse meZumine can be obtained in nearly theoretical amount by heating methyl thiocyanurate with an excess of strong aqueous ammonia for several hours a t 180". I t s properties agree wizh those assigned to it by Liebig (Annnlen 10 el). The author has also succeeded in obtaining two plntinochlorides from it ( C3H,N6),H,PtC16 + 2H20 and C3H,N,H2PtCI (?). The amines are found to react with methyl thiocyanurate in the same way as ammonia.The primary methy lamido-base C3N3( S3Je),*NHMe i3 produced on heating methyl thiocyanurate with a 33 per cent. aqueous solution of methylamine for several hours at 100". It is readily soluble in alcohol and ether and crystallises in well-formed prisms melting a t 174-175" ; it forms crystalline salts with hydro- chloric nitric and oxalic acids mid also yields a sparingly soluble i'latinochloride and an aurochloride. Hydrochloric acid deconiposes the base a t 100" into ethyl mercaptan methylamine and cyanuric acid. The secondary methylarnido-base C,N,(NHMe),*SMe is produced simul- taneously with the primary compound. It is very readily soluble in alcohol less so in ether and is best crystallised from a large bulk of boiling water from which it separates in slender needles meltiug a t 144".I t s salts are mostly very readily soluble the nitrate crystal- lising best ; the platinochloride is very sparingly and the aurochloride moderately soluble. The base is decomposed by hydrochloric acid a t 200" and yields the same products as the primary base. The tertiayy naethy lamido-base trimethylmelamine is prepared by heating methyl thiocyanurate with 33 per cent. aqueous methylaniine tor several hours a t 180" ; or a mixture of the primary and secondary bases may first be prepared at a temperature of 130-140" and this then heated at l70-18O0 with more methylamine. Trimethylmel- amine is very readily soluble both in water and in alcohol and the author has not succeeded i n obtaining it quite pure ; its hydrochlo- ride nitrate and sulphate are also extremely soluble the oxalate more sparingly so.Like melamine i t yields two platinochlorides [ C,N,( N HMe)3]2,H2P t C Is and C3N3( NHMe),H,Pt C1,.By the action of ammonia on cyanuric chloride Liebig (Atznalen 10 45) obtained the compound C3H4N5C1 which he termed chloro- cyanamide but which the author shows to be C3N3(NHz),Cl that is an intermediate product between cyanuric chloride and melamine and it may in fact be converted into the latter by a few hours' heatinq a t 100" with strong aqueous ammonia. A nearly theoretical yield of melamine may likewise be obtained directly from cyanuric chloride. A solution of methylamine in absolute methyl alcohol like- wise reacts with cyanuric chloride with production of dimeth yZamido- cyariuric chloride C3N3( NHMe)?Cl; it is nearly insoluble in water alcohol and ether soluble with slight decomposition in boiling glacial acetic acid from which hot water precipitates it in needles melting a t 241" with decomposition.I n acid solutions the chlorine soon becomes replaced by hydroxyl. When dimethylamidocyanuric chloride is heated with a solution of methylamine in methyl alcohol for a few hours at loo" it is converted into trimethylamine; this when heated a t 150" with hydrochloric acid splits up into methy lamine and cyanuric acid. On heating dimethylamidocyan uric chloride with aqueous ammonia a t 150° the chlorine is displaced and a base produced which is without doubt diniethyhnelumine C,N,(NHMe),*NH ; its salts are soluble the sulphate crystallising in six-sided plates and the oxalate in rhom- bic crystals ; i t yields two platinochlorides C,Hl,N6,H2PtCl6 and The dimethylainidocyanuric acid C,N,(NHMe)2*OH obtained from dimethylamidocyanuric chloride (see above) by the action of an acid (or of water at ZOO") is separated from its hydrochloride as a white indistinctly crystalline precipitate which is almost insoluble in boiling water insoluble in alcohol and ether; its platinochloride has the formula ( C5 H BN50) ,HZPt C 1,.D irneth y lamidocy anuric acid forms salts both with acids aud with bases ; the hydrochloride and nitrate are crystalline and soluble without decomposition ; the sodium salt and the methyl salt (obtained from dimethylamidocyanuric chloride and sodium methylate) crystallise in prisms.The mother-liquors from the preparation of dimethylamidocyanuric chloride contain (besides methylamine hydrochloride) a crystalline substance found to be methylamidonaetiioxycyanzLric chloride MeO*C3N3C1*NHMe ; it forms acicular crystals melting at 155" is soluble in alcohol and ether also in hydrochloric and nitric acids with formation of crystal- lisable salts. It may be boiled with acids without parting with its chlorine. Attempts to obtain hexamet?ylnaelam ine C3Ns(NMe2) by heating methyl thiocyanurate with dimethylamine were without success but its hydrochloride may be obtained by heating a mixture of equal weights of dimethylamine hydrochloride and cyannric chloride as long as hydrogen chloride is evolved. The base ci.ystallises in needles melting at 171-172" ; its platinochloride and aurochloride are de- scribed. When it is heated with hydrochloric acid a t 200" it splits up into cyannric acid and dimethylamine.Methyl thioayanurate is acted on by ethylamine in the same way as by ammonia and by methylamine with formation of corresponding products. The primary et l ~ y Zir mid o- bn se C3N3( S Me) 2* NHE t cry stallises from boiling dilute alcohol in lustrous needles melting a t 114" is sparingly soluble in boiling water readily in cold alcohol ; i t yields a platinochloride of the formiila ( C,H,2N4S,)z,H,PtC16. The secondary etlr y/u)nido-base C3N3(NHEt),-SMe forms needles melting a t 83-8 &' ; its hydrochloride is crystitlline extremely soluble in water less so in alcohol aud insoluble in ether ; the nitrate is more sparingly soluble ; the oxalate forms slender very soluble needles whilst the snlp'iate does not crystallise.A plat inocliloride aurochloride and stanno- chloride have also 1 been obtaiued. The tertiirry eth!/Zitt,iido-Case triethy Zmelainine CJN3(NHEt) can be obtained both from methyl thiocy anurate and from cyanuric chloride and forms prisms melting at 73-74'. It is soluble in alcohol ether and benzene ; the platino- chloride ( C9H,N6),H2PtC1 and aurochloride are described arid also a compound with silver nitrate ( C9Hl~N&,AgN03. Triethjlmel- amine is decomposed By hydrochloric ac4d at 150' into cyanuric acid and ethylamine. Hexethylmelamine C3N3(NEt2) is formed by the action of diethyl- amine on cyanuric chloride. The platinochloride ( C,H&6)2,H,Pt~16 and aurochloride CI5H,K6,HAuCl4 are described.Hydrochloric acid a t 150" decomposes the base into diethjlamine and ojanurio acid. In order to shvw that the higher amines also react with methyl thiocyanurate this latter -substance was digested with alcoholic amyl- amine at 10U". The primary anrylamido-base,. C3N,(SMe)z*NHC5H11 obtained crystallises in clusters of silky needles melting at 96". Hydrochloric acid decomposes- itL slowly a t the ordinary tempeiature. When the reac- tion bakes place at 200" the secondary base C3N3(NC5H,),*SMe is ob- tained and forms colourless crystals melting a t 106-107' ; its platrinoch1oride has the formula (~l~H,3~,S),HzPtC16. If the reaction takes place a t 250° the tertiary base trip3iperidylnrelamip.Le Piperidine also reacts with methyl thiocyanurate.C3&( N C5&3)3 is produced and crptallises in small needles melting at 213" ; it dis- solves rcadily in acids and yields a sparingly soluble platinochloride ( c,eH,N6)2,HzPtC16. Hydrochloric acid decomposes the base a t 150" into piperidine and cyanuric acid. Tripheitylmelamiwe CJN3(NHPh) may be obtained by the action of aniline on methylthiocyanurate or cyanuric chloride and hexa- phenylmelamine C,N3(NPhZ) may likewise be obtained from dipheriyl- amine and cyanuric chloride. Alkyl Isomelamines derived from the Alkyl Cyanamides and the Constitution of Melamine and of Cganuric Acid. A. K. M. been proposed for melamine the former is the one which most simply explains the formation of melamines and of mercaptan by the action of ammonia or amiies on methyl thiocyanurate and of melamines and lrydrocliloric acid from cyanuric chloride and ammonia or nmines (sse last Abstract).The second formula on the other hand would necessitate the assumption of complicated molecular changes ; in the formation of the hexalkylmelamines by the action of a secondarp amine one alkyl group of the latter must be assumed to detach itself from one nitrogen-atom aud to attach itself to another and the - >NMe should resulting hexalkylmelamine NNe C<NMe.C(N31e) NMeG (NAIe) be split u p by the action of water into methyl cyanurate and methyl- amine ; cyanuric acid and dimethylamine are however produced. The formation of the piperidine-derivative of melamine is met by similar difficulties if the imido-formula be taken as correct whilst the nmido-formula readily explains all the reactions.Alkylmelamines corresponding with ail imido-melamine can how- ever be obtained but these yield no cyanuric acid; they split u p into ammonia and alkyl cyanurates. l'rimethytisomelamine C3N3Me3 (NH) has been previously men- tioned by the author (Eer. 3 264) and by Bauniann (Ber. 6 1372). I n order to obtain it monomethylthiocarbanride is treated with dry mercuric oxide in absolute alcohol the methylcyanamide first formed r:x pidlg polymerising to trimetl-tylisomelamine. This i s very readily soluble in water and alcohol insoluble in ether the solution exhibit- ing a distinctly alkaline reaction. It crystallises in well-formed needles melts at 179" and readily sublimes ; the platinochloride chN6H12,H2PtC16 and aurochloride C&GH,,H&.u?CI& are described.Hydrochloric acid at 100" decomposes the base into ammonia arid methyl isocyanurate ; this decomposition takes place in stages and the author has succeeded in isolating one of the two intermediate pro- ducts namely NH C3N,Me,02; it forms a n aurochloride CsHioNdOa HAu C 1 and a hydrochloride C6HloN402,HC1. Triethy~isometamine C3N3E t3( NH) has also been previously mentioned (Hofmann Ber. 1 27). It forms stellate groups of needles melts at 92" and crystallises from water with 4 mols. H20. Platino- and auro-chlorides are described. It is decomposed by acids in the same way as the trimethyl-derivative and here again the one intermediate product HN C3N,Et30 can readily be isolated.In further support of the amido-nature of melamine the author mentions its decomposition by water into ammonia and cyanuric acid the constitution of which he indicates to be HO*CeN. C(oH)>N. He points out that the formation of cyanuric acid from carbamide does not prove it t o have the constitution CO<NH,CO>NH as the constitlution of carbamide has not been definitely established (compare this Journal 1866 161). There also appears to be little ground for the assumption of the iso-nature of cyanic acid. On the contrary the formation of cyanates from potassium cyanide the conversion of xmmonium cyanate into carbamide and of cyanic acid with the elemmts of water into ammonia and carbonic anhydride run perfectly N-C( OH) NH*CO parallel with the formation and behaviour of thiocjanic acid the normal constitution of which is not doubted.The formation of alkyl isocyanurntes from cyanuric acid may be accounted for by the fact that t,he normal ethers may be readily converted into the iso-ethers (Rer. 3 272 ; Rec. Tmv. Chinz. 1 191). The production of cyanuric chloride from phosphorus pentachloride and cjaiiuric acid and the re-formation of the latter by the action of water on the chloride (Annalen 116 357) also support the view that cyanuric acid contains li-ydroxyl-groups. Phosphorus pentachloride acts in the same way on the normal methyl salt of cyanuric acid with formation of methyl chloride phosphorus oxytrichloride and cyanuric chloride. Methyl isocyanurate however gives a very different reaction when heated with phosphorus pentachloride hydrochloric acid phosphorus tri- chloride and trichioromethyl isocyanui*ate N(CH2C1)*CO>N(CH2C1) co<N(CH2Cl)*C0 being formed.A. K. M. Allyl-sulphuric Acid. By F. SZYMAKSKI (AnnuZen 230 43- 50).-The preparation of rtllyl-sulphuric acid by the action of sul- pbnric acid on allyl alcohol was first described by Cahours and Hof- Inann (Ani-,aZen 102 293). Beilstein and Wiegand (Abstr. 1885 740) have recently stated that allyl alcohol is completely carboriised by sulphuric acid. The author finds that this is not the case when the alcohol is slowly added to the acid. The best results are obtained when the acid is diluted with an equal volunie of water. The barium salt has been previously described by Cahours and Hofmann (Zoc.cit.). The stroritiurn salt forms anhydrous rhombic prisms soluble in water and in alcohol. The anhydrous calcium salt crystallises in quadratic 1,lates. The copper salt crystallises in needles with 4 mols. H,O. It is soluble in water and alcohol On saturating allyl-sulphuric acid with lead carbonate a basic salt (C,H,SO&Pb + PbO + 6H20 is obtained which is soluble in water. The magnesium saZt Mg(C3H5SOA)2 + 4H20 crystallises in trans- parent needles soluhle in water. The potassium arnmoniuni and sodium salts are hygroscopic and soluble in water. The f e w o u s salt forms quadratic plates soluble in alcohol. w. c. w. It is hygroscopic. Methylene-derivatives. By 1;. HENRY (Conzpt. rend. 101,599- GOO).-Diethoxy,izethane CH,(OEt) obt'airied by the action of diiodo- methane on sodium ethoxide is a colourless mobile limpid liquid with :L pungent taste and a peculiar agreeable odour quite different from that of acetsl.It is only slightly soluble in vc-ater and quite iiisoluble in a concentrated solution of calcium chloride. It boils a t 82-83" under a pressure of 760 mm. ; sp. gr. a t 16.7" compared with the water a t the same temperature = 0.8275 ; vapour-density 3.44. C~I~Zorobromornetl~ane CH2C1Br obtained by the action of excess of bromine on chloriodomethane is a mobile colourless liquid with au agreeable ethereal odour and a sweetish pungent taste. It is insolu- IAe in water does not decompose when exposed to light and boils at44 ABSTRACTS OF CHEMICAL PAPERS. 68-69" under a pressure of 765 mm. ; sp. gr. at 19" compared with water at the same temperature = 1.9907 ; vapour-density 4.43.R~orniodornethutze CH2RrT is obtained by the action of a limited quantity of bromine or better of iodins chloride on diiodomethane. It is a colourless liquid which becomes purple when exposed to light. It has an agreeable etherealsodour and a sweetish bitter taste is insoluble in water and boils a t 138-140" under a pressure of 754 mm. ; sp. gr. a t 16.8" compared with1 water at tihe same temperature = 2.9262; vapour-density 7.65. C. H. B. Sulphatea of some Carbohydrates. By M HONIG and S. SCHUBERT (Mm~atsli. Chern. 6 708-749).-By the action of sulphuric acid on1 cellulose a t different temperatures varying from 7" to 40° and subsequent treatment of tbe product with barium caiBbonate salts were obtained which contained the same percentage of barium but which possessed a ,greatly varying rotatory p o m r ( [ a ] j = - 3.65" to + 72.99").Further experiments made t o ascertain the influence of the quantity of acid used showed that salts varying in composition but having the same rotatory power can be formed. Prolonged action of sulpl~uric acid causes an increase of. barium in the salt as well as an increase of rotdory power. When the action is allowed to take place at a& low temperature the product coiitains salts varying more from one another than if the reaction takes place a t a higher temperature. The following salts were separated :- They form white or yellowish-white voluminous powders with varying solubilities io water; the lead and calcium salts are similar.The hydrogen su1phate.s form white amorphous very hygroscopic com- pounds which dissolve very readily in water and in alcohol ; they are insoluble in ether. The aqueous solution decomposes slowly at the ordinary temperature more quickly when boiled losing sulphnric acid. similar way ; but the action is much slower than in the case of cellulose. The products have the same general formula C6,Hlo,0,-,( SO,) as those obtained from cellulose but turn po1arised:liglit to the right. When the hydrogen sulphates are boilea with alcohol they lose all the sulphuric acid leaving modified forms of cellulose and starch respectively. N. H. M. Organic Iodides of Nitrogen. Rg; F. RASCHKG (AnnuZen 230 221-224).-RfeOhylnmiiie~ hydrochloride is completely converted into m e t h y Zdiiodamine Nl,Me when the theoretical quantity of iodine (dissolved in potassium iodide) is- added to a solution of methylamine hydrochloride and sodium hydroxide MeNH2,HC1 + 41 + 3NaOH = NLMeI + NaCl + 2NaI -!- 3H,O.Dimeth.yZiodumine,NMezI is obtained from d imethylamine by a similar reaction as a yellow precipitate. It is sparingly soluble i n alcohol and ether. I t soon decomposes and acquires a dark colour. A solution of potash changes tthe colour of the compou a d to greenish-yellow without Anhydrous starch is acted on by sulpliuric acid inORGASIC CBEMISTRI'. 45 affecting its composition. Iododimethylamine and di-iodomethylamine decompose without exploding when they are touched by a hot body. Etkyldi-bdamine and diethyliodamiiie are obtained by sirnihr reactions in the form of brick-red and orange-coloured precipitates.They rapidly decompose into iodoform and a dark blue liquid. w. c. w. Synthesis of a Ketone from (Enanthylidhe. By A. &I. &$HAL (J. Pharm. [ 5 ] 811 155-158).-AmyZ meihyl ketone C5H,*COMe is obtained by dissolving mnanthylidine in sulphnric acid diluting with water and distilling. It forms an oily liquid of pungent odour boils a t 147-148" under 759.2 mm. pressure shows the property of a ketone jieldiiig a hydrogen sodium sulpbite compound &c. and on oxidation is converted into aceticband valeric acids. .A. J. G. Action of Bromine in Alkaline Solution on Amides. By A. W. HOFMANN (Ber. 18 27~-2741).-Chloracetamide -is acted on by bromine in alkaline solution with formation of a compouud CH,CI*NH*CO*NH.C,H,CLO.This substance me1 ts at; 180" and is spar- ingly soluble ; it is decomposed by acids or alkalis into chloracetic and hydrochloric .acids,*carbonic anhydride ammonia and met haldehyde. Ethoxyacetamide when treated with an a l h a h e solution of bromine yields a compound EtO*CH~.*NH*CO*NH*C,H?O.OEt. It crystallises in cdcmrless needles which melt at 80° and is decomposes by acids and alkalis into et,hoxyacetic acid alcohal ammonia and mcth- aldehyde. When 1 mol. of phenylacetamide is acted on by 1 mol. bromine and 4 mols. of a 5 per cent. solution of alkali and then distilled in steani much benzylamine is obbained together with some bromobenzylamine which may be 4 convert,ed by (the action of sodium amalgam into benzylamine.IJy drocinnamamide is prepared. by heating ammonium hydrocinna- mate for five hours a t 220" ; it forms small thin needles which melt a t 105". When treated with bromine in -alkaline solution and then distilled with steam it yields a .mixture of phenylethylamine and a bromine-derivative C8H8Br*NH2 which boils at 252-254". To obtain pure phenylethylamine the mixed product contained in the distillate is treated with sodium amalgam. The yield is about 60 per cent. of the theoretical. .The yield is about 30 per cent. N. H. M. Action of Ethyl Acetoacetate on the. Amidines Pyrimidines By A. PINNER (Bey. 18 2845-2852).-Jn order to test the general character of this -reaction (Abstr. 1885 158 751) the author has tried to prepare the corresponding pyrimidines from various amidines and he finds that with the exception of formamidine all t h e nmidines experimented with are capable of yielding pyrimidines.When formamidine hjdrochloride (25 grams) is treatled with the calculated amouirt of ethyl azetoacetate a 10 per cent. solution of sodium carbonate added and the whole allowed to remain several weeks a substance is obtained which crystallises in long broad silky needles melting at 70-71" is readily soluble in the ordinary solvents with46 ABSTRACTS OF CHEMICAL PAPERS. the exception of water and has neither acid nor basic properties ; its composition indicates it to be ethyZ cyanoacetoacetate CHS.C(CN) CH*COOEt. Acetamidine reacts readily with ethyl acet oacetate yielding di- nl.ethyZhycZroz~~?/1.imidine CMeqN C(oal>CH ; this forms lustrous needles melts at 192" is readily soluble in water and alcohol sparingly in ether and cold benzene.EtJi yZn7p,thyZhy~rox~pyrimI'dine CiHloN,O obtained from propionamidine and ethyl acetoacetate forms ,slender white needles melting at 160" and readily solnble in water and alcohol. The hydrochloride C,HloN20,HCi crystalliees in thick prisms melts at 240-2413' with decomposition is very readily soIubIe in water and somewhat less so in alcohol. The platino- chloride forms thick yellow prisms melting a t 236" with decom- position. Succinimidine rezcts with ethyl acetoacetate wihh elimination of only one molecule of water and production of a compound N -CMe C4HJT,HZ*C4H,O2. A description is given of some more derivatives of phenylmethyl- liydroxypyrimidine (Zoc.cit.). When a solution of silver nitrate is added to a hot aqueous or alcoholis solution of the pyrimidine a clear solution is obtained from which ammonia throws down a white granular precipitate of the silver salt ; i t is extremely soluble in excess of ammonia and in nitric acid. On adding bromine to a solution of phenylmethylhydroxgp.yrimidine in chloroform four atoms of the halogen are taken up with formation of the compound CllH10N20Br4 which crjstallises in yellow lustrous needles melting a t 245' with decomposition. It dissolves slowly with decomposition when boiled with alcohol and on cooling colourless transparent needles of the composition C1,H,N2Br separate melting a t 260". Phenylmethyl- hydroxypyrirnidine is not acted on by nascent hydrogen but may be reduced by distillation with zinc-dust the pheny Znzethy Zpyri- midine CI,HI,Nz obtained melts a t 74-78' and yields a platino- chloride melting at 190" with decomposition.Chromic acid and alkaline potassium peymanganate have little action on the hydroxj- compound whilst acid permanganate oxidises i t readily with produc- tion of bcnzamide. Attempts to reduceg~henylmethy7c7~Zoropyi.imidiize CI1H9N2Cl (Abstr. 1855 159) by the action of sodium amalgam on its alcoholic solu- tion yielded phemylmethy k e t h o x ~ ~ y r i m i d i i z e CIIH9N2*OEt which how- ever is more readily obtained by boiling the chloropyrimidine with sodium nlcoholate. It forms thick colourless transparent prisms melting a t 30-31° boils a t 300-301" is insoluble in water and ihlkalis readily soluble in alcohol ether and acids. The hydro- chloride C,H,N20Et,HC1 + 2H,O crystnllises in slender white very soluble needles and when dried melts a t 148-149" ; it breaks up at about 150" into phenylmethylhydroxypyrimidine and ethyl chloride.The plutinochloride (C,H,N20Et)2,HzPtC16 melts a t 197" with decom- position. The hydriodide Cl,H9N20Et,HI( + &HzO 3) forms yellowORGANIC CHEJIISTRY. 47 prisms or long needles very sparingly soluble in cold moderately solnble in hot water ; i t meIts a t 143.5". Phenylm ethy~~lyrin2idinean~~lide F,H,N,*NHPh is obtained on heat- ing the chloropyrimidine with a,niline. The hydrochloride forms small slender needles which blacken a t 236" and melt with decompo- sition a t 240". The free base melts a t 150-153" and its nitrate at 85-87".A. K. If. Condensation of Acetoacetates with Bibasic Acids. By .R. FITTIG (Bei-. 18 2526-2527).-Ethereal acetoacetates condense readily with bibasic acids with elimination of 2 mols. HzO. With succinic acid and ethyl acetoacetate %I crystalline compound CloH1205 melting a t 75-5-76' is obtained. This is the monethyl salt of a bibasic acid C,H805 ; the free acid is crystalline melts a t 199-200° and loses carbonic anhydride a t a slightly higher temperature. From ethyl acetoacetate and sodium pyrotartrate the monethyl salt of the homologous acid C9H1005 which melts a t 194O is obtained. The investigation of these acids is proceeding. Condensation of Aldehydes with Bibasic Acids. By R. F~TTIG (Ber. 18 2523-2525) .-By the condensation of succinic acid with acetaldehyde propaldehyde isobutaldehyde valeraldehyde or cpnanthaldehyde a single lactonic acid .is formed in each case in accordance with the equation XmCHO + COOH*CH,-CH,*COOH = < ~ ~ ~ ~ 2 > C H * C O O H ; with pyrotartaric acid on the other hand A.J. G. two isomeric lactonic acids < ~ ~ ~ ~ z > CMe-COOH and < &,:%t>CH-COOH are obtained. Benzaldehyde and pyrotartaric acid give i n addition to the acid described by Penfield a second isomeric acid melting a t 123.5". These lactonic acids when heated lose carbonic anhydride arid are converted mainly into monobasic acids the isomeric lactones being obtained as bye-products. The constitution of these unsaturated acids is still uncertain except in the case of the acid C6H1,02 derived from the lactonic acid prepared from propaldehyde and succinic acid which has been shown to be identical with hydrosorbic acid. Salicylaldehyde and succinic aldehyde yield a dicozcniarin very similar in chemical behaviour to coumarin.succinic aldehyde yield two acids of the formub Anisaldehyde and MeO*CsH4*CR CH*CH,*COOH and MeO*CGH,*CH CH.C(COOH) CHC6H,*OMe respectively. No description is given of these su bstnnces. A. J. G.45 ARSTRACTS OF CHEMICAL PA1 ERS. Tartronic Acids. By A. PrNNEn (Rer. 18 2852-2854).--The author finds that no better jield of this acid is obtained by Baponi- fying trichlorolactic acid directly,with haryta water and he prefers t o use the method previously given (Abstr. 1885 759). Experiments in which other precipitants (in the place of barium chloride) were employed gave unsatisfactory results. In the preparat>im of ethyl tartronate only a part of the acid is converted into normal ethyl salt some hydrogen ethyl-derivatirn being also probably formed.The normal salt boils .at 222-225" is readily decomposed by water and is readily converted into the amide by the aktion of ammonia. The only secondary products produced in the preparation of tartronic acid which the author has been able to confirm are di- chloracetic acid and a small quantity of oxalic acid. Tartivnnmide OH*OH ( CON Ha)z forms six-sided sales melting at 195-1 96" with decomposition. I t is sparingly soluble in cold water moderately in hotr and sparingly in alcdhol. Malic Acids. By H. VAN'T HOFF jun.(Bey. 18,2713-2714; corn- yare Abstr. IF8.5 1202).-Inactive mdlic acid from monobromo- succinic acid prepared from fumaric acid and hydrobrsmic acid (identical with that examined by Anschutz &id. p. 1049) and an inactiue nialic acid obtained by the action of soda and water on tnaleic acid are shown by crystallographic measurements to be identical with .Pasteur's acid. A. K. M. N. H. M. Decomposition of Malic Acid obtained from Fumaric Acid. By G. J. W. BEEMER (Rec. Tmv. Chim. 4 180-182).-It is usually st,ated that the inactive malic aoid obtained from fumaric.acid is a distinct modification and cannot be decomposed into the lavo- and dextro-acids. :This is however not the rase as by the fractional crystallisation of its cinchonine salt it malic acid is obtained whose hydrogen ammonium salt shows a specific rotary power identical with that of the corresponding salt of the natural acid (Ber.,.13 352).Constitution of Isosaccharic Acid. By H. KTLIANI (Bey. 18 2514-2518).-In the author's last paper on this subject (Abstr. 1885 'i44) the position of m e of the hydroxyl-groups was still left unsettled ; he now shows that the dihydroxypropenyltricarboxplic acid obtained by oxidising isosaccharic acid (Zoc. cit.) yields a dihy- droxj-glutaric acid not identical with the /%V-dihydroxy-acid ; this must therefore be the a-y-acid A. P. COOH*CH( OH).CH,*CH(OH) 'COOH. From this isosaccharic acid must have the constitution COOH*C(OH) (CH2*OH)*CH,*CH( OH) *COOH. a-l- DiAydmzyg)Iutaric acid is best obtained by heating dih ydroxy- propenyltricarboxylic acid for four hours at 120" I t crystallises in colourless prisms begins to soften at 106" with loss of water and only fuses completely at a considerably higher temperature; it isORGANIC CHEMISTRY.4 9 nearly insoluble in ether readily soluble in alcohol and water. The calcium salt C5H606Ca -k 3H20 forms white nodular crystals sparinglg soluble in water. S- -Dihy droxyg Zutaric acid COO H*CH,*CH( OH) *CH( OH) *C 00 H is obtained by converting glut'aconic acid COOH-CH,*CH CH-COOH into dibromoglutaric acid by treatment with bromine and boiling the product in dilute solution for two hours and a half with calcium car- bonate. It crystallises in needles or six-sided plates melts a t 155- 156' and is sparingly soluble in alcohol very readily sduble in water.It is further distinguished from the a-yacid by the ready solubility of its calcium and cadmium salts. A. J. G. Oxidation of Benzene. By J. G. HOLDER (Arner. Chew,. J. 7 114-116).-When treated in the cold with manganese dioxide and sul- phuric acid benzene yields carbonic anhydride and a small quantity of benzoic acid ; neither formic nor phthalic acid could be detectld. By gradually adding sulphuric acid to benzene and lead dioxide i L vigorous reaction occurs and carbonic anhydride and benzoic acids i r e formed ; no succinic acid was observed. Potassium permanqanate acts very slowly ; lead dioxide and boiling dilute nitric acid yield only oxalic acid ; chromic acid yields only carbmic anhydride. H. B. Parachlorometanitrotoluene and its Reduction-products.By L. GATTERMANN and A. KAISER (Ber. 18 2599-2602).-This compound was prepared from metanitroparatoluidine hydrochloride by treatment wit8h cuprous chloride and sodium nitrite. It crystallises in yellow needles melts a t 7" to a strongly refractive golden-yellow oil of sp. gr. 1.297 at 22" (water at 62" = l) and boils at 260-261' under 745 aim. pressure. I t seems to be identical with the a-nitro. compound obtained by Wroblewsky by the direct nitration of pam- chlorotol uene. Parnc hlorometanityot oZuid ine C,H,MeC l-NH2 obtained by reduction of the nitro-compound crystallises in thin colourless tables melts at 29-30" and has an odour similar to that of naphthylamine. The hydrochloride crystallises in colourless needles the salphate in broar 1 needles or plates ; the acetyl compound crystallises in colourless needles and melts a t 96'.A. J. G. Action of Phenyl Cyanate on Polyhydric Alcohols. By H. TESMER (Ber. 18 2606-2610 compare Abstr. 1885 774) .-The author coutirrns the formula C6H90 (O*CO*NHPh) previously given for t,he quinovide of phenylcarbaniic acid. Quercyl penta~heriylcnrba.nznte C6H7( O*CO.NHPh) is prepared by heating quercite and phenyl cyanate in sealed tubes at 165" for two hours; it is an amorphous white mass melts somewhere betwetn 120-140" and is soluble in the ordinary solvents except light petro- leum. When heated with aqneous baryta a t 1-50" it is decomposed into aniline quercite and carbonic anhydride. SucchttryL pher~yZc~~bimate C6H,O,(0.CO*NHPh> + CONPh pre- VOL. L e50 ABSTRACTS OF CHEMICAL PAPERS.pared in a similar manner from saccharin crystallises in silky inter- Iitced needles melts at 230-240J with decomposition. It is sparingly soluble in benzene and alcohol soluble in ether readily soluble in aniline; aqueous baryta at 160-170" converts it in aniline and barium carbonate and saccharate. Metasaccharyl pliemylcarbamate C6H,02( O.CO*NHPh) + CONPh is obtained as an amorphous white powder which softens a t 205" melts about 210" and is soluble in most solvents. With aqueous baryta it yields aniline and barium carbonate and metasaccharate. IsosacchnryZ plienylcarbamate C6H,02(0*CO-NHPh) + COKPh also forms an amorph(lus white powder softens at 180" and melts at 181" ; with aqueous baryta it is decomposed in the same manner as the preceding compounds.Quercetyl phenylcarbama,te C2&06(0*CO*NHPh) prepared by heat- ing quercetin and phenyl cyanate at 160° is a pale yellow amorphous mass. It melts a t 'LOO-205" and is insoluble in most solvents. Aqueous baryta at 270" decomposes it into quercetin aniline and barium carbonate. Pl a v y u r p r y 1 p heny lcarbamate C J&03 ( 0 *C ONHP h ) 2 is prepared by heating flavopurpnrin and phenyl cyanate at 165" ; it crystallises in yellowish microscopic plates insoluble in most solvents ; boiling aniline dissolves it with formation of flavopurpurin and diphenyl- carbamide ; alkalis resolve it into flavopurpurin aniline and carbonic anhydride. A. J. G. Para- and Meta-phenylene Cyanate. By L. GATTEHMANN and E. WRAMPELMEYER (Ber. 18 2604-2606).-ParaphenyZene cyanate C6H4(N CO) is prepared by the actlion of carbonyl chloride on paraphenylenediamine ; it crystallises in white needles melts a t 91" boils a t 231" under 745 mm.pressure. It shows a close resemblance in reactions and properties to pbenyl cyanate giving paraphenylene- dicarbamide wit'h ammonia diphenylphenylenedicnrbamide wi tli ani- line &c. When heated with absolute alcohol it yields prrraphenylene- urethane C6H,(NH*COOEt)2 which crystallises in colourleso prisms and melts at 193". Paraphenylenecarbamide is also formed in the preparation of paraphenylene cyanate. Metaphenylene cyanate is prepared in similar manner to and closely resembles the para-compound. Resorcinol-derivatives. By G. ERRERA (Gurzetta 15 261-274). -Trinitrodi~benzo~~lresorcino7 ?J02.CsH,(0.C0.C6H,*N0,)2 obtained by the action of nitric acid (sp. gr 1.4) on dibenzoylresorcinol is a yellow amoiaphous substance melting at 123- 124" insoluble in water sparingly soluble in alcohol readily in benzene and chloroform.It is not decomposed by hydrochloric acid but is saponified completely by alcoholic potash into nitroresorcinol together with iso-dinitro- resorcinol and metlanitrobenzoic acid or the latter and benzoic acid according to the conditions of the experiment. The nitroresorcinol and metanitrobenzoic acid can be separated by treatment with acetic chloride o r by the different solubility of the copper salts or by the etherification of the acid. A. J. G.ORGANIC CHEMISTRY. 51 Trinitrodibenzoylresorcinol is reduced by tin and hydrochloric acid to amidoresorcinol and amidobeneoic acid.Mononitrodibenzoylresorcinot N02*C6H3(OEh)2 prepared either b y the action of zinc-dust on a mixture of nitrosoresorcinol (1 mol.) with benzoic chloride (2 mols.) or by the nitration of dibenzoylresor- cinol by a mixture of nitric and slslphuric acias crystallises in acicular needles melting a t 110" ; on hydrolysis it yields mononitroresorcinol and benzoic acid and on reduction benzoic acid and amidoresor- cinol . Mononitromonobenzoy I r e s o r c ~ ~ o Z N02*C6E3( OH) GBz obtained by heating a mixture of nitiwresorcinol and benzoic chloride in equi- molecular proportions crystallises in pale-yellow needles. Mononitrodiacetylrcorcino~ NOz*C6H3(OAe)2 from acetic chloride and nitroresorcinol forms long lamellar colourless crystals melting a t 90-91" ; it is converted by bromine into Weselsky's dibromonitro- resorcino1.V. H. V. Fluoresceins from Maleic Acid. By R. BUECKHARDT (Ber. 18 2864-2870) .-This is a continuation of the work published L-y Lunge and Burckbardt (Abstr. 1884 1340). CH ' 'IX is formen Dinzethy I m a l e ~ ~ u o r e s c e i i z 0 <C6H3(0Me) > C <o-co > C,H3( OMe) when a solution of rnalei'nfluoresce'in'in mkthyl alcohol is boiled witli alcoholic potash and methyl iodide and crystallises in red needles. Unsuccessfiil att.empts were made to obtain a bromine-derivative corresponding with eosin but no definite product could be obt,ained. Male'influormceh reacts with acetic chloride yielding a diacetyl-derivu- t h e C16HL006A~2 crystallising in yellowish-white needles me1 ting at 157" ; it is sparingly soluble in alcohol readily in glacial acetic acid and insoluble in water chloroform cai*bon bisulphide and benzene. CH'CH a-NuphthoZma1e~f2uoresceinn < co'o> CfC,oH,*OH) obtained on heating maleic anhydride (1 mol.) with a-naphthol (2 mols.) and zinc chloride a t 160° forms a violet powder which yields a red solution with alcohol the addition of ammonia producing an intense green-red fluorescence ; t,he solution changes on exposure to the air becoming first violet and then dirty brown.The compound is also soluble in ether glacial acetic acid chloroform ethyl acetate and methyl alcohol but is insoluble in benzene and carbon bisnlphide. It melts a t 118- 120". A second compound Cl4H,O4 is formed simultaneously with the last substance by the union of maleic anhydride (1 mol.) with a-naphthol (1 mol.).I t crystallises in small hygroscopic needles melting a t go" dissolves in the ordinary solvents with the exception of benzene toluene and carbon bisulphide ; also in hydrochloric acid water and ammonia. It forms a lead salt of the compositioti @-Naphthol yielded no fluorescent product with maleic anhydride the statement previously made (Zoc. cit.) referring to the employment of fuiuaric acid. The product of the latter reaction forms a yellow solution witli alcoh:)I which exhibits an intense moss-green fluor- escence on the addition of ammoilia. C?,Hl,Pb04. e 252 ABSTRACTS OF CHENICAL PAPERS. The reactions of several other phenols with maleic anhydride hare also been tested qualitatively. C hloro- and Ltromo-derivatives of Phloroglucinol.By K. HAZURA and R. Bmxm" (Monatsh. Chem. 6,702-707).-Heleabrorno- 1) hloroglucinol dibrornide C.16Br3(O13r)3,Br2 is obtained together with phlorobromine when a solution of 10 grams of phloroglucinol in 1 litre of water (at 40") is treated with 96 grams of bromine added 24 grams a t a time. It dissolves very readily in chloroform from which it arptallises in small yellowish-white needles melting a t 118". Sulphurous acid converts it into tribromophloroglucinol melting a t 151". When heated a t 156" it gives off a part of its bromine. Hexahyd.F.otrichloroy~loroy lucinol C6H9cl& 4- 3H20 is prepared from the above compound by the action of tin and hydrochloric acid ; it forms long white crystals which melt a t 125O.At 100" it loses its water of cry stallisa tion. TrichlorophlorogZuc~no7~ C6CI,H30s + 3H20 is prepared by the action of chlorine on a solution of phloroglucinol in glacial acetic acid. It softens when heated a t 120" amd melts at 129". At 100" it loses 3 mols. of water. N. H. M. A. K. M. Thymolphosphoric Acids. By G. DISCALZO (Gazxetta 15 278- 282).-Monothy~nolpl~osphonyZ chloride POC12*O*C6H,MePr prepared by heating a mixture of phosphorus oxychloride and thymol in equi- molecular proportions is a colourless mobile liquid boilin5 with slight decomposition a t 280-285". When heated with water it is converted into the corresponding acid PO(OH),*O*C6H3MePr a thick oily liquid sparingly soluble in wa%er soluble in alkalis decomposed completely on distillntion into thymol and metaphosphoric acid.I t s barium salt crystallises in prismatic laminae. DithymoZphosphonyZ chloride POCl (OC8H3MePr) prepared from a mixture of thymol ( 2 mols.) with phosphorus oxychloride (1 mol.) is a colourless fluorescent liquid boiling at 330-340" under a pressure of 320 mm. It is decomposed by water forming ditkymoZphosphoric acid PO( OH)(O*C6H3MePr)2. This substance is insoluble in water ; its barium salt crystallises with 5Hz0 in delicate colourless needles. V. H. V. Nitration of Parabromaniline. By H. HAGER (Bey. 18 2578). -When parabromaniline is nitrated the bromine-atom is displaced and picramide (trinitraniline) formed. Action of Isbutyric Acid on Aniline. By F. L. BARDWELL (Amer.Chem. J. 7,116-118).-Aniline and isobutyric acid do not react with each other until zinc chloride is added when isobutyranilide is formed ; the yield is increased by heating the mixture. It crystal- lises in colourless prisms and melts at 102.5". By the action of bromine-vapour on the aqueous solution a yellow precipitate is formed which when treated in alcoholic solution with charcoal yields colour- less needles of parabromisob?ctyrnnilide C6H4Br*NHCaH,0 ; itJ melts a t 128" and when heated wit11 aqueous hydrochloric acid yields para- A. J. G.ORQANIC CHEMlSTHY. 53 bromaniline ; treated with nitric and sulphuric acids it yields para- bromorthonit'raniline. H. B. Metadinitroazoxybenzene and Orthazoxytoluene. By H. KLINGER and H. PITSCHKE (Bsr. 18 2551-2556) .-Metadinitroazozy- benzene N0,.C6H4.N2(~.C6HI*N0 is obtained by treating metadinitro- benzene with a small quantity of sodium methoxide dissolved in methyl alcohol.It crystallises in long straw-yellow needles melts a t 141-142" is sparingly soluble in alcohol somewhat more soluble in ether and carbon bisulphide moderately soluble in benzene and toluene. Metndinitrohydroxyazobenxene N02*C6H,*N2*C6H3(OH) *No2 is ob- tained by heating a solution of the azoxy-compound in sulphuric acid at 140" ; it forms a yellowish-brown indistinctly crystalline mass and melts a t 172-173". It dissolves in dilute alkalis with yellowish-red colour. The silver salt C,2H,NaOa*OAg is obtained as a red crystalline precipitate. Orthazoxytoluene C6H,Me.N20*C6H4Me is prepared by the action of sodium mcthoxide on orthonitrotoluene ; it cry stallises in yellow monosymmetric tables or needles a b = 044158 1 ; @ = 68" 37' ; observed faces OP mPm o3P; melts at 59-60" and explodes when more strongly heated.When distilled with iron it yields orth- azotoluene together with a little orthotoluidine. When heated with sulphuric acid it undergoes a peculiar decomposition much orthazo- toluene being formed (44-48 per cent.) together with amorphous substances. A. J. G. Methylene-Blue Group. By A. BERNTHSEN (Annalen 230 i3 -21 1) .-A considerable portion of this research has already appeared in this Journal (Abstr. 1883 916; 1884 595 1156; 1885 259). L euco t hionine or &amid ot hiod ip hen y 1 amine NH<c6H3(NH2)>S [NI-I NH NH S = 4 1 4 61 LHs(NH2) is formed by the action of tin and hydrochloric acid on a-dinitro- diphenylamine sulphoxide Under similar treatment /%dinitro- diphenylamine sulphoxide NH<C6H'(No2) >SO yields Zeuco-isotl~io- nirze c6H4<~~>c6H,(NH2)~.On oxidation with ferric chloride isothionine NH/~6H2(NK2)>S is produced. I& is a dark crystal- line powder sparingly soluble in water and freely soluble in alcohol yielding violet-red solutions. It dissolves sparingly in warm benzene forming an orange-coloured liquid. The hydrochloride C,H,N3S,2HCl is freely soluble in water and alcohol. The aqueous soluhion is violet- red and dyes silk amethyst. The addit,ion of strong hydrochloric acid does not turn the solution blue as is the case with thionine. The salt dissolves in strong sulphuric acid with violet coloration.The composition of methylene-blue was ascertained from the analysis of the hydriodide C,H,N,SI and the hydrochloride C6H3(N02) 'N0c6H4 -54 ABST LlACTS OF CHEMICAL PAPERS. C,H,N,SCl+ 3H,O. The aqueous solution of the free base (tetra- methylthionine hydroxide) is obtained by treating a dilute solution of tJhe hydriodide lwith freshly precipitated silver oxide. On evaporat- ing the solrmbiion in a vacuum over sulphuric acid a t the ordinary tem- perature the Tree base remains as a dark amorphous mass. It dis- solves freely in alcohol and in water. The preparation and properties of leucomethylene-blue (formerly called methylene-white) have been already described (Absts. 1883 916). Pentamethylleucothionine- dimethiodide C,H,N,S,ZMeI is formed by the action of methyl iodide arid methyl alcoliol on leucomethylene blue a t 110".The com- pound is soluble in hot water but insoluble in ether. It is decom- posed by moist oxide of silver yielding the ammonium base CsH3(NMe3*OH) JZ-<C,H3(NMe,*OH)>S' On evaporating the alkaline liquid the base remains its a brittle amorphous mass soluble in alcohol and in water. It is decomposed by heat yielding methjl alcohol and pentamethylleucothionine. The consthtion of leucomethylene-blue or tetramethylparadiamidothio- dipheylamine is proved to be by the fact thad it yields on methylation the same pentamethylleuco- thioninedimethylammonium iodide which is obtained from leuco- thionine. The free base of methylene-blue is represented by the formula HO*NMe/ I CsHi---- S 'N*CsH3 (NMe) Nethylene-red is obtained as a bye-product in the preparation of methylene-blue.It is contained in the mother-liquor from which the niethylene-blue has been precipitated. The pure compound is deposited from alcohol in glistening green prisms soluble in water. The aqueous and alcoholic solutions exhibit a purple colour which disappears on the addition of an alkali. The coloiir does not re- appear on acidification. A blue colour is produced by oxidation. Reducing agents also destroy the purple colour and in this case sul- phuretted hydrogen is liberated. The hydrochloride of methylene- red has the composition CIsHI,N4S4,2HC1. On the addition of am- monia to methylene-red a yellow-coloured base is precipitated. It is soluble in alcohol and in ether.I t is precipitated from the alcoholic solution by water. When methylene-blue is treated with a dilute solution of an alkali it mixture of methylene-violet methylene-azure leucomethylene-blue and other leuco-products is formed. Methylene-violet is best ob- tained in the pure state by decomposing methylene hydriodide with silver oxide and boiling the aqueous solution of the base for several hours. The solution deposits crystals of pure methylene-violet and the mother-liquor contains methylene-azure. The precipitate of silver iodide is mixed with a considerable qnantity of leuco-bases. >.Metky lene-violet or r3osited from alcohol ORGANIC CHEMISTRY. \ CGHS- s dimet h y It hionol ine O<r?.C,tr,(NMe,) /> is in long needles soluble i n chloroform 55 de- and Sparingly soluble in hot water.The solutions have a red or violet- red colour and are fluorescent. The hydrochloride C14HI,N2S0,HC1 crystallises in long needles of a dark green colour. It is insoluble in cold dilute hydrochloric acid. The aqueous solution dyes wool or silk violet. The iodide and chromate are very slightly soluble in hot water; in other respects they resemble the corresponding salts of methylene- blue. Leucorn ethylene-violet is deposited from alcohol in white plates or scales. The solution in acids is stable but the solu- tion in alkalis absorbs oxygen with great avidity and deposits methylene-violet. The hydrochloride i H crystalline. I n order to obtain methylene-azure in a state of purity the mother-liquor from which the methylene-violet has been deposited is treated with an alka- line solution of stannous chloride.The liquid is mixed with half its volume of alcohol and left for some time in a closed vessel. The leuco-azure which is deposited as a crystalline mass is washed dissolved in dilute hydrochloric acid and oxidised by ferric chloride. On the addition of common salt rnethylene-azure is precipitated. It is dis- solved in water reprecipitated and converted into the hydriodide. This salt is more soluble in water than methylene-blue hydriodide which it closely resembles. The hydrochloride is also very soluble in water. The solution dyes silk blue. The hydrochloride dissolves in strong hydrochloric acid with a blue coloration and in strong sulphuric acid with a green colour.It is decomposed by boiling with a strong solution of potassium hydroxide with formation of dimethyl- amine. The preparation of oxythiodiphenylimide and hydroxythiodip henyl- amine has been already described (Abstr. 1885 260). The constitution of these compounds may be represented by the formulm- 0/76H3*S > and C,H4<kg> C,H,*OH. 'N*C6H4 Silk immersed in an alkaline solution of the latter compound is dyed crushed strawberry. S treating thiodiphenylamine with sulphuric acid diuted with one-fifth its weight of water at 160" for 24 hours. The product of the reaction is poured into water mixed with excess of sodium hydroxide and filtered. On the addition of hydrochloric acid t o the hot filtrate thionol hydrochloride is deposited in glistening green crystals.The free base is insoluble in cold water but dissolves freelyin acids. It is deposited from glacial acetic acid in plates. The alcoholic solu- tion is of a purple colour and the solution in strong sulphuric acid is blue. The sulphate 2ClaH,NS02,H2S04 forms green needles. The barium salt C1zH7NSO3Ba crystallises in plates exhibiting a green56 ABSTRACTS OF CHEBlICAL PAPJIRS. lustre. Silk immersed in a solution of thionol in potassium car- bonate acquires a violet colour which turns red on exposure to tlie air. Thionol is formed in small quantities by the continued action of alkalis on methyletie-blue ; it is also a product of the action of alkalis or of strong sulphuric acid on thionine. C6H3(0H)>S is formed by treating an am- Leucothionol NH< It is deposited from its On treatment with ') is formed by adding ferric chloride to amidophenol which has been saturated with snlphuretted hy- drogen. It is also produced by the prolonged boiling of thionine in water NCI2H6S(NH2)NH + H,O = NC12H6S(NH,)0 + NH3.Thionoline dissolves in hot alcohol forming a purple solution ; the C6H3(NH2)>S is soluble in acids and in alkalis. leuco-compound NH< The nitrate sulphate and hydrochloride of thionoline crystallise in needles. Strong sulphuric acid dissolves thionoline forming a blue C6H4 OH) nioniacal solution of thionol with zinc-dust. ethereal solution as a crystalline colourless mass. acetic anhydride it yields a triacetyl derivative. 'N-C6H3(NH2) CsH - Thionoline Q/ I C6H3( OH)- solution. Methylene-violet is dimethylthioDoline.w. c. w. Benzyl Compounds. By 0. BORGMANN (Chern. Centr. 1885 456-458). -This communication contains an account of several metabenzyl compounds prepared from metanitrobenzyl alcohol Home of which have already been described (Abstr. 1883 1121). Pyiniary metanitrobenzy lanaine N02*C,H1*CH2*NH is formed by treating metaiiitrobenzyl chloride with alcoholic ammonia ; it is a yellowisli oil absorbs carbonic anhydride from the air forming a solid salt and yields a sparingly soluble oxalate and platinochloride. The secondary amine NH(N02*C6H4*CH2) formed with the primary crystal- lises in yellowish rhombic leaflets melting at 87" ; its hydrochloride and platinochloride are both sparingly soluble salts. When reduced bp tin and hydrochloric acid it forms an anlido-compound the hydro- chloride of which crystallises from concentrated hydrochloric acid in long reddish needles having the composition N(NH2*C6H4*CH2)2,SHC1. The base crystallises in prisms melting at 86-87'.Z'ertiary metanitrobenzylanzine N (NO,*C,H,*CH,) is formed by digesting met anitrobenzyl chloride with aqueous ammonia ; it crystal- lises in monoclinic prisms melts at 162O is soluble in glacial acetic acid and benzene but only sparingly in alcohol is insoluble in ether and does not unite with hydrochloric acid. When reduced with tin and hydrochloric acid it yields the tertiary amido-compound which crystallises in colourless needles melts at 142O and forms a sparingly soluble platinochloride. Amidobenzyl chloride is very unstable and is formed by the reduction of the niti-o-compound with tin and hydrochloric acid.Metar~itrodibenzylnzethylamine NMe( NO2*C6H4-CH2) is formed by acting on nitrobenzyl chloride with an aqueous solution of methyl- amine ; i t melts at 81". By the action of dimethylamine metnnifro-ORGASIC CHEJlIST RT. 57 7/enz~ZdinzethyZamine N0,*C6H,*CH,*NMe is formed ; it is a yellowish oil and forms a well-defined platinochloride. MetanitrobenzyZphenyZamine Ilu'0,*CsH4.CH,*NHPh is formed by the action of aniline on nitrobenzyl chloride; it crystallises in long orange-red needles melting a t 86" ; its hydrochloride forms white leaflets is an unstable compound and does not form a platiuochloride. When reduced by tin and hydrochloric acid this base forins nzetamido- benzyZ~l~enllZai,ziize NH,.C,H',*CH,*NHPh melting a t 67".Metanitrobenzaldehyde when treated wit'h concentrated sodium hydroxide yields meta-azoxybenzoic acid ON,( C6H,*C0 OH),. P. P. B. Ethylortholuidines. By R. L. CHASE (Amer. Chem. J. 7 118- 120).-These compounds have been prepared by Reinhardt and Staedel (Abstr. 1883 578). Ethylortholuidine formed from ethyl iodide and orthotoluidine boils a t 204-206" ; its salts are exceedingly soluble in water ; the chloride platinochloride iodide acetyl- and nitroso- compounds are mentioned. Diethylorthotohidine was prepared from the monethjl-derivative and ethyl iodide it boils between 203-208" ; the hydriodide crystal- lises well from water it contains 1 mol. H,O. H. B. Consecutive Orthoxylidine and Orthoxylenol. By A. TOHL ( Ber. 18,2561-2562).-Mo~tonitrodibromortho-xylene C6H~fe,Br,.N02 [Me Br NO = 1 2 3 4 51 is obtained together with the dinitro-compound by adding 4 5 dibromortho-xylene to cold fuming nitric acid. It crystallises in colourless needles and melts a t 141".Dinitrodibromortho-xy Zene C6Me2Br2(N0,) crys tallises in small needles and melts at about 250". Uibronaort/io-xyZidine C6HMe2Br,.NH2 is prepared from the mono- nitro-derivative by heating it with iron and acetic acid. It crystallises in colourless needles melts at lOS" distils with steam is readily soluble in alcohol ether and glacial acetic acid and does not yield salts with acids. The bromine is to a great extent removed by iong treatment with tin and hydrochloric acid but complete replacement can only be effected by the action of sodium amalgam on a warm alcoholic solution.Ortho-xy Zidine C6H,Me2*NH2 [Me Me NH = 1 2 31 so obtained is a colourless oil which turns brown on long exposure to air does not solidify at - 15" and boils a t 2.21-222". The hydrochloride C6H3Me2*NH2,HC1 + H20 crystallises in large lustrous tables and sublimes readily; the nitrate and sulpbate are also described. AcetzyZide C6H3Me,-NHAc cry stallises in long slender needles and riielts at 131". Ortho-xyZemZ C6H3Me2.0H [Me OH = 1 2 31 prepared in the usual way from the xylidine crystallises in very long slender needles melts a t 75" boils at 218O and yields a blue coloration with ferric chloride in aqueous solution. The tribroino-deiivative C,Me,Br,-OH crystallises in slender needles and melts at 184".A. J. G. Paraxylidine. By E. NOLTING 0. WITT and S. FOREL (Ber. 18 2664-2668).-Crude xylidine was found to contain about 25 per cent.58 ABSTRACTS OF CEEitlICAL PAPERS. of pnraxylidine boiling a t 215" under 739 mm. pressure. Sp. gr. = 0.980 (water at 15" = 1). Nitraceto-xylide melting a t 166" is obtained by nitrating the acetyl-derivative ; it yields a nitro-zylidine which melts a t 142" and crystallises from benzene in brownish-yellow lustrous crystals readily soluble in alcohol and ether. When nitro-xylidine is reduced xylenediainine is formed ; this cryshllises from benzene in small white needles melting at 146.5-147" which when oxidised yield paraxyloquinone. Ethyl nitrite acts on nitro-xylidine with formation of the ethyl salt of nitioparaxylenol ; it is a yellow substance melting at 85"." N. H. M. The Six Isomeric Xylidines. By E. NOLYING and S. FOREL (Ber. 18 2668-2681).-A description of these compounds and some derivatives is given. When consecutive ortho-xylidine is oxidised it yields ortho-xyloquinone C6H2Mez02 [Me2 0 2 = 1 2 3 61. This compound sublimes in yellow needles which melt a t 55" ; it is rather readily soluble in alcohol ether &c. It is reduced by sulphurous acid to the quinol a white substance melting a t 221". Ortlzo-xylenol [Me2 OH - 1 2 31 is obtained from the diazo-derivative of the base; it crystnlliscs from water in white needles melts at 73" and sublimes uiichanged. The aqueous solution acquires a pale-violet colour when treated with ferric chloride. 171etaxylylquinone C6H,Me,0 [Me2 0 = 1 3 2 51 is prepared by oxidising metaxylidine ; it forms splendid yellow needles which melt a t 73".The corresponding qwin,oZ forms white needles melting a t 149". When symmetrical metaxylidine is nitrated a nitro-derivative [Me2 NH2 NO = 1 3 5 41 melting at 54" is formed; this when reduced yields metaxyleneorthodiamine melting a t 77". When the hydrochlorides of the xylidines are heated with methyl alcohol a t 300-320" amidotrimethylbenzenes are formed. Consecutive ortho-xylidine yields a liquid amidotrimeth2/lbenzene boiling a t 240' ; the acety2-derivaticve meits at 1130". Symmetrical metaxylidine yielded a crystalline isocumidine which melts a t 67-68" and boils a t 245" (uncorr.) ; the acetyl-derivative melts a t 163-164" ; the cumenol melts at 98-99".N. H. M. Arnidoazo-derivatives of the Three Xylenes. By E. NOLTING and S. FOREL (Bey. 18 2681-2686). - Amidoazometaaylene C6H3.Me2-"L*C6H2Me2.NH:! [Me Me N Me NH Me = 4 2 1 2 3 41 is prepared by the action of 69 grams of a 20-25 per cent. solution of sodium nitrite on a well-cooled mixture of 121 grams ineta- xy lidine and 157 grams metaxylidine hydrochloride. The product is extracted with ether and the resiciue left on evaporating the ether is warmed with 120 grams of metaxylidine and 10-15 grams of meta- xylidine hydrochloride at about 50". It is then boiled with dilute hydrochloric acid and the sparingly soluble hydrochloride thus obtained is washed with water alcohol aod ether. The base is liberated by means of ammonia and crystnllised from alcohol or benzene.It forms orange-yellow plates which melt at 78" is almost insoluble in water readily soluble in hot alcohol and in benzene. The 7aydrocl~Zoride forms a bright Fellow crystalline powder ; its alcoholicORQANIC UIIKJIJSTRY. 59 fiolution is peen. When reduced it yields a diamine melting at Amido-azometnxylene [Me Me N2 :Me Me NH = 6 2 1 3 5 41 crystallises in yellow plates melting at 77.5" ; it dissolves readily in alcohol and in benzene. The alcoholic solution of the hydrochloride is red. Amido-azometazyZene [N Me Ne NH = 1 2 6 41 cryst'al- lises from alcohol in yellow plates melting at 95". The solution of the hydrochloride in phenol is violet. Amido-axortho-zy Zene [Me Me N2 Me Me NH = 3 2 1 2 3 41 forms yellow plates and melts at 110.5".Amido-axortho-xylene [Me Me N Me Me NH = 6 3 1 4 5 21 forms yellow plates melting at 179" ; it is sparingly soluble in alcohol. The solution of the hydrochloride in phenol is green. Amido-azopuraxylene [Me Me N Me Me NH = 5 2 1 3 6 41 crystallises from alcohol in red plates melting at 150". The hydro- chloride is red ; its solution in phenol is violet-red. When the base is reduced a diamine melting a t 146.5-147" is formed. Experiments made by the authors show that the nmidoazoxylene described by Nietzki (Abstr. 1880 552) is a mixed amidoaso-metapara- xy7ene [Me Me K Me Me NH2 = 4 2 1 3 6 41 ; it melts at 110-111". N. H. M. 77-78'. Azo-derivatives of Carvacrol. By G. MAZZARA ( Gazzetta 15 305 -315) .-In continuation of experiments on the azo-derivatives of thymol and carvacrol (Abstr.1885 904 and 1132) the author describes the preparation of an azo-compound by heating 1 mol. of bidiazotriphenylmethane with 2 mols. carvacrol dissolved in potash. There is thus formed a purplish-red amorphous substance carvacrol- bidiazotriphenylmet hane to which is ascribed the composition [OH*CsB2MePh~N,~C,H,*CHPh*CsH4*N,C,H2MePh]20. It melts at 130" and is soluble in ether and chloroform ; its potassium-derivative is a red precipitate ; when heated with bidiazobenzene it is converted into a red crystalline substance the composition of which has not yet been definitely established. By 33. HAGER ( B e r . 18 2573-2577).-Diphenylurethane is best obtained by heating diphenyl- amine with ethyl ch lorocarbonate.Di-orthonitrophenylurethaize (N02G,H,)2N.COOEt is obtained together with the para-compound by adding diphenylurethane to nitric acid of sp. gr. 1.44 and pouring the solution into much water ; the mix- ture is separated by treatment with a little hot benzene from which the para-compound crystallises on cooling. The ortho-compound forms a brown syrupy. mass readily soluble in alcohol and seems to be miscible in all proportions with benzene. Potash convert,s it into orthonitrodi- phenylamine. When heated alone it yields a mixture of products from which a colonrless liquid boiling at 141-143" and of the formula C,HIoO was isolated. This is insoluble in water readily soluble in ether and unites with bromine to form a yellow liquid yielding on distillation an oil which gives a nitro-derivative melting a t 181-182".V. H. V. Derivatives of Diphenylurethane.60 ABSTRACTS OF CHENICAL PAPERS. Di-paralLitrophe~ylui.ethane crystallises in yellow needles melts a t 133-134" is readily soluble in benzene sparingly in alcohol and yields paranitrodiphenylamine when boiled with potash. Di-pnmmidophenylurethane ( NH,*C6H4),N*COOEt + H,O is pre- pared by reducing the nitro-compound with tin and hydrochloric acid ; it crystallises in violet needles and melts at 101" with decom- position. When treated with benzoic chloride it yields a benzoyZ- derivative (NHBZ.C~H~)~N*COOE~ crystallising in flesh-coloured needles and melting at 210" ; this is not identical with the substance to which the author had previously and erroneously assigned this formula (Abstr.1885 150). Hexabronzod~phenyluretl~ane (C,H,Br,),N*COOEt is obtained by the action of bromine on solutions of dipheriylurethane ; it crystallism in long greenish-brown needles and melts a t 184". When treated with nitric acid it yields a nitro-compound crystalliving in yellowish- bro wn needles and melting a t about 245" with decomposition New Synthesis of Vanillin. By M. ULRICH (Ber. 18 2571- 2573).-1n 1881 Meister Lucius and Briining patented a method for obtaining three isomeric mononitrometamethoxybenzaldehydes. Tiemann (Abstr. 1883 189) and Schnell (Ber. 17 1381) have stated that this method yields not mononitro- but two diiiitro-derivatives ; t'he author however finds that when metamethoxybenzaldehyde is nitrated according to the directions of the patent the three rnono- nitro-derivatives are formed.The main product of the reaction is a-nitro-metametl~oaybenznlde- hyde ; it crystallises in thick yellow prisms and melts a t 107". /?-nitro- rnetanzethoeybenzaldehyde is formed in small quantity ; it crystallises in needles and melts at 82-83" As both these acids give the indigo reaction they must be the two ortho-nitro-compounds [ COH Me NO = 1 3 2 and I 3 61 ; there is no evidence as to which is which. The third ni tro-compound crystallises in cauliflower-like masses inter- spersed with prisms melts at 97" and does not give the indigo reaction; it has the constitution [COH Me NO = 1 3 51. Ptrranitrometl~oxybenzalde7~yde [COH Me NO2 = 1 3 41 is ob- tained as follows methyl metamethoxycinnamate is nitrated a t 0" with nitric acid of sp.gr. 1.46 and the paranitro-methyl salt separated by crystadlisation from the product when it is obtained in flat white needles melting a t 163". The free pnranitro-acid irepared f r o m the methyl salt is then oxidised with aqueous potassium permanganate by which means it is converted into paranitromethoxy- benzaldehyde. This crystallises in hair-like needles me1 ts a t 62" and is soluble iu water alcohol and benzene. When treated with acetone and soda it yields a colourless solution from which after a time colourless needles melting at 84" separate. By replacing the nitro-group by hpdroxyl vaniZlin is obtained. Paramidacetophenone Ortharnidometacetyltoluene and some of their Derivatives.By J. KLINGEL (Ber. 18 2687- 2706).-Paramidacetopheiione is best prepared by boiling a mixture of 2 parts aniline 3 parts zinc chloride and 5 parts acetic anhydride A. J. G. A. J. G.ORGASIC CHEMISTRY. 61 for five hours; the product is boiled with hydrochloric acid and treated with sufficient soda solution to precipitate and redissolve the zinc hydroxide. A brown oil then appears which is sepa- rated and distilled with steam to expel aniline. The residue is extracted several times with boiling water and the united extracts evaporated down; on cooling the amide separates. The yield is 50-60 per cent. of the weight of aniline used. Several salts are described. Acetylamidacetophenone COMe*C6H4 NHAc forms small white needles which melt a t 166-167" ; it is readily soluhle in hot water and in alcohol. Hydroxyacetophenone COMe.C6H4*OH = 2 4 is prepared by acting with sodium nitrite on a well-cooled solution of the base in dilute hydrochloric acid and then slowly heating the product with water until it boils.The phenol is extracted with ether. It forms white needles melting a t 107" readily soluble in hot water alcohol and ether. When the aqueous solution is treated with ferric chloride it acquires a dark-brown colour. IocloacetoJihenone C,&I*COMe is prepared from the amide by means of the diazo-chloride; it crystallises in white plates which have an agreeable odour and melt a t 79". It dissolves readily in alcohol and ether. When oxidised it yields pariodobenzoic acid. Dimethylamid- acetophenone COMe*CsHc*NMez is obtained by the action of methyl iodide on amidacetophenone and forms yellowish plates melting at 58-59".It is readily soluble in alcohol ether and hot water. Acetopkenonea,zonaplLthoZ COMe*CGH,N NGloH6*OH is prepared by the action of the sodium compound of /%naphthol on the diazo- chloride obtained from amidacetophenone. It forms groups of slender red needles with a slightly green metallic lustre insoluble in water sparingly soluble i n ether readily in alcohol. Dilnte alkali dissolves it readily with formation of a dark-red solution. Orthar?zidonzefacetotoluene [COMe Me NH = 5 1 21 is pre- pared from toluidine in a manner similar to amidacetophenone as described above. I n appearance it is very similar to amidacetoplienone ; it melts a t 102" and boils at 280-284".It dissolves readily in hot water alcohol ether and dilute alkali and is almost insoluble in light petroleum and benzene. Several salts are described ; they resemble the salts of amidacetophenone. The acety 1-derivative melts at 143- 144" ; it is readily soluble in warm water and in alcohol. Acetocresol COMe*C7H,- OH is prepared similarly to hydroxy- acetophenone ; it crystallises in reddish prisms melting a t 104" readily soluble in alcohol ether and hot water. When treated with ferric chloride it gives a yellowish-brown coloration. Diwiethy Zamido-acetotohene COMe*C7H6*N&2 crystallises in groups of flat prisms melting a t 95'; it is readily soluble in alcohol ether and hot water almost insoluble in light petroleum. Acety Ziodotoluene COMe*C7H61 is prepared by the action of hydriodic acid on the corresponding diazo-chloride ; it forms a yellowish crystalliue mass melting at 3Y" very readily soluble in alcohol and ether sparingly soluble in light petroleum benzene and hot water.When oxidised it yields iodophthnlic acid. This crystal- lises in slender white needles which melt a t 203-204" is very sparingly soliible in boiling water and dissolves readily in glacial62 ABSTRACTS OF CHEIIICAL PAPERS. acetic acid alcohol ether and warm chloroform. The barium salt forms slender white needles very sparingly soluble in boiling water ; the calcium copper and silver salts were also prepared. When iodophtbalic acid is treated with concentrated potash solution it is partially converted into parahydroxybenzoic acid ; nascent hydrogen converts it into benzoic acid.N. H. M. Mixed Axo-compounds. By E. BAMBERGER and A. CALMAN (Rer. 18 2563-2567 ; compare Abstr. 1885 157).-A mixture of phenylazoacetophenone and ethyl phenylazobenzoylacetate is o btainecl by mixing aqueous solutions of diazobenzene chloride ethyl benzoyl- acefate and soda. Phenylazoacetophenone COPh*CH2*Nz*Ph is obtained by heating the mixtu1.e with alcoholic potash and precipitating with water ; i t crystallises in slender golden-yellow needles melts a t 128.5" and is readily soluble in hot alcohol or acetic acid. Pheny Zazobenzo y 1 acetic acid COP h* CH (N,Ph) *C 0 OH obtained from the potash salt prepared as above crystal!ises in long citron- jellow needles melts a t 141" is soluble in ether alcohol and acetic acid and yields phenylazoacetophenone when boiled for some time with dilute soda.Orthonitrophenylazoacetophenone ?J02*C6H4*N2*CH2*COPh crystal- lising in lustrous golden-yellow needles melting at 140-141" and ortlhonitropheny Zazobenz oy Zacetic acid NOz* C,H4*N2*CH( C 0 Ph) *C 0 OH crystallising in sulphur-yellow needles and melting a t 177" are formed in similar manner from orthonitrodiazobenzene chloride. When heated for some time a t the melting point the acid loses carbonic anhydride and is converted into the ketone. By the action of hydroxylamine hydrochloride on the ammonium salt the compound NO*C6H4-Na*CH( CPh NOH)*COOH is formed ; this crystallises in orange-yellow needles and melts at 142". M~tartitrotoly2i3arccxobelzxo2Jlacetic acid NO2*C6H3Me*N2* CH ( C OPh) C 0 OH prepared from metanitroparatoluidine crystallises in silky golden- yellow needles melts at 194" and is very sparingly soluble in cold alcohol or acetic acid.NOz-C6H3Me*Nz*CH2*COPh crystallises in lustrous citron-yellow needles melts at 168" and with hydroxylamine yields the ketozime NOz*C,H3Me*Nz~CHz.CPh NOH ; The corresponding acetophenone this crystallises in reddish-yellow needles and melts at 174". A. J. 0. Crystallographic Examination of some Organic Com- pounds. By J. ZINGEL (Zeit. Kyyst. Min. 10 41$-420).-The crystalline systems and axial ratios are as follows :-Metatrimeth- amidobenzoic acid chloride ~&fe3C10C6H4*COOH ; monosymmetric ; u b c = 1.9388 1 0,8757 ; /3 = 88" 49'. Metadimethamido- benzoic acid NMe2*C6H4*COOH; asymmetric; a c = 1 1.9403.ORGANIC CHEMISTRY.63 Dinitroparatoluidine (m. p. 69-71'). Rhombic; a b c = 0-9965 1 0.5184. 2 4-Dinit,rophenyl metanitrobenzoate asym- metric; a b c = 0.7137 1 1.7671. A. J. G. Phenylacetic Acid. By R. MEYER (Chem. Centr. 1885 516- 51 8) .-Orthoparadinitrophenylacctic acid is prepared by adding phenylacetic acid to conceritrated nitric acid and pouring the mixture into concentrated sulphuric acid. The acid crystallises in colourless needles melting a t 160" (Abstr. 1884 178). Ethyl dinitrophenylacetatP crystallises in colourless needles melting a t 35"; it is more stable than the acid. Paramido-orthonitrophenylncefic acid is formed by reducing the dinitro-compound with ammonium sulphide ; it crystallises in long reddish-yellow needles which are soluble in alkalis and also in acids ; it melts a t 184-186".Attempts made to convert this compound into ortlionitrophenylacetic acid by the diazo-reaction have been without sumess. Ethyl amidonitr~henylacefate crystallises in long yellow needles melting a t 100"; this compound when treated with an alcoholic solution of ethyl nitrite and hydrochloric acid yields it compound having the composition C,H,N205 which crystallises in needles melting at 163". When heated with hydrochloric acid in sealed tubes a t 150-160° this compound is resolved into ethy-l chloride carbonic anhydride ammonia and orthonitrobenzoic acid ; this owes its production to the formation of nitrosomethy lorthonitro- 7)enrene; it would therefore appear that the compound is ethyl orthonitrophenyl&trosoacefate NOz*C6H,*CH(NO)*COoEt [2 11.Nitrosonaethylorthonitropal.adiazobenzeiLe chloride NO,* C6H3' (NiCL) C HZNO is obtained by treating amidonitrophenylacetic acid with hydrochloric acid and amyl or ethyl nitrite. When heated with hydrobromic acid it yields the bromide NO2*C7H5BrNO which melts a t 151-152". The chloride boiled with alcohol yields nifrosornethylorthonltrobenzene NO,*C,H,*CH,*NO (1 21 which when heated in sealed tubes with hydrochloric acid a t 150-160" is resolved into ammonia and ortho- nitrobenzoic acid. Nitrosomethylnit'mbenzene when oxidiscd by potassium dichromate or permanganate or ferric sulphate yields orthonitrobenxaldehyde melting a t 43.5-44.5'. Reduced by ammonium sulphide it forms nitrosomethylorthailzidobenzerzs NH2*C6H1*CH2*N0 which crystallises in needles melting at 132-133".The methyl-derivative of nitrosomethylnitrobenzene N02*C6 B,*CHMe*NO melts a t 58"; the ethyl compound is an oil. Methylnitrosoamido- benzene TU'H;C6H4*CHMe*N0 is an oil volatile in steam ; its hydro- chloride crystallises in needles melting at 109". Orthonitrobenzo.nitrile N02*C6H4*CN [ 1 21 is formed by heating ni trosomethylnitrobenzene with acetic anhydride and sodium acetate. The nitrosomethylamidobenzene yields under like conditions a diacetyl compound NHAc*CsH,*CHAc-NO melting a t 127*5-128*5".64 ABSTRACTS OF CHEMICAL PAPERS. Dinitrophenylacetic acid reduced by tin and hydrochloric acid yields anlido-oxindole NH2*CsH3< ;%>GO from which by the diazo-reaction the paradiaxonitroso-oxindol e chloride has been prepared ; it crystallises in yellow needles and when boiled with alcohol yields nitroso-oxindole.Derivatives of Durene. By J. U. NEF ( B e r . 18 2801-2807). -Dur?ylic acid is best obtained by heating durene with dilute nitric acid (1 vol. acid of sp. gr. 1.4 to 3 vols. water) for three to four hours in a reflux apparatus ; the product is allowed to cool filtered and the residue extracted with sodium carbonate solution the un- altered durene being again treated with dilute acid. On adding hydrochloric acid to the alkaline solution durylic acid is precipitated together with some nitro-compounds which are removed by treatment with zinc and glacial acetic acid and distillation in a current of steam. The durylic acid obtained melts at 149" and agrees in all properties with the acid described by Janiiasch ( Z e i f s .f. Chenz. 6 449) whilst the yield amounts to 15-20 grams from 40 grams durene. Dinitrodwry lic acid (see also Gissmann Abstr. 1883 334) is best prepared by dissolving finely divided durylic acid in pure con- centrated sulphuric acid cooling with ice and gradually adding a solution of nitre in pure sulphuric acid with constant stirring. After four or five hours the product is poured upon ice the nitro-acid filtered off washed and purified by means of its calcium salt. Its properties have been described by Gissrriann (loc. cit.). When dinitrodurylic acid is dissolved in a dilute solution of potas- sium carbonate and potassium permanganate solution gradually added dinitropyrornellitic acid is produced.It has a strongly acid odour is readily soluble even in cold water extremely so in ether and crystallises from both solvents in very long silky colourless needles ; soluble also in alcohol and glacial acetic acid but insoluble in chloro- form benzene and light petroleum. When i t is heated in a capillary tube it loses water (100-160") and becomes yellow and it decom- poses a t 203" with evolution of gas. The silver salt C6(NO2),(COOAg) forms a golden-yellow amorphous precipitate. Attempts to reduce dinitropyromellitic acid to the diamido-acid proved unsuccessful. Ethy I d initroyyrom el Zit at e c6 (NO,) (CO OE t ) 1 obtained by heating the silver salt with ethyl iodide and ether for one to two hours at loo" forms magnificent colourless needles readily soluble in hot and sparingly in cold alcohol readily in benzene chloroform glacial acetic acid acetone and ethyl acetate more sparingly i n ether.It melts a t 130". When its hot solution in glacial acetic acid is treated with zinc-dust ethyl axopyi'ondlitate C&,( COOEt) is produced. This has a deep cinnabar-red colour is insoluble in water and dilute acids ; it yields a colourless salt with concentrated hydrochloric acid dissolves readily in glacial acetic acid alcohol and ether and melts a t 134". It sublimes without decomposition when heated. When P. P. B.ORGAXIC CHEMISTRY. G5 diamidodurene (from dinitrodurene) is treated with ferric chloiaide a green coloration is produced and at once chanqes to yellow owing to the formation of duroquinone C602Me4.This crystallises from light petroleum in long yellow needles melting a t 111". It sublimes rzadily emitting but a faint quinone odour dissolves very readily in ether chloroform benzene alcohol and acetone. Zinc-dust and sods solution sulphurous acid and sodium amalgam reduce it but it is reproduced on agitation with air. It is insoluble in alkalis and nearly so in hot water. Potassium permariganate and sodium carbonate solution and also chromic acid and glacial acetic acid decompose it. From the great stability of duroquinone the author hopes to succeed i n preparing the quinone of pyromellitic acid which would have the same composition as croconic acid. Dibromoparahydroxybenzoic Acid. By A. ALESSI (G'uszetta 15 242-247).-In order to determine the constitution of the di- bromoparnliydroxybenzoic acid obtained by Balbiano from the distil- lation of sodium dibronianisate with calcium oxide (Abstr.1834 1 172) dibromanisic acid was converted by excess of concentrated bydriodic acid into a dibromohydroxybenzoic acid. This was found to be identical with Bidbiano's acid. As in the acid from dibrom- nnisic acid the substituted groupings must be in the relative position OMe Br B r C0,H = 1 2 6 the composition of Ba1l)iano's Reid has the same constitution. V. H. V. A. K. M. Salts of Anisic Acid. By G. BORRELLA (Gazzettcx 15 304-305). -The copper manganese nickel cobalt zinc and cadmium salts of anisic acid crystallise with H,O ; there can also be obtained basic copper OMe*CGH4*COOCuOH and chromium salts.In analysing the metallic salts of the organic acids it is con- Yenient to precipitate the heavy metals in the form of oxalates t,he alcohol necessary for the complete precipitation serving to dissolve the liberated acid. V. H. V. Inner Condensations. By A. ROSSING (Cher12. Cerjtr. 188.5 598 -395).-~0rtho-~Zdehydo~henoxyncet~c acid COH*C6H1*OCH,*cOOH produced by the action of monochloracetic acid on salicylaldehyde crystallises in large yellow leaflets melting at 132". Its salts with the alkali metals and metals of the alkaline earths are soluble in water its copper and silver salts sparingly soluble in water. I t reduces ammo- niacal solutions of silver salts and forms a double compound with liydrogen sodium sulphite. It unites directly with aniline forming the compound This compound unites with acids forming well-defined salts froni which the base can be obtained by careful addition of ammonia 01- caustic alkalis or better still by decomposition with an alcoholic 6 olution of sod ium eth ox ide.Its ethyl salt melts a t 114". NH Ph* CH (OH)*CGH4* 0.C H C 0 0 H. VOL. L. I;66 ABSTRACTS OF CHENICAL PAPERS. Aldehydophenoxgacetic acid unites directly with phenylhydrazine forming the conipound N,HPh CH*C,H,*O.CH,*COOH which melts a t 105". By oxidising agents aldehydophenoxyacetic acid is con- verted into salicy Zoxy acetic acid CO OH*C6H~~O~@H,*CO@H which crystallises in white needles melting a t 186-187'. Ethyl salicyl- oxyacetate is a light yellow oil which decomposes when heated and is converted into the corresponding diamide NH,*CO*C,H,.O*CH,*CONH ; when heated in sealed tubes with ammonia; this crystallises in yellow needles melting a t 158".When aldehydo-pheiioxyacetic acid is heated with acetic oxide ant1 sodium acetate it yields orthocumaroayacetic acid CO OH* CH CH*C,H,* O-CH,. C 0 0 H wliich crystallises from water in needles melting a t 190". This corn- poiind like cinnamic acid combines with 'bromine to form a di- bromide melting a t 219-220" which when heated with alcoholic potash yields orthopropiolpheelzoxyacetic acid COOH*C i C*CsH4*O*CH,*COOH ; this forms small yellow crystals melting at 208". When aldehydo-phenoxyacetic acid is heated with five parts of acetic oxide and 4-5 parts of sodium acetate for three hours it yields an oil boiling a t 170° which is identical with cnmarone C6H,<- >CH (Abstr.1888 474). If orthocumaroxyacetic acid is heated with phosphoric acid it loses water and yields the anhydride CH CH CHGO C6H4<-0. C H,. C 0 ->O which melts & 176"; when boiled with water it is easily recon- verted into the acid. ' This anhydride unites directly with bromine forming the dibromide GH,< O.CH,.CO,O >CO crystallising in CHBrGHBr yellow needles melting a t 213". When the cornpound of aldehydo-phenoxyacetic acid and phenFl- hFdrazine is heated witrh sulphuric acid a bluish-green amorphous substance is produced which dissolves in alcohol forming a bluish- green solution and in alkalis forming cherry-red solutions. This cornpound is precipitated from its alcoholic solutions by ether as a lustroils black powder having the composition CgH7NO3 and melting a t 108".This same oompound can be prepared by heating a mixture of monochloracetic. acid with ortho-oxy benzylidene phenyl- hydrazine in sealed tubes a t 1'00". Orthoxybenzylidene phenylhydra- zine when heated with acetic oxide yields a diacetic derivative AcO*C,H.,CH N2AcPh which crystallises in needles or prisms melting a t 133". On dry distillation this compound yields acetanilide xud a reddish-yellow substance cont)aining nitrogen. The diacetyl- derivative forins a dibromide which is easily decomposed acd when boiled with alcohol yields ucetozydibromobeizxyZiden,ep~enylli~d~az~n(~,ORCANTC CHEJIIS'I'RY. 6 7 AcO*C,H,Br,*CH N,HPh melting a t 188" ; this is decomposed by boiling with caustic soda ; from the alkaline solution hydrochloric acid precipitates the compound H0.C,H2Br2.CH N?HPh melting a t 148".P. P. B. Constitution of the Phthalic Acids. By E. NGr,mG (Bey. 18 2687).-The constitution of the phthalic acids has long been known hut the proofs are of a complex nature. The author now advances a himple proof. The three xylenes when oxidised readily yield the three phthalic acids. Three isomeric nitroxylenes xylidines and xylenols are derived from metaxylene two from orthoxylene one only from paraxylene. Therefore tl ie carboxyl-groups must occupy the 1 3 positions in isophthalic acid the 1 2 positions in phthslic acid and the 1 4 positions in terephthalic acid. A. J . G. Nitration of Phenylparaconic Acid. Bp H. ERDIIASN (Be).18 2741-2743) .-Paranitrophenylparaconic acid is prepared by the niteration of phenylparaconic acid. It forms very bright yellow plates which melt a t 155". It is insoluble in carbon bisulphicle and dissolves sparingly in chloroform benzene and ether readily in alcohol glacial acetic acid hot xylene &c. When heated at 200" evolution of carbonic anhydride takes place. Potassium permanga- riate converts i t into paranitrobenzoio acid. I n the preparation of this acid the ortho-acid is also formed (compare Abstr. 1885 1224). N. H. A!€. Derivatives of Durene. By 0. JACOBSEN and E. SCHNAPAUFF (Bey. 18 2841-2844) .-When powdered durene is gradually added to about 2+ times its weight of cooled sulphuric monochloride tlurenesulphonic chloride is obtained as the chief product together with durylsulphone and alittle durenesulphonic chloride.On treating the product with ice and water the sulphuric hydrochloric and sulphonic acids are separated from the sulphonic chloridc a n d t,he sulphone and on adding an excess of soda to the acid filtrate thv sodium sulphonate separates out. The sulphonic chloride may bo separated from the sulphone by crystallisation from alcohol and finally from ether. Durenesui$honic acid C,H,*XO,H dissolves readily in water b u t only sparingly in moderately dilute sulphuric acid ; the sodium potassium barium and copper salts are described. DurenesuZphonic chloritle CloH13*S02C1 crystallises from warm ethcr in brittle prisnis of vitreous lustre melts a t 99" dissolves readily in warm sparingly in ice-cold alcohol and very readily in ether.D1iren~suZ~honnmide CIOH13.S02NH2 crystallises from alcohol in long prisms melting at 155" ; it is very readily solnble in hot sparingly in cold alcohol and in ether and is almost insoluble in cold water ; it is decomposed by concentrated hydrochloric acid a t 190". D;)Lr!jZsuZphone (CioH,3)2S0 is readily s9luble in alcohol ether benzene and light petroleum whilst boiling water dissolv2.s but ttwes. It can bc distilled under diminished pressure without decomposition but a t the It crptallises in long prisms melting a t 37". f 2G8 ABSTRAOTS OF CHEMICAL PAPERS. atmospheric pressure it yields sulphurous acid and durene. When heated with concentrated hydrochloric acid at 200" it splits up into durene and sulphuric acid.When sodium durcnesulphonate is fused with potash either durenol or hydroxydurjlic acid is produced accordingly to the temperature and time of heating. DzirenoZ CIOHl3-OH crystallises from warm alcohol in large flat prisms melts a t 117" and boils a t 249-250". Bwmodurenol C10H,2Br*OH crystallises from hot dilute alcohol in long vitreous prisms melting a t 118". It is readily soluble in alcohol and ether insoluble in water. Nitrodwend Cl0Hl2(NO2)*OH separates from hot dilute alcohol as a bright yellow inass. It melts a t 130" is almost insoluble in water very readily soluble in dcohol and also in alkalis and alkaline cai-bonates with dark yellow coloration. HydyoxpZurylic acid C,HMe,( OH)*COOH is almost insoluble in cold sparingly soluble in hot water but very readily in alcohol.Its constitution is [COOH OH Me = 1 2 3 4 G I . It crystal- lises i n small needles melts at 148" and may be sublimed without decomposition. Its salts give a didy brown precipitate with ferric chloride whilst a solution of the free acid in diIute alcohol gives a transient blue coloration. The calcium salt ( CI,H,0,),Ca + 2H,O is described. When the acid is heated at 190-200" with hydro- chloric acid carbonic anhydride and pseudocumenol (melting a t 85-88"> are produced. Phenylacridine. By A. CLAW and C. NICOLAYSEN (Ber. 18 2706-2712) .-Potassium permanganate acts on phenylncridine in presence of free sulphuric acid with formation of a mixture of paraphenylquinolinecarboxylic acids from which a di- and a mono- cwboxylic acid were separated. Yurap7ter~ylquinolilredicarbosylic acid I'h*CgNH,(COOH) forms lustrous needles melting at 200-215".The barium salt (with 4 mols. H,O) crystallises in slender colourless needles. Barium parnphenylpuinolinecarbo~y late ( CIbH10N02)2Ba,6H20 crjstallises in needles. Yhenylamidobenzoic <acid NHPh*C6H4*COOH is obtained by the oxidation of phenylacridine methyl chloride with potassium per- ruanganate. Itl forms small colourless needles rnelting at 2.22" (uncorr.) alniost insoluble in water readily soluble in ether chloro- form &c. The sodium saZt (with 4 mols. H,O) fornis coloarless 1 lates readily soluble in water; the barium (with 5 mols. H20) and silver salts are also described. An acid having all the properties of that just described is obtained by heating metamidobenzoic acid with aniline hydrochloride a t 220".Phenylacridine hydrochloride crystallises from pure water in red octahedra (with 5 mols. €LO) ; the long yellow anhydrous needles described by Bernthsen are obtained from a solution containing free 11s drocli loric acid. a-Naphthylaminephthale'in. By A. VANNI ( Gazzetta 15 346- 34i).-On heating phtlialic anh.ydride and a-niiplithjlamine in equal molecular pioportiuns at a temperature of lW" 5t fused mass is A. K. M. N. H. M.ORGANIC CHEJIISTRY. formed ; thin is heated with boiling alcohol and as it cools deposits a-naphthylaminephthalejin f i 9 the filtered so!ution in the form of colourless transparent prismatic tables. It is insoluble in water sparingly soluble in alcohol and ether and melts at 166".It is decomposed by concentrated sulphuric acid forming a pale yellow sii bstance which dissolves in ammonia with an orange-red coloration ; with concentrated potash it forms an oil which ultimately solidifies ; the compound formed gives a violet coloration with water. V. H. V. Relations of @- to p-Hydrojuglone. By F. MSLIUS ( J h . 18 2.567-2571).-The acetyl- or benzoyl-derivatives prepared froin a- and from P-hydrqjuglone are identical and seem to be the P-derivatives inasmuch as they yield @-hydrojuglone when treated with alkalis or sulphuric acid. The compoiind previously described as triacetyl-a-h.vdro jnglone (Abst'r. 1885 170) Ehould therefore be ternled t?.iac~tllZ-$-h?//Zrf!jtigtone. It cry stall ises in colourless prisms and melts at 129-130". Triberizoyl-3- h?ydr.oj!l'uy/one CIOH50JBzI crystallises in colourless needles melts a t 228-229" and like t h e acetyl-derivative can be sublimed unchanged.a-Hpdrojuglone when heated above its melting point in an atmo- sphere of hydrogen is conrerted into P-hydrojuglone which distils ; on the other hand when the p-compound is subjected to prolonged boiling with dilute hydrochloric acid it is converted into a-hydro- jnglone. A. J. G. (Monatsh. Cheiii. 6 754-~59).-dntlzragt~llolamida Action of Ammonia on Anthragallol. By S. V. GEORGIEVICS i s prepared by boiling anthragallol with excess of ammonia f i i ~ 20-30 minutes; the fine blue solution so obtained is evaporatrct down aiid the solid substance crystallised from alcohol or glaciitl acetic acid. It forms greenish-black needles or R reddish-brown crystalline powder sparingly soluble in hot water alcohol antt benzene &c. Alkalis a,nd srilphuric acid dissolve it uncbanged with formation of blue and intense red solutions respectively.Nitrous acid acts on it with formation of ayellom substance which melts at 190-200" ; it does not contain nitrogen and is probably dihydroxy- anthragallol [(OH) = 2 31. Two nitro-derivatives of anthragallol were obtained from gallic acid by the action of meta- and of para-nitrobenzoic acid. A~zthragallolsulpTonic acid is prepared by heating anthragallol with 3-4 times its weight of sulphuric acid at 130-140". The aqueous solution acquires a red colour when treated with the smallest trace of alkali. The sodium aiid potassium salts have cnloiiring properties.N. H. Id.70 ABSTRACTS OF CHEJIICAL PAPERS. Terpenes and Ethereal Oils. By 0. WALLACH (111) (Annulen 230 225-2'12).-Yure borneol prepared by the action of sodium on camphor melts a t 206-207" riot a t 198" as generally stated. This componnd behaves like a saturated secoridary alcohol but it has the property of uniting with bromine and hydrogen bromide &c. to form nnstable additive products. For example when bromine is added to a solution of horneol in light petroleum a crystalline preci- pitate is deposited which consists chiefly of Oorneol bromide CloHlsO*Br2 mixed with a small quantity of (C,oH,O),Hr,. Cineol like borneol unites with bromine in two different proportions forming compounds which have the same composition as the borneol bromides.When borneol bromide is covered with light petroleum and left for some time in a closed vessel decornposition ensues resulting in the formation of borneol and borneol hydrobromide (C,oH,80)2,HBr. The same compound is obtained as a white crystalline powder by the action of hydrogen bromide on a solution of borneol in light petroleum. It is dccornposed by water and alcxohol. The hydriodide (CloH,80)2,HI is tt white crystalline compound which decomposes spontaneously . Rornyl chZoride Cl0HI7C1 is easily prepared by adding boriieol to a mixture of phosphorus pentachloride and light petroleum. The action is finished in half an hour. The crude product is poured into water and repeatedly washed. Bornyl chloride is not identical with pinene hydrochloride. It is readily converted into camphene by heating with aniline. Camphene is decomposed by dehydrating agents such as zinc chloride and strong sulphuric acid or by the action of heat alone.In each case the decomposition products are liquid. Monobromocamphene is obtained as an oily liquid when bromine is added to a solution of camphene in alcohol and ether. Camphelie is formed by the action of dehydrating agents on borneol but the hydrocarbon cannot be isolated (except when potassium pyrosulphate is the dehydrating agent) as it is decomposed by zinc chloride or phosphoric anhydride or strong sulphuric acid. The so-called hydrocarbon " borneen," which Pelouze ( A n n a l e n 40 :327) Kachler (ibid. 164 78) and Oppenheim (this Journal 1874 891) obtained by the action of phosphoric anhydride on borneol is a mixture of the decomposition products of camphene.The author confirms Tilden's statement (Trans. 1878,SO and %I.) that Kussian and Swedish oil of turpentine contain the same cou- stituents namely austpalene splvestrene and dipeutene. The hydrocarbon obtained by decomposing sylvestrene chloride with auiline closely resembles sylvestrene but the identity of the bodies is not proved. The hydrocarbons yield a chloridc melting at 7 2 O and a liquid bromide. " !l'erpinol " described by Wiggers ( A n n a l e a 57 252) and by List (ibid. 67 367) does not exist. Terpine hydrate C10H2002 + H20 melts at 117". It is a saturated compound and is decomposed by boiling with acids or dehydrating agents yielding terpineol C,H,O and other products.When a Tiiixture of I part of sulphuric acid anti 2 of water is used terpiueol terpinene CJT and terpinulene are formecl. Wlicn veryORGANIC CHEXISTHY. 71 tlilute sulphuric acid is used the chief product is terpinene. Dilute phosphoric acid and glacial acetic acid on the other hand yield terpineol as the principal product. Terpine hydrate is almost completely converted into dipentene by prolonged treatment wit'li potassium pyrosulphate. Terpineol CIOH1,*OH is a nonsaturated monatomic alcohol. It is a thick liquid boiling a t 215" and is sparingly soluble in water. I t nnites with bromine to form an unstable bromide. Bipentene tetrabromide melting at 124" is formed by the action of r7,n excess of bromine on terpineol. The hydroxyl in terpineol is easily replaced by chlorine or iodine yielding for example the chloride CloHl,CI melting a t 50" and the iodide melting a8t 77".Terpineol unites with carbanil forming phenylterpinylurethane which crystallises in white needles melting a t 110". Boiling with dilute acids or treatment with dehydrating agents converts terpineol into terpene or dipentene but if ferpiiieol is left at the ordinary tempera- ture in contact with dilute sulphuric or hydrochloric acid it unites with water forming terpine hydrate CloHzo02 + H20. Terpine has the same boiling point as dipentene but the two cBompounds are not identical as the former yields a liquid bromine- clerivative. Terpine is formed by the inversion of pinene witb :ilcoholic sulphuric acid. It boils between 185; and 190" and yields an unstable tetrabromide crystal- lisiog in mouoclinic plates.The relation between camphene borneol and camphor is shown by tlie following formulE :- Terpinolen,e has not yet been obtained in a pure state. Cmiphenc. Borneo]. Camphor. Borneol bears the same relation to camphene that terpineol does to dipentene. w. c. w. Action of Picric Acid on Terebenthene. By - LEXTREIT (J. Pharna. [ 5 ] 11 211-213).-Terebentliene when heated with picric acid at 150" gives a limpid liquid which after further heating a t the same temperature deposits crystals on cooling. When freed from excess of picric acid and a brown colouring matter i t forms thiu friable transparent flakes which rapidly take a yellow tint whcn exposed to light. It is insoluble in water slightly soluble in cold alcohol readily in ether carbon bisulphide and boiling alcohol.When heated it first fuses aud then decomposes with a gentle defla- gration. It seems to be a compound of picric acid and camphene of the formula ClUHl6,C6H3( N02)30. It is more stable towards aqneous72 ABSTRACTS OW CHEXICXL PAPERS. alkalis than are the known picrates of hydrocarbons. Further with an alcoholic solution of potash a very explosive crystalline precipitate of a purplish-red colour is formed quite different from potassium picrate. The compound is rapidly decomposed by a boiling aqueous solution of soda; a white sublimate is carried over with the steam which is insoluble in water but soluble in almost all proportions in cold alcohol and ether. Its odour resembles both that of camphor and of camphcne. It fuses at 179" camphor at 175" and camphene a t 45".Its rotative power is aD = - 36". Its composition is very nearly the same as that of camphor. Natural Camphor Oils. By P. MACEWAN (Pharm. J. Trans. [ 3 ] 15 1045-1046) .-Borneo Formosa and Japanese oils are referred to. The Bornean oil sp. gr. about O W O consists chiefly of borneene with a small quantity of resinous matter but with no camphor (borneol) in solution. In contact witth copper it acquires a green colour in a day or two. The Formosa camphor oil sp. gr. 0.943 is a saturated oleaceous solution of camphor ; when rubbed on the hand there is at first a strong carnphoraceous odour which soon goes off and a sassafras-like odour remains but the oil dries quickly on the skin and leaves no mark.Japanese camphor oil in crude form according to Oishi (Abstr. 1885 270) has sp. gr. 0.959 and contains camphor. The sample examined by the author evidently purified of sp. gr. 0.951 had a strong sassafras-like odour and contained no camphor. Scarcely any of it distilled below 140" about 10-12 per cent. consisting of a liquid isomeride of camphor distilled between 180" and 185" nearly one-half distilled over up to about 205" ; t,he residue has a sp. gr. of 0519.5. Treated with nitric acid and then after a minute with water the Japanese oil yields a clear crimson solution the Formosa oil a very slightly green milky solution ; with hydrochloric acid they both yield salmon-coloured solutions. This oil is used in the United States to adulterate oil of wintergreen.Picric acid behaves similarly with thymol. J. T. D. A. L. Camphophenylhydrazine. By L. BALBIANO (Gazzattri 15 246- 245).-As the formation of camphoroxime seems to indicate the presence of the carbonyl-group in camphor (Abstr. 1883 728 ; 1884 SlO) although the evidence thus far is not sufficient to decide between the aldehjdic and ketonic groiips the author has studied the reaction between pheuylhydrazine hydrochloride and camphor in the presence of sodium acetate. Jn this way camphopheuylhjdrazine C,H,-N,HPh is produced. It is a yellowish oil distilling a t 235- 245" under a pressure of 170 mm. soluble in dry ether and decom- posed by hydrogen chloride to form phenylhydrazine hydrochloride. Borneo camphor does not react with hytlroxlamine under the same conditions in which camphor yields camphoroxime ; whilst by treat- ment with phenylhydrazine in the presence of diluents bromocamphor yields pl:enjlhydrazine hjdrobromide and resinous substances. V.H. V. Euonymin. By G. ROMM (Chem. Centr. 1885 442-445).-This glucoside is not to be confounded with the medical preparation of the same name as the latter contains no poison and is employed as anP 6) ORGANIC CHEMISTRY. 4 * ) aperient. The author prepares it by extracting the powdered rinds of Euyonrnus atropurpureus with $0 per cent. alcohol distilling and evaporating the extract diluting with water and filtering ; the filtrate is then precipitated by lead acetate again filtered and the clear liquor freed from lead by sulphuretted hydrogen. After neutralisa- tion with magnesium carbonate precipitation with tannic acid arid treatment with zinc oxide euonymin is obtained in ciystals on em- yoration of its ethereal solution.The bark of Euon?ynzu.s europpiis contains no euonymin. Constitution of Santonin. By S. CANNIZZARO (Ber. 18 2746- 2751).-After reviewing the evidence a t presmt available as to the const,itution of santonin the author suggest,s the formula- J. K. C. CH CH.CK*CHMe-CO as agreeing fairly with its reactions. Derivatives of Santonin. By V. Vrr,r,;\vrcccma (Ber. 18 28.79 -2864) .-Photosardonic acid C15H2205 is best obtain3d by exposing :I solution of 10 grams santonin in a litre of acetic acid (sp. gr. 1-06> to the action of light for about a month ; the product is evaporated to a syrupy consistence in a vacuum the residue washed with water aud then treated with a warm solution of sodium cstrbonate.The undis- solved residue may be dissolved i n alcohol from which it crystallises in prisms melting a t 182-183" and of the composition CI7H2?O5 namely 1 mol. santonin + 1 mol. acetic acid. On adding hydrochloric acid to the sodium carbonate extract photosantonic acid separates and is purified by repeated crystallisation from alcohol. Its properties agree with those assigned to i t by Sektini (Abstr. 1877 471). It loses 1 mol. H,O at loo" and melts a t 154-155". The composition of its salts indicates that the water lost at 100" is not water of crystallisa- tion as assumed by Sestini but that undried photosantonic acid bears the same relation to the dried acid as santonin does to santonic acid.Barium and silver photosantonates C,5H,0,Ba and ClsH,oO Agz are described. Photosantonin C I ~ H ? ~ O ~ is best prepayen by exposing a solution of santonin (20 grams) in alcohol (1 lit're) to the direct action of light for three months. The alcohol is distilled off in a vacuum and the thick residual oil treated with lukewarm sodium carbonate solut,ion to romove photosantonic acid. On treating the insoluble portion with ether two isomeric photosantonins C17Hz10~ are obtained ; one modi- fication forms platy crystals melting at 154-255" and is dex5ro- rotatory ; [aID = + 76.77" for a solution containing 0.3825 gram in 50 C.C. alcohol a t 13". The other modification which is the chief product melts a t 68-6b0 and is identical with Sestini's photo- santonin.It is readily soluble in alcohol and ether and almost insoluble in cold water; [ = - 121.6" for a solution containing 1*0010 gram in 50 C.C. alcohol a t 14" and - 118.4" for 1.0980 gram in 50 C.C. alcohol also at 14". The composition of photo- santonin shows that it is not the diethyl salt of photosantonic acid as74 ABSTRACTS OF CHEJCICAL PAPERS. Sestini assumed but the monethyl-derivative of dehydrated photo- santonic acid which is regarded as a lactonic acid thus:-Photo- santonic acid HO*C13H~g(COOH)z ; photosantonic acid dried a t 1 OO" CO0H*C,Hlg <:;> ; photosantonin COOEt*C,H,<$~>. The last compound may also be obtained from photosantonic acid alcohol and sulphuric acid and by the action of ethyl iodide on the silver salt.When gaseous hydrogen chloride is passed into a solution of photo- santonic acid in absolute alcohol the diethyl-derivative of an acid containing the elements of a inolecule of water less than photo- santonic acid is obt'ained ; it is termed ethyl cle72.ydropkotosantonate C,H,(COOEt) an! forms a colourless liquid which does not solidify a t - 10". A solution of 0.7306 gram in 25 C.C. alcohol has a dextro- rotatory power ah 20*4" [&ID = 3. 20.4". The free acid which is isomeric with dehydrated photosantonic acid melts at 132-133". It is very readily soluble in alcohol and ether ; its dextrorotatory power is [aID = + 31-9" for a solution containing 0.7114 gram in 50 C.C. alcohol. The barium salt C15HieOJ3a is very readily soluble. A. I(. M. Papain. By S. H. C.MARTIN (Pharm. J. Trans. [3] 15,129-130). -A glycerol extract of commercial papain retains the fermentative act,ivity of the powder and contains a heminlbumose in quantity together with a mere ,trace of globulin. When the latter is precipi- tated by magnesium sulphate and the hemialbumose by subsequent saturation with sodium sulphate the solution is no longer active. The aqueous solution of the precipitated hemialbumose is however very active and when tested on coagulated egg-albumin produced peptones ; it is therefore evident that the ferment OE papaw-juice is associated wihh the hemialbunwse but as yet bas not been separated from it. Papain acts on animal albumin in manner similar to pepsin but not so rapidly ; with milk i t behaves like pancreatic jnice tirst curdling it the curdling being intensified by raising ths temperature (but not above 62") and hindered by making the milk alkaline or by diluting it to some extent or by boiling previous to adding cold water; the curd is gradually dissolved with the production of peptones leucine and tyrosine.A hemialburnose is formed as an intermediate product between the case'in and peptones. With regard to the action of papain on the proteids of papaw- juice i t converts the globulins into an albumose corresponding with Vine's hemialbumose ; leucine and tyrosine being also formed but no tisue peptones have been dekected. D. A. L. Pyrrylene Dimethyl Ketone. By G. CTAMTCTAM and P. SILBER (Gazzetta 15 248-250).-1n this paper it is shown that pyrrylene dimethyl ketone (dipseudacetopyrroline) is producible not only from pseudacetopyrroline and acetic anhydride as indicated formerly (Abstr.1885 378) but also directly from pyrroline by nieans of the same reaction. By an excess of fuming nitric acid it is converted into a mono-nitro-derivative C4NH,( NO,) Ac melting a t 149" md possessing acid properties. V. H. V.ORGAXIC C HEJLISTRT. 75 Synthesis of Pyrroline-derivatives. By L. LEDERER and C. PAAL (Ber. 18 2591-8599).-1t has been already shown that pyrro- line derivatives are formed by the action of ammonia 011 acetophenone- acetone and on acetonylacetone (Abstr. 1885 516 1206) and of ammonia and primary amines on ethyl acetosuccinate (Knorr ibid. 554 994) the reaction is now extended to ethyl acetophenoneacetaacetnte. Ethy lie methylpheny lp yrrolinecarhoaylate C4NH,MePh*C 0 OE t [Me COOEt P h = 2 3 51 is obtained by allowing a mixtare of ethyl acetophenoneacetate and aqueous ammonia to remain for 24 hours; it crystallises in colourless tables or small needles and inel ts a t 120".C&NH:,MePh-COOH prepared from the ethyl salt by saponification &c. crystallises in long flat yellowish needles readily soluble in acetic acid benzene and hot alcohol. When heated it partially decomposes a t 175" and melts a t 190"; it sublimes in small part but does not yield methylphenyl- pyrroline. Ethylic dimethy~henylpyrrolineonrboxylate C,NHMe,Ph*COOEt [Me Me COOEt Ph = 1 2 3 51 preysred in manner similar with mbthylamine crystallises in colourless plates softens a t 90° melts a t 112" and is readily soluble in alcohol ether and benzene.Met hy Zp h e q idly lpy wolinecarboay lic acid CJIg CAN HMePh- C 0 OH LC3H5 Me Ph COOH = 1 2 8. 5j. The ethyt salt is prepared by heating ethyl acetophenoneacetoacetate wit,h allylamine and a little absolute alcohol in settled tubes a t 180" for an hour; it is a thick oil and does not crjstallise. The free acid crystnllises in .short lustrous prisms is readily soluble in alcohol ether benzene and acetic acid and melts at 158". B e t h y ip heiatllaZlyllpt/rroZine C,H,*C,NHMePh [I 2 51 is prepared by distilling the acid ; it crystallises in large plates melts at 58" to a colourless oil with blue fluorescence boils at ;277-278" and is soluble in all proportions in ether almhol benzene light petroleum and acetic acid.i~~ethy1~henyIpyrrolinecnrboxylic acid N e th y Idip hen y l p yrrolheca rbox y Z ic acid C,NHNePh,*COOH i P h I Me COOK Ph = 1 2 3 51 crystallises in small needles melts at 226" and is readily soluble in acetic acid and benzene. The ethyl salt C4NHMePh,*COOEt is pre- pared hy boiling ethyl acetophelloneacetoacetate (1 part) with aniline (1.5 part) dissolved in acetic acid; it crystallises i n small prisms melts a t loo" and is sparingly soluble in alwhol and acetic acid. L~~ethy7dipher~ylpyr~oline CBNH2MePh is prepared by heathg the free acid a t above 226" ; it crystaliises in large ca~ourless tables melts a t 81" i8 not very readily volatile with steam and is readily soluble in benzene and light petroleum. iUet R y lphenyEos.thotolylp yrrolinecarbox y I ic acid C6H1MaC4NHMePh*CO0 H ciystnllises in small prisms and melts a t 199" ; it is readily soluble in the udinarj- solvents except water.The ethyl salt is obtained by boil-76 ABSTRACTS OF CHEMICAL PAPERS. ing aniline acetic acid and orthotoluidine as a thick oil that cannot be crystallised. il/lethy123he?aylorthotolyl~~yr,.oline C6H4Me*C4NH2MePh [l 2 51 is obtained by the dry distillation of the free acid ; it crystnllises in plates melts a t 44" to a pale yellow fluorescent oil boils a t 325-328" and is readily soluble in alcohol ether benzene and light petroleum. Methylphenylpuratoly lcarboxylic acid C6H4Me*C4NHMePh.COOH resembles benzoic acid in appearance and melts at 227". The eth! E salt Cz1HZ1147O2 crystnllises in prisms or tables and melts a t 11.5".Methy~~l~enyl23aratolyl~2/rrrtline C6E14Me*C4NH2MePh crystnllises in concentric paups of slender needles or in tables melts at 91" boils above 550° and is readily soluble in light petroleum and benzene. 1C~efhyl;when2/l-a-n~phthylpyrrolinrcnrboxylic acid CloH7*C4NHMePh-COOH [ C J € Me COOH Ph = 1 2 3 51 is prepared by heating a-naphthylamine and ethyl acetophenoneacetate in sealed tubes at 13U0 and saponifying the uncrystallisable product. It crystallises in needles melts a t 244" and is readily soluble in alcohol benzene and acetic acid. Metky7phe97yI-a-naphthylpyrroliiap CI0H7*CsNH2MePh crystallises in plates melts at 74" boils above 360" and is very readily soluble in benzene light petroleum aBd alcohol. &Id h y Zp hen y I- @nap h thy lp y rrolin,e C,H7- CsN H,MeP h cry s t allises i n concetitrically grouped needles and melts a t 52".The carLozyZic (wid C ,H,.C,NH Ne Ph* C 00 H crystal lises in small white needles an( 1 melis at 249". Its ethyl salt C24HzlN02 crystallises in lustrous plates and melts at 115". A. J. G. Pyridine-derivatives. By H. WEIDEL and F. Bf,Au (itfOl70,f~h. Chern. 6,651-666) .-When 30 grams of dibroniopyridine are heated for 24 honrs at 160" with 80 C.C. of absolute alcohol and a slight excess of potash diethoxy- and ethoxy-hydroxypyridine are formed. Diethoxypyridine C5NHI,( OEt) forms an almost colourless oil which is heavier than water ; i t is readily soluble in alcohol and ether. It boils with decomposition at 243-246" under 749.9 mm. pressure. With mineral acids it yields crystalline salts which are very deli- quescent.The plntinoch Zoride forms lustrous yellow needles. DihydroxypyG%ze C5NHB(OH)P is obtained by hydrolysis of the diethy 1-derivative by hydriodic acid and amorphous phosphorus at 1.20". It forms small yellowish-white crystals which become brown a t 200" almost black a t 230° and melt with total decomposition a t 237-239". It dissolves readily in hot water alcohol alkaline caT- bonates and in dilute acids. When a neutral solution of dihydroxy- pyridine is treated witlh ferric chloride it acquires a reddish-brown colour. The compound is probably identical with the dihydroxy- pyridine prepared by Geigy (Inaug. Diss. Munich 1885) from pyri- dinedisulphonic acid. Ethoxyhydroxypyridine EtO*C,NX,*OH forms colourless plates which become yellowish when exposed to light; i t is sparingly soluble in water readily in alcohol and in a mixture of alcohol and ether. TheORGANIC CLIEMISTRY.77 crystals are triclinic; a 2 c = 0.97'408 1.01795 1; = $jo 1' ; y = 88" 29'; @ = 91" 04'. It melts a t 127-128" (uncorr.) atid does not dist8il without decomposition. The nityate and pZatino- chloride are described. When fused with potash it yields dihydroxy- pyridine. Sodium ethoxide acts on dibromopyridine at 150" with formation of diet,hylpyridine together with a trace of the monethyl salt. By t,he action of alcoholic potash on bromopyridine (the intermediate liroduct formed in the preparation of dibromopyridine) ethoxypridine was obtained ; it forms a colourless liquid which boils below 200° and when reduced yields a hydroxypyridine identical with that already obtained fmm /3-pyridinemonosulphonic aeid (compave A bstr.1884 1050 and 1370). It is therefore a meta-derivative and the dibromo- comDound obtained from it probablg has both bromine-atoms in the meti-position from the fact &at it yields only one monethyl salt. N. H. M. Constitntion of Synthetical Hydropyridine-derivatives. By A. HANTZSCH (Bw. 18 2x9-2586) .-The constitution of these compounds has never been definitely ascertained although it has been assumed that both the hydrogen-atoms are in union with carbon- - - CH-CH atoms in the pyridine-ring thus giving the formula N<c-c>C for the nucleus of this group. Kuckert has Iiowever recently shown that a substituted hydropyridine-derivative is obtained by the con- densation with paraldehyde and sulphuric acid of the product obtained by the action of methylamine on ethyl acetoacetate from this it f ,Ilows that the nitrogen must be exerting imidic functions and that the constitution of the hydropyridine nucleus must be HN<C C ' C .' c> CH.The ketone CsH,O obtained by the action of hydrochloric acid on ethyl hydrocolliclinecarboxy!ate (Abstr. 1883 84) when treated wit,h hydroxylamine jields a crystalline oximido-compound C,H NOH. By heating ethyl acetoacetate with benzaldehyde and methylamine two non-nitrogenous products C19H2406 and C19H,C)> are obtained. 'l'he part played by the methylamine in the reaction is obscure but unless it or some other primary amine is present thesa substances are not formed.J3thyZ benz y 2 idinediacetoacetate C19H,0s = C HP h (CH Ac-C 00 Et) crystallises in long white needles melts a t 15%-153° and is sparingly soluble in alcohol and ether ; when treated with bromine it yields a substitution-derivative Cl9HZ3Bro6 nieltitig at 159". Ethyl dehydrobenzylidinediacetoawtate C19H2,05 crystallises in lustrous prisms melts a t 87-38" and is readily soluble in nearly all solvents. The author assigns to i t the constitution CMe C(COOEt)>CHPh '<CMe C(CO0Et) regarcling it as a hgdropyridine-derivative in which the imido-group is replaced by oxygen. A. J. G.78 ABSTRACTS O F CHEMICAL PAPERS. p-Dipyridyl. By T. LEOKE and V. OLIvExr (Gazzetfa 15 274- 277).-A dipyridyl Cl,H6N7 is produced by the dry distillation of pyridinesulphonic acid and separation of the distillate by concentrated potash.It crystallises in c:olourless prisms melting at G8" and boiling a t 286-288" ; its platinochloride is an orange-yellow powder insoluble in water alcohol and ether This dipyridyl is probably identical with that obtained by Skraup and Vortmann by the dry distillation of dipyridyldicarboxylic acid (Abstr. 1883 88) as evidenced by its direct conversion into nicotinic acid and of the formation of the same acid from the sulphonic acid originally used. It is proposed to call it p-dipyridyl and to assign to it the following structure :- C,H,N*C,H,N [N CaH*;N = 1 31. V. H. V. Pyridin e- choline Pyridine-neurine and Pyridine -muscarine . By T. COPPOLA (Gazzetta 15 330-345) .-The alkaloids choline neurine and niuscarine are analogous not only in their chemical constitution inasmuch as they can be regarded as hydroxyethylene- ringl- and dihydroxyethylenetrimethgl ammonium hydroxides but also in the physiological symptoms producccl by them namely stimulation of the inhibitory ganglia of the heart arrestation of the diastole and excitation of the secretmy nerves.I n this paper the chemical pro- perties and functions of their pyridine-derivatives ape described. P!jridine-c?ioline hydrochloride OH*C2H4*C5H5NC1 obtained by heating a mixture of pyridine and ethylene chlorhydrin in equal molecular proportions forms colourless prismatic crystals very deliquescent and soluble in alcohol and water insoluble in ether. I t s plntino- and awo-ahlorides are yellow amorphous powders ; its hydroxide is very readily decomposed.Pyyidiiie-netwine l;yd&xIide C5H5( CzE3)NI obtained by heating the above compound with coilcentrated hydriodic acid crystallises in opaque white prisms very soluble in Bding alcohol aud water insoluble in ether. Its platino- and auro-ohlorides are yellow amor- phous powders. Pyridine-muscarhe hydi*ochZoriiie C2H3(OH),*C,H,NCI obtained from pyridine-choline by heating i b with nitric acid (sp. gr. 0.148),forms orange-yellow deliqnescen t laminae ; its platinochloi-idc! ci.ys tallises in orange-yellow needles its nurochloride is an amorphous powdei. The physiological function of the al3ove compounds is perfectly similar in that they all arrest voluntary movements and a t first excite but afterxards paralyse the cardiac pulsations. As regards their toxic efEects they differ considerably in degree.The variation of physiological function with chemical constitution more especially as regards the effect of the substitution of hydrogen-atoms by different groups especially h ydroxyl and the choline neurine and mnscarine radicles is discussed a t some length. By S. HOOGEWERFF and W. A. v. DORP (Rec. Frccv. Chim. 4 125-12s) .-By adding concentrated sulphuric acid to an alcoholic solutioii of the crude quinoline from coal-tar the sulphates of quinoline and isoquinoliae C9H,N are precipitated and by re- pented rectification of the free bases obtained from this precipitate two fractions are obtained one boiling from 230" to 236O which is chiefly V. H. V. Isoquinoline.ORUXNlC CHENLSTRP.7!) quinoline and the other boiling from 236" to 243" containing isoquino- line this is purified by the repeated recrly~t~allisation of its sulpliate from alcohol. The free base melts a t 18-23" and boils at 236-2.37.5" (uncorr.). The suZphate CsH7K,H,SOa forms hygroscopic prisms or tablets and melts a t 205-208". The chromate ( CSH7N),H,Cr,0 forms reddish-yellow needles and is decomposed a t about 150". The pZutinochZori.de ( CSH7N),I3[,PtCI6 + 2H20 forms slender yellowish- red needles ; i t becomes anhydrous a t 110". The picsrnte is but little soluble in alcohol or water and crystallises in yellow needles ; it melts a t 222-223.5'. A. P. Constitution of Quinoline-derivatives prepared from Meta- substituted Amines. By L. GATTERMANN and A.KAISER (Ber. 18 2602-2604) .-Whilst the constitution of quinoline-derivatives pre- pared from ortlio- and para-substituted amines is certain inasmuch as only one substance can be formed in each case ; in those from metn- compounds two quinoline-~erivatives are theoretically obt'ainable according as the linking of the pyridine-ring occurs a t the ortho- or para-position relatively to the substituting group. It seems as though this question can be solved by the use of compounds in which one or the other of these positions is occupied by halogens &c. ChZoronzeth?llquinoZine C9NH,MeC1 [Me Cl = 1 41 is prepared by Skraup's method from parachlorometatoluidine ; it crystallises in colourless needles of quinoline-like odour melts a t 49" and is soluble in water readily soluble in ether alcohol and benzene.The merciiro- chZoride C,H,NCI,HHgCl crystallises in broad needles or tables the platinochloride (C,oH8NCl)2,H2PtC16 forms yellowish-brown tables o r broad needles the picrate crystallises in large brownish-yellow tables nnd melts at 172". When heated with excess of hydrogen iodide dissolved in acetic acid the chlorine is replaced and a methylquinolino obtained. The author cannot as pet speak posit?ivel yas to the identity or non-identity of this with Skraup's " metatoluquinoline." A. J. G. Paraquinaniso'il. By 2. H. SKRAUP (Monatsh. Chem. 6 f60- $84).-Paraquinanisoil is best prepared by heating a mixture OE i 8 grams anisidine 50 grams nitraniso'il 320 grams glycerol and 125 grams sulphuric acid for two hours ; 50 grams more of sulphuric acid are added and the heating continued for two hours longer.The product is then diluted with water distilled with steam and the residue treated with potassium dichromate which causes a precipita- tion of quinanisoil chromate ; this is then purified. Pure quinanisoil forms a. yellowish oil which soon acquires a green then a reddish- violet colour ; it boils with slight decomposition at 304-305" (uncorr.). Sp. gr. a t 20" = 1.542 (water at 20" = 1). Para- puina&oiZ hydrochhride CsNHOMe,HC1 + 2H,O forms colourless prisms readily soluble in cold wnter and hot alcohol insoluble i n ether. The chromate forms long gold-coloured silky needles which when exposed to air lose their lustre and become brownish ; i t is very sparingly soluble in cold water.The nedral sulphate acid sdphate tartrate and other salts are described. The aqueous solutions of the salts all shorn a It loses its water of crystallisation orer sulpliuric acid.SO ABSTRACTS OF CHEMICAL PAPERS. blue fluorescence. Chlorine-water and ammonia act on the salts giving the green colour characteristic of quinine compounds. Paraquinanisoil rnethiodide crystallises from water in long gold- colourcd lustrous needles which melt with evolution of gas at 235". It is insoluble in ether readily soluble in hot water and alcohol. Thalline CSHloNeEO is prepared by reducing quinanisol with tin and hydrochloric acid ; it forms thick white prisms sparingly soluble i n water and light petroleum very readily in alcohol ether and benzene. It melts at 42-43" and boils a t 288" (uncorr.; bar. = 735 mm.). When treated with ferric chloride or other oxidising agents it acquires first a yellow afterwards a dark emerald-green colonr. Silver nitrate produces this coloration with separation of silver. ThaZZine hydrochloride C,H,NO,HCl crystallises in well-formed prisms sparingly soluble in alcohol. The sulphate (with 2 mols. H,O) and other salts are described. Acefylthtrlline CloHl,PU'O*Ac forms clear broad monoclinic prisms which melt at 46-47". Its bolubility resembles that of thalline. Bromine acts on thalline with formation of a compound CloH,Br3NO ; it is a pale yellow powder melting at 19t3-194". MethyZthal7ine CloH,2NOMe is prepared by the action of methyl iodide on thallme. I t forms a thick colourless oil which when kept lwcomes brown ; it boils at 277-278-5' (uncorr.).When a solution in dilute hydrochloric acid is treated with ferxic chloride i t acquires a cherry-red colour which changes to reddiah-yellow when kept long. The hydrochloride and sulphate crystallise in well-formed prisms readily soluble in water Thaliiie hydriodide ( CloH,NO),HI and p a t e r n a r y dirrzethylthall&w iodide CIOH12NOMe21 are formed in the preparation of methylthalline. 'J'he former compound crystallises in flat prisms melting a t 155- 136" imoluble in ethylbenzene light petroleum readily soluble in hot alcohol. The latter compound forms long prisms insoluble in light petroleum readily soluble in alcohol and in water from which i t crystal- lises with 1 mol. H20. I t melts with evolution of gas a t 223-224".Boiling aqueous potash hydrochloric and nitric acids do not act on it. EtlujZtlialliize C,H,EtNO is a thick oil which boils a t 287- 287*5O with slight decomposition. It is insoluble in water very readily soluble in alcohol ether and in mineral acids. Some salts were prepared ; they are very hygroscopic and cryatallise with diffi- culty. EthyZtlLa2lirLe et7~iodide forms white needles readily soluble in alcohol and in water insoluble in ether ; it melts with evolution of ;'as a t 1:31-133° ; when distilled it decomposes into ethyl iodide and t' t hvlt ha1 lin e. Benzyl chloride acts on thalline with formation of a base probably Lenzylthalline ; when treated with ferric chloride it gives tho same characteristic red colour as methyl- and ethyl-thalline. The physiological properties of several of the compounds mentioned in the paper are described.The papei. concludes with remarks on the constitution of quinine. Para- and Ortho-phenylquinoline. By W. LA COSTE and C. SORGER (Aiinaleii 230 1-42).-l'arayhenylquinoline is prepared by N. H. M.ORGANIC CHEMISTRY. 81 the action of sulphuric acid glycerol and nitrobenzene on paramido- diphenyl. The base is precipitnted from the acid solution by the addition of an alkali collected dried and dissolved in warm benzene. The solution is left in contact with solid potassinm hydroxide for some hours and is then filtered. After removing the benzene by distillation. the residue is distilled under reduced pressure. Paraphenylquinoline CgNH,Ph [Ph = 31 melts at 110-111" nnd boils a t 260" under 77 mm.pressiire; its sp. gr. is 1.1945 at 20". It is sparingly soluble in water but dissolves freely in alcohol chloroform benzene and carbon bisul phide. Phenylqninoline is deposited from ether in rhombic pyramids from alcohol in combinations of the pyramid and basic plate and from benzene in twin pyramids ; all the salts are soluble in water fmming fluorescent solutions. The twtratp CgNH,Ph,H,C,HaO + 3H20 crystallises in needles melting a t 153". The dichromate (CgNH6Ph)2,H2Cr207 forms reddish-yellow needles which melt at 136". The methiodide C9NR6Ph,MeI + 2H20 crystal- lises in long needles melting at 194". The ethiodide crystallises with 2 mols. H20 in pale yellow needles and also with 1 mol. H,O in thick yellow prisms.When phenylquinoline is treaked with tin and hydrochloric acid i t unites with four atoms*of hvdroyen to form a tetrahydro-cornpound. The hydrochloride C9NH,Ph,HC1 + 1+H20 crystallises in needles. It is sparingly soluble in cold water and is partially decomposed by hot water. It also dissolves in alcohol and in chloroform. The picrote CgNH,Ph,C6H,(No2),*o~ is deposited from a hot aqueous solution in needles which dissolve freely in alcohol chloroform and benzene. It melts a t 165'. The nitroso-compound C9NHgPh.N0 forms yellow cryst#als freely soluble in benzene and chloroform. The acetyl-derivative C9NHgPhAc crystallises in white silky needles. It melts at looo and is freely soIuble in alcohol benzene chloroform and carbon bisulphide. The benzoyl-derivative forms white plates melting at 137".It is freely soliible in alcohol. Meth y ItetTa~~ydroparaphen~~ Zquinoline hydrochloride The free base is soluble in alcohol ether and hot water. C9NHgMePh HCl prepared by the action of tin and hydrochloric acid on phenylquino- line methochloride is a crystalline substance soluble in alcohol and chloroform. The hydriodide CgNH,MePh,HI resembles the hydrochloride but is more easily decomposed by water. It dipolves in alcohol chloroform and benzene. The methiodide melts a t 194". It crystallises in plates or prisms soluble in alcohol and in chloroform. The substitution products of paraphenylquinoline do not crystal- lise easily and can only be prepared with difficulty in the pure state. The mononitro-derivative CljNHlo*N02 is formed by the action of fuming nitric acid on an acetic acid solution of paraphenylquinoline.It melts at 173" and is soluble in alcohol ether benzene and in hot water. The compound also dissolves in dilute acids and forms two The platinoch loyide easily decomposes. The picrnte melts at 147". 9 VOL. L.82 ABSTRACTS O F CHEMICAL PAPERS. crgstallino platinochlorides of which one is insoluble in hot water. The dinitro-compound is obtained by adding phenylquinoline to fuming nitric acid. It melts at 208" and dissolves in alcohol and benzene. Phenylquinoline dissolves in cold fuming sulphuric acid yielding two isomeric monosulphonic acids. The a-snlphonic acid C,H,NSO + 2Hz0 can be separated from its isomeride by the greater solubility of the latter and also of its ammonium salt in water.The a-acid crystal- lises in lon5 needles soluble in hot water. It does not melt a t 300". When oxidised with potassium permanganate it yields parasulpho- benzoic acid. The ammonium salt of a-phenylquinolinesulphonic acid crystallises in plates which dissolve freely in hot water. Tbe sodiuni and calcium salts dissolve freely in water the potassium and barium salts are sparingly soluble. p$heizylq.uilzoZines.ulpkonic acid Cl5H,NSO3 + H20 dissolves freely in water but is insoluble in chloroform and ether. The ammonium salt crystallises in anhydrous scales. Ortho~henyZqi~inoli?te C9NH6Ph [Ph = 11 is prepared by a process analogous to that employed in the preparation of the para-compound. It is a thick fluorescent oil which darkens on exposure to the air.It dissolves freely in alcohol ether benzene carbon bisulphide and chloraoform and boils between 270" and 276' under a pressure of 80 mm. Tbe salts of the base are soluble in water forming fluorescent solutions. The platinochloride crystallises in needles ; the dichromnte in plates melting at 126" and dissolving in water and warm alcohol. The methiodide forms reddish-yellow plates melting' a t 163". It is freely soluble in water alcohol and chloroform. Ortlzop heny lyzcino- linemethyl platinochloride ( C,NH6PhMe),PtCl6 is a crystalline salt soluble in hot water. It melts at 198". w. c. w. Colouring Matters derived from the Quinoline Bases. By 0. DE CONINCK (Rec. Trau. Chim. 4 58-60).-The reaction of an alcoholic solution of potassium hydroxide on the iodides of the ethyl and methyl derivatives of the quinoline bases by which a red colour- ing matter is produced (Rec.Traw. Chim. 3 337) appears to be general for all the alkyl-derivatives of quinoline as the author has prepared a red crystalline colouring matter from the iodide of the propyl-derivative ; he also confirms the constitution assigned to ths cyanine-derivatives obtained by the action of potassium hydroxide on the iodide of ethyl-lepidine and ethylquinoline (Abstr. 1885 673). Quinoxalines. 111. By 0. HINSBERG (Ber. 18 2870-2875) .- A. P. Dihydro-ox y tolu puinoaaline is obtained by heating ethyl chloracetate (2 mols.) with toluylene- diamine (3 mols.) for several days on a water-bath and is purified by means of its sparingly soluble sodium-derivative. It crystallises in moderately large yellowish needles is readily soluble in hot waterOROANlC CHEMISTRY.8 3 and alcohol moderately in ether and also in alkalis and acid>. The potassium-derivative is readily soluble in water and in potash solution; the sodium-derivative C9H,N20Na + H20 forms lustrous scales and is almost completely precipitated from its aqnems solutions by the addition of soda. Dihydro-oxytoluquinoxaline in alkaline solution is oxidised by atmospheric oxygen to hydroxytol u- quinoxaline ; neutral solutions are not so readily acted on but are also oxidised by weak oxidising agents. When toluylenediamine and ethyl chloracetate are heated together in equal molecnlar proportions the compound C13H16N203 i s produced and may be purified by crysta1lisa.tion from alcohol.It forms colourless lustrous scales melts at l47" is sparingly soluble in water nearly insoluble in ether and moderately soluble in alcohol. Concentrated mineral acids and acetic acid dissolve it readily whilst alkalis dissolve it only on warming. Silver nitrate and nitrous acid oxidise it apparently t o a product melting a t 247-2418". On saponi- fying the substance C13H16N203 with alkali a sparingly soluble acid is obtained crystallising in white needles. The formation and constitu- tion of the above compound may probably be expressed thus :- + EtOH + CTH~(NH~C~),. A. K. M. Papaverine. By C. GOLDSCHMIEDT (Monatsh. Chern. 6 667-701 ; compare Abstr. 1885 1080).-Analyses of papaverine and of a large number of its salts confirm the correctness of the formula C20H,NOa assigned to papaverine by Merck and others.Papaverine cry stallises in rhomhic prisms a b c = 0.3193 1 0.4266. Crystallographic measurements of various derivatives and salts are also given. N. H. 31. Hydrobromapoquinine. By P. JULIUS (Monatslz . Chem. 6 750-753),-Hydrobrornapoquinine C,H23BrN2021 is prepared by heat- ing quinine hydrate a t 100" with three times its weight of water saturated with hydrobromic acid a t 0". It forms a white amorphous powder which melts a t N9-210" is insoluble in water readily soluble in alcohol. The hydrobmnide C19H23BrN202,2HBr + H20 crystallises in groups of white needles readily soluble in water and in alcohol. The pZatinochZoride is described. N. H. M. Cupreine and Homoquinine By 0. HESSE (AnfiaZen 230 55-73) .-The author confirms the accuracy of his former statement (Abskr.1885 276) that homoquinine is a compound of quinine and the new alkalo'id discovered by P a d and Cownley called cupreine. Many of the properties of cupreine have been already described. The base crystallises with 2 mols. H20 which are expelled a t 120". The anhydrous substance melts a t 198'. The alcoholic solution gives a dark reddish-brown coloration with ferric chloride and an intense green coloration m-ith chlorine and ammonia. The neutral salts of cupreine dissolve in water forming yellow solutions which are rendered colourless by the addition of acids. The solutions are not 08.2 ABSTRACTS OF CHEMICAL PAPERS. fliiorescent. The neutral sulphate ( C,H&"02),H,S04 + 6H,O crystallises in needles ; the hydrogen snlphate C1,HnN2O2,HzSO~ + H20 forms flat prisms sparingly soluble in cold water.There are two hydrochlorides C,H2,N,02,HC1 + H,O crystallising in colourless needles and C19H22N,02,SHCl forming pale yellow prisms. The normal platinochloride ( C,9H22N,0,)2,H2PtC16 + 4H20 is amorphous ; the acid salt forms orange-coloured plates. The normal tartrate and thiocyanate are sparingly soluble in water. Cnpreine does not combine with ammonia but it forms compounds with potassium sodium lead and silver. Anhydrous cupreiiie dissolves in acetic anhydride forming a diacetyl compound C19H,Ac2N202 crystallising in six-sided plates. It melts at 88" and is soluble in alcohol ether and chloroform. The hydro- chloride also crystallises in six-sided plates soluble i n alcohol and .water.Cupreine is converted into apoquinine by the action of hydrochloric acid at 140". Cupeine methiodide forms colourless crystals sparingly soluble in cold alcohol and water. The corresponding chloride ClsH,N202,MeC1 and platinochloride Cl9E2,NzO,MeHPtC1 + 2H20 are also crystalline. The sulphate crystallises in needles which are freely dissolved in water. By decomposing this salt with baryta-water the hydroxide is obtained. The aqueous solution of the hydroxide gives a red coloration with excess of bleaching powder in presence of ammonia and a green coloration when ammonia is added to a mixture of the acidified solution and a small quantity of bleaching powder. The alcoholic solution of the hydroxide is fluorescent.Homoquinine is easily prepared by adding ammonia to a solution of equal molecular weight of quinine and cupreine in dilute sulphuric acid and dissolving the precipitate in ether. Homoquinine is not a simple alkaloid but a compound of the composition Cocaine and its Salts. By B. H. PAUL (Pharrn. J. Trans. [3] 16 325-326).-The author's experiments indicate that the solubility of coca'ine i n water is much less than 1 in 700; moreover that on evaporating the aqueous solution the cocaine ia decomposed leaving a gummy mass whieh crystallises and has many properties similar to those attributed to ecgonine (compare Merck Abstr. 1885 997). It yields benzoic acid by the action of caustic soda lime or sodium arbonate bu.t not apparently by the action of hydrochloric acid.It combines with benzoic acid but can b4 separated from the acid by repeated crystallisation from water. Cocaline hydrochloride is only slightly soluble in water from which solution it can be crystallised with water of crystallisation but after prolonged heating on a water- bath it remains in a resinous state for a considerable time a t least. The acetate is very soluble and is diEcult to crystallise owing t o the volatilisation of the acetic acid during evaporation. The solution of the benzoate dries to a thick gummy residue. Ammonia precipi- tates the alkaloid without apparent decomposition and when added in excess does not redissolve it. D. A. L.ORGANIC CHEMISTRY. 85 Alkaloi'ds from Erythroxylon. By C. J. BENDER (Chem. Ce?zti*. 1885 490-493).-The author has subjected the leaves of the coca- plant (Eyythroxylon cocu) to a careful investigation.Besides cocaine he obtained an amorphous alkaloid to which he gives the name cocuzcine and a volatile base which he names erythroxyline. There also seem to be one or two other alkaloids present but the author was unable to obtain them in a pure state or to determine whether they were present in the %resh leaves or formed during the process of extraction. L. T. T. Bases in Jaborandi Leaves. By E. HARNACK (Chem. Centr. 1885 628-629) .-Besides pilocarpine and jaborine Merck (Harnack and Meyer Abstr. 1880 898) obtained from the leaves of the jaborandi a third syrupy alkaloid which yielded a nitrate crystallising in well-defined prisms. The author has investigated bhis alkalo'id to which he gives the name pilocurpidine.Jt very closely resembles pilocarpine both in physiological and chemical properties but it does not give a precipitate with auric chloride. Its formula is CloH14N202. It is easily converted into an amorphous base juboridine C10HlzN203 which resembles jnborine and atropine in properties. Jaboridine appears to be identical with jaborandine C10H12N203 ottained by Parodi (Rivista furm. 1875 3) from false jaborandi (Piper jaborundi) and by Chastaing by the oxidation of pilocarpine with fumiiig nitric acid. The anttior believes that the jaborine hitherto obtained has always contained jaboridine as an impuriby. From the formula and properties of pilocarpine C,IF16N202 this substance would appear to be a methyl-derivative of pilocarpidine ; and the author points out that the latter has the composition OP a di-hydroxy- derivative of nicotine or of an isomeride thereof. Jaboridine is an oxidation product of pilocarpidine formed by the replacement of two atoms of hydrogen in the latter by an atom of oxygen.Alkalo'ids of Fenugreek Seeds. By E. JAHNS (Ber. 18 2518 - 2523).-The seeds of Frigonellu fGenurn grGecum contain t rigonelline and a liquid base identified as choline. Trigonelline C7H7N02 + H20 crystallises in coburless flat prisms of feeble saline taste ; it is readily soluble in water sparingly soluble in cold alcohol insoluble in ether chloroform and benzene ; it is carbonised when heated. The reactions with the various reagents for alkalo'ids are described. The hydrochloride C7H7N02,HCl crystallises in an- hydrous tables ; the platinochloride ( C,H7N02),H2PtC16 crystallises in prisms.Two' atdrochlorides were obtained C7H7N02,HAuC14 crystallising in four-sided plates or flat prisms and melting at 198" and 4C7H7NO2,3HAuCl4 crptallising in slender needles and melting at 186". A. J. G. L. T. 2'. Products of the Action of Hydrochloric Acid on the Albumi- noids. By J. B ORBACZEWSKI (Monatsh. Chem. 6 639-650).- When 500 grams of elastin (previously freed from fat by extracting the finely powdered substance for two weeks with ether) are boiled for 72 hours with I litre of hydrochloric acid diluted with an equal86 ABSTRACTS OF CHEMICAL PAPERS. volume of water and 25 grams of zinc chloride a small quantity of ammonia is given off and the solution after precipitation of the zinc by hydrogen aulphide is found to contain leucine glycocine and tyrosine.Other compounds are also present but could not be isolated. The formation of these substances and the absence of glutaminic and aspartic acids and of hydrogen sulphide from the prodnet of %he reaction show that elastin does not belong to the'same class of compounds as do albumin and keratin. It also differs from the horn substances and all other albuminoids which have as yet been examined. PJ EL 11.3s ABSTRACTS OF CHEhlICAL PAPERS.Organic Chemistry.Melting and Boiling Points of Cyanogen Bromide. By E.3fULDER (Rec. Trav. Chim. 4 151-152).-Cyanogen bromide be-comes somewhat transparent a t 16" but melts a t about 52' it boils a t61.3" (corr.).A. P.Normal Cyanuric Acid. By E. MULDER (Rec. Tmv. C'him. 4,91-1Ol).-In continuation of his researches on the derivatives ofnormal cyanic acid (Abstr. 1883 304 and Rec. Tmv. Crlziliz. 2 133)the author finds that both normal ethyl cyanurate and the crudeprodact a(CN*OEt*C,H,O) (Abstr. Zoc. cit.) when saponified withaqueous soda at the ordinary temperature and then neutralised withltydrochloric acid yield a white crystalline deposit haring the compo-sition C3N303HEtZ and probably the constitution C.3N3(OEt)2*OH orC,N,(OEt);CONH. Normal ethyl cyanurate yields isoqanuric acidon acidification with hydrochloric acid normal cy;innric aqid seemingt o be incapable of existing in the free state. The author considersthat Wurtz's diethglcyanuric acid is most probably identical withthat obtained by Habich and Limpricht and has the constitutionc:,O,(NE!t), KK.A. P. *Additive Compounds of Normal Ethyl Cyanurate with'Cyanogen Bromide. By E. MULDER (Eec. Trac. Claim. 4 147-150) .-On treating normal ethyl cyanurate with excess of cyanogeiibromide an additive compound C,N30,Et,2CNBr is formed. I t I Sliquid a t the ordinary temperature crystallising a few degrees lower.The author considers that i t has the constitutionCBr(0Et)N C(0 Et)NC'N< CBr( OEt) --N (CN ) >When heated for several hours a t 125" until no further pressure isdeveloped a yellow liquid is formed which by continued heating a tthe same temperature in an open tube is converted into a hardand vitreous niass.On treating cyanogen bromide with excess of norms1 ethyl cyanurate,a second additive compound seems to be formed having the composi-tion C3N3O3Et,CNBr.A. P.Action of Ammonia and Amines on Methyl Thiocyanurateand Cyanuric Chloride. Normal Alkyl Melamines. By A. W.H.OFMANX (Ber. 18 2755-2781).-The final product of the action ofammonia on methyl thiocyanurate is melamine but by modifying theconditions of the experiment either of the intermediate products maybe produced. To obtain the primary aqnido-base C,N,( SMe)2.NH,the methyl tliiocjanurate is digested with a moderate excess of strongalcoholic ammonia for about five hours a t 100". The purified basecq-stallises from boiling alcohol in rhombic plates melting at 200; iOROAWC CIHIEJITSTKT. 39is readily soluble in hot more sparingly in cold alcohol and is notcluite insoluble in wat8er.I t s solutions give no reaction with vegetablecolours and no sulphur reaction with alkaline lead salts. The basedissolves sparingly in hydrochloric acid and is reprecipitated on theaddition of water. On boiling i t for a. long time with hydrochloricacid it is decomposed with production of mercaptan ammonia aridcyanuric acid. The platinochloride and aurochloride,are described. The secondary amido-base C3N,(NH2),.SMe is obtainedon digesting methyl thiocyanurate with alcoholic ammonia for aboutfive hours at 160". It differs from the primary basc by its readysolubility in water and more sparing solubility i n alcohol ; it melts a t268" dissolves readily in hydrochloric acid and yields a platino-chloride (C,H,N5S)2,H2PtC16.When boiled with hydrochloric acid itgives the same decomposition-products as the monamido-compound.The tertiary amido-buse meZumine can be obtained in nearly theoreticalamount by heating methyl thiocyanurate with an excess of strongaqueous ammonia for several hours a t 180". I t s properties agree wizhthose assigned to it by Liebig (Annnlen 10 el). The author has alsosucceeded in obtaining two plntinochlorides from it,( C3H,N6),H,PtC16 + 2H20 and C3H,N,H2PtCI (?).The amines are found to react with methyl thiocyanurate in the sameway as ammonia. The primary methy lamido-base C3N3( S3Je),*NHMe,i3 produced on heating methyl thiocyanurate with a 33 per cent.aqueous solution of methylamine for several hours at 100". It isreadily soluble in alcohol and ether and crystallises in well-formedprisms melting a t 174-175" ; it forms crystalline salts with hydro-chloric nitric and oxalic acids mid also yields a sparingly solublei'latinochloride and an aurochloride.Hydrochloric acid deconiposesthe base a t 100" into ethyl mercaptan methylamine and cyanuric acid.The secondary methylarnido-base C,N,(NHMe),*SMe is produced simul-taneously with the primary compound. It is very readily soluble inalcohol less so in ether and is best crystallised from a large bulk ofboiling water from which it separates in slender needles meltiug a t144". I t s salts are mostly very readily soluble the nitrate crystal-lising best ; the platinochloride is very sparingly and the aurochloridemoderately soluble.The base is decomposed by hydrochloric acida t 200" and yields the same products as the primary base.The tertiayy naethy lamido-base trimethylmelamine is prepared byheating methyl thiocyanurate with 33 per cent. aqueous methylaniinetor several hours a t 180" ; or a mixture of the primary and secondarybases may first be prepared at a temperature of 130-140" and thisthen heated at l70-18O0 with more methylamine. Trimethylmel-amine is very readily soluble both in water and in alcohol and theauthor has not succeeded i n obtaining it quite pure ; its hydrochlo-ride nitrate and sulphate are also extremely soluble the oxalate moresparingly so. Like melamine i t yields two platinochlorides,[ C,N,( N HMe)3]2,H2P t C Is and C3N3( NHMe),H,Pt C1,40 ABSTRACTS OF CHEMICAL PAPERS.By the action of ammonia on cyanuric chloride Liebig (Atznalen,10 45) obtained the compound C3H4N5C1 which he termed chloro-cyanamide but which the author shows to be C3N3(NHz),Cl that isan intermediate product between cyanuric chloride and melamine,and it may in fact be converted into the latter by a few hours'heatinq a t 100" with strong aqueous ammonia.A nearly theoreticalyield of melamine may likewise be obtained directly from cyanuricchloride. A solution of methylamine in absolute methyl alcohol like-wise reacts with cyanuric chloride with production of dimeth yZamido-cyariuric chloride C3N3( NHMe)?Cl; it is nearly insoluble in water,alcohol and ether soluble with slight decomposition in boiling glacialacetic acid from which hot water precipitates it in needles melting a t241" with decomposition.I n acid solutions the chlorine soon becomesreplaced by hydroxyl. When dimethylamidocyanuric chloride is heatedwith a solution of methylamine in methyl alcohol for a few hours at loo" it is converted into trimethylamine; this when heated a t 150"with hydrochloric acid splits up into methy lamine and cyanuric acid.On heating dimethylamidocyan uric chloride with aqueous ammonia a t150° the chlorine is displaced and a base produced which is withoutdoubt diniethyhnelumine C,N,(NHMe),*NH ; its salts are soluble thesulphate crystallising in six-sided plates and the oxalate in rhom-bic crystals ; i t yields two platinochlorides C,Hl,N6,H2PtCl6 andThe dimethylainidocyanuric acid C,N,(NHMe)2*OH obtained fromdimethylamidocyanuric chloride (see above) by the action of an acid(or of water at ZOO") is separated from its hydrochloride as a whiteindistinctly crystalline precipitate which is almost insoluble in boilingwater insoluble in alcohol and ether; its platinochloride has theformula ( C5 H BN50) ,HZPt C 1,.D irneth y lamidocy anuric acid formssalts both with acids aud with bases ; the hydrochloride and nitrateare crystalline and soluble without decomposition ; the sodium saltand the methyl salt (obtained from dimethylamidocyanuric chlorideand sodium methylate) crystallise in prisms.The mother-liquors from the preparation of dimethylamidocyanuricchloride contain (besides methylamine hydrochloride) a crystallinesubstance found to be methylamidonaetiioxycyanzLric chloride,MeO*C3N3C1*NHMe ;it forms acicular crystals melting at 155" is soluble in alcohol andether also in hydrochloric and nitric acids with formation of crystal-lisable salts.It may be boiled with acids without parting with itschlorine.Attempts to obtain hexamet?ylnaelam ine C3Ns(NMe2) by heatingmethyl thiocyanurate with dimethylamine were without success butits hydrochloride may be obtained by heating a mixture of equalweights of dimethylamine hydrochloride and cyannric chloride aslong as hydrogen chloride is evolved. The base ci.ystallises in needlesmelting at 171-172" ; its platinochloride and aurochloride are de-scribed.When it is heated with hydrochloric acid a t 200" it splitsup into cyannric acid and dimethylamine.Methyl thioayanurate is acted on by ethylamine in the same way as(C5H&),H,PtC16ORGANIC CHEMISTRY. 41by ammonia and by methylamine with formation of correspondingproducts. The primary et l ~ y Zir mid o- bn se C3N3( S Me) 2* NHE t cry stallisesfrom boiling dilute alcohol in lustrous needles melting a t 114" issparingly soluble in boiling water readily in cold alcohol ; i t yields aplatinochloride of the formiila ( C,H,2N4S,)z,H,PtC16. The secondaryetlr y/u)nido-base C3N3(NHEt),-SMe forms needles melting a t 83-8 &' ;its hydrochloride is crystitlline extremely soluble in water less so inalcohol aud insoluble in ether ; the nitrate is more sparingly soluble ;the oxalate forms slender very soluble needles whilst the snlp'iatedoes not crystallise.A plat inocliloride aurochloride and stanno-chloride have also 1 been obtaiued. The tertiirry eth!/Zitt,iido-Case,triethy Zmelainine CJN3(NHEt) can be obtained both from methylthiocy anurate and from cyanuric chloride and forms prisms meltingat 73-74'. It is soluble in alcohol ether and benzene ; the platino-chloride ( C9H,N6),H2PtC1 and aurochloride are described arid alsoa compound with silver nitrate ( C9Hl~N&,AgN03. Triethjlmel-amine is decomposed By hydrochloric ac4d at 150' into cyanuric acidand ethylamine.Hexethylmelamine C3N3(NEt2) is formed by the action of diethyl-amine on cyanuric chloride.The platinochloride ( C,H&6)2,H,Pt~16,and aurochloride CI5H,K6,HAuCl4 are described. Hydrochloric acida t 150" decomposes the base into diethjlamine and ojanurio acid.In order to shvw that the higher amines also react with methylthiocyanurate this latter -substance was digested with alcoholic amyl-amine at 10U". The primary anrylamido-base,. C3N,(SMe)z*NHC5H11,obtained crystallises in clusters of silky needles melting at 96".Hydrochloric acid decomposes- itL slowly a t the ordinary tempeiature.When the reac-tion bakes place at 200" the secondary base C3N3(NC5H,),*SMe is ob-tained and forms colourless crystals melting a t 106-107' ; itsplatrinoch1oride has the formula (~l~H,3~,S),HzPtC16. If the reactiontakes place a t 250° the tertiary base trip3iperidylnrelamip.Le,Piperidine also reacts with methyl thiocyanurate.C3&( N C5&3)3,is produced and crptallises in small needles melting at 213" ; it dis-solves rcadily in acids and yields a sparingly soluble platinochloride,( c,eH,N6)2,HzPtC16. Hydrochloric acid decomposes the base a t 150"into piperidine and cyanuric acid.Tripheitylmelamiwe CJN3(NHPh) may be obtained by the actionof aniline on methylthiocyanurate or cyanuric chloride and hexa-phenylmelamine C,N3(NPhZ) may likewise be obtained from dipheriyl-amine and cyanuric chloride.Alkyl Isomelamines derived from the Alkyl Cyanamides,and the Constitution of Melamine and of Cganuric Acid.A.K. M.been proposed for melamine the former is the one which most simplyexplains the formation of melamines and of mercaptan by the actionof ammonia or amiies on methyl thiocyanurate and of melamines an42 ABSTRACTS OF CHEMICAL PAPERS,lrydrocliloric acid from cyanuric chloride and ammonia or nmines(sse last Abstract).The second formula on the other hand wouldnecessitate the assumption of complicated molecular changes ; in theformation of the hexalkylmelamines by the action of a secondarpamine one alkyl group of the latter must be assumed to detach itselffrom one nitrogen-atom aud to attach itself to another and the ->NMe should resulting hexalkylmelamine NNe C<NMe.C(N31e) NMeG (NAIe)be split u p by the action of water into methyl cyanurate and methyl-amine ; cyanuric acid and dimethylamine are however produced.The formation of the piperidine-derivative of melamine is met bysimilar difficulties if the imido-formula be taken as correct whilst thenmido-formula readily explains all the reactions.Alkylmelamines corresponding with ail imido-melamine can how-ever be obtained but these yield no cyanuric acid; they split u pinto ammonia and alkyl cyanurates.l'rimethytisomelamine C3N3Me3 (NH) has been previously men-tioned by the author (Eer.3 264) and by Bauniann (Ber. 6 1372).I n order to obtain it monomethylthiocarbanride is treated with drymercuric oxide in absolute alcohol the methylcyanamide first formedr:x pidlg polymerising to trimetl-tylisomelamine. This i s very readilysoluble in water and alcohol insoluble in ether the solution exhibit-ing a distinctly alkaline reaction.It crystallises in well-formedneedles melts at 179" and readily sublimes ; the platinochloride,chN6H12,H2PtC16 and aurochloride C&GH,,H&.u?CI& are described.Hydrochloric acid at 100" decomposes the base into ammonia aridmethyl isocyanurate ; this decomposition takes place in stages and theauthor has succeeded in isolating one of the two intermediate pro-ducts namely NH C3N,Me,02; it forms a n aurochloride,CsHioNdOa HAu C 1,and a hydrochloride C6HloN402,HC1.Triethy~isometamine C3N3E t3( NH) has also been previouslymentioned (Hofmann Ber. 1 27). It forms stellate groups ofneedles melts at 92" and crystallises from water with 4 mols. H20.Platino- and auro-chlorides are described. It is decomposed by acidsin the same way as the trimethyl-derivative and here again the oneintermediate product HN C3N,Et30 can readily be isolated.In further support of the amido-nature of melamine the authormentions its decomposition by water into ammonia and cyanuric acid,the constitution of which he indicates to be HO*CeN.C(oH)>N.He points out that the formation of cyanuric acid from carbamidedoes not prove it t o have the constitution CO<NH,CO>NH as theconstitlution of carbamide has not been definitely established (comparethis Journal 1866 161). There also appears to be little ground forthe assumption of the iso-nature of cyanic acid. On the contrary theformation of cyanates from potassium cyanide the conversion ofxmmonium cyanate into carbamide and of cyanic acid with theelemmts of water into ammonia and carbonic anhydride run perfectlyN-C( OH)NH*CORGAXIC CHENIYTRY. 43parallel with the formation and behaviour of thiocjanic acid thenormal constitution of which is not doubted.The formation of alkylisocyanurntes from cyanuric acid may be accounted for by the factthat t,he normal ethers may be readily converted into the iso-ethers(Rer. 3 272 ; Rec. Tmv. Chinz. 1 191). The production of cyanuricchloride from phosphorus pentachloride and cjaiiuric acid and there-formation of the latter by the action of water on the chloride(Annalen 116 357) also support the view that cyanuric acid containsli-ydroxyl-groups. Phosphorus pentachloride acts in the same way onthe normal methyl salt of cyanuric acid with formation of methylchloride phosphorus oxytrichloride and cyanuric chloride.Methylisocyanurate however gives a very different reaction when heatedwith phosphorus pentachloride hydrochloric acid phosphorus tri-chloride and trichioromethyl isocyanui*ate,N(CH2C1)*CO>N(CH2C1),co<N(CH2Cl)*C0being formed. A. K. M.Allyl-sulphuric Acid. By F. SZYMAKSKI (AnnuZen 230 43-50).-The preparation of rtllyl-sulphuric acid by the action of sul-pbnric acid on allyl alcohol was first described by Cahours and Hof-Inann (Ani-,aZen 102 293). Beilstein and Wiegand (Abstr. 1885 740)have recently stated that allyl alcohol is completely carboriised bysulphuric acid. The author finds that this is not the case when thealcohol is slowly added to the acid.The best results are obtainedwhen the acid is diluted with an equal volunie of water. The bariumsalt has been previously described by Cahours and Hofmann (Zoc. cit.).The stroritiurn salt forms anhydrous rhombic prisms soluble in waterand in alcohol. The anhydrous calcium salt crystallises in quadratic1,lates. The copper salt crystallises in needles with 4 mols. H,O.It is soluble in water and alcohol On saturating allyl-sulphuric acidwith lead carbonate a basic salt (C,H,SO&Pb + PbO + 6H20 isobtained which is soluble in water.The magnesium saZt Mg(C3H5SOA)2 + 4H20 crystallises in trans-parent needles soluhle in water. The potassium arnmoniuni andsodium salts are hygroscopic and soluble in water. The f e w o u s saltforms quadratic plates soluble in alcohol.w. c. w. It is hygroscopic.Methylene-derivatives. By 1;. HENRY (Conzpt. rend. 101,599-GOO).-Diethoxy,izethane CH,(OEt) obt'airied by the action of diiodo-methane on sodium ethoxide is a colourless mobile limpid liquid with:L pungent taste and a peculiar agreeable odour quite different fromthat of acetsl. It is only slightly soluble in vc-ater and quite iiisolublein a concentrated solution of calcium chloride. It boils a t 82-83"under a pressure of 760 mm. ; sp. gr. a t 16.7" compared with the watera t the same temperature = 0.8275 ; vapour-density 3.44.C~I~Zorobromornetl~ane CH2C1Br obtained by the action of excess ofbromine on chloriodomethane is a mobile colourless liquid with auagreeable ethereal odour and a sweetish pungent taste.It is insolu-IAe in water does not decompose when exposed to light and boils a44 ABSTRACTS OF CHEMICAL PAPERS.68-69" under a pressure of 765 mm. ; sp. gr. at 19" compared withwater at the same temperature = 1.9907 ; vapour-density 4.43.R~orniodornethutze CH2RrT is obtained by the action of a limitedquantity of bromine or better of iodins chloride on diiodomethane. Itis a colourless liquid which becomes purple when exposed to light. Ithas an agreeable etherealsodour and a sweetish bitter taste is insolublein water and boils a t 138-140" under a pressure of 754 mm. ; sp. gr.a t 16.8" compared with1 water at tihe same temperature = 2.9262;vapour-density 7.65. C. H. B.Sulphatea of some Carbohydrates. By M HONIG and S.SCHUBERT (Mm~atsli.Chern. 6 708-749).-By the action of sulphuricacid on1 cellulose a t different temperatures varying from 7" to 40°,and subsequent treatment of tbe product with barium caiBbonate saltswere obtained which contained the same percentage of barium butwhich possessed a ,greatly varying rotatory p o m r ( [ a ] j = - 3.65" to + 72.99"). Further experiments made t o ascertain the influence ofthe quantity of acid used showed that salts varying in composition,but having the same rotatory power can be formed. Prolongedaction of sulpl~uric acid causes an increase of. barium in the salt aswell as an increase of rotdory power. When the action is allowed totake place at a& low temperature the product coiitains salts varyingmore from one another than if the reaction takes place a t a highertemperature.The following salts were separated :-They form white or yellowish-white voluminous powders with varyingsolubilities io water; the lead and calcium salts are similar. Thehydrogen su1phate.s form white amorphous very hygroscopic com-pounds which dissolve very readily in water and in alcohol ; they areinsoluble in ether. The aqueous solution decomposes slowly at theordinary temperature more quickly when boiled losing sulphnric acid.similar way ;but the action is much slower than in the case of cellulose.Theproducts have the same general formula C6,Hlo,0,-,( SO,) as thoseobtained from cellulose but turn po1arised:liglit to the right.When the hydrogen sulphates are boilea with alcohol they lose allthe sulphuric acid leaving modified forms of cellulose and starchrespectively. N.H. M.Organic Iodides of Nitrogen. Rg; F. RASCHKG (AnnuZen 230,221-224).-RfeOhylnmiiie~ hydrochloride is completely converted intom e t h y Zdiiodamine Nl,Me when the theoretical quantity of iodine(dissolved in potassium iodide) is- added to a solution of methylaminehydrochloride and sodium hydroxide MeNH2,HC1 + 41 + 3NaOH =NLMeI + NaCl + 2NaI -!- 3H,O.Dimeth.yZiodumine,NMezI is obtained from d imethylamine by a similarreaction as a yellow precipitate. It is sparingly soluble i n alcohol andether. I t soon decomposes and acquires a dark colour. A solution ofpotash changes tthe colour of the compou a d to greenish-yellow withoutAnhydrous starch is acted on by sulpliuric acid iORGASIC CBEMISTRI'.45affecting its composition. Iododimethylamine and di-iodomethylaminedecompose without exploding when they are touched by a hot body.Etkyldi-bdamine and diethyliodamiiie are obtained by sirnihrreactions in the form of brick-red and orange-coloured precipitates.They rapidly decompose into iodoform and a dark blue liquid. w. c. w.Synthesis of a Ketone from (Enanthylidhe. By A. &I. &$HAL(J. Pharm. [ 5 ] 811 155-158).-AmyZ meihyl ketone C5H,*COMe isobtained by dissolving mnanthylidine in sulphnric acid diluting withwater and distilling. It forms an oily liquid of pungent odour boilsa t 147-148" under 759.2 mm. pressure shows the property of aketone jieldiiig a hydrogen sodium sulpbite compound &c. and onoxidation is converted into aceticband valeric acids..A. J. G.Action of Bromine in Alkaline Solution on Amides. ByA. W. HOFMANN (Ber. 18 27~-2741).-Chloracetamide -is acted onby bromine in alkaline solution with formation of a compouud,CH,CI*NH*CO*NH.C,H,CLO. This substance me1 ts at; 180" and is spar-ingly soluble ; it is decomposed by acids or alkalis into chloracetic andhydrochloric .acids,*carbonic anhydride ammonia and met haldehyde.Ethoxyacetamide when treated with an a l h a h e solution of bromine,yields a compound EtO*CH~.*NH*CO*NH*C,H?O.OEt. It crystallisesin cdcmrless needles which melt at 80° and is decomposes by acidsand alkalis into et,hoxyacetic acid alcohal ammonia and mcth-aldehyde.When 1 mol.of phenylacetamide is acted on by 1 mol. bromine and4 mols. of a 5 per cent. solution of alkali and then distilled in steani,much benzylamine is obbained together with some bromobenzylamine,which may be 4 convert,ed by (the action of sodium amalgam intobenzylamine.IJy drocinnamamide is prepared. by heating ammonium hydrocinna-mate for five hours a t 220" ; it forms small thin needles which melta t 105". When treated with bromine in -alkaline solution and thendistilled with steam it yields a .mixture of phenylethylamine and abromine-derivative C8H8Br*NH2 which boils at 252-254". To obtainpure phenylethylamine the mixed product contained in the distillateis treated with sodium amalgam.The yield is about 60 per cent.of the theoretical..The yield is about 30 per cent.N. H. M.Action of Ethyl Acetoacetate on the. Amidines Pyrimidines,By A. PINNER (Bey. 18 2845-2852).-Jn order to test the generalcharacter of this -reaction (Abstr. 1885 158 751) the author hastried to prepare the corresponding pyrimidines from various amidines,and he finds that with the exception of formamidine all t h e nmidinesexperimented with are capable of yielding pyrimidines. Whenformamidine hjdrochloride (25 grams) is treatled with the calculatedamouirt of ethyl azetoacetate a 10 per cent. solution of sodiumcarbonate added and the whole allowed to remain several weeks asubstance is obtained which crystallises in long broad silky needles,melting at 70-71" is readily soluble in the ordinary solvents wit46 ABSTRACTS OF CHEMICAL PAPERS.the exception of water and has neither acid nor basic properties ; itscomposition indicates it to be ethyZ cyanoacetoacetate,CHS.C(CN) CH*COOEt.Acetamidine reacts readily with ethyl acet oacetate yielding di-nl.ethyZhycZroz~~?/1.imidine CMeqN C(oal>CH ; this forms lustrousneedles melts at 192" is readily soluble in water and alcohol sparinglyin ether and cold benzene.EtJi yZn7p,thyZhy~rox~pyrimI'dine CiHloN,O,obtained from propionamidine and ethyl acetoacetate forms ,slender,white needles melting at 160" and readily solnble in water andalcohol. The hydrochloride C,HloN20,HCi crystalliees in thickprisms melts at 240-2413' with decomposition is very readilysoIubIe in water and somewhat less so in alcohol.The platino-chloride forms thick yellow prisms melting a t 236" with decom-position.Succinimidine rezcts with ethyl acetoacetate wihh elimination ofonly one molecule of water and production of a compound,N -CMeC4HJT,HZ*C4H,O2.A description is given of some more derivatives of phenylmethyl-liydroxypyrimidine (Zoc. cit.). When a solution of silver nitrate isadded to a hot aqueous or alcoholis solution of the pyrimidine aclear solution is obtained from which ammonia throws down a white,granular precipitate of the silver salt ; i t is extremely soluble in excessof ammonia and in nitric acid. On adding bromine to a solution ofphenylmethylhydroxgp.yrimidine in chloroform four atoms of thehalogen are taken up with formation of the compound CllH10N20Br4,which crjstallises in yellow lustrous needles melting a t 245' withdecomposition.It dissolves slowly with decomposition when boiledwith alcohol and on cooling colourless transparent needles of thecomposition C1,H,N2Br separate melting a t 260". Phenylmethyl-hydroxypyrirnidine is not acted on by nascent hydrogen but maybe reduced by distillation with zinc-dust the pheny Znzethy Zpyri-midine CI,HI,Nz obtained melts a t 74-78' and yields a platino-chloride melting at 190" with decomposition. Chromic acid andalkaline potassium peymanganate have little action on the hydroxj-compound whilst acid permanganate oxidises i t readily with produc-tion of bcnzamide.Attempts to reduceg~henylmethy7c7~Zoropyi.imidiize CI1H9N2Cl (Abstr.,1855 159) by the action of sodium amalgam on its alcoholic solu-tion yielded phemylmethy k e t h o x ~ ~ y r i m i d i i z e CIIH9N2*OEt which how-ever is more readily obtained by boiling the chloropyrimidine withsodium nlcoholate.It forms thick colourless transparent prisms,melting a t 30-31° boils a t 300-301" is insoluble in water andihlkalis readily soluble in alcohol ether and acids. The hydro-chloride C,H,N20Et,HC1 + 2H,O crystnllises in slender white verysoluble needles and when dried melts a t 148-149" ; it breaks up atabout 150" into phenylmethylhydroxypyrimidine and ethyl chloride.The plutinochloride (C,H,N20Et)2,HzPtC16 melts a t 197" with decom-position. The hydriodide Cl,H9N20Et,HI( + &HzO 3) forms yelloORGANIC CHEJIISTRY. 47prisms or long needles very sparingly soluble in cold moderatelysolnble in hot water ; i t meIts a t 143.5".Phenylm ethy~~lyrin2idinean~~lide F,H,N,*NHPh is obtained on heat-ing the chloropyrimidine with a,niline.The hydrochloride formssmall slender needles which blacken a t 236" and melt with decompo-sition a t 240". The free base melts a t 150-153" and its nitrate at85-87". A. K. If.Condensation of Acetoacetates with Bibasic Acids. By.R. FITTIG (Bei-. 18 2526-2527).-Ethereal acetoacetates condensereadily with bibasic acids with elimination of 2 mols. HzO. Withsuccinic acid and ethyl acetoacetate %I crystalline compound CloH1205,melting a t 75-5-76' is obtained. This is the monethyl salt of abibasic acid C,H805 ; the free acid is crystalline melts a t 199-200°,and loses carbonic anhydride a t a slightly higher temperature.Fromethyl acetoacetate and sodium pyrotartrate the monethyl salt of thehomologous acid C9H1005 which melts a t 194O is obtained. Theinvestigation of these acids is proceeding.Condensation of Aldehydes with Bibasic Acids. By R.F~TTIG (Ber. 18 2523-2525) .-By the condensation of succinic acidwith acetaldehyde propaldehyde isobutaldehyde valeraldehyde orcpnanthaldehyde a single lactonic acid .is formed in each case inaccordance with the equation XmCHO + COOH*CH,-CH,*COOH =< ~ ~ ~ ~ 2 > C H * C O O H ; with pyrotartaric acid on the other hand,A. J. G.two isomeric lactonic acids,< ~ ~ ~ ~ z > CMe-COOH and < &,:%t>CH-COOH,are obtained. Benzaldehyde and pyrotartaric acid give i n addition tothe acid described by Penfield a second isomeric acid melting a t123.5".These lactonic acids when heated lose carbonic anhydride,arid are converted mainly into monobasic acids the isomeric lactonesbeing obtained as bye-products. The constitution of these unsaturatedacids is still uncertain except in the case of the acid C6H1,02,derived from the lactonic acid prepared from propaldehyde andsuccinic acid which has been shown to be identical with hydrosorbicacid.Salicylaldehyde and succinic aldehyde yield a dicozcniarin,very similar in chemical behaviour to coumarin.succinic aldehyde yield two acids of the formubAnisaldehyde andMeO*CsH4*CR CH*CH,*COOH andMeO*CGH,*CH CH.C(COOH) CHC6H,*OMerespectively. No description is given of these su bstnnces.A.J. G45 ARSTRACTS OF CHEMICAL PA1 ERS.Tartronic Acids. By A. PrNNEn (Rer. 18 2852-2854).--Theauthor finds that no better jield of this acid is obtained by Baponi-fying trichlorolactic acid directly,with haryta water and he preferst o use the method previously given (Abstr. 1885 759). Experimentsin which other precipitants (in the place of barium chloride) wereemployed gave unsatisfactory results.In the preparat>im of ethyl tartronate only a part of the acid isconverted into normal ethyl salt some hydrogen ethyl-derivatirnbeing also probably formed. The normal salt boils .at 222-225" isreadily decomposed by water and is readily converted into the amideby the aktion of ammonia.The only secondary products produced in the preparation oftartronic acid which the author has been able to confirm are di-chloracetic acid and a small quantity of oxalic acid.Tartivnnmide OH*OH ( CON Ha)z forms six-sided sales melting at195-1 96" with decomposition.I t is sparingly soluble in cold water,moderately in hotr and sparingly in alcdhol.Malic Acids. By H. VAN'T HOFF jun. (Bey. 18,2713-2714; corn-yare Abstr. IF8.5 1202).-Inactive mdlic acid from monobromo-succinic acid prepared from fumaric acid and hydrobrsmic acid(identical with that examined by Anschutz &id. p. 1049) and aninactiue nialic acid obtained by the action of soda and water ontnaleic acid are shown by crystallographic measurements to beidentical with .Pasteur's acid.A.K. M.N. H. M.Decomposition of Malic Acid obtained from Fumaric Acid.By G. J. W. BEEMER (Rec. Tmv. Chim. 4 180-182).-It is usuallyst,ated that the inactive malic aoid obtained from fumaric.acid is adistinct modification and cannot be decomposed into the lavo- anddextro-acids. :This is however not the rase as by the fractionalcrystallisation of its cinchonine salt it malic acid is obtained whosehydrogen ammonium salt shows a specific rotary power identical withthat of the corresponding salt of the natural acid (Ber.,.13 352).Constitution of Isosaccharic Acid. By H. KTLIANI (Bey. 18,2514-2518).-In the author's last paper on this subject (Abstr.,1885 'i44) the position of m e of the hydroxyl-groups was still leftunsettled ; he now shows that the dihydroxypropenyltricarboxplicacid obtained by oxidising isosaccharic acid (Zoc. cit.) yields a dihy-droxj-glutaric acid not identical with the /%V-dihydroxy-acid ; thismust therefore be the a-y-acid,A.P.COOH*CH( OH).CH,*CH(OH) 'COOH.From this isosaccharic acid must have the constitutionCOOH*C(OH) (CH2*OH)*CH,*CH( OH) *COOH.a-l- DiAydmzyg)Iutaric acid is best obtained by heating dih ydroxy-propenyltricarboxylic acid for four hours at 120" I t crystallises incolourless prisms begins to soften at 106" with loss of water andonly fuses completely at a considerably higher temperature; it iORGANIC CHEMISTRY. 4 9nearly insoluble in ether readily soluble in alcohol and water. Thecalcium salt C5H606Ca -k 3H20 forms white nodular crystals sparinglgsoluble in water.S- -Dihy droxyg Zutaric acid COO H*CH,*CH( OH) *CH( OH) *C 00 H,is obtained by converting glut'aconic acid,COOH-CH,*CH CH-COOH,into dibromoglutaric acid by treatment with bromine and boiling theproduct in dilute solution for two hours and a half with calcium car-bonate.It crystallises in needles or six-sided plates melts a t 155-156' and is sparingly soluble in alcohol very readily sduble in water.It is further distinguished from the a-yacid by the ready solubilityof its calcium and cadmium salts. A. J. G.Oxidation of Benzene. By J. G. HOLDER (Arner. Chew,. J. 7,114-116).-When treated in the cold with manganese dioxide and sul-phuric acid benzene yields carbonic anhydride and a small quantityof benzoic acid ; neither formic nor phthalic acid could be detectld.By gradually adding sulphuric acid to benzene and lead dioxide i Lvigorous reaction occurs and carbonic anhydride and benzoic acidsi r e formed ; no succinic acid was observed.Potassium permanqanateacts very slowly ; lead dioxide and boiling dilute nitric acid yield onlyoxalic acid ; chromic acid yields only carbmic anhydride. H. B.Parachlorometanitrotoluene and its Reduction-products.By L. GATTERMANN and A. KAISER (Ber. 18 2599-2602).-Thiscompound was prepared from metanitroparatoluidine hydrochlorideby treatment wit8h cuprous chloride and sodium nitrite. It crystallisesin yellow needles melts a t 7" to a strongly refractive golden-yellowoil of sp.gr. 1.297 at 22" (water at 62" = l) and boils at 260-261'under 745 aim. pressure. I t seems to be identical with the a-nitro.compound obtained by Wroblewsky by the direct nitration of pam-chlorotol uene.Parnc hlorometanityot oZuid ine C,H,MeC l-NH2 obtained by reductionof the nitro-compound crystallises in thin colourless tables melts at,29-30" and has an odour similar to that of naphthylamine. Thehydrochloride crystallises in colourless needles the salphate in broar 1needles or plates ; the acetyl compound crystallises in colourlessneedles and melts a t 96'. A. J. G.Action of Phenyl Cyanate on Polyhydric Alcohols. By H.TESMER (Ber. 18 2606-2610 compare Abstr. 1885 774) .-Theauthor coutirrns the formula C6H90 (O*CO*NHPh) previously givenfor t,he quinovide of phenylcarbaniic acid.Quercyl penta~heriylcnrba.nznte C6H7( O*CO.NHPh) is prepared byheating quercite and phenyl cyanate in sealed tubes at 165" for twohours; it is an amorphous white mass melts somewhere betwetn120-140" and is soluble in the ordinary solvents except light petro-leum. When heated with aqneous baryta a t 1-50" it is decomposedinto aniline quercite and carbonic anhydride.SucchttryL pher~yZc~~bimate C6H,O,(0.CO*NHPh> + CONPh pre-VOL.L 50 ABSTRACTS OF CHEMICAL PAPERS.pared in a similar manner from saccharin crystallises in silky inter-Iitced needles melts at 230-240J with decomposition. It is sparinglysoluble in benzene and alcohol soluble in ether readily soluble inaniline; aqueous baryta at 160-170" converts it in aniline andbarium carbonate and saccharate.Metasaccharyl pliemylcarbamate C6H,02( O.CO*NHPh) + CONPh isobtained as an amorphous white powder which softens a t 205" meltsabout 210" and is soluble in most solvents. With aqueous baryta ityields aniline and barium carbonate and metasaccharate.IsosacchnryZ plienylcarbamate C6H,02(0*CO-NHPh) + COKPh,also forms an amorph(lus white powder softens at 180" and melts at,181" ; with aqueous baryta it is decomposed in the same manner asthe preceding compounds.Quercetyl phenylcarbama,te C2&06(0*CO*NHPh) prepared by heat-ing quercetin and phenyl cyanate at 160° is a pale yellow amorphousmass.It melts a t 'LOO-205" and is insoluble in most solvents.Aqueous baryta at 270" decomposes it into quercetin aniline andbarium carbonate.Pl a v y u r p r y 1 p heny lcarbamate C J&03 ( 0 *C ONHP h ) 2 is preparedby heating flavopurpnrin and phenyl cyanate at 165" ; it crystallises inyellowish microscopic plates insoluble in most solvents ; boilinganiline dissolves it with formation of flavopurpurin and diphenyl-carbamide ; alkalis resolve it into flavopurpurin aniline and carbonicanhydride.A. J. G.Para- and Meta-phenylene Cyanate. By L. GATTEHMANN andE. WRAMPELMEYER (Ber. 18 2604-2606).-ParaphenyZene cyanate,C6H4(N CO) is prepared by the actlion of carbonyl chloride onparaphenylenediamine ; it crystallises in white needles melts a t 91",boils a t 231" under 745 mm. pressure. It shows a close resemblancein reactions and properties to pbenyl cyanate giving paraphenylene-dicarbamide wit'h ammonia diphenylphenylenedicnrbamide wi tli ani-line &c.When heated with absolute alcohol it yields prrraphenylene-urethane C6H,(NH*COOEt)2 which crystallises in colourleso prisms,and melts at 193". Paraphenylenecarbamide is also formed in thepreparation of paraphenylene cyanate.Metaphenylene cyanate is prepared in similar manner to and closelyresembles the para-compound.Resorcinol-derivatives. By G. ERRERA (Gurzetta 15 261-274).-Trinitrodi~benzo~~lresorcino7 ?J02.CsH,(0.C0.C6H,*N0,)2 obtained bythe action of nitric acid (sp. gr 1.4) on dibenzoylresorcinol is a,yellow amoiaphous substance melting at 123- 124" insoluble in water,sparingly soluble in alcohol readily in benzene and chloroform.It isnot decomposed by hydrochloric acid but is saponified completelyby alcoholic potash into nitroresorcinol together with iso-dinitro-resorcinol and metlanitrobenzoic acid or the latter and benzoic acid,according to the conditions of the experiment. The nitroresorcinoland metanitrobenzoic acid can be separated by treatment with aceticchloride o r by the different solubility of the copper salts or by theetherification of the acid.A. J. GORGANIC CHEMISTRY. 51Trinitrodibenzoylresorcinol is reduced by tin and hydrochloric acidto amidoresorcinol and amidobeneoic acid.Mononitrodibenzoylresorcinot N02*C6H3(OEh)2 prepared either b ythe action of zinc-dust on a mixture of nitrosoresorcinol (1 mol.)with benzoic chloride (2 mols.) or by the nitration of dibenzoylresor-cinol by a mixture of nitric and slslphuric acias crystallises in acicularneedles melting a t 110" ; on hydrolysis it yields mononitroresorcinoland benzoic acid and on reduction benzoic acid and amidoresor-cinol .Mononitromonobenzoy I r e s o r c ~ ~ o Z N02*C6E3( OH) GBz obtained byheating a mixture of nitiwresorcinol and benzoic chloride in equi-molecular proportions crystallises in pale-yellow needles.Mononitrodiacetylrcorcino~ NOz*C6H3(OAe)2 from acetic chlorideand nitroresorcinol forms long lamellar colourless crystals melting a t90-91" ; it is converted by bromine into Weselsky's dibromonitro-resorcino1.V. H. V.Fluoresceins from Maleic Acid. By R. BUECKHARDT (Ber. 18,2864-2870) .-This is a continuation of the work published L-yLunge and Burckbardt (Abstr.1884 1340).CH ' 'IX is formen Dinzethy I m a l e ~ ~ u o r e s c e i i z 0 <C6H3(0Me) > C <o-co > C,H3( OMe)when a solution of rnalei'nfluoresce'in'in mkthyl alcohol is boiled witlialcoholic potash and methyl iodide and crystallises in red needles.Unsuccessfiil att.empts were made to obtain a bromine-derivativecorresponding with eosin but no definite product could be obt,ained.Male'influormceh reacts with acetic chloride yielding a diacetyl-derivu-t h e C16HL006A~2 crystallising in yellowish-white needles me1 ting at157" ; it is sparingly soluble in alcohol readily in glacial acetic acid,and insoluble in water chloroform cai*bon bisulphide and benzene.CH'CH a-NuphthoZma1e~f2uoresceinn < co'o> CfC,oH,*OH) obtained onheating maleic anhydride (1 mol.) with a-naphthol (2 mols.) and zincchloride a t 160° forms a violet powder which yields a red solutionwith alcohol the addition of ammonia producing an intense green-redfluorescence ; t,he solution changes on exposure to the air becomingfirst violet and then dirty brown.The compound is also soluble inether glacial acetic acid chloroform ethyl acetate and methyl alcohol,but is insoluble in benzene and carbon bisnlphide. It melts a t 118-120". A second compound Cl4H,O4 is formed simultaneously withthe last substance by the union of maleic anhydride (1 mol.) witha-naphthol (1 mol.). I t crystallises in small hygroscopic needlesmelting a t go" dissolves in the ordinary solvents with the exceptionof benzene toluene and carbon bisulphide ; also in hydrochloric acid,water and ammonia.It forms a lead salt of the compositioti@-Naphthol yielded no fluorescent product with maleic anhydride,the statement previously made (Zoc. cit.) referring to the employmentof fuiuaric acid. The product of the latter reaction forms a yellowsolution witli alcoh:)I which exhibits an intense moss-green fluor-escence on the addition of ammoilia.C?,Hl,Pb04.e 52 ABSTRACTS OF CHENICAL PAPERS.The reactions of several other phenols with maleic anhydride harealso been tested qualitatively.C hloro- and Ltromo-derivatives of Phloroglucinol. By K.HAZURA and R. Bmxm" (Monatsh. Chem. 6,702-707).-Heleabrorno-1) hloroglucinol dibrornide C.16Br3(O13r)3,Br2 is obtained together withphlorobromine when a solution of 10 grams of phloroglucinol in1 litre of water (at 40") is treated with 96 grams of bromine added24 grams a t a time.It dissolves very readily in chloroform fromwhich it arptallises in small yellowish-white needles melting a t 118".Sulphurous acid converts it into tribromophloroglucinol melting a t151". When heated a t 156" it gives off a part of its bromine.Hexahyd.F.otrichloroy~loroy lucinol C6H9cl& 4- 3H20 is prepared fromthe above compound by the action of tin and hydrochloric acid ; itforms long white crystals which melt a t 125O. At 100" it loses itswater of cry stallisa tion.TrichlorophlorogZuc~no7~ C6CI,H30s + 3H20 is prepared by the actionof chlorine on a solution of phloroglucinol in glacial acetic acid.Itsoftens when heated a t 120" amd melts at 129". At 100" it loses3 mols. of water. N. H. M.A. K. M.Thymolphosphoric Acids. By G. DISCALZO (Gazxetta 15 278-282).-Monothy~nolpl~osphonyZ chloride POC12*O*C6H,MePr preparedby heating a mixture of phosphorus oxychloride and thymol in equi-molecular proportions is a colourless mobile liquid boilin5 with slightdecomposition a t 280-285". When heated with water it is convertedinto the corresponding acid PO(OH),*O*C6H3MePr a thick oily liquid,sparingly soluble in wa%er soluble in alkalis decomposed completelyon distillntion into thymol and metaphosphoric acid. I t s barium saltcrystallises in prismatic laminae.DithymoZphosphonyZ chloride POCl (OC8H3MePr) prepared from amixture of thymol ( 2 mols.) with phosphorus oxychloride (1 mol.) is acolourless fluorescent liquid boiling at 330-340" under a pressure of320 mm.It is decomposed by water forming ditkymoZphosphoric acid,PO( OH)(O*C6H3MePr)2. This substance is insoluble in water ; itsbarium salt crystallises with 5Hz0 in delicate colourless needles.V. H. V.Nitration of Parabromaniline. By H. HAGER (Bey. 18 2578).-When parabromaniline is nitrated the bromine-atom is displacedand picramide (trinitraniline) formed.Action of Isbutyric Acid on Aniline. By F. L. BARDWELL (Amer.Chem. J. 7,116-118).-Aniline and isobutyric acid do not react witheach other until zinc chloride is added when isobutyranilide isformed ; the yield is increased by heating the mixture.It crystal-lises in colourless prisms and melts at 102.5". By the action ofbromine-vapour on the aqueous solution a yellow precipitate is formed,which when treated in alcoholic solution with charcoal yields colour-less needles of parabromisob?ctyrnnilide C6H4Br*NHCaH,0 ; itJ melts a t128" and when heated wit11 aqueous hydrochloric acid yields para-A. J. GORQANIC CHEMlSTHY. 53bromaniline ; treated with nitric and sulphuric acids it yields para-bromorthonit'raniline. H. B.Metadinitroazoxybenzene and Orthazoxytoluene. By H.KLINGER and H. PITSCHKE (Bsr. 18 2551-2556) .-Metadinitroazozy-benzene N0,.C6H4.N2(~.C6HI*N0 is obtained by treating metadinitro-benzene with a small quantity of sodium methoxide dissolved inmethyl alcohol.It crystallises in long straw-yellow needles melts a t141-142" is sparingly soluble in alcohol somewhat more soluble inether and carbon bisulphide moderately soluble in benzene and toluene.Metndinitrohydroxyazobenxene N02*C6H,*N2*C6H3(OH) *No2 is ob-tained by heating a solution of the azoxy-compound in sulphuric acidat 140" ; it forms a yellowish-brown indistinctly crystalline mass andmelts a t 172-173". It dissolves in dilute alkalis with yellowish-redcolour. The silver salt C,2H,NaOa*OAg is obtained as a red crystallineprecipitate.Orthazoxytoluene C6H,Me.N20*C6H4Me is prepared by the action ofsodium mcthoxide on orthonitrotoluene ; it cry stallises in yellow,monosymmetric tables or needles a b = 044158 1 ; @ = 68" 37' ;observed faces OP mPm o3P; melts at 59-60" and explodeswhen more strongly heated.When distilled with iron it yields orth-azotoluene together with a little orthotoluidine. When heated withsulphuric acid it undergoes a peculiar decomposition much orthazo-toluene being formed (44-48 per cent.) together with amorphoussubstances. A. J. G.Methylene-Blue Group. By A. BERNTHSEN (Annalen 230 i3-21 1) .-A considerable portion of this research has already appearedin this Journal (Abstr. 1883 916; 1884 595 1156; 1885 259).L euco t hionine or &amid ot hiod ip hen y 1 amine,NH<c6H3(NH2)>S [NI-I NH NH S = 4 1 4 61,LHs(NH2)is formed by the action of tin and hydrochloric acid on a-dinitro-diphenylamine sulphoxide Under similar treatment /%dinitro-diphenylamine sulphoxide NH<C6H'(No2) >SO yields Zeuco-isotl~io-nirze c6H4<~~>c6H,(NH2)~.On oxidation with ferric chloride,isothionine NH/~6H2(NK2)>S is produced. I& is a dark crystal-line powder sparingly soluble in water and freely soluble in alcohol,yielding violet-red solutions. It dissolves sparingly in warm benzene,forming an orange-coloured liquid. The hydrochloride C,H,N3S,2HCl,is freely soluble in water and alcohol. The aqueous soluhion is violet-red and dyes silk amethyst. The addit,ion of strong hydrochloricacid does not turn the solution blue as is the case with thionine. Thesalt dissolves in strong sulphuric acid with violet coloration.The composition of methylene-blue was ascertained from theanalysis of the hydriodide C,H,N,SI and the hydrochloride,C6H3(N02)'N0c6H4 54 ABST LlACTS OF CHEMICAL PAPERS.C,H,N,SCl+ 3H,O.The aqueous solution of the free base (tetra-methylthionine hydroxide) is obtained by treating a dilute solution oftJhe hydriodide lwith freshly precipitated silver oxide. On evaporat-ing the solrmbiion in a vacuum over sulphuric acid a t the ordinary tem-perature the Tree base remains as a dark amorphous mass. It dis-solves freely in alcohol and in water. The preparation and propertiesof leucomethylene-blue (formerly called methylene-white) have beenalready described (Absts. 1883 916). Pentamethylleucothionine-dimethiodide C,H,N,S,ZMeI is formed by the action of methyliodide arid methyl alcoliol on leucomethylene blue a t 110".The com-pound is soluble in hot water but insoluble in ether. It is decom-posed by moist oxide of silver yielding the ammonium base,CsH3(NMe3*OH)JZ-<C,H3(NMe,*OH)>S'On evaporating the alkaline liquid the base remains its a brittle,amorphous mass soluble in alcohol and in water. It is decomposedby heat yielding methjl alcohol and pentamethylleucothionine. Theconsthtion of leucomethylene-blue or tetramethylparadiamidothio-dipheylamine is proved to beby the fact thad it yields on methylation the same pentamethylleuco-thioninedimethylammonium iodide which is obtained from leuco-thionine. The free base of methylene-blue is represented by theformula HO*NMe/ ICsHi---- S'N*CsH3 (NMe)Nethylene-red is obtained as a bye-product in the preparation ofmethylene-blue.It is contained in the mother-liquor from which theniethylene-blue has been precipitated. The pure compound isdeposited from alcohol in glistening green prisms soluble in water.The aqueous and alcoholic solutions exhibit a purple colour whichdisappears on the addition of an alkali. The coloiir does not re-appear on acidification. A blue colour is produced by oxidation.Reducing agents also destroy the purple colour and in this case sul-phuretted hydrogen is liberated. The hydrochloride of methylene-red has the composition CIsHI,N4S4,2HC1. On the addition of am-monia to methylene-red a yellow-coloured base is precipitated. Itis soluble in alcohol and in ether. I t is precipitated from the alcoholicsolution by water.When methylene-blue is treated with a dilute solution of an alkali,it mixture of methylene-violet methylene-azure leucomethylene-blue,and other leuco-products is formed.Methylene-violet is best ob-tained in the pure state by decomposing methylene hydriodide withsilver oxide and boiling the aqueous solution of the base for severalhours. The solution deposits crystals of pure methylene-violet andthe mother-liquor contains methylene-azure. The precipitate ofsilver iodide is mixed with a considerable qnantity of leuco-bases.>Metky lene-violet orr3osited from alcoholORGANIC CHEMISTRY.\CGHS- sdimet h y It hionol ine O<r?.C,tr,(NMe,) /> isin long needles soluble i n chloroform55de-andSparingly soluble in hot water.The solutions have a red or violet-red colour and are fluorescent. The hydrochloride C14HI,N2S0,HC1,crystallises in long needles of a dark green colour. It is insoluble incold dilute hydrochloric acid. The aqueous solution dyes wool orsilk violet. The iodide and chromate are very slightly soluble in hotwater; in other respects they resemble the corresponding salts ofmethylene- blue. Leucorn ethylene-violet is deposited from alcohol inwhite plates or scales. The solution in acids is stable but the solu-tion in alkalis absorbs oxygen with great avidity and depositsmethylene-violet. The hydrochloride i H crystalline. I n order toobtain methylene-azure in a state of purity the mother-liquor fromwhich the methylene-violet has been deposited is treated with an alka-line solution of stannous chloride.The liquid is mixed with half itsvolume of alcohol and left for some time in a closed vessel. Theleuco-azure which is deposited as a crystalline mass is washed dissolvedin dilute hydrochloric acid and oxidised by ferric chloride. On theaddition of common salt rnethylene-azure is precipitated. It is dis-solved in water reprecipitated and converted into the hydriodide.This salt is more soluble in water than methylene-blue hydriodide,which it closely resembles. The hydrochloride is also very solublein water. The solution dyes silk blue. The hydrochloride dissolvesin strong hydrochloric acid with a blue coloration and in strongsulphuric acid with a green colour.It is decomposed by boiling witha strong solution of potassium hydroxide with formation of dimethyl-amine.The preparation of oxythiodiphenylimide and hydroxythiodip henyl-amine has been already described (Abstr. 1885 260). The constitutionof these compounds may be represented by the formulm-0/76H3*S > and C,H4<kg> C,H,*OH.'N*C6H4Silk immersed in an alkaline solution of the latter compound is dyedcrushed strawberry.S,treating thiodiphenylamine with sulphuric acid diuted with one-fifth itsweight of water at 160" for 24 hours. The product of the reactionis poured into water mixed with excess of sodium hydroxide andfiltered. On the addition of hydrochloric acid t o the hot filtrate,thionol hydrochloride is deposited in glistening green crystals.The free base is insoluble in cold water but dissolves freelyin acids.It is deposited from glacial acetic acid in plates.The alcoholic solu-tion is of a purple colour and the solution in strong sulphuric acid isblue. The sulphate 2ClaH,NS02,H2S04 forms green needles. Thebarium salt C1zH7NSO3Ba crystallises in plates exhibiting a gree56 ABSTRACTS OF CHEBlICAL PAPJIRS.lustre. Silk immersed in a solution of thionol in potassium car-bonate acquires a violet colour which turns red on exposure to tlieair. Thionol is formed in small quantities by the continued action ofalkalis on methyletie-blue ; it is also a product of the action of alkalis,or of strong sulphuric acid on thionine.C6H3(0H)>S is formed by treating an am- Leucothionol NH<It is deposited from itsOn treatment with') is formed by adding ferric chlorideto amidophenol which has been saturated with snlphuretted hy-drogen.It is also produced by the prolonged boiling of thionine inwater NCI2H6S(NH2)NH + H,O = NC12H6S(NH,)0 + NH3.Thionoline dissolves in hot alcohol forming a purple solution ; theC6H3(NH2)>S is soluble in acids and in alkalis. leuco-compound NH<The nitrate sulphate and hydrochloride of thionoline crystallise inneedles. Strong sulphuric acid dissolves thionoline forming a blueC6H4 OH)nioniacal solution of thionol with zinc-dust.ethereal solution as a crystalline colourless mass.acetic anhydride it yields a triacetyl derivative.'N-C6H3(NH2)CsH -Thionoline Q/ IC6H3( OH)-solution. Methylene-violet is dimethylthioDoline.w. c. w.Benzyl Compounds. By 0. BORGMANN (Chern. Centr. 1885,456-458). -This communication contains an account of severalmetabenzyl compounds prepared from metanitrobenzyl alcohol Homeof which have already been described (Abstr. 1883 1121).Pyiniary metanitrobenzy lanaine N02*C,H1*CH2*NH is formed bytreating metaiiitrobenzyl chloride with alcoholic ammonia ; it is ayellowisli oil absorbs carbonic anhydride from the air forming a solidsalt and yields a sparingly soluble oxalate and platinochloride. Thesecondary amine NH(N02*C6H4*CH2) formed with the primary crystal-lises in yellowish rhombic leaflets melting at 87" ; its hydrochlorideand platinochloride are both sparingly soluble salts.When reducedbp tin and hydrochloric acid it forms an anlido-compound the hydro-chloride of which crystallises from concentrated hydrochloric acid inlong reddish needles having the composition N(NH2*C6H4*CH2)2,SHC1.The base crystallises in prisms melting at 86-87'.Z'ertiary metanitrobenzylanzine N (NO,*C,H,*CH,) is formed bydigesting met anitrobenzyl chloride with aqueous ammonia ; it crystal-lises in monoclinic prisms melts at 162O is soluble in glacial acetic acidand benzene but only sparingly in alcohol is insoluble in ether anddoes not unite with hydrochloric acid. When reduced with tin andhydrochloric acid it yields the tertiary amido-compound whichcrystallises in colourless needles melts at 142O and forms a sparinglysoluble platinochloride.Amidobenzyl chloride is very unstable and is formed by thereduction of the niti-o-compound with tin and hydrochloric acid.Metar~itrodibenzylnzethylamine NMe( NO2*C6H4-CH2) is formed byacting on nitrobenzyl chloride with an aqueous solution of methyl-amine ; i t melts at 81".By the action of dimethylamine metnnifroORGASIC CHEJlIST RT. 577/enz~ZdinzethyZamine N0,*C6H,*CH,*NMe is formed ; it is a yellowishoil and forms a well-defined platinochloride.MetanitrobenzyZphenyZamine Ilu'0,*CsH4.CH,*NHPh is formed by theaction of aniline on nitrobenzyl chloride; it crystallises in long,orange-red needles melting a t 86" ; its hydrochloride forms whiteleaflets is an unstable compound and does not form a platiuochloride.When reduced by tin and hydrochloric acid this base forins nzetamido-benzyZ~l~enllZai,ziize NH,.C,H',*CH,*NHPh melting a t 67".Metanitrobenzaldehyde when treated wit'h concentrated sodiumhydroxide yields meta-azoxybenzoic acid ON,( C6H,*C0 OH),.P.P. B.Ethylortholuidines. By R. L. CHASE (Amer. Chem. J. 7 118-120).-These compounds have been prepared by Reinhardt and Staedel(Abstr. 1883 578). Ethylortholuidine formed from ethyl iodide andorthotoluidine boils a t 204-206" ; its salts are exceedingly solublein water ; the chloride platinochloride iodide acetyl- and nitroso-compounds are mentioned.Diethylorthotohidine was prepared from the monethjl-derivativeand ethyl iodide it boils between 203-208" ; the hydriodide crystal-lises well from water it contains 1 mol.H,O. H. B.Consecutive Orthoxylidine and Orthoxylenol. By A. TOHL( Ber. 18,2561-2562).-Mo~tonitrodibromortho-xylene C6H~fe,Br,.N02[Me Br NO = 1 2 3 4 51 is obtained together with thedinitro-compound by adding 4 5 dibromortho-xylene to cold fumingnitric acid. It crystallises in colourless needles and melts a t 141".Dinitrodibromortho-xy Zene C6Me2Br2(N0,) crys tallises in small needles,and melts at about 250".Uibronaort/io-xyZidine C6HMe2Br,.NH2 is prepared from the mono-nitro-derivative by heating it with iron and acetic acid. It crystallisesin colourless needles melts at lOS" distils with steam is readilysoluble in alcohol ether and glacial acetic acid and does not yieldsalts with acids. The bromine is to a great extent removed by iongtreatment with tin and hydrochloric acid but complete replacementcan only be effected by the action of sodium amalgam on a warmalcoholic solution.Ortho-xy Zidine C6H,Me2*NH2 [Me Me NH = 1 2 31 so obtained,is a colourless oil which turns brown on long exposure to air doesnot solidify at - 15" and boils a t 2.21-222".The hydrochloride,C6H3Me2*NH2,HC1 + H20 crystallises in large lustrous tables andsublimes readily; the nitrate and sulpbate are also described.AcetzyZide C6H3Me,-NHAc cry stallises in long slender needles andriielts at 131".Ortho-xyZemZ C6H3Me2.0H [Me OH = 1 2 31 prepared in theusual way from the xylidine crystallises in very long slender needles,melts a t 75" boils at 218O and yields a blue coloration with ferricchloride in aqueous solution.The tribroino-deiivative C,Me,Br,-OH,crystallises in slender needles and melts at 184". A. J. G.Paraxylidine. By E. NOLTING 0. WITT and S. FOREL (Ber. 18,2664-2668).-Crude xylidine was found to contain about 25 per cent58 ABSTRACTS OF CEEitlICAL PAPERS.of pnraxylidine boiling a t 215" under 739 mm. pressure. Sp. gr. = 0.980(water at 15" = 1). Nitraceto-xylide melting a t 166" is obtained bynitrating the acetyl-derivative ; it yields a nitro-zylidine which meltsa t 142" and crystallises from benzene in brownish-yellow lustrouscrystals readily soluble in alcohol and ether. When nitro-xylidine isreduced xylenediainine is formed ; this cryshllises from benzene insmall white needles melting at 146.5-147" which when oxidised,yield paraxyloquinone.Ethyl nitrite acts on nitro-xylidine with formation of the ethyl saltof nitioparaxylenol ; it is a yellow substance melting at 85"."N. H. M.The Six Isomeric Xylidines. By E. NOLYING and S. FOREL(Ber. 18 2668-2681).-A description of these compounds and somederivatives is given. When consecutive ortho-xylidine is oxidised ityields ortho-xyloquinone C6H2Mez02 [Me2 0 2 = 1 2 3 61. Thiscompound sublimes in yellow needles which melt a t 55" ; it is ratherreadily soluble in alcohol ether &c. It is reduced by sulphurousacid to the quinol a white substance melting a t 221". Ortlzo-xylenol[Me2 OH - 1 2 31 is obtained from the diazo-derivative of thebase; it crystnlliscs from water in white needles melts at 73" andsublimes uiichanged.The aqueous solution acquires a pale-violetcolour when treated with ferric chloride.171etaxylylquinone C6H,Me,0 [Me2 0 = 1 3 2 51 is preparedby oxidising metaxylidine ; it forms splendid yellow needles whichmelt a t 73". The corresponding qwin,oZ forms white needles meltinga t 149". When symmetrical metaxylidine is nitrated a nitro-derivative[Me2 NH2 NO = 1 3 5 41 melting at 54" is formed; this,when reduced yields metaxyleneorthodiamine melting a t 77".When the hydrochlorides of the xylidines are heated with methylalcohol a t 300-320" amidotrimethylbenzenes are formed. Consecutiveortho-xylidine yields a liquid amidotrimeth2/lbenzene boiling a t 240' ;the acety2-derivaticve meits at 1130". Symmetrical metaxylidine yieldeda crystalline isocumidine which melts a t 67-68" and boils a t 245"(uncorr.) ; the acetyl-derivative melts a t 163-164" ; the cumenol meltsat 98-99".N. H. M.Arnidoazo-derivatives of the Three Xylenes. By E. NOLTINGand S. FOREL (Bey. 18 2681-2686). - Amidoazometaaylene,C6H3.Me2-"L*C6H2Me2.NH:! [Me Me N Me NH Me = 4 2 1 2 3 41,is prepared by the action of 69 grams of a 20-25 per cent. solutionof sodium nitrite on a well-cooled mixture of 121 grams ineta-xy lidine and 157 grams metaxylidine hydrochloride. The product isextracted with ether and the resiciue left on evaporating the ether iswarmed with 120 grams of metaxylidine and 10-15 grams of meta-xylidine hydrochloride at about 50". It is then boiled with dilutehydrochloric acid and the sparingly soluble hydrochloride thusobtained is washed with water alcohol aod ether.The base isliberated by means of ammonia and crystnllised from alcohol orbenzene. It forms orange-yellow plates which melt at 78" is almostinsoluble in water readily soluble in hot alcohol and in benzene. The7aydrocl~Zoride forms a bright Fellow crystalline powder ; its alcoholifiolution is peen. When reduced it yields a diamine melting atAmido-azometnxylene [Me Me N2 :Me Me NH = 6 2 1 3 5 41,crystallises in yellow plates melting at 77.5" ; it dissolves readily inalcohol and in benzene. The alcoholic solution of the hydrochlorideis red.Amido-azometazyZene [N Me Ne NH = 1 2 6 41 cryst'al-lises from alcohol in yellow plates melting at 95".The solution ofthe hydrochloride in phenol is violet.Amido-axortho-zy Zene [Me Me N2 Me Me NH = 3 2 1 2 3 41,forms yellow plates and melts at 110.5".Amido-axortho-xylene [Me Me N Me Me NH = 6 3 1 4 5 21,forms yellow plates melting at 179" ; it is sparingly soluble in alcohol.The solution of the hydrochloride in phenol is green.Amido-azopuraxylene [Me Me N Me Me NH = 5 2 1 3 6 41,crystallises from alcohol in red plates melting at 150". The hydro-chloride is red ; its solution in phenol is violet-red. When the base isreduced a diamine melting a t 146.5-147" is formed.Experiments made by the authors show that the nmidoazoxylenedescribed by Nietzki (Abstr. 1880 552) is a mixed amidoaso-metapara-xy7ene [Me Me K Me Me NH2 = 4 2 1 3 6 41 ; it meltsat 110-111".N. H. M.77-78'.Azo-derivatives of Carvacrol. By G. MAZZARA ( Gazzetta 15,305 -315) .-In continuation of experiments on the azo-derivatives ofthymol and carvacrol (Abstr. 1885 904 and 1132) the authordescribes the preparation of an azo-compound by heating 1 mol. ofbidiazotriphenylmethane with 2 mols. carvacrol dissolved in potash.There is thus formed a purplish-red amorphous substance carvacrol-bidiazotriphenylmet hane to which is ascribed the composition[OH*CsB2MePh~N,~C,H,*CHPh*CsH4*N,C,H2MePh]20. It melts at130" and is soluble in ether and chloroform ; its potassium-derivativeis a red precipitate ; when heated with bidiazobenzene it is convertedinto a red crystalline substance the composition of which has not yetbeen definitely established.By 33.HAGER ( B e r . 18,2573-2577).-Diphenylurethane is best obtained by heating diphenyl-amine with ethyl ch lorocarbonate.Di-orthonitrophenylurethaize (N02G,H,)2N.COOEt is obtainedtogether with the para-compound by adding diphenylurethane to nitricacid of sp. gr. 1.44 and pouring the solution into much water ; the mix-ture is separated by treatment with a little hot benzene from which thepara-compound crystallises on cooling. The ortho-compound forms abrown syrupy. mass readily soluble in alcohol and seems to be misciblein all proportions with benzene. Potash convert,s it into orthonitrodi-phenylamine. When heated alone it yields a mixture of products fromwhich a colonrless liquid boiling at 141-143" and of the formulaC,HIoO was isolated.This is insoluble in water readily soluble inether and unites with bromine to form a yellow liquid yielding ondistillation an oil which gives a nitro-derivative melting a t 181-182".V. H. V.Derivatives of Diphenylurethane60 ABSTRACTS OF CHENICAL PAPERS.Di-paralLitrophe~ylui.ethane crystallises in yellow needles melts a t133-134" is readily soluble in benzene sparingly in alcohol andyields paranitrodiphenylamine when boiled with potash.Di-pnmmidophenylurethane ( NH,*C6H4),N*COOEt + H,O is pre-pared by reducing the nitro-compound with tin and hydrochloricacid ; it crystallises in violet needles and melts at 101" with decom-position. When treated with benzoic chloride it yields a benzoyZ-derivative (NHBZ.C~H~)~N*COOE~ crystallising in flesh-colouredneedles and melting at 210" ; this is not identical with the substanceto which the author had previously and erroneously assigned thisformula (Abstr.1885 150).Hexabronzod~phenyluretl~ane (C,H,Br,),N*COOEt is obtained by theaction of bromine on solutions of dipheriylurethane ; it crystallism inlong greenish-brown needles and melts a t 184". When treated withnitric acid it yields a nitro-compound crystalliving in yellowish- bro wnneedles and melting a t about 245" with decomposition,New Synthesis of Vanillin. By M. ULRICH (Ber. 18 2571-2573).-1n 1881 Meister Lucius and Briining patented a methodfor obtaining three isomeric mononitrometamethoxybenzaldehydes.Tiemann (Abstr.1883 189) and Schnell (Ber. 17 1381) have statedthat this method yields not mononitro- but two diiiitro-derivatives ;t'he author however finds that when metamethoxybenzaldehyde isnitrated according to the directions of the patent the three rnono-nitro-derivatives are formed.The main product of the reaction is a-nitro-metametl~oaybenznlde-hyde ; it crystallises in thick yellow prisms and melts a t 107". /?-nitro-rnetanzethoeybenzaldehyde is formed in small quantity ; it crystallises inneedles and melts at 82-83" As both these acids give the indigoreaction they must be the two ortho-nitro-compounds [ COH Me NO,= 1 3 2 and I 3 61 ; there is no evidence as to which is which.The third ni tro-compound crystallises in cauliflower-like masses inter-spersed with prisms melts at 97" and does not give the indigoreaction; it has the constitution [COH Me NO = 1 3 51.Ptrranitrometl~oxybenzalde7~yde [COH Me NO2 = 1 3 41 is ob-tained as follows methyl metamethoxycinnamate is nitrated a t 0"with nitric acid of sp.gr. 1.46 and the paranitro-methyl saltseparated by crystadlisation from the product when it is obtainedin flat white needles melting a t 163". The free pnranitro-acidirepared f r o m the methyl salt is then oxidised with aqueous potassiumpermanganate by which means it is converted into paranitromethoxy-benzaldehyde. This crystallises in hair-like needles me1 ts a t 62",and is soluble iu water alcohol and benzene. When treated withacetone and soda it yields a colourless solution from which after atime colourless needles melting at 84" separate.By replacing thenitro-group by hpdroxyl vaniZlin is obtained.Paramidacetophenone Ortharnidometacetyltoluene andsome of their Derivatives. By J. KLINGEL (Ber. 18 2687-2706).-Paramidacetopheiione is best prepared by boiling a mixtureof 2 parts aniline 3 parts zinc chloride and 5 parts acetic anhydrideA. J. G.A. J. GORGASIC CHEMISTRY. 61for five hours; the product is boiled with hydrochloric acid andtreated with sufficient soda solution to precipitate and redissolvethe zinc hydroxide. A brown oil then appears which is sepa-rated and distilled with steam to expel aniline. The residueis extracted several times with boiling water and the unitedextracts evaporated down; on cooling the amide separates. Theyield is 50-60 per cent.of the weight of aniline used. Several saltsare described. Acetylamidacetophenone COMe*C6H4 NHAc formssmall white needles which melt a t 166-167" ; it is readily soluhle inhot water and in alcohol. Hydroxyacetophenone COMe.C6H4*OH= 2 4 is prepared by acting with sodium nitrite on a well-cooledsolution of the base in dilute hydrochloric acid and then slowlyheating the product with water until it boils. The phenol isextracted with ether. It forms white needles melting a t 107" readilysoluble in hot water alcohol and ether. When the aqueous solutionis treated with ferric chloride it acquires a dark-brown colour.IocloacetoJihenone C,&I*COMe is prepared from the amide by meansof the diazo-chloride; it crystallises in white plates which have anagreeable odour and melt a t 79".It dissolves readily in alcohol andether. When oxidised it yields pariodobenzoic acid. Dimethylamid-acetophenone COMe*CsHc*NMez is obtained by the action of methyliodide on amidacetophenone and forms yellowish plates melting at58-59". It is readily soluble in alcohol ether and hot water.Acetopkenonea,zonaplLthoZ COMe*CGH,N NGloH6*OH is preparedby the action of the sodium compound of /%naphthol on the diazo-chloride obtained from amidacetophenone. It forms groups of slender,red needles with a slightly green metallic lustre insoluble in water,sparingly soluble i n ether readily in alcohol. Dilnte alkali dissolvesit readily with formation of a dark-red solution.Orthar?zidonzefacetotoluene [COMe Me NH = 5 1 21 is pre-pared from toluidine in a manner similar to amidacetophenone asdescribed above.I n appearance it is very similar to amidacetoplienone ;it melts a t 102" and boils at 280-284". It dissolves readily in hotwater alcohol ether and dilute alkali and is almost insoluble in lightpetroleum and benzene. Several salts are described ; they resemblethe salts of amidacetophenone. The acety 1-derivative melts at 143-144" ; it is readily soluble in warm water and in alcohol.Acetocresol COMe*C7H,- OH is prepared similarly to hydroxy-acetophenone ; it crystallises in reddish prisms melting a t 104",readily soluble in alcohol ether and hot water.When treated withferric chloride it gives a yellowish-brown coloration.Diwiethy Zamido-acetotohene COMe*C7H6*N&2 crystallises in groupsof flat prisms melting a t 95'; it is readily soluble in alcohol ether,and hot water almost insoluble in light petroleum.Acety Ziodotoluene COMe*C7H61 is prepared by the action ofhydriodic acid on the corresponding diazo-chloride ; it forms ayellowish crystalliue mass melting at 3Y" very readily soluble inalcohol and ether sparingly soluble in light petroleum benzene andhot water. When oxidised it yields iodophthnlic acid. This crystal-lises in slender white needles which melt a t 203-204" is verysparingly soliible in boiling water and dissolves readily in glacia62 ABSTRACTS OF CHEIIICAL PAPERS.acetic acid alcohol ether and warm chloroform.The barium saltforms slender white needles very sparingly soluble in boiling water ;the calcium copper and silver salts were also prepared. Wheniodophtbalic acid is treated with concentrated potash solution it ispartially converted into parahydroxybenzoic acid ; nascent hydrogenconverts it into benzoic acid. N. H. M.Mixed Axo-compounds. By E. BAMBERGER and A. CALMAN(Rer. 18 2563-2567 ; compare Abstr. 1885 157).-A mixture ofphenylazoacetophenone and ethyl phenylazobenzoylacetate is o btaineclby mixing aqueous solutions of diazobenzene chloride ethyl benzoyl-acefate and soda.Phenylazoacetophenone COPh*CH2*Nz*Ph is obtained by heatingthe mixtu1.e with alcoholic potash and precipitating with water ; i tcrystallises in slender golden-yellow needles melts a t 128.5" and isreadily soluble in hot alcohol or acetic acid.Pheny Zazobenzo y 1 acetic acid COP h* CH (N,Ph) *C 0 OH obtainedfrom the potash salt prepared as above crystal!ises in long citron-jellow needles melts a t 141" is soluble in ether alcohol and aceticacid and yields phenylazoacetophenone when boiled for some timewith dilute soda.Orthonitrophenylazoacetophenone ?J02*C6H4*N2*CH2*COPh crystal-lising in lustrous golden-yellow needles melting at 140-141" andortlhonitropheny Zazobenz oy Zacetic acid NOz* C,H4*N2*CH( C 0 Ph) *C 0 OH,crystallising in sulphur-yellow needles and melting a t 177" areformed in similar manner from orthonitrodiazobenzene chloride.When heated for some time a t the melting point the acid losescarbonic anhydride and is converted into the ketone.By the actionof hydroxylamine hydrochloride on the ammonium salt the compoundNO*C6H4-Na*CH( CPh NOH)*COOH is formed ; this crystallises inorange-yellow needles and melts at 142".M~tartitrotoly2i3arccxobelzxo2Jlacetic acid,NO2*C6H3Me*N2* CH ( C OPh) C 0 OH,prepared from metanitroparatoluidine crystallises in silky golden-yellow needles melts at 194" and is very sparingly soluble in coldalcohol or acetic acid.NOz-C6H3Me*Nz*CH2*COPh,crystallises in lustrous citron-yellow needles melts at 168" andwith hydroxylamine yields the ketozime,NOz*C,H3Me*Nz~CHz.CPh NOH ;The corresponding acetophenone,this crystallises in reddish-yellow needles and melts at 174".A.J. 0.Crystallographic Examination of some Organic Com-pounds. By J. ZINGEL (Zeit. Kyyst. Min. 10 41$-420).-Thecrystalline systems and axial ratios are as follows :-Metatrimeth-amidobenzoic acid chloride ~&fe3C10C6H4*COOH ; monosymmetric ;u b c = 1.9388 1 0,8757 ; /3 = 88" 49'. Metadimethamido-benzoic acid NMe2*C6H4*COOH; asymmetric; a c = 1 1.9403ORGANIC CHEMISTRY. 63Dinitroparatoluidine (m. p. 69-71'). Rhombic; a b c =0-9965 1 0.5184. 2 4-Dinit,rophenyl metanitrobenzoate asym-metric; a b c = 0.7137 1 1.7671. A. J. G.Phenylacetic Acid. By R. MEYER (Chem. Centr. 1885 516-51 8) .-Orthoparadinitrophenylacctic acid is prepared by addingphenylacetic acid to conceritrated nitric acid and pouring the mixtureinto concentrated sulphuric acid.The acid crystallises in colourlessneedles melting a t 160" (Abstr. 1884 178). Ethyl dinitrophenylacetatPcrystallises in colourless needles melting a t 35"; it is more stablethan the acid.Paramido-orthonitrophenylncefic acid is formed by reducing thedinitro-compound with ammonium sulphide ; it crystallises in long,reddish-yellow needles which are soluble in alkalis and also in acids ;it melts a t 184-186". Attempts made to convert this compoundinto ortlionitrophenylacetic acid by the diazo-reaction have beenwithout sumess. Ethyl amidonitr~henylacefate crystallises in long,yellow needles melting a t 100"; this compound when treated withan alcoholic solution of ethyl nitrite and hydrochloric acid yields itcompound having the composition C,H,N205 which crystallises inneedles melting at 163".When heated with hydrochloric acid insealed tubes a t 150-160° this compound is resolved into ethy-lchloride carbonic anhydride ammonia and orthonitrobenzoic acid ;this owes its production to the formation of nitrosomethy lorthonitro-7)enrene; it would therefore appear that the compound is ethylorthonitrophenyl&trosoacefate NOz*C6H,*CH(NO)*COoEt [2 11.Nitrosonaethylorthonitropal.adiazobenzeiLe chloride,NO,* C6H3' (NiCL) C HZNO,is obtained by treating amidonitrophenylacetic acid with hydrochloricacid and amyl or ethyl nitrite. When heated with hydrobromic acidit yields the bromide NO2*C7H5BrNO which melts a t 151-152".The chloride boiled with alcohol yields nifrosornethylorthonltrobenzene,NO,*C,H,*CH,*NO (1 21 which when heated in sealed tubes withhydrochloric acid a t 150-160" is resolved into ammonia and ortho-nitrobenzoic acid.Nitrosomethylnit'mbenzene when oxidiscd by potassium dichromateor permanganate or ferric sulphate yields orthonitrobenxaldehyde,melting a t 43.5-44.5'.Reduced by ammonium sulphide it formsnitrosomethylorthailzidobenzerzs NH2*C6H1*CH2*N0 which crystallisesin needles melting at 132-133".The methyl-derivative of nitrosomethylnitrobenzene,N02*C6 B,*CHMe*NO,melts a t 58"; the ethyl compound is an oil. Methylnitrosoamido-benzene TU'H;C6H4*CHMe*N0 is an oil volatile in steam ; its hydro-chloride crystallises in needles melting at 109".Orthonitrobenzo.nitrile N02*C6H4*CN [ 1 21 is formed by heatingni trosomethylnitrobenzene with acetic anhydride and sodium acetate.The nitrosomethylamidobenzene yields under like conditions a,diacetyl compound NHAc*CsH,*CHAc-NO melting a t 127*5-128*5"64 ABSTRACTS OF CHEMICAL PAPERS.Dinitrophenylacetic acid reduced by tin and hydrochloric acid,yields anlido-oxindole NH2*CsH3< ;%>GO from which by thediazo-reaction the paradiaxonitroso-oxindol e chloride,has been prepared ; it crystallises in yellow needles and when boiledwith alcohol yields nitroso-oxindole.Derivatives of Durene.By J. U. NEF ( B e r . 18 2801-2807).-Dur?ylic acid is best obtained by heating durene with dilute nitricacid (1 vol. acid of sp. gr. 1.4 to 3 vols. water) for three to fourhours in a reflux apparatus ; the product is allowed to cool filtered,and the residue extracted with sodium carbonate solution the un-altered durene being again treated with dilute acid.On addinghydrochloric acid to the alkaline solution durylic acid is precipitatedtogether with some nitro-compounds which are removed by treatmentwith zinc and glacial acetic acid and distillation in a current ofsteam. The durylic acid obtained melts at 149" and agrees in allproperties with the acid described by Janiiasch ( Z e i f s . f. Chenz. 6,449) whilst the yield amounts to 15-20 grams from 40 gramsdurene. Dinitrodwry lic acid (see also Gissmann Abstr. 1883 334) isbest prepared by dissolving finely divided durylic acid in pure con-centrated sulphuric acid cooling with ice and gradually adding asolution of nitre in pure sulphuric acid with constant stirring.Afterfour or five hours the product is poured upon ice the nitro-acidfiltered off washed and purified by means of its calcium salt. Itsproperties have been described by Gissrriann (loc. cit.). Whendinitrodurylic acid is dissolved in a dilute solution of potas-sium carbonate and potassium permanganate solution graduallyadded dinitropyrornellitic acid is produced. It has a strongly acidodour is readily soluble even in cold water extremely so in ether andcrystallises from both solvents in very long silky colourless needles ;soluble also in alcohol and glacial acetic acid but insoluble in chloro-form benzene and light petroleum. When i t is heated in a capillarytube it loses water (100-160") and becomes yellow and it decom-poses a t 203" with evolution of gas.The silver salt C6(NO2),(COOAg),forms a golden-yellow amorphous precipitate. Attempts to reducedinitropyromellitic acid to the diamido-acid proved unsuccessful.Ethy I d initroyyrom el Zit at e c6 (NO,) (CO OE t ) 1 obtained by heatingthe silver salt with ethyl iodide and ether for one to two hours at loo" forms magnificent colourless needles readily soluble in hot andsparingly in cold alcohol readily in benzene chloroform glacialacetic acid acetone and ethyl acetate more sparingly i n ether. Itmelts a t 130". When its hot solution in glacial acetic acid is treatedwith zinc-dust ethyl axopyi'ondlitate C&,( COOEt) is produced.This has a deep cinnabar-red colour is insoluble in water and diluteacids ; it yields a colourless salt with concentrated hydrochloric aciddissolves readily in glacial acetic acid alcohol and ether and meltsa t 134".It sublimes without decomposition when heated. WhenP. P. BORGAXIC CHEMISTRY. G5diamidodurene (from dinitrodurene) is treated with ferric chloiaide agreen coloration is produced and at once chanqes to yellow owing tothe formation of duroquinone C602Me4. This crystallises from lightpetroleum in long yellow needles melting a t 111". It sublimesrzadily emitting but a faint quinone odour dissolves very readily inether chloroform benzene alcohol and acetone. Zinc-dust andsods solution sulphurous acid and sodium amalgam reduce it but itis reproduced on agitation with air.It is insoluble in alkalis andnearly so in hot water. Potassium permariganate and sodiumcarbonate solution and also chromic acid and glacial acetic acid,decompose it.From the great stability of duroquinone the author hopes to succeedi n preparing the quinone of pyromellitic acid which would have thesame composition as croconic acid.Dibromoparahydroxybenzoic Acid. By A. ALESSI (G'uszetta,15 242-247).-In order to determine the constitution of the di-bromoparnliydroxybenzoic acid obtained by Balbiano from the distil-lation of sodium dibronianisate with calcium oxide (Abstr. 1834,1 172) dibromanisic acid was converted by excess of concentratedbydriodic acid into a dibromohydroxybenzoic acid. This was foundto be identical with Bidbiano's acid.As in the acid from dibrom-nnisic acid the substituted groupings must be in the relative positionOMe Br B r C0,H = 1 2 6 the composition of Ba1l)iano's Reidhas the same constitution. V. H. V.A. K. M.Salts of Anisic Acid. By G. BORRELLA (Gazzettcx 15 304-305).-The copper manganese nickel cobalt zinc and cadmium salts ofanisic acid crystallise with H,O ; there can also be obtained basiccopper OMe*CGH4*COOCuOH and chromium,salts. In analysing the metallic salts of the organic acids it is con-Yenient to precipitate the heavy metals in the form of oxalates t,healcohol necessary for the complete precipitation serving to dissolvethe liberated acid. V. H. V.Inner Condensations. By A. ROSSING (Cher12.Cerjtr. 188.5 598-395).-~0rtho-~Zdehydo~henoxyncet~c acid COH*C6H1*OCH,*cOOH,produced by the action of monochloracetic acid on salicylaldehyde,crystallises in large yellow leaflets melting at 132". Its salts with thealkali metals and metals of the alkaline earths are soluble in water itscopper and silver salts sparingly soluble in water. I t reduces ammo-niacal solutions of silver salts and forms a double compound withliydrogen sodium sulphite. It unitesdirectly with aniline forming the compoundThis compound unites with acids forming well-defined salts froniwhich the base can be obtained by careful addition of ammonia 01-caustic alkalis or better still by decomposition with an alcoholic6 olution of sod ium eth ox ide.Its ethyl salt melts a t 114".NH Ph* CH (OH)*CGH4* 0.C H C 0 0 H.VOL.L. I66 ABSTRACTS OF CHENICAL PAPERS.Aldehydophenoxgacetic acid unites directly with phenylhydrazine,forming the conipound N,HPh CH*C,H,*O.CH,*COOH which meltsa t 105". By oxidising agents aldehydophenoxyacetic acid is con-verted into salicy Zoxy acetic acid CO OH*C6H~~O~@H,*CO@H whichcrystallises in white needles melting a t 186-187'. Ethyl salicyl-oxyacetate is a light yellow oil which decomposes when heated andis converted into the corresponding diamide,NH,*CO*C,H,.O*CH,*CONH ;when heated in sealed tubes with ammonia; this crystallises inyellow needles melting a t 158".When aldehydo-pheiioxyacetic acid is heated with acetic oxide ant1sodium acetate it yields orthocumaroayacetic acid,CO OH* CH CH*C,H,* O-CH,.C 0 0 H,wliich crystallises from water in needles melting a t 190". This corn-poiind like cinnamic acid combines with 'bromine to form a di-bromide melting a t 219-220" which when heated with alcoholicpotash yields orthopropiolpheelzoxyacetic acid,COOH*C i C*CsH4*O*CH,*COOH ;this forms small yellow crystals melting at 208".When aldehydo-phenoxyacetic acid is heated with five parts of aceticoxide and 4-5 parts of sodium acetate for three hours it yields anoil boiling a t 170° which is identical with cnmarone C6H,<- >CH(Abstr. 1888 474). If orthocumaroxyacetic acid is heated withphosphoric acid it loses water and yields the anhydrideCHCH CHGOC6H4<-0. C H,. C 0 ->O,which melts & 176"; when boiled with water it is easily recon-verted into the acid.' This anhydride unites directly with bromine,forming the dibromide GH,< O.CH,.CO,O >CO crystallising in CHBrGHBryellow needles melting a t 213".When the cornpound of aldehydo-phenoxyacetic acid and phenFl-hFdrazine is heated witrh sulphuric acid a bluish-green amorphoussubstance is produced which dissolves in alcohol forming a bluish-green solution and in alkalis forming cherry-red solutions. Thiscornpound is precipitated from its alcoholic solutions by ether as alustroils black powder having the composition CgH7NO3 and meltinga t 108". This same oompound can be prepared by heating amixture of monochloracetic. acid with ortho-oxy benzylidene phenyl-hydrazine in sealed tubes a t 1'00".Orthoxybenzylidene phenylhydra-zine when heated with acetic oxide yields a diacetic derivativeAcO*C,H.,CH N2AcPh which crystallises in needles or prismsmelting a t 133". On dry distillation this compound yields acetanilidexud a reddish-yellow substance cont)aining nitrogen. The diacetyl-derivative forins a dibromide which is easily decomposed acd whenboiled with alcohol yields ucetozydibromobeizxyZiden,ep~enylli~d~az~n(~ORCANTC CHEJIIS'I'RY. 6 7AcO*C,H,Br,*CH N,HPh melting a t 188" ; this is decomposed byboiling with caustic soda ; from the alkaline solution hydrochloricacid precipitates the compound H0.C,H2Br2.CH N?HPh meltinga t 148". P. P. B.Constitution of the Phthalic Acids. By E. NGr,mG (Bey. 18,2687).-The constitution of the phthalic acids has long been known,hut the proofs are of a complex nature.The author now advances ahimple proof. The three xylenes when oxidised readily yield thethree phthalic acids. Three isomeric nitroxylenes xylidines andxylenols are derived from metaxylene two from orthoxylene oneonly from paraxylene. Therefore tl ie carboxyl-groups must occupythe 1 3 positions in isophthalic acid the 1 2 positions in phthslicacid and the 1 4 positions in terephthalic acid. A. J . G.Nitration of Phenylparaconic Acid. Bp H. ERDIIASN (Be). 18,2741-2743) .-Paranitrophenylparaconic acid is prepared by theniteration of phenylparaconic acid. It forms very bright yellow plateswhich melt a t 155". It is insoluble in carbon bisulphicle anddissolves sparingly in chloroform benzene and ether readily inalcohol glacial acetic acid hot xylene &c.When heated at 200",evolution of carbonic anhydride takes place. Potassium permanga-riate converts i t into paranitrobenzoio acid.I n the preparation of this acid the ortho-acid is also formed(compare Abstr. 1885 1224). N. H. A!€.Derivatives of Durene. By 0. JACOBSEN and E. SCHNAPAUFF(Bey. 18 2841-2844) .-When powdered durene is gradually addedto about 2+ times its weight of cooled sulphuric monochloride,tlurenesulphonic chloride is obtained as the chief product togetherwith durylsulphone and alittle durenesulphonic chloride. On treatingthe product with ice and water the sulphuric hydrochloric andsulphonic acids are separated from the sulphonic chloridc a n d t,hesulphone and on adding an excess of soda to the acid filtrate thvsodium sulphonate separates out.The sulphonic chloride may boseparated from the sulphone by crystallisation from alcohol andfinally from ether. Durenesui$honic acid C,H,*XO,H dissolvesreadily in water b u t only sparingly in moderately dilute sulphuricacid ; the sodium potassium barium and copper salts are described.DurenesuZphonic chloritle CloH13*S02C1 crystallises from warm ethcrin brittle prisnis of vitreous lustre melts a t 99" dissolves readilyin warm sparingly in ice-cold alcohol and very readily in ether.D1iren~suZ~honnmide CIOH13.S02NH2 crystallises from alcohol in longprisms melting at 155" ; it is very readily solnble in hot sparingly incold alcohol and in ether and is almost insoluble in cold water ; it isdecomposed by concentrated hydrochloric acid a t 190".D;)Lr!jZsuZphone (CioH,3)2S0 is readily s9luble in alcohol ether,benzene and light petroleum whilst boiling water dissolv2.s butttwes.It can bcdistilled under diminished pressure without decomposition but a t theIt crptallises in long prisms melting a t 37".f G8 ABSTRAOTS OF CHEMICAL PAPERS.atmospheric pressure it yields sulphurous acid and durene. Whenheated with concentrated hydrochloric acid at 200" it splits up intodurene and sulphuric acid.When sodium durcnesulphonate is fused with potash eitherdurenol or hydroxydurjlic acid is produced accordingly to thetemperature and time of heating. DzirenoZ CIOHl3-OH crystallisesfrom warm alcohol in large flat prisms melts a t 117" and boils a t249-250".Bwmodurenol C10H,2Br*OH crystallises from hot dilutealcohol in long vitreous prisms melting a t 118". It is readilysoluble in alcohol and ether insoluble in water. Nitrodwend,Cl0Hl2(NO2)*OH separates from hot dilute alcohol as a bright yellowinass. It melts a t 130" is almost insoluble in water very readilysoluble in dcohol and also in alkalis and alkaline cai-bonates withdark yellow coloration.HydyoxpZurylic acid C,HMe,( OH)*COOH is almost insoluble incold sparingly soluble in hot water but very readily in alcohol.Its constitution is [COOH OH Me = 1 2 3 4 G I . It crystal-lises i n small needles melts at 148" and may be sublimed withoutdecomposition.Its salts give a didy brown precipitate with ferricchloride whilst a solution of the free acid in diIute alcohol gives atransient blue coloration. The calcium salt ( CI,H,0,),Ca + 2H,O,is described. When the acid is heated at 190-200" with hydro-chloric acid carbonic anhydride and pseudocumenol (melting a t85-88"> are produced.Phenylacridine. By A. CLAW and C. NICOLAYSEN (Ber. 18,2706-2712) .-Potassium permanganate acts on phenylncridine inpresence of free sulphuric acid with formation of a mixture ofparaphenylquinolinecarboxylic acids from which a di- and a mono-cwboxylic acid were separated. Yurap7ter~ylquinolilredicarbosylic acid,I'h*CgNH,(COOH) forms lustrous needles melting at 200-215".The barium salt (with 4 mols. H,O) crystallises in slender colourlessneedles. Barium parnphenylpuinolinecarbo~y late ( CIbH10N02)2Ba,6H20,crjstallises in needles.Yhenylamidobenzoic <acid NHPh*C6H4*COOH is obtained by theoxidation of phenylacridine methyl chloride with potassium per-ruanganate.Itl forms small colourless needles rnelting at 2.22"(uncorr.) alniost insoluble in water readily soluble in ether chloro-form &c. The sodium saZt (with 4 mols. H,O) fornis coloarless1 lates readily soluble in water; the barium (with 5 mols. H20) andsilver salts are also described.An acid having all the properties of that just described is obtainedby heating metamidobenzoic acid with aniline hydrochloride a t 220".Phenylacridine hydrochloride crystallises from pure water in redoctahedra (with 5 mols.€LO) ; the long yellow anhydrous needlesdescribed by Bernthsen are obtained from a solution containing free11s drocli loric acid.a-Naphthylaminephthale'in. By A. VANNI ( Gazzetta 15 346-34i).-On heating phtlialic anh.ydride and a-niiplithjlamine in equalmolecular pioportiuns at a temperature of lW" 5t fused mass isA. K. M.N. H. MORGANIC CHEJIISTRY.formed ; thin is heated with boiling alcohol andas it cools deposits a-naphthylaminephthalejin,f i 9the filtered so!utionin the form of colourless transparent prismatic tables. It is insolublein water sparingly soluble in alcohol and ether and melts at 166". Itis decomposed by concentrated sulphuric acid forming a pale yellowsii bstance which dissolves in ammonia with an orange-red coloration ;with concentrated potash it forms an oil which ultimately solidifies ;the compound formed gives a violet coloration with water.V.H. V.Relations of @- to p-Hydrojuglone. By F. MSLIUS ( J h . 18,2.567-2571).-The acetyl- or benzoyl-derivatives prepared froina- and from P-hydrqjuglone are identical and seem to be theP-derivatives inasmuch as they yield @-hydrojuglone when treatedwith alkalis or sulphuric acid. The compoiind previously describedas triacetyl-a-h.vdro jnglone (Abst'r. 1885 170) Ehould therefore beternled t?.iac~tllZ-$-h?//Zrf!jtigtone. It cry stall ises in colourless prisms,and melts at 129-130". Triberizoyl-3- h?ydr.oj!l'uy/one CIOH50JBzI,crystallises in colourless needles melts a t 228-229" and like t h eacetyl-derivative can be sublimed unchanged.a-Hpdrojuglone when heated above its melting point in an atmo-sphere of hydrogen is conrerted into P-hydrojuglone which distils ;on the other hand when the p-compound is subjected to prolongedboiling with dilute hydrochloric acid it is converted into a-hydro-jnglone.A. J. G.(Monatsh. Cheiii. 6 754-~59).-dntlzragt~llolamida,Action of Ammonia on Anthragallol. By S. V. GEORGIEVICSi s prepared by boiling anthragallol with excess of ammonia f i i ~20-30 minutes; the fine blue solution so obtained is evaporatrctdown aiid the solid substance crystallised from alcohol or glaciitlacetic acid. It forms greenish-black needles or R reddish-brown,crystalline powder sparingly soluble in hot water alcohol anttbenzene &c.Alkalis a,nd srilphuric acid dissolve it uncbanged,with formation of blue and intense red solutions respectively.Nitrous acid acts on it with formation of ayellom substance which meltsat 190-200" ; it does not contain nitrogen and is probably dihydroxy-anthragallol [(OH) = 2 31.Two nitro-derivatives of anthragallol were obtained from gallic acidby the action of meta- and of para-nitrobenzoic acid.A~zthragallolsulpTonic acid is prepared by heating anthragallol with3-4 times its weight of sulphuric acid at 130-140". The aqueoussolution acquires a red colour when treated with the smallesttrace of alkali. The sodium aiid potassium salts have cnloiiringproperties. N. H. Id70 ABSTRACTS OF CHEJIICAL PAPERS.Terpenes and Ethereal Oils.By 0. WALLACH (111) (Annulen,230 225-2'12).-Yure borneol prepared by the action of sodium oncamphor melts a t 206-207" riot a t 198" as generally stated. Thiscomponnd behaves like a saturated secoridary alcohol but it hasthe property of uniting with bromine and hydrogen bromide &c. toform nnstable additive products. For example when bromine isadded to a solution of horneol in light petroleum a crystalline preci-pitate is deposited which consists chiefly of Oorneol bromide,CloHlsO*Br2 mixed with a small quantity of (C,oH,O),Hr,. Cineol,like borneol unites with bromine in two different proportions formingcompounds which have the same composition as the borneol bromides.When borneol bromide is covered with light petroleum and left forsome time in a closed vessel decornposition ensues resulting in theformation of borneol and borneol hydrobromide (C,oH,80)2,HBr.The same compound is obtained as a white crystalline powder by theaction of hydrogen bromide on a solution of borneol in light petroleum.It is dccornposed by water and alcxohol.The hydriodide (CloH,80)2,HI is tt white crystalline compound,which decomposes spontaneously .Rornyl chZoride Cl0HI7C1 is easily prepared by adding boriieol to amixture of phosphorus pentachloride and light petroleum. Theaction is finished in half an hour.The crude product is poured intowater and repeatedly washed. Bornyl chloride is not identical withpinene hydrochloride. It is readily converted into camphene byheating with aniline. Camphene is decomposed by dehydratingagents such as zinc chloride and strong sulphuric acid or by theaction of heat alone.In each case the decomposition products areliquid. Monobromocamphene is obtained as an oily liquid whenbromine is added to a solution of camphene in alcohol and ether.Camphelie is formed by the action of dehydrating agents on borneol,but the hydrocarbon cannot be isolated (except when potassiumpyrosulphate is the dehydrating agent) as it is decomposed by zincchloride or phosphoric anhydride or strong sulphuric acid.The so-called hydrocarbon " borneen," which Pelouze ( A n n a l e n 40,:327) Kachler (ibid. 164 78) and Oppenheim (this Journal 1874,891) obtained by the action of phosphoric anhydride on borneol is amixture of the decomposition products of camphene.The author confirms Tilden's statement (Trans. 1878,SO and %I.),that Kussian and Swedish oil of turpentine contain the same cou-stituents namely austpalene splvestrene and dipeutene.Thehydrocarbon obtained by decomposing sylvestrene chloride withauiline closely resembles sylvestrene but the identity of the bodies isnot proved. The hydrocarbons yield a chloridc melting at 7 2 O and aliquid bromide." !l'erpinol " described by Wiggers ( A n n a l e a 57 252) and byList (ibid. 67 367) does not exist.Terpine hydrate C10H2002 + H20 melts at 117". It is a saturatedcompound and is decomposed by boiling with acids or dehydratingagents yielding terpineol C,H,O and other products. When aTiiixture of I part of sulphuric acid anti 2 of water is used,terpiueol terpinene CJT and terpinulene are formecl. Wlicn verORGANIC CHEXISTHY.71tlilute sulphuric acid is used the chief product is terpinene. Dilutephosphoric acid and glacial acetic acid on the other hand yieldterpineol as the principal product. Terpine hydrate is almostcompletely converted into dipentene by prolonged treatment wit'lipotassium pyrosulphate.Terpineol CIOH1,*OH is a nonsaturated monatomic alcohol. It is athick liquid boiling a t 215" and is sparingly soluble in water. I tnnites with bromine to form an unstable bromide.Bipentene tetrabromide melting at 124" is formed by the action ofr7,n excess of bromine on terpineol. The hydroxyl in terpineol iseasily replaced by chlorine or iodine yielding for example thechloride CloHl,CI melting a t 50" and the iodide melting a8t 77".Terpineol unites with carbanil forming phenylterpinylurethane whichcrystallises in white needles melting a t 110".Boiling with diluteacids or treatment with dehydrating agents converts terpineol intoterpene or dipentene but if ferpiiieol is left at the ordinary tempera-ture in contact with dilute sulphuric or hydrochloric acid it uniteswith water forming terpine hydrate CloHzo02 + H20.Terpine has the same boiling point as dipentene but the twocBompounds are not identical as the former yields a liquid bromine-clerivative. Terpine is formed by the inversion of pinene witb:ilcoholic sulphuric acid.It boilsbetween 185; and 190" and yields an unstable tetrabromide crystal-lisiog in mouoclinic plates.The relation between camphene borneol and camphor is shown bytlie following formulE :-Terpinolen,e has not yet been obtained in a pure state.Cmiphenc.Borneo].Camphor.Borneol bears the same relation to camphene that terpineol does todipentene. w. c. w.Action of Picric Acid on Terebenthene. By - LEXTREIT (J.Pharna. [ 5 ] 11 211-213).-Terebentliene when heated with picricacid at 150" gives a limpid liquid which after further heating a t thesame temperature deposits crystals on cooling. When freed fromexcess of picric acid and a brown colouring matter i t forms thiu,friable transparent flakes which rapidly take a yellow tint whcnexposed to light. It is insoluble in water slightly soluble in coldalcohol readily in ether carbon bisulphide and boiling alcohol.When heated it first fuses aud then decomposes with a gentle defla-gration.It seems to be a compound of picric acid and camphene ofthe formula ClUHl6,C6H3( N02)30. It is more stable towards aqneou72 ABSTRACTS OW CHEXICXL PAPERS.alkalis than are the known picrates of hydrocarbons. Further withan alcoholic solution of potash a very explosive crystalline precipitateof a purplish-red colour is formed quite different from potassiumpicrate. The compound is rapidly decomposed by a boiling aqueoussolution of soda; a white sublimate is carried over with the steam,which is insoluble in water but soluble in almost all proportions incold alcohol and ether. Its odour resembles both that of camphor andof camphcne.It fuses at 179" camphor at 175" and camphene a t 45".Its rotative power is aD = - 36". Its composition is very nearly thesame as that of camphor.Natural Camphor Oils. By P. MACEWAN (Pharm. J. Trans. [ 3 ] 15,1045-1046) .-Borneo Formosa and Japanese oils are referred to.The Bornean oil sp. gr. about O W O consists chiefly of borneene witha small quantity of resinous matter but with no camphor (borneol) insolution. In contact witth copper it acquires a green colour in a dayor two. The Formosa camphor oil sp. gr. 0.943 is a saturatedoleaceous solution of camphor ; when rubbed on the hand there isat first a strong carnphoraceous odour which soon goes off and asassafras-like odour remains but the oil dries quickly on the skinand leaves no mark.Japanese camphor oil in crude form accordingto Oishi (Abstr. 1885 270) has sp. gr. 0.959 and contains camphor.The sample examined by the author evidently purified of sp. gr. 0.951,had a strong sassafras-like odour and contained no camphor. Scarcelyany of it distilled below 140" about 10-12 per cent. consisting of aliquid isomeride of camphor distilled between 180" and 185" nearlyone-half distilled over up to about 205" ; t,he residue has a sp. gr. of0519.5. Treated with nitric acid and then after a minute with water,the Japanese oil yields a clear crimson solution the Formosa oil a veryslightly green milky solution ; with hydrochloric acid they both yieldsalmon-coloured solutions. This oil is used in the United States toadulterate oil of wintergreen.Picric acid behaves similarly with thymol.J.T.D. A. L.Camphophenylhydrazine. By L. BALBIANO (Gazzattri 15 246-245).-As the formation of camphoroxime seems to indicate thepresence of the carbonyl-group in camphor (Abstr. 1883 728 ; 1884,SlO) although the evidence thus far is not sufficient to decidebetween the aldehjdic and ketonic groiips the author has studied thereaction between pheuylhydrazine hydrochloride and camphor in thepresence of sodium acetate. Jn this way camphopheuylhjdrazine,C,H,-N,HPh is produced. It is a yellowish oil distilling a t 235-245" under a pressure of 170 mm. soluble in dry ether and decom-posed by hydrogen chloride to form phenylhydrazine hydrochloride.Borneo camphor does not react with hytlroxlamine under the sameconditions in which camphor yields camphoroxime ; whilst by treat-ment with phenylhydrazine in the presence of diluents bromocamphoryields pl:enjlhydrazine hjdrobromide and resinous substances.V.H. V.Euonymin. By G. ROMM (Chem. Centr. 1885 442-445).-Thisglucoside is not to be confounded with the medical preparation of thesame name as the latter contains no poison and is employed as aP 6) ORGANIC CHEMISTRY. 4 * )aperient. The author prepares it by extracting the powdered rindsof Euyonrnus atropurpureus with $0 per cent. alcohol distilling andevaporating the extract diluting with water and filtering ; the filtrateis then precipitated by lead acetate again filtered and the clearliquor freed from lead by sulphuretted hydrogen.After neutralisa-tion with magnesium carbonate precipitation with tannic acid aridtreatment with zinc oxide euonymin is obtained in ciystals on em-yoration of its ethereal solution. The bark of Euon?ynzu.s europpiiscontains no euonymin.Constitution of Santonin. By S. CANNIZZARO (Ber. 18 2746-2751).-After reviewing the evidence a t presmt available as to theconst,itution of santonin the author suggest,s the formula-J. K. C.CH CH.CK*CHMe-COas agreeing fairly with its reactions.Derivatives of Santonin. By V. Vrr,r,;\vrcccma (Ber. 18 28.79-2864) .-Photosardonic acid C15H2205 is best obtain3d by exposing :Isolution of 10 grams santonin in a litre of acetic acid (sp. gr. 1-06>to the action of light for about a month ; the product is evaporated toa syrupy consistence in a vacuum the residue washed with water audthen treated with a warm solution of sodium cstrbonate.The undis-solved residue may be dissolved i n alcohol from which it crystallises inprisms melting a t 182-183" and of the composition CI7H2?O5 namely,1 mol. santonin + 1 mol. acetic acid. On adding hydrochloric acidto the sodium carbonate extract photosantonic acid separates and ispurified by repeated crystallisation from alcohol. Its properties agreewith those assigned to i t by Sektini (Abstr. 1877 471). It loses1 mol. H,O at loo" and melts a t 154-155". The composition of itssalts indicates that the water lost at 100" is not water of crystallisa-tion as assumed by Sestini but that undried photosantonic acid bearsthe same relation to the dried acid as santonin does to santonic acid.Barium and silver photosantonates C,5H,0,Ba and ClsH,oO Agz aredescribed.Photosantonin C I ~ H ? ~ O ~ is best prepayen by exposing a solution ofsantonin (20 grams) in alcohol (1 lit're) to the direct action of lightfor three months.The alcohol is distilled off in a vacuum and thethick residual oil treated with lukewarm sodium carbonate solut,ion toromove photosantonic acid. On treating the insoluble portion withether two isomeric photosantonins C17Hz10~ are obtained ; one modi-fication forms platy crystals melting at 154-255" and is dex5ro-rotatory ; [aID = + 76.77" for a solution containing 0.3825 gram in50 C.C. alcohol a t 13".The other modification which is the chiefproduct melts a t 68-6b0 and is identical with Sestini's photo-santonin. It is readily soluble in alcohol and ether and almostinsoluble in cold water; [ = - 121.6" for a solution containing1*0010 gram in 50 C.C. alcohol a t 14" and - 118.4" for 1.0980gram in 50 C.C. alcohol also at 14". The composition of photo-santonin shows that it is not the diethyl salt of photosantonic acid a74 ABSTRACTS OF CHEJCICAL PAPERS.Sestini assumed but the monethyl-derivative of dehydrated photo-santonic acid which is regarded as a lactonic acid thus:-Photo-santonic acid HO*C13H~g(COOH)z ; photosantonic acid dried a t 1 OO",CO0H*C,Hlg <:;> ; photosantonin COOEt*C,H,<$~>. Thelast compound may also be obtained from photosantonic acid alcohol,and sulphuric acid and by the action of ethyl iodide on the silver salt.When gaseous hydrogen chloride is passed into a solution of photo-santonic acid in absolute alcohol the diethyl-derivative of an acidcontaining the elements of a inolecule of water less than photo-santonic acid is obt'ained ; it is termed ethyl cle72.ydropkotosantonate,C,H,(COOEt) an! forms a colourless liquid which does not solidifya t - 10".A solution of 0.7306 gram in 25 C.C. alcohol has a dextro-rotatory power ah 20*4" [&ID = 3. 20.4". The free acid which isisomeric with dehydrated photosantonic acid melts at 132-133". Itis very readily soluble in alcohol and ether ; its dextrorotatory poweris [aID = + 31-9" for a solution containing 0.7114 gram in 50 C.C.alcohol.The barium salt C15HieOJ3a is very readily soluble.A. I(. M.Papain. By S. H. C. MARTIN (Pharm. J. Trans. [3] 15,129-130).-A glycerol extract of commercial papain retains the fermentativeact,ivity of the powder and contains a heminlbumose in quantity,together with a mere ,trace of globulin. When the latter is precipi-tated by magnesium sulphate and the hemialbumose by subsequentsaturation with sodium sulphate the solution is no longer active.The aqueous solution of the precipitated hemialbumose is however veryactive and when tested on coagulated egg-albumin produced peptones ;it is therefore evident that the ferment OE papaw-juice is associatedwihh the hemialbunwse but as yet bas not been separated from it.Papain acts on animal albumin in manner similar to pepsin but notso rapidly ; with milk i t behaves like pancreatic jnice tirst curdling it,the curdling being intensified by raising ths temperature (but notabove 62") and hindered by making the milk alkaline or by dilutingit to some extent or by boiling previous to adding cold water; thecurd is gradually dissolved with the production of peptones leucine,and tyrosine.A hemialburnose is formed as an intermediate productbetween the case'in and peptones.With regard to the action of papain on the proteids of papaw-juice i t converts the globulins into an albumose corresponding withVine's hemialbumose ; leucine and tyrosine being also formed but notisue peptones have been dekected. D.A. L.Pyrrylene Dimethyl Ketone. By G. CTAMTCTAM and P. SILBER(Gazzetta 15 248-250).-1n this paper it is shown that pyrrylenedimethyl ketone (dipseudacetopyrroline) is producible not only frompseudacetopyrroline and acetic anhydride as indicated formerly(Abstr. 1885 378) but also directly from pyrroline by nieans of thesame reaction. By an excess of fuming nitric acid it is convertedinto a mono-nitro-derivative C4NH,( NO,) Ac melting a t 149" mdpossessing acid properties. V. H. VORGAXIC C HEJLISTRT. 75Synthesis of Pyrroline-derivatives. By L. LEDERER and C.PAAL (Ber. 18 2591-8599).-1t has been already shown that pyrro-line derivatives are formed by the action of ammonia 011 acetophenone-acetone and on acetonylacetone (Abstr. 1885 516 1206) and ofammonia and primary amines on ethyl acetosuccinate (Knorr ibid.554,994) the reaction is now extended to ethyl acetophenoneacetaacetnte.Ethy lie methylpheny lp yrrolinecarhoaylate C4NH,MePh*C 0 OE t[Me COOEt P h = 2 3 51 is obtained by allowing a mixtare ofethyl acetophenoneacetate and aqueous ammonia to remain for24 hours; it crystallises in colourless tables or small needles andinel ts a t 120".C&NH:,MePh-COOH,prepared from the ethyl salt by saponification &c. crystallises in long,flat yellowish needles readily soluble in acetic acid benzene and hotalcohol. When heated it partially decomposes a t 175" and melts a t190"; it sublimes in small part but does not yield methylphenyl-pyrroline.Ethylic dimethy~henylpyrrolineonrboxylate C,NHMe,Ph*COOEt[Me Me COOEt Ph = 1 2 3 51 preysred in manner similarwith mbthylamine crystallises in colourless plates softens a t 90°,melts a t 112" and is readily soluble in alcohol ether and benzene.Met hy Zp h e q idly lpy wolinecarboay lic acid CJIg CAN HMePh- C 0 OHLC3H5 Me Ph COOH = 1 2 8.5j. The ethyt salt is preparedby heating ethyl acetophenoneacetoacetate wit,h allylamine and a littleabsolute alcohol in settled tubes a t 180" for an hour; it is a thick oil,and does not crjstallise. The free acid crystnllises in .short lustrousprisms is readily soluble in alcohol ether benzene and acetic acid,and melts at 158". B e t h y ip heiatllaZlyllpt/rroZine C,H,*C,NHMePh[I 2 51 is prepared by distilling the acid ; it crystallises in largeplates melts at 58" to a colourless oil with blue fluorescence boils at;277-278" and is soluble in all proportions in ether almhol benzene,light petroleum and acetic acid.i~~ethy1~henyIpyrrolinecnrboxylic acid,N e th y Idip hen y l p yrrolheca rbox y Z ic acid,C,NHNePh,*COOH i P h I Me COOK Ph = 1 2 3 51,crystallises in small needles melts at 226" and is readily soluble inacetic acid and benzene.The ethyl salt C4NHMePh,*COOEt is pre-pared hy boiling ethyl acetophelloneacetoacetate (1 part) with aniline(1.5 part) dissolved in acetic acid; it crystallises i n small prisms,melts a t loo" and is sparingly soluble in alwhol and acetic acid.L~~ethy7dipher~ylpyr~oline CBNH2MePh is prepared by heathg the freeacid a t above 226" ; it crystaliises in large ca~ourless tables melts a t81" i8 not very readily volatile with steam and is readily soluble inbenzene and light petroleum.iUet R y lphenyEos.thotolylp yrrolinecarbox y I ic acid,C6H1MaC4NHMePh*CO0 H,ciystnllises in small prisms and melts a t 199" ; it is readily soluble inthe udinarj- solvents except water.The ethyl salt is obtained by boil76 ABSTRACTS OF CHEMICAL PAPERS.ing aniline acetic acid and orthotoluidine as a thick oil that cannotbe crystallised. il/lethy123he?aylorthotolyl~~yr,.oline,C6H4Me*C4NH2MePh [l 2 51,is obtained by the dry distillation of the free acid ; it crystnllises inplates melts a t 44" to a pale yellow fluorescent oil boils a t 325-328",and is readily soluble in alcohol ether benzene and light petroleum.Methylphenylpuratoly lcarboxylic acid C6H4Me*C4NHMePh.COOH,resembles benzoic acid in appearance and melts at 227". The eth! Esalt Cz1HZ1147O2 crystnllises in prisms or tables and melts a t 11.5".Methy~~l~enyl23aratolyl~2/rrrtline C6E14Me*C4NH2MePh crystnllises inconcentric paups of slender needles or in tables melts at 91" boilsabove 550° and is readily soluble in light petroleum and benzene.1C~efhyl;when2/l-a-n~phthylpyrrolinrcnrboxylic acid,CloH7*C4NHMePh-COOH [ C J € Me COOH Ph = 1 2 3 51,is prepared by heating a-naphthylamine and ethyl acetophenoneacetatein sealed tubes at 13U0 and saponifying the uncrystallisable product.It crystallises in needles melts a t 244" and is readily soluble inalcohol benzene and acetic acid.Metky7phe97yI-a-naphthylpyrroliiap,CI0H7*CsNH2MePh crystallises in plates melts at 74" boils above360" and is very readily soluble in benzene light petroleum aBdalcohol.&Id h y Zp hen y I- @nap h thy lp y rrolin,e C,H7- CsN H,MeP h cry s t allises i nconcetitrically grouped needles and melts a t 52". The carLozyZic (wid,C ,H,.C,NH Ne Ph* C 00 H crystal lises in small white needles an( 1melis at 249". Its ethyl salt C24HzlN02 crystallises in lustrous plates,and melts at 115". A. J. G.Pyridine-derivatives. By H. WEIDEL and F. Bf,Au (itfOl70,f~h.Chern. 6,651-666) .-When 30 grams of dibroniopyridine are heatedfor 24 honrs at 160" with 80 C.C. of absolute alcohol and a slightexcess of potash diethoxy- and ethoxy-hydroxypyridine are formed.Diethoxypyridine C5NHI,( OEt) forms an almost colourless oil,which is heavier than water ; i t is readily soluble in alcohol and ether.It boils with decomposition at 243-246" under 749.9 mm.pressure.With mineral acids it yields crystalline salts which are very deli-quescent. The plntinoch Zoride forms lustrous yellow needles.DihydroxypyG%ze C5NHB(OH)P is obtained by hydrolysis of thediethy 1-derivative by hydriodic acid and amorphous phosphorus at1.20". It forms small yellowish-white crystals which become browna t 200" almost black a t 230° and melt with total decomposition a t237-239". It dissolves readily in hot water alcohol alkaline caT-bonates and in dilute acids. When a neutral solution of dihydroxy-pyridine is treated witlh ferric chloride it acquires a reddish-browncolour.The compound is probably identical with the dihydroxy-pyridine prepared by Geigy (Inaug. Diss. Munich 1885) from pyri-dinedisulphonic acid.Ethoxyhydroxypyridine EtO*C,NX,*OH forms colourless plates whichbecome yellowish when exposed to light; i t is sparingly soluble inwater readily in alcohol and in a mixture of alcohol and ether. ThORGANIC CLIEMISTRY. 77crystals are triclinic; a 2 c = 0.97'408 1.01795 1; =$jo 1' ; y = 88" 29'; @ = 91" 04'. It melts a t 127-128" (uncorr.),atid does not dist8il without decomposition. The nityate and pZatino-chloride are described. When fused with potash it yields dihydroxy-pyridine.Sodium ethoxide acts on dibromopyridine at 150" with formationof diet,hylpyridine together with a trace of the monethyl salt.Byt,he action of alcoholic potash on bromopyridine (the intermediateliroduct formed in the preparation of dibromopyridine) ethoxypridinewas obtained ; it forms a colourless liquid which boils below 200° andwhen reduced yields a hydroxypyridine identical with that alreadyobtained fmm /3-pyridinemonosulphonic aeid (compave A bstr. 1884,1050 and 1370). It is therefore a meta-derivative and the dibromo-comDound obtained from it probablg has both bromine-atoms in themeti-position from the fact &at it yields only one monethyl salt.N. H. M.Constitntion of Synthetical Hydropyridine-derivatives. ByA. HANTZSCH (Bw. 18 2x9-2586) .-The constitution of thesecompounds has never been definitely ascertained although it has beenassumed that both the hydrogen-atoms are in union with carbon- - -CH-CH atoms in the pyridine-ring thus giving the formula N<c-c>Cfor the nucleus of this group.Kuckert has Iiowever recently shownthat a substituted hydropyridine-derivative is obtained by the con-densation with paraldehyde and sulphuric acid of the product obtainedby the action of methylamine on ethyl acetoacetate from this itf ,Ilows that the nitrogen must be exerting imidic functions and thatthe constitution of the hydropyridine nucleus must beHN<C C ' C .' c> CH.The ketone CsH,O obtained by the action of hydrochloric acid onethyl hydrocolliclinecarboxy!ate (Abstr. 1883 84) when treated wit,hhydroxylamine jields a crystalline oximido-compound C,H NOH.By heating ethyl acetoacetate with benzaldehyde and methylamine,two non-nitrogenous products C19H2406 and C19H,C)> are obtained.'l'he part played by the methylamine in the reaction is obscure butunless it or some other primary amine is present thesa substances arenot formed.J3thyZ benz y 2 idinediacetoacetate C19H,0s = C HP h (CH Ac-C 00 Et),crystallises in long white needles melts a t 15%-153° and is sparinglysoluble in alcohol and ether ; when treated with bromine it yields asubstitution-derivative Cl9HZ3Bro6 nieltitig at 159".Ethyl dehydrobenzylidinediacetoawtate C19H2,05 crystallises inlustrous prisms melts a t 87-38" and is readily soluble in nearlyall solvents.The author assigns to i t the constitutionCMe C(COOEt)>CHPh,'<CMe C(CO0Et)regarcling it as a hgdropyridine-derivative in which the imido-groupis replaced by oxygen.A. J. G78 ABSTRACTS O F CHEMICAL PAPERS.p-Dipyridyl. By T. LEOKE and V. OLIvExr (Gazzetfa 15 274-277).-A dipyridyl Cl,H6N7 is produced by the dry distillation ofpyridinesulphonic acid and separation of the distillate by concentratedpotash. It crystallises in c:olourless prisms melting at G8" and boilinga t 286-288" ; its platinochloride is an orange-yellow powder insolublein water alcohol and ether This dipyridyl is probably identicalwith that obtained by Skraup and Vortmann by the dry distillation ofdipyridyldicarboxylic acid (Abstr. 1883 88) as evidenced by itsdirect conversion into nicotinic acid and of the formation of the sameacid from the sulphonic acid originally used.It is proposed to call itp-dipyridyl and to assign to it the following structure :-C,H,N*C,H,N [N CaH*;N = 1 31. V. H. V.Pyridin e- choline Pyridine-neurine and Pyridine -muscarine .By T. COPPOLA (Gazzetta 15 330-345) .-The alkaloids choline,neurine and niuscarine are analogous not only in their chemicalconstitution inasmuch as they can be regarded as hydroxyethylene-,ringl- and dihydroxyethylenetrimethgl ammonium hydroxides but alsoin the physiological symptoms producccl by them namely stimulationof the inhibitory ganglia of the heart arrestation of the diastole andexcitation of the secretmy nerves. I n this paper the chemical pro-perties and functions of their pyridine-derivatives ape described.P!jridine-c?ioline hydrochloride OH*C2H4*C5H5NC1 obtained byheating a mixture of pyridine and ethylene chlorhydrin in equalmolecular proportions forms colourless prismatic crystals verydeliquescent and soluble in alcohol and water insoluble in ether.I t s plntino- and awo-ahlorides are yellow amorphous powders ; itshydroxide is very readily decomposed.Pyyidiiie-netwine l;yd&xIide C5H5( CzE3)NI obtained by heatingthe above compound with coilcentrated hydriodic acid crystallises inopaque white prisms very soluble in Bding alcohol aud water,insoluble in ether.Its platino- and auro-ohlorides are yellow amor-phous powders.Pyridine-muscarhe hydi*ochZoriiie C2H3(OH),*C,H,NCI obtainedfrom pyridine-choline by heating i b with nitric acid (sp.gr. 0.148),formsorange-yellow deliqnescen t laminae ; its platinochloi-idc! ci.ys tallises inorange-yellow needles its nurochloride is an amorphous powdei.The physiological function of the al3ove compounds is perfectlysimilar in that they all arrest voluntary movements and a t first excitebut afterxards paralyse the cardiac pulsations. As regards theirtoxic efEects they differ considerably in degree. The variation ofphysiological function with chemical constitution more especially asregards the effect of the substitution of hydrogen-atoms by differentgroups especially h ydroxyl and the choline neurine and mnscarineradicles is discussed a t some length.By S. HOOGEWERFF and W. A. v. DORP (Rec. Frccv.Chim.4 125-12s) .-By adding concentrated sulphuric acid to analcoholic solutioii of the crude quinoline from coal-tar the sulphatesof quinoline and isoquinoliae C9H,N are precipitated and by re-pented rectification of the free bases obtained from this precipitate twofractions are obtained one boiling from 230" to 236O which is chieflyV. H. V.IsoquinolineORUXNlC CHENLSTRP. 7!)quinoline and the other boiling from 236" to 243" containing isoquino-line this is purified by the repeated recrly~t~allisation of its sulpliatefrom alcohol. The free base melts a t 18-23" and boils at 236-2.37.5"(uncorr.). The suZphate CsH7K,H,SOa forms hygroscopic prisms ortablets and melts a t 205-208". The chromate ( CSH7N),H,Cr,0,forms reddish-yellow needles and is decomposed a t about 150".ThepZutinochZori.de ( CSH7N),I3[,PtCI6 + 2H20 forms slender yellowish-red needles ; i t becomes anhydrous a t 110". The picsrnte is but littlesoluble in alcohol or water and crystallises in yellow needles ; it meltsa t 222-223.5'. A. P.Constitution of Quinoline-derivatives prepared from Meta-substituted Amines. By L. GATTERMANN and A. KAISER (Ber. 18,2602-2604) .-Whilst the constitution of quinoline-derivatives pre-pared from ortlio- and para-substituted amines is certain inasmuch asonly one substance can be formed in each case ; in those from metn-compounds two quinoline-~erivatives are theoretically obt'ainable,according as the linking of the pyridine-ring occurs a t the ortho- orpara-position relatively to the substituting group.It seems as thoughthis question can be solved by the use of compounds in which one orthe other of these positions is occupied by halogens &c.ChZoronzeth?llquinoZine C9NH,MeC1 [Me Cl = 1 41 is prepared bySkraup's method from parachlorometatoluidine ; it crystallises incolourless needles of quinoline-like odour melts a t 49" and is solublein water readily soluble in ether alcohol and benzene. The merciiro-chZoride C,H,NCI,HHgCl crystallises in broad needles or tables theplatinochloride (C,oH8NCl)2,H2PtC16 forms yellowish-brown tables o rbroad needles the picrate crystallises in large brownish-yellow tables,nnd melts at 172". When heated with excess of hydrogen iodidedissolved in acetic acid the chlorine is replaced and a methylquinolinoobtained.The author cannot as pet speak posit?ivel yas to the identityor non-identity of this with Skraup's " metatoluquinoline."A. J. G.Paraquinaniso'il. By 2. H. SKRAUP (Monatsh. Chem. 6 f60-$84).-Paraquinanisoil is best prepared by heating a mixture OEi 8 grams anisidine 50 grams nitraniso'il 320 grams glycerol and125 grams sulphuric acid for two hours ; 50 grams more of sulphuricacid are added and the heating continued for two hours longer. Theproduct is then diluted with water distilled with steam and theresidue treated with potassium dichromate which causes a precipita-tion of quinanisoil chromate ; this is then purified. Pure quinanisoilforms a. yellowish oil which soon acquires a green then a reddish-violet colour ; it boils with slight decomposition at 304-305"(uncorr.).Sp. gr. a t 20" = 1.542 (water at 20" = 1). Para-puina&oiZ hydrochhride CsNHOMe,HC1 + 2H,O forms colourlessprisms readily soluble in cold wnter and hot alcohol insoluble i nether. Thechromate forms long gold-coloured silky needles which when exposed toair lose their lustre and become brownish ; i t is very sparingly solublein cold water. The nedral sulphate acid sdphate tartrate and othersalts are described. The aqueous solutions of the salts all shorn aIt loses its water of crystallisation orer sulpliuric acidSO ABSTRACTS OF CHEMICAL PAPERS.blue fluorescence. Chlorine-water and ammonia act on the salts,giving the green colour characteristic of quinine compounds.Paraquinanisoil rnethiodide crystallises from water in long gold-colourcd lustrous needles which melt with evolution of gas at 235".It is insoluble in ether readily soluble in hot water and alcohol.Thalline CSHloNeEO is prepared by reducing quinanisol with tinand hydrochloric acid ; it forms thick white prisms sparingly solublei n water and light petroleum very readily in alcohol ether andbenzene. It melts at 42-43" and boils a t 288" (uncorr.; bar. =735 mm.). When treated with ferric chloride or other oxidising agents,it acquires first a yellow afterwards a dark emerald-green colonr.Silver nitrate produces this coloration with separation of silver.ThaZZine hydrochloride C,H,NO,HCl crystallises in well-formedprisms sparingly soluble in alcohol.The sulphate (with 2 mols.H,O) and other salts are described. Acefylthtrlline CloHl,PU'O*Ac,forms clear broad monoclinic prisms which melt at 46-47". Itsbolubility resembles that of thalline. Bromine acts on thalline withformation of a compound CloH,Br3NO ; it is a pale yellow powder,melting at 19t3-194".MethyZthal7ine CloH,2NOMe is prepared by the action of methyliodide on thallme. I t forms a thick colourless oil which when keptlwcomes brown ; it boils at 277-278-5' (uncorr.). When a solutionin dilute hydrochloric acid is treated with ferxic chloride i t acquiresa cherry-red colour which changes to reddiah-yellow when kept long.The hydrochloride and sulphate crystallise in well-formed prisms,readily soluble in water,Thaliiie hydriodide ( CloH,NO),HI and p a t e r n a r y dirrzethylthall&wiodide CIOH12NOMe21 are formed in the preparation of methylthalline.'J'he former compound crystallises in flat prisms melting a t 155-136" imoluble in ethylbenzene light petroleum readily soluble in hotalcohol. The latter compound forms long prisms insoluble in lightpetroleum readily soluble in alcohol and in water from which i t crystal-lises with 1 mol.H20. I t melts with evolution of gas a t 223-224".Boiling aqueous potash hydrochloric and nitric acids do not act on it.EtlujZtlialliize C,H,EtNO is a thick oil which boils a t 287-287*5O with slight decomposition. It is insoluble in water veryreadily soluble in alcohol ether and in mineral acids. Some saltswere prepared ; they are very hygroscopic and cryatallise with diffi-culty. EthyZtlLa2lirLe et7~iodide forms white needles readily soluble inalcohol and in water insoluble in ether ; it melts with evolution of;'as a t 1:31-133° ; when distilled it decomposes into ethyl iodide andt' t hvlt ha1 lin e.Benzyl chloride acts on thalline with formation of a base probablyLenzylthalline ; when treated with ferric chloride it gives tho samecharacteristic red colour as methyl- and ethyl-thalline.The physiological properties of several of the compounds mentionedin the paper are described.The papei. concludes with remarks on theconstitution of quinine.Para- and Ortho-phenylquinoline. By W. LA COSTE and C.SORGER (Aiinaleii 230 1-42).-l'arayhenylquinoline is prepared byN.H. MORGANIC CHEMISTRY. 81the action of sulphuric acid glycerol and nitrobenzene on paramido-diphenyl. The base is precipitnted from the acid solution by theaddition of an alkali collected dried and dissolved in warmbenzene. The solution is left in contact with solid potassinmhydroxide for some hours and is then filtered. After removing thebenzene by distillation. the residue is distilled under reduced pressure.Paraphenylquinoline CgNH,Ph [Ph = 31 melts at 110-111" nnd boilsa t 260" under 77 mm. pressiire; its sp. gr. is 1.1945 at 20". It issparingly soluble in water but dissolves freely in alcohol chloroform,benzene and carbon bisul phide. Phenylqninoline is deposited fromether in rhombic pyramids from alcohol in combinations of thepyramid and basic plate and from benzene in twin pyramids ; all thesalts are soluble in water fmming fluorescent solutions.The twtratp,CgNH,Ph,H,C,HaO + 3H20 crystallises in needles melting a t 153".The dichromate (CgNH6Ph)2,H2Cr207 forms reddish-yellow needles,which melt at 136". The methiodide C9NR6Ph,MeI + 2H20 crystal-lises in long needles melting at 194". The ethiodide crystallises with2 mols. H20 in pale yellow needles and also with 1 mol. H,O in thick,yellow prisms.When phenylquinoline is treaked with tin and hydrochloric acid i tunites with four atoms*of hvdroyen to form a tetrahydro-cornpound.The hydrochloride C9NH,Ph,HC1 + 1+H20 crystallises in needles.It is sparingly soluble in cold water and is partially decomposed byhot water.It also dissolves in alcohol and in chloroform.Thepicrote CgNH,Ph,C6H,(No2),*o~ is deposited from a hot aqueoussolution in needles which dissolve freely in alcohol chloroform andbenzene. It melts a t 165'.The nitroso-compound C9NHgPh.N0 forms yellow cryst#als freelysoluble in benzene and chloroform. The acetyl-derivative C9NHgPhAc,crystallises in white silky needles. It melts at looo and is freelysoIuble in alcohol benzene chloroform and carbon bisulphide.The benzoyl-derivative forms white plates melting at 137". It isfreely soliible in alcohol.Meth y ItetTa~~ydroparaphen~~ Zquinoline hydrochloride,The free base is soluble in alcohol ether and hot water.C9NHgMePh HCl,prepared by the action of tin and hydrochloric acid on phenylquino-line methochloride is a crystalline substance soluble in alcohol andchloroform.The hydriodide CgNH,MePh,HI resembles the hydrochloride butis more easily decomposed by water.Itdipolves in alcohol chloroform and benzene. The methiodide meltsa t 194". It crystallises in plates or prisms soluble in alcohol and inchloroform.The substitution products of paraphenylquinoline do not crystal-lise easily and can only be prepared with difficulty in the pure state.The mononitro-derivative CljNHlo*N02 is formed by the action offuming nitric acid on an acetic acid solution of paraphenylquinoline.It melts at 173" and is soluble in alcohol ether benzene and in hotwater. The compound also dissolves in dilute acids and forms twoThe platinoch loyide easily decomposes.The picrnte melts at 147".9 VOL.L82 ABSTRACTS O F CHEMICAL PAPERS.crgstallino platinochlorides of which one is insoluble in hot water.The dinitro-compound is obtained by adding phenylquinoline tofuming nitric acid. It melts at 208" and dissolves in alcohol andbenzene.Phenylquinoline dissolves in cold fuming sulphuric acid yielding twoisomeric monosulphonic acids. The a-snlphonic acid C,H,NSO +2Hz0 can be separated from its isomeride by the greater solubility ofthe latter and also of its ammonium salt in water. The a-acid crystal-lises in lon5 needles soluble in hot water. It does not melt a t 300".When oxidised with potassium permanganate it yields parasulpho-benzoic acid. The ammonium salt of a-phenylquinolinesulphonicacid crystallises in plates which dissolve freely in hot water.Tbesodiuni and calcium salts dissolve freely in water the potassium andbarium salts are sparingly soluble. p$heizylq.uilzoZines.ulpkonic acid,Cl5H,NSO3 + H20 dissolves freely in water but is insoluble inchloroform and ether. The ammonium salt crystallises in anhydrousscales.Ortho~henyZqi~inoli?te C9NH6Ph [Ph = 11 is prepared by a processanalogous to that employed in the preparation of the para-compound.It is a thick fluorescent oil which darkens on exposure to the air. Itdissolves freely in alcohol ether benzene carbon bisulphide andchloraoform and boils between 270" and 276' under a pressure of80 mm.Tbe salts of the base are soluble in water forming fluorescentsolutions. The platinochloride crystallises in needles ; the dichromntein plates melting at 126" and dissolving in water and warm alcohol.The methiodide forms reddish-yellow plates melting' a t 163".It isfreely soluble in water alcohol and chloroform. Ortlzop heny lyzcino-linemethyl platinochloride ( C,NH6PhMe),PtCl6 is a crystalline salt,soluble in hot water. It melts at 198". w. c. w.Colouring Matters derived from the Quinoline Bases. By0. DE CONINCK (Rec. Trau. Chim. 4 58-60).-The reaction of analcoholic solution of potassium hydroxide on the iodides of the ethyland methyl derivatives of the quinoline bases by which a red colour-ing matter is produced (Rec. Traw. Chim. 3 337) appears to begeneral for all the alkyl-derivatives of quinoline as the author hasprepared a red crystalline colouring matter from the iodide of thepropyl-derivative ; he also confirms the constitution assigned to thscyanine-derivatives obtained by the action of potassium hydroxide onthe iodide of ethyl-lepidine and ethylquinoline (Abstr.1885 673).Quinoxalines. 111. By 0. HINSBERG (Ber. 18 2870-2875) .-A. P.Dihydro-ox y tolu puinoaaline,is obtained by heating ethyl chloracetate (2 mols.) with toluylene-diamine (3 mols.) for several days on a water-bath and is purified bymeans of its sparingly soluble sodium-derivative. It crystallises inmoderately large yellowish needles is readily soluble in hot wateOROANlC CHEMISTRY. 8 3and alcohol moderately in ether and also in alkalis and acid>.The potassium-derivative is readily soluble in water and in potashsolution; the sodium-derivative C9H,N20Na + H20 forms lustrousscales and is almost completely precipitated from its aqnemssolutions by the addition of soda.Dihydro-oxytoluquinoxaline inalkaline solution is oxidised by atmospheric oxygen to hydroxytol u-quinoxaline ; neutral solutions are not so readily acted on but are alsooxidised by weak oxidising agents.When toluylenediamine and ethyl chloracetate are heated togetherin equal molecnlar proportions the compound C13H16N203 i sproduced and may be purified by crysta1lisa.tion from alcohol. Itforms colourless lustrous scales melts at l47" is sparingly soluble inwater nearly insoluble in ether and moderately soluble in alcohol.Concentrated mineral acids and acetic acid dissolve it readily whilstalkalis dissolve it only on warming.Silver nitrate and nitrous acidoxidise it apparently t o a product melting a t 247-2418". On saponi-fying the substance C13H16N203 with alkali a sparingly soluble acid isobtained crystallising in white needles. The formation and constitu-tion of the above compound may probably be expressed thus :-+ EtOH + CTH~(NH~C~),.A. K. M.Papaverine. By C. GOLDSCHMIEDT (Monatsh. Chern. 6 667-701 ;compare Abstr. 1885 1080).-Analyses of papaverine and of a largenumber of its salts confirm the correctness of the formula C20H,NOaassigned to papaverine by Merck and others. Papaverine cry stallisesin rhomhic prisms a b c = 0.3193 1 0.4266. Crystallographicmeasurements of various derivatives and salts are also given.N. H.31.Hydrobromapoquinine. By P. JULIUS (Monatslz . Chem. 6,750-753),-Hydrobrornapoquinine C,H23BrN2021 is prepared by heat-ing quinine hydrate a t 100" with three times its weight of watersaturated with hydrobromic acid a t 0". It forms a white amorphouspowder which melts a t N9-210" is insoluble in water readilysoluble in alcohol. The hydrobmnide C19H23BrN202,2HBr + H20,crystallises in groups of white needles readily soluble in water and inalcohol. The pZatinochZoride is described. N. H. M.Cupreine and Homoquinine By 0. HESSE (AnfiaZen 230,55-73) .-The author confirms the accuracy of his former statement(Abskr. 1885 276) that homoquinine is a compound of quinine andthe new alkalo'id discovered by P a d and Cownley called cupreine.Many of the properties of cupreine have been already described.The base crystallises with 2 mols.H20 which are expelled a t 120".The anhydrous substance melts a t 198'. The alcoholic solution givesa dark reddish-brown coloration with ferric chloride and an intensegreen coloration m-ith chlorine and ammonia. The neutral salts ofcupreine dissolve in water forming yellow solutions which arerendered colourless by the addition of acids. The solutions are not.fluorescent. The neutral sulphate ( C,H&"02),H,S04 + 6H,O,crystallises in needles ; the hydrogen snlphate C1,HnN2O2,HzSO~ +H20 forms flat prisms sparingly soluble in cold water. There are twohydrochlorides C,H2,N,02,HC1 + H,O crystallising in colourlessneedles and C19H22N,02,SHCl forming pale yellow prisms.Thenormal platinochloride ( C,9H22N,0,)2,H2PtC16 + 4H20 is amorphous ;the acid salt forms orange-coloured plates. The normal tartrate andthiocyanate are sparingly soluble in water. Cnpreine does notcombine with ammonia but it forms compounds with potassium,sodium lead and silver.Anhydrous cupreiiie dissolves in acetic anhydride forming a diacetylcompound C19H,Ac2N202 crystallising in six-sided plates. It meltsat 88" and is soluble in alcohol ether and chloroform. The hydro-chloride also crystallises in six-sided plates soluble i n alcohol and.water.Cupreine is converted into apoquinine by the action of hydrochloricacid at 140". Cupeine methiodide forms colourless crystals sparinglysoluble in cold alcohol and water. The corresponding chloride,ClsH,N202,MeC1 and platinochloride Cl9E2,NzO,MeHPtC1 + 2H20,are also crystalline. The sulphate crystallises in needles which arefreely dissolved in water. By decomposing this salt with baryta-water,the hydroxide is obtained. The aqueous solution of the hydroxidegives a red coloration with excess of bleaching powder in presence ofammonia and a green coloration when ammonia is added to a mixtureof the acidified solution and a small quantity of bleaching powder.The alcoholic solution of the hydroxide is fluorescent.Homoquinine is easily prepared by adding ammonia to a solution ofequal molecular weight of quinine and cupreine in dilute sulphuricacid and dissolving the precipitate in ether. Homoquinine is not asimple alkaloid but a compound of the compositionCocaine and its Salts. By B. H. PAUL (Pharrn. J. Trans. [3],16 325-326).-The author's experiments indicate that the solubilityof coca'ine i n water is much less than 1 in 700; moreover that onevaporating the aqueous solution the cocaine ia decomposed leaving agummy mass whieh crystallises and has many properties similar tothose attributed to ecgonine (compare Merck Abstr. 1885 997). Ityields benzoic acid by the action of caustic soda lime or sodiumarbonate bu.t not apparently by the action of hydrochloric acid. Itcombines with benzoic acid but can b4 separated from the acid byrepeated crystallisation from water. Cocaline hydrochloride is onlyslightly soluble in water from which solution it can be crystallisedwith water of crystallisation but after prolonged heating on a water-bath it remains in a resinous state for a considerable time a tleast. The acetate is very soluble and is diEcult to crystallise owingt o the volatilisation of the acetic acid during evaporation. The solutionof the benzoate dries to a thick gummy residue. Ammonia precipi-tates the alkaloid without apparent decomposition and when added inexcess does not redissolve it. D. A. LORGANIC CHEMISTRY. 85Alkaloi'ds from Erythroxylon. By C. J. BENDER (Chem. Ce?zti*.,1885 490-493).-The author has subjected the leaves of the coca-plant (Eyythroxylon cocu) to a careful investigation. Besides cocaine,he obtained an amorphous alkaloid to which he gives the namecocuzcine and a volatile base which he names erythroxyline. Therealso seem to be one or two other alkaloids present but the author wasunable to obtain them in a pure state or to determine whether theywere present in the %resh leaves or formed during the process ofextraction. L. T. T.Bases in Jaborandi Leaves. By E. HARNACK (Chem. Centr.,1885 628-629) .-Besides pilocarpine and jaborine Merck (Harnackand Meyer Abstr. 1880 898) obtained from the leaves of thejaborandi a third syrupy alkaloid which yielded a nitrate crystallisingin well-defined prisms. The author has investigated bhis alkalo'id,to which he gives the name pilocurpidine. Jt very closely resemblespilocarpine both in physiological and chemical properties but it doesnot give a precipitate with auric chloride. Its formula is CloH14N202.It is easily converted into an amorphous base juboridine C10HlzN203,which resembles jnborine and atropine in properties. Jaboridineappears to be identical with jaborandine C10H12N203 ottained byParodi (Rivista furm. 1875 3) from false jaborandi (Piperjaborundi) and by Chastaing by the oxidation of pilocarpine with,fumiiig nitric acid. The anttior believes that the jaborine hithertoobtained has always contained jaboridine as an impuriby. From theformula and properties of pilocarpine C,IF16N202 this substancewould appear to be a methyl-derivative of pilocarpidine ; and theauthor points out that the latter has the composition OP a di-hydroxy-derivative of nicotine or of an isomeride thereof. Jaboridine is anoxidation product of pilocarpidine formed by the replacement of twoatoms of hydrogen in the latter by an atom of oxygen.Alkalo'ids of Fenugreek Seeds. By E. JAHNS (Ber. 18,2518 - 2523).-The seeds of Frigonellu fGenurn grGecum containt rigonelline and a liquid base identified as choline. Trigonelline,C7H7N02 + H20 crystallises in coburless flat prisms of feeble salinetaste ; it is readily soluble in water sparingly soluble in cold alcohol,insoluble in ether chloroform and benzene ; it is carbonised whenheated. The reactions with the various reagents for alkalo'ids aredescribed. The hydrochloride C7H7N02,HCl crystallises in an-hydrous tables ; the platinochloride ( C,H7N02),H2PtC16 crystallisesin prisms. Two' atdrochlorides were obtained C7H7N02,HAuC14,crystallising in four-sided plates or flat prisms and melting at 198",and 4C7H7NO2,3HAuCl4 crptallising in slender needles and meltingat 186". A. J. G.L. T. 2'.Products of the Action of Hydrochloric Acid on the Albumi-noids. By J. B ORBACZEWSKI (Monatsh. Chem. 6 639-650).-When 500 grams of elastin (previously freed from fat by extractingthe finely powdered substance for two weeks with ether) are boiledfor 72 hours with I litre of hydrochloric acid diluted with an equalvolume of water and 25 grams of zinc chloride a small quantity ofammonia is given off and the solution after precipitation of the zincby hydrogen aulphide is found to contain leucine glycocine andtyrosine. Other compounds are also present but could not beisolated. The formation of these substances and the absence ofglutaminic and aspartic acids and of hydrogen sulphide from theprodnet of %he reaction show that elastin does not belong to the'sameclass of compounds as do albumin and keratin. It also differs fromthe horn substances and all other albuminoids which have as yetbeen examined. PJ EL 11