J O U R N A L OF THE CHEMICAL SOCIETY. ABSTR*ACTS OF CHEMICAL PAPEFLS PUBLISHED IN BRITISH AND FOREIGN JOURNALS. PART I. Organic Chemistry. Elementary Composition of the Mfneral Oils. By CAnrl ENGLER and L. JEZIORANSKI (Bey., 1895, 28, 2501-2505) .-The fiuthors have mado analyses of samples of oil from Galicia, Sumatra, Baku (Bibi-Eibat), Alsace (Pechel bronn), and Pennsylvania, and also of the various fractions obtained from these oils, namely, below 150c, 150-20@', residue. From the analyses, arid from the amount of each fraction absorbed by concentrated sulphuric acid, the aut'liors con- clude that the lower fractions consist mainly of saturated hydrocar- bons of the paraffin series, except in the case of the Baku oil, whereas the portion boiling above 200' consists, in all cases, mainly of uiisatu- rated hydrocarbons of the olefine series.Fractional Distillation applied to American Petroleum and Russian Kerosene. By J. ALFRED WANKLTN and Wrrmm J. COOPER (Phil. .Mug., 1895, [ 5 ] , 40, 225--228).--'i'he paper contains the re- sults of the authors' experiments on the fractional distillatioil of American petroleum, and the vapour density, specific gravity, and composition of the various fractions, the results being compared with those obtained by the authors in the case of Russian kerosene. They consider that each of these petroleums contains a homologous series of hydrocarbons with st common increment of 7, instead of 14, a result that would require the accepted atomic weight of carbon to be halved. For a like carbon contents, the hydrocmbons of trhe Russia11 series, which contain '2 atoms of hydrogen less per molecule, always show a slightly greater specific gravity, the increment varying from 0.025 to 0.035.L. M. J . J. J. S. VOL, LXX. i. b2 ABSTRACTS OF OHEMICAL PAPERS. Russian Kerosene. By 5. ALFRED WAXKLYN and WILT,IAM J. COOPER (Cheiiz. A7e1c.9, 1895, 72, 7).-A tabular whume' is giren of the work done on the hydrocarbons existing in comnlercial Russian kerosene (Abstr,, 1895, i, 77 and 437). Hexylene and Hexylic Hydride derived from. Mannitol by Reduction with Hydriodic acid. By J. ALFRED WANKLTN (Chem. News, 1895, 72, 75j.-The specific gravity of hexylene at Oo is given :IS O.iO17, and of hexylic b-ydride a t OOas 0.6759, differing by 0.0258. A similar difference, of 0.025 to 0.035, is observed between the densi- t'ies of the hjdrocarbons of the same carbon condensation obtained from Russian and American petroleums respectively, the former being the denser.Unsaturated Hydrocarbons. By AL EXANDRE DESGREZ (Ann. Chim. Ph?ys., 1894, [7], 3, 209--246).-Berthelot (Ann. Chim Phys., [3], 43, 385, and [5], 23, 184) has shown that unsaturated hydro- carbons can be made to combine with the elements of water in- directly by means of sulphuric acid; and B6bal and Desgrez (Abstr., 1892, 1162) have shown that unsaturated hydrocarbons also mite with the elements of acetic acid at a fairly high temperature tlo form ethei*eal saJts. The author now demonstrates that the ele- ments of vater can be directly added to the hydrocarbons of the acetylene series.For this purpose, the hydrocarbon is placed with water in iron tubes, enamelled inside, and heated in a bath of sodium and potassium nitrates. Instead of acetylene, the author has used acetylenedicarboxylic acid, and finds that, when the acid and water arc heated at 315O for 20 minutes, a quantity of paraldehyde is formed. Tetrolic acid, when heated with water in a similar manner, gives rise to acetone. CEhanthylidene, with water at 3 2 5 O , yields methyl amyl ketone. Caprylidene, when heated with water for three hours at 320-330°, yields methjl hexyl ketone. Pheiiylacetylene, under similar condi- tions, gives ncetophenone ; methylbutylacetylene yields a mixture of equal quantities of niethyl amyl ketone and ethyl bulyl ketone. The ketone distils at 146-147", and does not unite with sodium hydrogeii sulphite.A number of experiments were made with rnethylan~~.lacet3-lene and water, from which the author concludes that the yield of ketone increases with the period of heating: that a maxininni is rcttcheci with a period of three hours, from which point t,he yield again decreases, and, further, t h a t the yield increases with the temperatiire, reaching a maximum of 75 per cent. of the theo- retical at 360". The product consists of n mixture of methylamyl- acekone and ethyl butyl ketone. Dip11 oiylrtcetylene (tolane), under similatr conditions, yields deoxy- benzo'in, w-liicli c u i be separated from the unaltered tolane by means of alcohol. It is finally sho:i.n that the above hydrocarbons contained no trace of hydrogcn c,liloricte, which might act as a condensing agent, and, t.hereforc, tlici general reaction given above shows a direct synthesis of ketones fivm thc ~ ~ ~ ~ s i L t u ~ a t e d hydrocarbons of the acetylene series.D. A. L. D. A. L. J. J . S .ORGANIC OHENISTRY. Compounds of Mercuric Cyanide with Metallic Chlorides. By RAOUL VXRET (Compf. rend., 1895, 121, 348-351).-Experiments vere made with the view of ascertaining whethtr compounds of the type 2Hp(CN),,bI"C12 + nH,O have really this constitution, or are compounds of a double cyanide and mercuric chloride, Hg (C N) ,M" ( CN) 2, Hg C I,. The first column contains the heat of dissolutioii of ihe crystallised salt; the secoiid column the heat developed by mixing dilute solu- tions of mercuric cyanide and the metallic chloride ; the third column the heat of formation of the solid double salt from solid mercuric cyanide, the solid metallic chloride and liquid water.2Hg(CK),.2NaCl + 2$H,O . . . . , . . 2Hg(CN),,2NH4C1 + 1$H20.. . . . . 2Hg(CN)2,BaC12 + 5H,O.. . . . . . . . 2Hg(CN)2,SrC12 + 6H,O . . . . . . . . . ZHg(CN)?,MgCi, + GH,O.. . , . . . . . 2Hg(CN),,ZnCl, + 7H,O.. . . . , . . . Hg(CN),,CdCI, + 2H,O ... .... .. ~H~(CN)~,C:LCI? + GHZO .. .. .. . .. 'I. 1 11. 1 1x1. I -16.20 Cal. I + 0 33 Cal. -14'80 ,, +0*38 ,, -17.1 ,, \ +O*46 ,, -15.80 ,, +O'45 ,, -14.20 ,, +O.GO ,, -13'30 ,, +O'60 9, - 9.30 ,, 1 +0'38 9, - ,, j +0.50 ,, + 7.95 Cal. + 3. '18 ,, +13-55 ,, +21 -25 ,, +26*1 ,, +404 ,, +23% )., + 6-48 ,, These results ifidicate that the whole of the cyanogen remains in direct combination with the mercury, and this view is supported by the fact that the cold solutions of the double salts are not alkaline t o litmus, and, if heated a t 30' wit11 a soluble picrate, no isopurpurate is formed.If, howerer, the solutions are boiled, they become slightly alkaline, and give the isopurpurate reaction, from which i t follows that, a t the higher temperature, there is a migration of atoms, and part of the cyanogen becomes combined with the alkali or alkaline- earth metal. C. H. B. Copper Ferrocyanide. By GTTSTAV RAUTER (Zed. mzgw. Chc117 ., 1895, 315--3316).-This is an investigation of the nature of the pre- cipitate formed, under varying conditions, by the interaction of copper sulphate and potassium ferrocyanide. Tile upshot is that the precipitate always retains potassium ferro- cyanide, but that this must not be looked onas a chemical constituerit but only as an impurity.Owing to thegreat difficulty experienced i n completely washing the roluminous deposit, a8 certain amount of potash is obstinately retained. L. DE K. Sulphur as a Preservative of Chloroform. By L. ALrATN ( J . Plzarm., 1895, [6], 2,252-255).-Chloroform, saturated with sul- phur in the cold, may be kept in direct sunlight for months, without iindergoing change ; in particular, no carbonyl chloride is formed. This stability is not due to any change produced by the sulphur, for the redistilled liquid rapidly decomposes when exposed to the mrne b 24 ABSTRACTS OF CEEMIOAL PAPERS. conditions. As the anadhetic properties of the chloroform are not modified by the presence of' tbe sulphur, the asddition of this pre- servative is to be recommended. JN.W. Nitro-alcohols. By LOUIS HENRY (Conzpt. r e d . , 1895. 121, 210 -213) .-Nitromethane and formaldehyde, in presence of a small yixantity of potsssiuni carbonate, react quantitatively with production of tertiitry nitrotrihydroxybdans, NO,*C(CH,*OH),, a white, solid compound, which cr-j-stallises in needles or in large prisms melting at 1.58-159', and soluble in watep, alcohols, and acetone, but less soluble in ether. Attempts to obtain products of the interaction of one molecule of nitromethane and one and two molecules respectively of formaldehyde were unsuccessful. Nitroetliane and formaldehyde, in presence of potassium carbonate, yield the compound N02*CMe( CH,*OH),, which is teTtias.y nitrodi- 'hydrozybzrtane or tertiary ?Litroisob.zctylenic glycol.It crystallises very readily, melts at 139-140°, and is soluble in water, alcohols, and acetone, but less soluble in ether. Secondary nitropropane and form- aldehyde, under similar conditions, yield the nitroisobntylic alcohol, NO,*CMe,*CH,*OH, which melts at 82", crystallises very readily, ifi very soluble in alcohols and acetone, but less soluble in water, and more soluble in ether than the two preceding compounds. From these results i t follows that the reaction capacities of the three nitroparaffins with respect to formaldehyde are proportional to the number of hydrogen atoms attached to the group C*N02, and there is little doubt that tertiary nitrobntane, N02*CMe3, would have no action on formaldehyde or the other aldehydes of the same series.Glucoseacetone. By EMIL FISCHER (Ber., 1895, 28, 2496-2497). -The author has previously shown (Abstr., 1895, i, 440) that &glucose, arabinose, and fructose react with two molecules of acetone, and rhamnose with only one ; it is now shown that glucose can also form a condensation product with one molecale of acetone. Thin substance has the composit,ion C6HlOo6:CMe2, and the author terms it, glucose-acetone. It diil'ers from the alcoholic glucosides in the fact that it is riot acted on by emidsin or by the enzyme of yeast; i t forms small, felted needles, melts a t 160-161O (corr.), is soluble in water, and is IEvorotatory. It has a bitter taste, does not snblirne a t loo", but may be distilled in small quantities without undergoing decom- position ; it is readily decomposed by dilute acids, but has no action on Fehling's solution.C. H. B. J. J. S. Inversion of Maltose and Isomaltose by means of Yeast. By CARL J. LINTNER (Chem. Centr., 1895, i, 271-272 ; from Z e d . Ges. Brauu.., 17,414-415).-Referring to the investigations of E. Fischer on the influence of the configurat,ion of the molecule on the action of enzymes, the author has observed t)hat the hydrolysis of maltose pro- ceeds most rapidly with yeast powder, the aqueous extract is less active, and precipitated invertin least,. Isomaltose is more readily attacked than maltose. The enzyme is less soluble than invertin, and appearsORGANIC CBlUllSTRY. 5 to be more closely allied to the glycolytic ferments.The presence of dextrose in small quant'ity in Munich lager beer, is due to the action of yeast on isomaltose. J. B. T. The Inulin of Garlic, Hyacinth, Narcissus, and Tuberose. By R. CHEVASTELOK ( J . €'harm., 1895, [6], 2, 83-86 ; from Inaug. Diss., Paris, 1894) .-The reserve material of the bulbs and other underground parts of certain monocotyledons is a kind of inulin. To separate this substance, the bulbs, he., are cut into small fragments, and digested with ether, to cause the expulsion of the sap from t8he cells ; the sap collecting a t the bottom of the vessel, together with a further amount remaining in the fragments, and liberated by pressure, is puritied with basic lead acetate and aninial charcoal, and the inulin precipitated by baryta water.The insoluble barytn compound of the carbohydrate is decomposed by carbonic anhydride, and the inulin precipibated with alcohol-ether as a syrup. Finally, this is dried in succession by washing with alcohol and ether, and then under diminished pressuye, and a t 100'. The inulin of garlic, CGHI0O5, is a white, inodorous, amorphous powder, distinct from the inidin of the Jerusalem artichoke. Its taste is insipid, and it is very deliquescent. It melts at 175-176', and is soluble in water and dilute alcohol, but only sparingly in strong alcohol. It does not reduce alkaline copper tartrate, and is completely hydroljsed by acids to levulcse. I t is precipitated neibher by normal nor by basic lead acetat,e, except in presence af ammonia. It is not hydrolysed by amylase (malt diastase), but is resolved into levulose by an enzyme inulase, which is secreted by Aspergillus niyer, and is similar to the enzyme of the inulin of the Jerusalem artichoke, and of Atracty7is. The inulin of garlic is not fermented either by hydrolytic or non-hydrolytic yeasts. The sap from the offshoots of the garlic bulbs contains only traces of reducing sugars, and yields nothing but levulose on hydrolysis, so that i t contnixis no reserve material but inulin.The inulin of the sap of the bulbs of various species of hyacinth is identical with that from garlic. The bulbs also contain a small amount of levulose, and a large amount of starch, so that here the reserve material is stored in both soluble and insoluble forms.The inulin from the bnlbs of the narcissus and tuberose is also identical with that from garlic ; neither. OE these contains starch, but the nsrcissus sap contains both glucose and levulose, whilst that of thc tuberose contains glucose only. Various other bulbous monocotyledons were examined, such as thc onion, tulip, and iris. Glyoxylic acid and its Behaviour towards Carbohydrates. By CARL BOE'rTIXGER (Arch. Phas.na., 1895, 233, 287-394) .-Gly- oxylic acid acts as a hydrolSsing agent towards starch and cane sugar, and i t prevents the fermentation of the products formed, for it acts on yeast as a poison. From gljoxylic acid and glucose, a syrup is obtained, which is asserted to have the constant compositioii The rotatory power is [ a ] ~ = -39'.JN. W.(-i ABSTRACTS OF CHEMICAL PAPXRS. CGHI2O6,C2H2O3 + H20 ; with galactose n sirsilar compound nzay have been obtained, and with levulose a. compound C6HI2O6,.2C2H3O2. C. F. B. Preparation of Glycogen. S y D. Huizisas (PJluger's AYC~L~V, . d95, 61, 32--38).--On account of the opalescence of glycogen solu- tions, the presence of albumoses in small quantity can only be ascer- tained by mean3 of the biuret reaction or hy Millon's reagent, ; with the former, not less than 0.5 per cent. can be detected; with the latter, a distinct orange colour is obtained when the solution contains 0.1 per cent. ; if the albumose is precipitated by means of a solution containing sodium tungstate (100 parts), phosphoric acid (50 parts), concentrated hydrochloric acid (10 parts), and water (500 parts), and the dried precipitate treated with 114illon's reagent, the presence of 0.02 per cent. of slbumose may be distinctly recoguised.The above experiments were made with nlbuiiiose prepared t'rom egg albumin ; the presence of glycogen is withuut effect on the reactions. The boiling water usually employed €or the preparation of glycogen extracts albumoses in considerable quantity, and their subsequent separation is attended with considerable ditEcnltJy ; triclilorscetic acid, which Frankel used instead of water, also dissolves dbuinoses, as do sulphosalicylic acid and formaldehyde solutions ; satui*ated solution of mercuric chloride extracts pure gl-jcogen, but the resulting liquid is often unsuitable for filtration ; the best resulcs were obtained by the use of equal parts of saturatbd solution of mercuric chloride and Esbach's reagent, made by dissolving picric acid (10 grams) and citric acid ( 2 ~ grams) in water (1 litre).The glycogen, after wash- ing with alcohol and ether-alcohol, was free from albumoses, and contained 0.62-0.80 per cent. of ash. This method, although good for the preparation of glycogen, is not adapted for its quantitative esti- mation, as i t yielded only 78-89 per cent. of the total glycogen determined by Kiilz's method. J. B. T. Oxycellulose. By R. W. TROMP DE HAAS and BERNHARD TOLLENS (Annulen, 1895, 286, 296-300; compare Abstr., 1893, i, 295).- The authors have hydrolysed, with sulphuric acid, oxycellulose obtained by treating fir saw-dust with nitric acid. Twent.y grams of oxycellulose was added slowly to 100 grams of concentrated sulphuric acid mixed wit,h 20 grams of water, SO grams of water being added after an hour ; on the following mornizig, 2.5 litres of water were added to the liquid, which was heated in a reflux apparatus for five hours i n boiling water.After neutralising the pale pellow liquid with calcium carbonate, the filtered solution yielded 3 grams oE dextrose, having the specific rotatory power [alD = -+ 51.2". Determination of cellulose by Lange's method indicated the presence of about 20 per cent., whilst 3 per cent. of furfuraldehyde was obtained from the oxycellu- lose by distillation with hydrochloric acid. From these results, the authors conclude that the oxyccllnlose obtained from fir-wood is not identical with the oxycelluloses investi- gated by Cross and Revan, Witz, and NastjulcoE.M. 0. F.ORGAN10 OHEMISTRY. 7 Remarks on the Foregoing Paper. By BERSIIIRO TOLLENS (Annulen, 1895, 286, 301-:302).--Many substances wliich yield furfuraldehyde when distilled with hydrochloric acid aye fourid to contain, in some form, pentoses or glycuronic acid. This is not the case with the oxycellulose described in the foregoing abstract, and the author suggests glycoson, CsH,,Os, as a possible source of the production of furf uraldehyde from this substance. Constitution of Pectin Substances. By B ERXKLI: n TOLLENS (Annulex, 286, 292-295) .-From a consideration of the properties O E these substances and the products of their hydrolysis, the author regards them as carbohydrates combined chemically with acids, this view having been already advanced by O'Sullivan regarding the vegetable gums.31. 0. F. 31. 0. F. Pectin Substances. By R. W. TROJIP DE HAAS and ELRNEARD TOLLENS (Annulen, 1895, 280, 278-292) . - S h y attempts have been made to establish a relationship between pectins and vegetable gums (carbohydrates). Accurate determinations of composition are essen- tial t o generalisations of this character, and the authors have accord- ingly prepared and analysed pectin substances from various sources, the proportion between hjdrogen and oxygen being indicated in each case. The. pectins were precipitated by alcohol in the juice espressed from the fruits, and, after being washed with ether, were dried over sulphuric acid. The analytical results are einbodied in the following table.Pectin. 1 Percentage of C. 1 R:itio of 11 to 0. Percentage of Ash. --_____ -_-] __-__.___ I_---- I Apple A ............... Apple U ............... Cherry ............... Rhubarb A.. .......... Rhubarb B.. Currant.. ............. J 1 Plum ' Swede A .............. Swede B . . ............ .......... I ................ 4.3 *35 43 '46 4.2 '42 43 '31 42 -89 46 *S7 42 a 9 2 41 *08 42 -33 From this it is clear hhat the pectins are allied in composition to the carbohydrates, and that the low proportion of bycicogen to oxygen (1 : 10-12) recorded by previous observers is not confirmed. Hydi.olysis of these pectins leads to the formation of liexoses or pentoses. 11. 0. F. Preparation of Methylamine. By AND R 6 B KOCH ET and It.CAMBIER ( J . Pham., 1895, [6], 2, 172-173 ; from Rcc. Chim. Itdustr., June, 1895 ; compare Abstr., 1805, i, 642).-Formaldehyde (90 kilos. of 40 per cent.) is distilled with ammonium chloride (10 kilos.). The action commences at 40°, whcn methylal passes over, and the distii- late up to 95' contains 60--79 per cent. of that snbstance. TheS ABSTRACTS OF OHENICAL PAPERS. residue is evaporaked down until ammonium chloride commences to crystallise ont, and, oii cooling, the whole excess of that substance separates. The liquid remaining is a nearly pure solution of methyl- amine hydrochloi~ide, from which the pnre substance is obtained by evaporation under low pyessure and recrystallisation from alcohol. The yield of 93 per cent. methylamine hydrochloride, melting a t 210°, is 8.5 kilos.with the above quantities, and, a t the same time, 3.8 kilos. of methylal and 2.2 kilos. of carbonic anhydride are formed, and 3.5 kilos. of ammonium chloride recovered unchanged. Jx. W. Chloro-derivatives of Amines. By ARMAXD BERG (Ann. Chim. Phys., 1895, [7 3, 3? 2E9--3Gl).-The normal butylamines hare been prepared according t o Hofmann's method by the action of butylic chloride on a dilute alcoholic solution of ammonia. The bases are first separated by means of their hydrochlorides, and then the primary base is purified by conversion into dibutyloxainide, C202(NHC,H,)2. which melts a t 153O, and is but sparingly soluble in water. The mother liquor contains butylamine butyloxamate, C4He'NH*C0.COO*hTH3.C~H~, which, when heated in aqueous solu- tion with calcium chloride, yields calcium butyloxamate, (C4H,.NHGO-COO),Ca + 2H,O.B u t y h n i ? t e oxdate, Cz02( ONH,*C4Hg),, is deposited on evaporating the mother liquid of the oxaniate. Dibuty lamiiie hyld~.ochlode is made use of in the separation of the secondary base. The azwocldoride, NH2( C4HS)2A~Clr, is precipitated when coiicentrated solutions of gold chloride and dibntylamine hydro- chloride are mixed ; it crystallises in long, golden needles, and melts at 170@. The sfai~izichZo?-ide, 2NH2(C4Hg)2Cl,SnC14 + H20, crystal- lises in long. colourless needles. Dibutylamine hydrogen oxalate, C O O H * C O ~ . ~ H , ( C , I ~ ~ ~ ~ , is much more readily soluble in water than the correspondiui diisobutylamine salt. a t 59.5'. Dibutylarniiae picrate melts The tributjlamin e hydrochloride is extremely deliquescent .The picrnte melts a t 100*5@, and is very sparingly soluble in water. The isobutylamiiies have been prepared by tt similar method ; the author finds that when a mixture of isobutylic chloride (1 inol.) and aqueous ami~ionia (1 mol.), to which j u s t sufficient alcohol for solution has been added, is heated at 110--115O, the primary base is the chief product. It may be purified by conversion into the oxamide (Malbot, Abstr., 1891, 817). The pure base boils a t 67-9-68', (Reimer gives 62-65@, and Perkin 68-49'.) The secondary and tertiary bases are best separated bj- coilversion into the acid oxalates. Diisobutylamine boils at 140*6-140.8". (Reimer gives 122-125', RIalbot 137', and Perkin 139-14r)O.) The amylamiiies have been prepared and separated by similar methods.Anrylamiiie amy Eoxumate, C5H,I.~H*CO*C00.NH3.C5H,1 + HzO, cr-j-stallises in colonrless needles, and is readily soluble in hot water. C'irIciwn umjZorca?)aate, ( C5H,,*NH*C0.COO)4Ca + HzO, is sparingly soluble in cold water, readily in boiling, and crystallises in slender, colouriess needles.ORGANIC CHEMISTRY. 9 Most of the chloramines have been described before (Abstr., 1690, 952; 1892, 804 and 1172; 1893, i, 296 and 497). The inonochlor- amines were prepared by the action of a concentrated solution of scdium hypochloi*ite on an aqueous solution of the hydrochloride of the amine. ButyZchZorarnine, C,Hg*NHC1, is a faintly yellowish oil, has a sharp odour, is insolnble in water, decomposes on heating, and has a sp..pr. of 0.992 at 0". Butyldichloramine, C4Hg*NC1,, is a yellow liquid, with a sp. gr. = 1.112 at 0". It boils a t 71" under a pressure of SO mm. Dibutylchlornrnine, (C,H,),NCI, is an oily liquid with a sp. gr. of 0.906 at 0", and boils a t 99" under a, pressure of 52 mm. ; it slowly decom- poses when kept. These chloramines undergo decompositions similar t o those given f o r the chloramines which ha,ve bee11 previously described; thus when acted on by reducing agents they are con- verted into the hydrochlorides of the corresponding bases. Quinol, pyrognllol, and gallic acid give colorations with the chloramines. Sulphuric acid acts on the monochloramines, converting them into thc base and the corresponding dichloramines.Aniylchloramine nntl silver nitrite act in the presence of alcohol, forming the silver deriva- tive of arnylnitramine, whicli crystallises in fine tablets. The reactions with potassium iodide and potassium cya1:ide arc' similar to those previously described. Constitution of the Isonitramines. By WILHELM TRAWL (Bcr., The dichloramines were prepared by Tcherniak's method. J. J. S. 1895, 28, 2297-2302 ; compare hbstr., 1895, i, 592).-The isoni- traminic acids are convei-ted, by boiling with dilute hydrochloric acid, into the corresponding amidoxylic acids, which may be reconverted into the isonitrnminic acids hy the action of iiitrous acid. Hydrowyl- atrznidoucetic acid, HO*NH.CH,*COOB, crgstallises in lusti-ous, rhombic tablets melting at 135", and reduces Fehiing's solut,ion at the ordinary temperat ure.Hydroxylnniidophenylpropio7tic acid, CH,.P h* CH ( NH-OH ) C 0 OH, crystallises in prisms melting a t 157-158". When this acid is treated with nitrous acid, it yields isonitraminephenylpropionic acid, identical with that' prepared from ethylic benzylacetoacetate and nitric oxide, along with another substance which has the formula C,H,NO. This second compound does not reduce Fehling's solution, and explodes when heated. XOH The isonitrttmink acids probably have the constitution RON< I 0 ' since they are formed by the action of nitroas acid on tlie amidoxylic acids. A. H. Existence of Imido-ethers derived from Hydrocyanic acid. By ADOLF PINNER (Ber., 1895, 28, 2454-2458).-A reply to the crihi- cisms of J. U. Nef ( A n u a l e n , 1695, 287, 328).Nef has stated t h a t the substance, previously described by the author as the hydrochloride of the ethylic ether of' forniimide, NH:CH.OEt,HCl, is a mixture of five different compounds. I n this paper remons ars given whv it should still be considered a homogeneous substance. J. J. S .10 ABSTRACTS OF CHEMICAL PA4PERS. Condensation of Isovaleraldehyde. By L. KOHN (Compt. rend., 1895, 121, 259-26O) .-Isovaleraldeliyde and potassium hydroxide do not yield secondar,y glycols analogous to those obtained by Fossek from isobutaldehyde, but two products are formed. One boils at 82' under a pressnro of 15 mm., or 187' uiider 746 mm., and oxidises very easilywith formation of an acid, CloH,,02. The other Foils at 140' under a pressure.of 18 mm., and seems to be a polymeride of valeral. C. H. R. Action of finely divided Silver on Halogen Derivatives of Aliphatic acids. By CARL HELL (Bey., 1895, 28, 2439-2445; compare J. Wislicenus, Annalen, 149, 215 ; Hell, Ber., 6,28 ; 7 , 319 ; 10, 2229 ; 13, 473 ; 22, 48).-The author considers that tlhe general equations previously given by him to represent the action of finely divided silver on the halogen derivatives of the fatty acids do not, account for the formation of many of the compounds obtained in the reaction. It is now suggested that in the formation of dicarhoxylic acids from a-halogen (e.g. bromine) derivatives of the fatty acids, two reactions occur : (1) the bromine atoms are removed by the silver, and the ta-o residues then unite to form a dicarboxylic acid ; (2) hydrogen bromide is removed by the union of the bromine of 1 mol.with a hydrogen atom in the a-position to tbe bromine of R second molecule. The author considers that this accounts for the formation of tetra- methylnuccinic and trimethylglutaric acids from bromisobutyric acid, and that it, also accounts for the formation of both stereoisomeric dialkylsuccinic acids by siinilar methods. Thus by reaction (1) we obtain one modification, R*~H*CooH + 2AgBr, COOH*CH*R 2R*CHBr*COOH + Ag2 = and by reaction (2) we obtain tlhe second modification- R*FBr* C 0 OH R*CH.COOH ' 2R-CBrH*COOH = HBr + t 28gBr. R. 7 H* C 0 0 H R.CH*C 0 OH + HBr + Ag2 = R*yBr*COOH R*C€I*CQOH A third reaction, which often occurs simultaneously, is the removal of hydrogen bromide from 1 mol., and t,he formation of an unsaturated acid cf the acrylic se:*ies. The formation of pyrocinchonic acid from a-brornopropionic acid and silver is probab!y due to a similar reaction.J. J. S. Electrolytic Synthesis of Nonocarboxylic acids of the Fatty Series. By WILHELN VON MILLER and HANS HOFER (Ber., 1893, 28, 2427-2439 ; cornpare Abst,r., 1894, i, 228) .-The authors have made electrol-ytic experiments with mixtures of potassium acet)ate and potassium etliylic succinate iii Hofer's apparatus (Ber., 27, 464). They show t h a t when a so1ut)ion of potassium ethylic succinate isORGANIC CHEMISTRY. I1 used as the positive electrolyte, and a concentrated solution of potas- sium carbonate (kept neuti'al by passing in carbonic anliydride) as the negative, theoretical Fields of ethylic adipate may bc obtained ; whereas C~um-Brow-11 and Walker by their method obtained a yield of only 35 per cent.(Abstr., 1891, 1192; 1893, i, 394). If a mixture of potassium acetate and potassium ethylic succinate is used as the positive electrolyte, and the negative is the same as in the previous case, a yield of 40-69 per cent. of ethylic butyrate can be obtained. A small quantity of the adipate is formed a t the same time, this amount varying with the cornpsition of the original iiiixture used. By replacing the potassium acetate by potassium propionatc, butyrate, and isobutyrate respectively, the authors have succeeded ill synthesising ethjlic valcrate, caproate, and isobutylacetate. The gases evolved during the electrolysis were examined in each case.They contain carbonic anhydride (73-62 peia cent.), oxygen (0*3-0*4 per cent.), carbonic oxide (1-3 per cent.). It has also been found possible to obtain ethylic iodide, togethe]. with iodof'orm and sodium iodate, by the electrolysis of a solutiou containing sodium propionate as the positive eiectrolyte and potas- sium iodidc as the negative. With potassium succiiiste as the posi- tive, ,G-iodopropionic acid is obtained. When sodiuni piaopionate ant1 potassium nitrite mere used a s the two electrolytes, a sninll quantity of nitroethnnc was obtained ; and when potassium acetate and potassium glycollatc were used, the authors obtained formaldehyde a t the negative pole and ethylic alcohol at tlie positive. Similar experiments with a mixture of potassium ethylic malonate and potassium acetate a t the positive pole, and potassium carbonate at tlie negative, gave e t h ~ l i c rropionate as the chief product; but with a mix kure of potassium ethylic mnlonate and potassium pro- pionate a t the positive pole, ethylic valerate was f'orrned, and simi- larly with a mixture of the mdonate nud potassium butyrate, ethylic valerate was tlie chief product. J.J. S. p-Hydroxy-x-dimethylisocaproic acid and Diisopropylgly- COlliC acid. Ijy ALEXANDER BARYLOWITSCH (Be?-., 1895, 28, A%;&- 2466) .-Re forma tsky has obtained ~3-h!tds.omy-a-dii,z ethyl iso:aproic wid. CHMe,*CH (i)H)*CMe,*COOH, bp the action of zinc a n d ethylic bromisobutjrate on isobutaldehyde. This acid melts a t 9A0, wliereas the acid described by Wohlbriick and Hantzsch under the same name melts a'; 111--119".The author has further investigated the acid of ~~olilbrucl;-Haiitzsch (Abstr., lSS7, 10'39), and finds that it is not p-hydroxy-a-dimetllylisocaproic acid, but is identical with the diisopropylgl~collic acid, OH*C( CHMe,),*COOH, previously described by hlarkovni koff. 2. J. S . Glucic acid (?). By HEINRICH TYIs'rER (Chem. C e ~ t r . , 1895, i, 371 -372 ; from Z. V e r . h'iibenzuck, 1894, 104C3-lO.jl) .-Invert sugar solution (1 per cent.), heated with lime water (0.5 per cent.) tit 66.50 , gives a white, volnmiuous, flocculent precipitate which prob- ably consists of basic calcium gIucate; it clissoIves when further12 ABSTRACTS OF CHEMICAL PAPERS. heated, becomes dark brown on exposure to air, and is sparingly soluble in water.TI:e precipitate cannot be removed by filtration; it was mashed six times with lime water by decantation, treated with dilute sulphuric acid, and extracted with ether ; this extract, when evaporated, left, a syrup, together with needle-shaped crystals, probably consisting of glucic acid ; after remaining for some time in a, desiccator, the neeciles disappeared, and crystals resembling those of cane sugar were produced (apoglucic acid ?) ; finally, tbese dissolved, the syrup darkened, gas was evolved, and a black resin was formed which yielded carbonic anhydride and formic acid when distilled with steam. The acid could not be recrystallised. J. B. T. New Synthesis of Uric acid and of its Methyl Derivatives. By EMIL FISCHER and LORESZ ACH (Ber., 1895, 28, 2473-2480; compare Liebig and Wohler, AnnaZen, 24, 284; Schlieper and Baeyer, Annalen, 127, 3 ; Horbaczewski, Abstr., 1885, 105U ; 1887, 918 ; Behrend and Rooseii, Abstr., lSSi, %l).-When Schlieper and Baeyer's pseudo-uric acid is fused with a large excess of oxalic acid at a temperature of 145-185' for 10 minutes, it loses a molecule of water, acd yields uric acid.The dimethylpseudouric acid of Techom (Abstr., 1895, i, 84), when treated i n a similar manner, yields a dimethyluric acid, which melts at 370"; it is moderately soluble in hot water, sparingly in cold water, in alcohol, and in acetone, but, readily dissolves in ammonia, forming an antnaonium salt, which can be obtained in a crystalline form by concentrating the solution.The siZner salt is a gelatinous precipitate, which decomposes slowly at ordinary temperatures, but much more readily when warmed. Another compound, which is formed in small quantity by the action of oxalic acid on dimethylpseudouric acid is E. Fischer and Reese's deoxyamalic acid (Abstr., 1884, 466) ; this forms a sparingly soluble sodium sali-,, and readily yields murexoin when treated with bromine and then with ammonia. If dimethylpseudo- uric acid is added to n mixture of acetic anhydride and zinc chloride, a, yield of 25 per cent. of ppdimethyluric acid is ob- tained. When the lead salt of this acid is heated, at lfLO0, with methylic iodide and ether, a new P-trimefhyZunk acid is formed. This @-acid melts between 313' and 32V, at the same time undergoing decomposition ; it is readily soluble in dilute alkalis, moderately in hot alcohol, and only sparingly in cold water and in alcohol.It gives the murexide reaction, is not readily acted on by phosphorus pentachloride, and, when heated with concentrated hydrochloric acid a t 150°, yields carbonk anhydride, methplamine, arid glycocine. When the lead saIt of /%crimeth~luric acid is further methylated, it yields the same tetrameth7luric acid as is obtained from the a-tri- metbyl acid. J . J. S. Formation of Methyluric Acids from Theobromine. By EMIL FIXHER (Ber., 1S115, 28, 24S0---2495).-When bromotheo- bromine is heated with normal potassium hydroxide solution for eightORGANIC CHEMISTRT. 13 Iiours on the water bath, the chief product is 8-dimetTayZzwic ~Me*Co*f?NMe>CO, accompanied by a small quantity of a bromine Clerivative, which can be removed by reduction with hydriodic acid.The acid is decomposed at a higher temperature, when it evolves unpleasant smelling gases ; it is only sparingly soluble in cold water, and crystallises from boiling water in prismatic plates, and readily gives the murexide reaction. The ammonium, sodium, and potassiunt salts are readily soluble in water, the silrer suit forms a colourless, amoyphous powder soluble in ammonia. When the lead salt is treated with methylic iodide and ether a t 165-170', i t yields the trimethyluric acid previously described b.y the author (Abstr., 1884, 13091, to which the formula I Chlorocaffe'ine, when heated with alcoholic potash, readily yields ethoxycaffeine ; aqueous potash reacts in a more complicated manner, and even with very dilute alkali only a small quantity of hyclroxy- caffejine is formed. Bromoxanthine is very stable, and the greater part remains unaltered, even when heated for six hours at 135-14V' with normal potassium hydroxide.ChZo.rodiox~dimethy~p~6rin, C7H7N40,CI, is obtained when &dimethyl- uric acid (1.5 parts) is heated with pbosphorus pentachloride (2 parts) and oxychloride (4 parts) at 140-145". It forms small, colourless needles, and melts at 290' (corr,), at the same time undergoing decomposition. When reduced with hydriodic acid and phospho- nium iodide, it give5 13-dioxydimethylpuriii, which is entirely decom- posed at 370'; this is readily soluble in dilute alkalis and mineral acids, gives an amorphous silver salt, an aus.ochZoride which crystal- lises in fine, yellow needles, and also a yellow pZatinocTaZo?-ide.The base, in conti-adistinction to the xanthine bases, does not give the murexide reaction. p-TrichZos.omethyZ~~rin, is the final product of the action of phos- phorus pentachloride on &dimet h yluric acid, on theobromine or on caffe'ine, the yield is much better when chlordioxydirnetl~ylpurin is first formed, and this is then treated with an excess of phosphorus pentachloride. It is readily soluble i n hot alcohol and in benzene, sparingly in hot water, crystallises in fine, colourless needles, melts at ls9-161" (corr.1, and map be distilled in small quantities. p- Dichloyoxytnetlz y Zpuriia, CCl.N.C-NH /CO, is formed when /3- trichloromethylpurin is boiled with 40 times its weight of 20 per cent.hydrochloric acid for 10-15 minutes. It crystallises in small, colourless needles, melts and evolves gas a t 278" (corr.), and is readily soluble in hot acetone bnt only sparingly in chloroform. It bas acid properties, readily dissolves in cold alkalis, and yields a silver deri- uatice which crystallises in slender needles; when the silver or lead salt is methylated, i t yields dichl~roxydimet~hylpurin (Abstr., 1884, 996). g- OxymefhyZpurin, C,H6N40, is obtained by the reduction of 6-dichloroxymethylpurin with hydriodic acid and phosphoniuni CO-NH*C-NH ?JMe*CO*$*NMe>CO is given. C 0 -NHORMe C C 1: $ *N Me ,14 ABSTRACTS OF CEEMICAII PAPERS. iodide ; it crystallises in fine, colourless needles, melts a t 266-267" (con.), and is readily soluble in hot, water, hut only sparingly in cold.It forms salts with both acids and alkalis, the platinochlon2e forms large, yellow crystals, and the aurochloride, C6H6N10,HAuC14, large, yellow plates. When heated a t 130" with hydrochloric acid (sp. gr. 1-19>, tri- chloromethylpurin is converted into y-methylzcric acid, THO C 0.g *NMe> o, C0.NH.C-NH This acid crystallises with lH,O, which it loses a t 140°, decomposes :tt 370-330" without melting, and readily gives the murexide test. The sodium and ammonium salts are readily soluble in water, the silver calt is obtained quite colourless on the addition of a small quantity of siIver nitrate to a solution of the ammoninm salt ; i€ too much silver nitrate is used, the salt becomes black.When heated with fuming hydrochloric acid at 170°, it is decomposed into carbonic mhydride, ammonia, and sarcosine ; and when oxidised with potas- sium chlorate and hydrochloric acid, it. yields allosan and mono- ineth ylurea. When trimethyluric acid is treated with phosphoms pentachloride and oxychloricle a t 130-150°, the dichloroxydimethylpurin previously described is formed. J. J. S. Action of Sulphurous Acid on Potassium Cyanide : Diazo- methanedisulphonic acid. By HANS VON PECHBIASB and PHILIPP MANCK (Rer., 1895, 28, 2374-2383 ; compare ibid., Ref., 522).- Hydrogen potassium anzidomethanedisulpkonate, HS 03*CH ( NH2)*S03K, is obtained by dissolving 100 grams of 99 per cent. potassium cyanide in a solution of hydrogen potassium sulphite, prepared bey saturatin: a solution of 150 grams of caustic potash in 600 grams of water with sulphurous anhydride ; the acid liquid is heated on the water hath, and becomes alkaline after 30-40 minutes.The solution is then carefully acidified with hydrochloric acid, and again warmed, addi- tion of acid being repented until the acidity is permanent, this being usually the case after 14-2 hours. On adding concentrated hydro- chloric acid to the cold liquid, about 200-250 grams of the hydrogen potassium salt crystallises out. It is a suowvy powder, which dissolves but sparingly i n water, yielding an acid solution ; boiling water resolves i t into the components. Uipotassirinz nrrricZomt.thanedisulphonnfe is prepared by dlowing the mixed solution of potassium cyanide and hydrogen potassium sulphite to remain for several days a t thc ordinary temperature without previous treatment with acid; i t crystallises from the liquid in rhombohedra, or in nodules of slender needles.It is more cou- veniently prepared by neutralising a solution of the foregoing salt with potassium carbonate. Recrystallised from h9t water rendered feebly nll~aline, i t contains 1H20, which is removed a t 105'; it dissolves very readily in water, undergoing decomposition when the solution is boiled, yielding the components. Formic acid, ammonia, potns s'lu ni tlii osulp h at c, and potassium t h iocyaiizte are also produced,ORGANIC OHEMIS rRY. 15 the two Iast-named being secondary products due to the action of potassium snlphi te on formic acid and of potassium thiosulphate on potassium cyanide respectively .Dipotassimn diazontethn nedisulpho?iala, C ( S O,K), < #H20, is pre- pared in the following manner. Hydrogen potassium amidomethane- disulphonate (23 grams) is mixed with water (34 grams) and treated with a 66 per cent. solution of potassium nit,rite (15 grams) at 15-16’ ; as the salt passes into solution, the temperature gradually rises to 40-45’, and, after 10-15 minutes, the orange-yellow liquid, which effervesces slightly, is 1-enderecl alkaline with caustic potash, and allowed to cool. The salt, recrystallised from 2 parts of boiling water containing a small quantity of potash, is obtained in orange- yellow needles or prisms containing lB20, which is removed in a vacuum at 60-!30°.At higher temperatures, water and sulphurous anhydride are liberated, the salt becoming colourless ; in dealing with a small quantity, this change occurs a t 210°, and the residue consists of potassium sulpbate, thiosulphate, and formate. The salt is readily soluble in water, forming a neutral solution which gradu- ally becomes acid and evolves gas, eneygetic liberation of nitrogen taking place in the boiling liquid; this gas is evolved quantita- tirely on treating the salt with acids. Dipotassium iodowtethanedklphonate, CHI ( S O,K),, 2 H20, is pre- pared by adding 30 per cent, hydriodic acid (12 grams) to a solution of the diazo-salt (10 grams) in water (100 grams) ; after 10 hours, the solution is treated with alcohol, and the precipitate thus obtained redissolved in a small quantity of warm water to which acetone is then added, the salt being obtained in aggregates of long needles.It contains 2H,O which is eliminated at 105’; the boiling solutiou yields silver iodide when treated with silver nitrate. Dipotassium diodomethaneJisiLl~1~o~~ate, C I?( SOsK),, is obtained by adding iodine (15 grams) in small quantities to a solution of tho diazo-salt (30 grams in I20 grams of water), mixed with a solution of potassium hydrogen carbonate (22 grams in 88 grams of water) ; it crystallises from boiling water in lustrous, rectangulay leaflek, and becomes yellow when exposed to light. Silver nitrate precipitates silver iodide from the hoiling solution, but no change is produced in qolutions of this or the foregoing salt by salts of other metals.Sodium amalgam converts both ioclomethanedisulphonates into di- potassium methanedisulphonate. N Basic po tass t t c m szdp h o h yd m z i r n e t 1~ y 1 euediszi lphonat e , NK c (S03K)z<~.so,K’H?O’ is obtained by gently heating the diazo-salt (30 parts) witli a solu- tion of potassium sulpliite, prepared by neutrnlisiug with potassium carbonate (9-10 parts) a solution of hydrogen potassium sulpliite (45 parts), formed by satuyating a solution of caustic potash (I : 5 ) with sulphurous anhydride. It is very soluble in water, forming an alkali tie solution which yields a precipitate with barium chloride ; this is dissolved by h~droclilo~~ic mid, and on heating the liquid,16 ABSTRAOTS OF CHEMICAL PAPERS. barium sulphate is thrown down, this being due to the quantitative elimination of the snlphonic group attached to nitrogen.When the salt is decomposed with sulphuric acid, hydrazine sulphate is formed, cai*bonict and sulphurous anhydrides being eliminated (compare Absty., 1895, i, 647). 1 4 ~ ~ 0 , crystallises in small, lustrous prisms from a concentrated solution of the basic salt which has been saturated with glacial acetic acid. It is readily soluble in water, and the solution gives no precipitate with barium chloride. Hydro,~y~nefIianetriszilphho?zic acid, C( S03H)3*OE, is obtained, in the form of its potassium salt, when the hydrazi-compound or the diazo- salt is treated with boiling water; the yield is more satisfactory when the latter is heated with a solution of hydrogen potassium sulphite.The potassium salt is identical with the compound described by Albrecht (Annalen, 1872, 161, 139). The barium salt vrystsllises in lustrous leaflets, and contains 4Hz0. The ?iovrnaZ salt, C(SOBK)z< NH I N*SO3Ko M. 0. F. Chloro-derivatives of ax-Dithienyl. By OTTO ERERHARD (Bey., 1895, 28, 2:38%2$86) .-Monochlorodit~hienyI, obtained by thc action of concentrated sulphuric acid on monochlorothiopben (Abstr.. 1894, i, 117) is converted by excess of sulphuryl chloride into tetrachloro-aa-dithienyl, CaH,C1,S2 ; this crystallises in small, yellowish-brown needles, melting at 126.5-127O (corr.).’ When i t is heated with two molecular proportions of sulphuryl chloride at POO”, it yields perchlorodithierzy E, C8C1&, which forms long, reddish-yellow needles, melting a t 211*5-212*5° (corr.).Tetra- chlorodi thienyl is converted by bromine into tetrachlorodihromo- (lithien#, C8Brz*CI,Sz, which crystalliseu i n hard yellowish needles, and melts a t 189*5-190° (corr.). All these products can also be pre- pared from the synthetical acr-dithienyl, and this fact proves that the dithieiiyl derivatives previously described by the author belong to the same series. A. H. Synthesis of Aromatic Hydrocarbons. Ry ALBERT TOHL (Bw.. 1895, 28, 24.59-24G3; compare Abstr., 1891, 1022; Tohl and Geyger, Abstr., 1892, 968 ; T6hl and Karchowski, Abstr., 1892, 990, and Jmnasch and Wigner, Abstr., 1895, i, 655). In preparing para- propyltoluene by Fittig’s method of synthesis, the author observed t h a t propylic bromide gave a much better yield than the iodide.The author in conjunction with Tripke now shows that a fairly good yield of propylmesitylene may be obtained by the action of propylic bromide on mesitylic iodide, or still bettcr on inesitylic bromide in the presence of sodium and ether. Ethylmesitylene has been obtained in a similar manner, but the yield is not so good as that obtained by Jannasch when working with ,z xylene solution. Cymene lias also been syrithesised in a similar manaer by the action of sodium on ieopropylic bromide and parabromotolaene. P~opylrnesitylene boils a t 220 -22l0, does iiot solidi€y at -20°, has a sp. gr. = 0.8773 at No, and when oxidised yields mesitylenecarboxjlic acid (Jannasch and Weiler, Abstr., 1895, i, 283).0 R GA N LO C HEBIIST RP. 1': Dibronzopropylmesity leizc crystallises from alcohol in slender, long needles and melts at 56".Barium prop1jlmesitylenesiclpho?zate, (C12H1,S03)2Bn -f- 2H20, crystal- lises from water in small, glistening plates. The sodium salt, C1,H1,*S03Na + 2H20, is readiiy soluble in water. The cnlcium salt crystallises with lHzO, and the maguesizm salt with 2H20, but the copper salt is anhydrous. Propylmesitylenesulphonamide crystallises from concentrated solutions in small needles, which melt at 93-99". Dinitropropylmesitylene, obtained by dissolving the hydrocarbon in cold, fuming nitric acid, crystadlises in small colourless needles, and melts a t 93-94". A substance, which melts at 135O, is also formed, but the constitution of this product has not yet been determined. NitropropylntssityZene, obtained by slowly dropping double the theoretical quantity of fuming nitric acid into the hydrocarbon, is an oily product, and on reduction yields amidopi.opyE/7zesifyZene, which is also an oil.The amido-compound yields a sulphate, which is readily soluble in water, crystallises in small needles and melts at 117", and an acetyE derivative which me1 ts a t 161". Ethylmesitylene boils at 207-209" (uncorr.) whereas Jannasch gives 212-214" as the boiling point. Dibromethylmesitylene, C6Br,Me3FX, melts at 219", and the dinitm-derizatiue, C,Me,Et(NO,),, at 1 2 3 O . The sulphonic acid yields a barium salt which is very readily soluble in water, and also a sodium salt, CIIHl,-SO,Na + HzO, which loses its water of crystallisation when kept over sulphuric acid.J. J. S. Action of the Monobromo-derivatives of the Aromatic Hydrocarbons on the Lead Salts of the Thiophenols. By ED. BOURGEOIS (Ber., 1895, 28, 2312--2330).-When an aromatic monobromo-derivative is heated with the lead salt of an aromatic thiophenol, the latter dissolves at a temperature which is usually below 175'. When the solution is heated, action takes place in two stages; in the first between 180' and 190°, 2(RS),Pb + 4R'Br = (RS),Pb,PbBr, + RSH' + 2R'Br, the double compound of the lead salt and lead bromide separate in the solid form, a t a higher tem- perature, 225-230", the reaction is completed i n accordance with the equation (RS),Pb,PbBr, + 2R'Br = RSR' + BPbBr,. The author proposes to measure the velocity of the reaction during the first stage, which is undisturbed by secondary rlctions, and thus to obtain some idea as to the effect of the nature of the aromatic group on the power of the bromine atom to enter into reaction.'l'he following new snlphides have been obtained by the above method i n the course of the preliminary experiments. All the snlphides when pure have a faint and not unpleasant odour, but acquire the usual smell of garlic whendistilled. Phenylic metatolylic sulphide boils at 309*5O, and has the sp. gr. 1.1058 at 0"/4". Yhenylic paratolylic sulphide melts at 15*7", boils at 31 P5', and has the sp. gr. 1.09 at its melting point. as-Phenylic orthoxylylir, sulphide, (file2 : S = 1 : 2 : 4), boils at 181.5O (pressure = 11 mm.) and has the sp. gr. 1.0962 a t 0°/40. as-Phenylic metaxylylic szclphide, [Me2 : S = 1 : 3 : 41, VOL. LXX.i. C18 ABSTHAOTS OF OHEMIOAL PAPERS. boils at 172.5" (pressure = 11 mm.) and has the sp. gr. 1.0935 a t 0°/4'. PIJenylic parnzylylic sulphide [Me2 : S = 1 : 4 : 21 boils aii 171' (pressure = 11 mm.) and has the sp. gr. 1.0913 at 0°/4". Phenylic mesitylic s d p h i d e boils at 180" (pressure = 11 mm.) and has the sp. gr. 1.081 7 at 0°/4". U ? - t l ~ ~ p a ~ a d i t ~ l ~ l i ~ sdphide boils at 173' (pressure = 11 mm.) and has the sp. gr. 1.0889 at 0°/4'. Metapara- ditolylic d p h i d e crystallises in lustrous needles, melts at 27.8", and boils at 179" (pressure = 11 mm.). Paratolylic orthozylylic sulphide [Me2 : S = 1 : 2 : 41 forms crystalline granules melting at 28.6". It, boils at 193*7' (pressure = 11 mni.).Pdmtolylic rnetaxylylic szd- phide [Me, : S = 1 : 3 : 41 boils at 188" (pressare = 11 mm.) and has the sp. pr. 1.0716 atl 0"/4'. Paratolylic: paraxylylic szclphide, [Me2 : S = 1 : 4 21 melts at 6' and boils at 185" (pressure = 11 rnrn.). Ptrmtolylic mesitylic suZphide crystallises in sma11, lustrous needles, melts a t 89-6", and boils at 190" (pressure= 11 mm.). Ortho-zylylic a-naphthylic sulphide is ayellocv liquid which boils at 2413' (pressure=ll mm.), and has the ~ p . gr. 1.1346 at 15"/4". Ortho-xylylic P-naphthylic subhide melts at, 68" and boils at 2-51-5' (pressure = 11 mm.). dletaxylylic a-naphthylic sulphide is a yellowish liquid, which boils st 259.5' (pressure = 11 mm.) and has the sp. gr. 1.1355 at 15'/4O. Jfetazylylic @inphthylic sulphide crystallises in lustrous needles, me1 ts at 39.6' and boils at 244.5" ( pressnre = 11 mm.).Paraxyl!/lic a-naphthylic sulplzide forms needles, melts at 36.2' and boils at 235' (pressure = 11 mm.). Paruxylylic 0-naphthylic sulphide also forms needles, melts at 36.7s and boils at 240' (pressure = 11 rnrn.). Afesifylic a-naphthylic sulphide crystallises in large, lustrous tablets, melts a t 120.6" and boils at 24.5' (pressure = 1 1 mm.). Mesitylic p-napldhylzc szdphide crystal- lises in prisms melting at 87*5', and boils at 245" (pressure = 11 mm.). The temperatures given are corrected. A. H. potassium Derivatives of Quinone and Quinol. By CHARLES ASTRE (Compt. Tend., 1895, 121, 326--328).-When an ethereal solu- tion of quinone is boiled with potassium, hydrogen is liberated, and the compound CaH,KO(OH) + Et,O is obtained as a deep green compoui~d, which oxidises very rapidly Then exposed t o air, and becomes incandescent when heated at 100" or brought in contsct with a mineral acid.In presence of benzene, the action of potassium on quinone yields quinhydrone and tt brownish-green crystallii b com- poiind which oxidises with great rapidity, becomes iricatidescent in moist air, and takes fire if rubbed i n presence of air. In contact with water, it is converted into a blue compound, which rapidly becomes brown ; in contact with iriorgsnic acids, it becomes incmdescent. It seems to have the composition Cl2H,OdK3. The action of potassium on quinol in presence of ether, yields a white, crystalline compound, OH*C6H4*OK,CJ14(OIr),, wliich rapidly oxidises, and becomes first blue, then greyish-white, and finally very dark brown, in presence of moist air or oxygen.The formation of these conipounda supports the view that quinone is R diketone. C. H. B. The liquid has the sp. gr. 1.072 at 6"/4'.ORGANIC CHEMISTRY, 19 Action of Sodium Alkyloxides on Chloranil. Acetals derived from Substituted Quinones. By C. LOKING JACKSON and H. S. GRTSDLEY (Amer. Chena. J., 1895, 17, 579-607).-DichZoro- diphenozyquinone, C,Cl,O,( 0 P h),, is prepared by heating chloranil (25 grams) with an aqueous solution of phenol (25 grams) and potas- sium hydroxide (12 grams) on the water bath, and recrystallising the separated solid from benzene. It crystallises in aggregates of rcd needles, melts at 2 4 3 O , and dissolves sparingly in alcohol, benzene, and chloroform, freely in hotJ glacial acetic acid, and not at all in water, ether, light petroleum, carbon bisulphide, or acetone.Caustic soda hyclrolyses it, forming chloranilic acid. It is not reduced by flulphurous acid at loo3, but hydriodic acid converts it into dichloro- diphewoxypinol. C6C1,(O~I),(OPh),, which crystallises in large colourless prisms and in arborescent needies, melts a t 1 97-19g0, and dissolves in most solvents except water, benzene, and light p etro 1 e u ui. When warmed with aniline, dichlorodiphenoxyquinone yields dic hlo rodiani lido y ninon e. Tetrethylic dic;hloroquinonedimalmate, c6c120,[ CH(COOE t)2]2, is prepared by mixing dichlorodiphenoxyquinone with alcohol and ethylic sodiomalonate, when a dark blue precipitate separates ; this is washed with alcohol, dissolved in water, and the solution treated with acid.The new compound crystallises in long, slender, stellate needles, melts at 132O, and dissolves in alcohol, b u t not in water. By reduc- tion, it yields the corresponding quinol, already described by Stieglitz (Abstr., 1891, 455). A s already indicated, the sodio-derivative C6C1,0,[CNa(COOEt),],, has a blue colour, and is soluble i n water, but not in alcohol. When the quinone is boiled with sodium car- bonate in absolute alcohol, trtrethylic diethoxyquinonedimaionate, C,O,(OEt),[ CH(COOEt),],, is obtained ; this forms nearly white crjstals, melts at 115O, and dissolves i n alcohol and ether, but not in water. Dichlorodirnet h oxyquinone dim eth y 1 h emiacetal, C6C1, (OH) (OMe),, is prepared by warming dichlorodiphenoxyquinone (10 grams) with a methylic alcohol solution of sodiuni (6.5 grams) methoxide ; the white crystalline compound which separates, is dissolved in water and treated with dilute sulphuric acid, when the new compound is precipitated.The same compound is formed when chloranil is treated with a solu- tion of scidium methoxide in methylic alcohol, It is a wbde, amorphous solid, insoluble in all common solvents, and is easily convertpd into dichlorodimethoxyquinone (methylic chloranilate, Abstr., 1890, 136) either by heat or by dilute acids ; i t is a feeble acid, forming a white crystalline compound with sodium methoxide. Dzchiorodiethoxyyui- none diethylhemiacetal, C6C1,( OH),(OEt),, is similarly prepared, sodium ethoxide and ethylic alcohol being substituted for the meth- oxide and rnethylic alcohol respectively; i t is a white, amorphous solid, which dissolves slightly in alcohol, but is partially decomposed thereby ; i t is insoluble in all other conimon solvents.A t 140-143° it is converted into dichlorodiethoxyquinone (106. cit.), and melts ; dilute acids effect the same change. Dichlorodimthoxyquinone diethyl- hemincetal, C~C12(OMe)2(OH)2(OEt)2, was prepared from diclilorodi- C f l20 ABSTRAOTS OF CHEMICIAL PAPERS. methoxyqninone and sodium ethoxide i n alcoholic solution ; it is similar in properties to the two preceding compounds. The authors discuss the constitution of these hemiacetals in some detail. They find them to be incapable of redaction to quinols or of forming oximes with hydroxylaniine hydrochloride, so that the ketonic character of the parent quinones has been lost; from this i t is concluded that the sodium salt of dichlorodimethoxyquinone dimethylhemiacetal, for instance, has the constitution OMe C(0Me):CCl ONa OKa>C<CCl:C(OMe)>C<OMe It is suggested that the constitution of phenoquinone and quin- hydrone is similar to that of these hemiacetals.A. G. B. Hydrolysis and Synthesis of Dihydroresorcinol. By DAXIE L VORLAKDEE (Ber., 1895, 28, 2348-2349 ; compare Abstr., 1894, i, 528)-It has been already shown (Zoc. cit.) that phenyldihydrores- orcinol is converted into phenylacetylbutyric acid when treated with hydrolytic q e n t s . The autlior finds that di hydroresorcinol behaves i n the same way on fiubjection to similar treatment, yielding y-acetlyl- butyric acid when heated with a concentrated solution of barium hydroxide during several hours a t 150-160' ; the semiembarone dis- solves with di5culty in water, and crystallises in lustrous leaflets melting a t 164-166'.The reaction by which dihydroresorcinol is converted into y-acetyl- butyric acid is reversible, dihydroresorcinol being produced when ethylic Ppacetylbutyrate is treated with sodium ethoxide ; this is tho simplest case of passing between the aromatic and aliphatic series. Dihydroresorcinol is not formed by the action of ethylic sodaceto- acetate on ethylic acrylate, the product being ethjlic a-acetylgluta- rate. M. 0. F. Action of Bromine on Anetho'il.B.y CARL HELL and 0. vos Gijh'THERT (J. pr. Chem., 1893, [2], 52, 193-210 ; compare Abstr., 1895, i, 341).-In the preparation of bromanethoyl dibromide, the use of hot alcohol must be avoided, since, when hot, this solvent reacts with the dibromide, removing 1 mol. HBr, and forming a conzpoulld which crystallises in long prisms and melts at 62'. A study of the behaviour of the dibromide with hot water led to no definite conclusion. When bromanethoil dibromide is dissolved in aniline, aniline hydrobromide separates, and the filtrate from t h i s yields a yellow powder, ClaHlsOBrN (m. p. "So), when decomposed by hydrochloric acid ; this compound yields bromanisic acid when oxidised with potassium pe rmangan ate. The dibromo- ke ton e obtained by ox idisi ng bromanethoYl dibromide (Abstr., 1895, i, 341) also yields an amline derivative, C,,H,,@,BrN, when heated witch aniline ; this crystallises in small aggregates of needles, melts at 119', and dissolves easily in ether, alcohol, benzene, and chloroform, but only sparingly in light petroleum ; it dissolves in strong snlphuric acid, and is precipitated unchanged therefrom by water ; the compoiind appears to bare beenORQANIO OREMISTRY.21 formed by the substitution of the aniline residue for the bromine atom of the side chain. Anetho'il dibromide also yields a ketone, CIOH11Br02, when oxidised with chromic acid in an acetic acid solution (compare Zoc. cit.) ; t<his forms large, strongly refractive crystals, melts a t 65-47', and dig- solves in alcohol, ether, and light petroleum; the compound has a pungent odour, and burns the skin.When heated with alcoholic ammonia on t,he water bath, the ketone dissolves, and the solution ieaves, when evaporated, a compound, which is probably an isoindole- like compound of the form N< I * this is a yellow, C3fe CH(CGH4.0Me) ' crystalline powder, melts at 1 7 6 O , andhissolves easily in ether, but only sparingly in alcohol, and not at all in light petroleum. Oxidation with potassium permanganate converts the ketone into anisic acid. Two dibromanethozl dibronzides, CloHIoBrrO, weye obtained I)y heat- ing bromanethoil dibromide with bromine (1 mol.) in a sealed tube; the one crystallises when the ethereal solution of the product of the action is evaporated, and forms slender needles which melt at 113--ll.Po; the other remains as a syrup when the ether has been evaporated, and crystallises from this after a time ; it melts at 89", and is much more soluble in light petroleum than its isomeride.Reduction with zinc dust convel'ts the dibromide inta dibromanethoil. The dibromide reacts with aniline to form the co~upoui~d CI,H150Br2N, which melts at 82'. Oxidation with chromic acid in acetic acid soln- tion, converts the dibromide into a ketone, C,,H,Br,O,, which contains two nucleal bromine atoms ; it is a yellow powder, melts at 135O, and dissolves easily in ether, benzene, aud chloroform. Two acids were extracted by sodium carbonate from the crude product of the oxidation of the dibromide ; one of these melts at 85", and is also formed when the ketone is oxidised by potassium permanganate ; but neither has been identified. The compound CloH,Br2N0, which is obtained by the action of alcoholic ammonia at 180° on the ketone, is insoluble in most organic solvents, and sublimes, without melting, at a high tem- perature.The behaviour of the ketone with aniline is also described. The Cholesterols of Cryptogams. By ERXEST G ~ R A R D (J. Pharm., 1895, [ 6 ] , 1,601-608 ; compare Abst8r., 1892,1d!X).-The author has extracted cholesterol fyom orclinary brewer's yeast, from a common mould (Mzccor mucedo), and from a, lichen (Lobaria pulrnonacea). The processes adopted in the three cases were similar. Yeast (30 kilos.) containing 25-30 per cent. of solid matter is extracted with a large quantity of 96 per cent. alcohol. The 1-esidne, dried at 40-50", and the aqueous solution left on distilling off the alcohol, are extracted with ether, and the combined ethereal extracts, which contain the cholesterol, together with the fatty matter and other substances, are evaporated to dryness ; the cholesterol and €ats are then extracted from this residue Tvith light petroleum, and, after the removal of the solvent, are boiled with alcoholic potash to liberate the cholesterol.The alcohol having been removed, the cholesterol is extracted with ether from the aqueous alkaline soap solution, and A. G. B.22 ABSTRACTS OF CHEMICAL PAPERS. the crystals thus obtained are washed with alcohol, and recrydallised from ether or benzene. The cholesterol of yeast crgstallises in rectangular plates or slender needles melting at 135--136O, and has a specific: rotatory power, [a], = -105'.It is very sparingly solnblc, even in boiling alcohol, but readily in the usual organic solvents. Tbe benzoate could not be prepared in a pure state. The mould was cultivated i n a 6 per cent. solution of milk sugar containing the usual inorganic salts. Owing to the comparatively small amount of material available, the amount o€ cholesterol obtained was very minute, but i t crptallised in plates, and a.ppeared from its reactions to be identical with Tanret's ergosterine. The product obtained from the lichen also crystnllised in needles and plates, and exhibited siniilar reactions. The cholesterol from cryptogams differs from animal cholesterol in its colour reactions with sulphuric acid. The latter gives a yellosrish colour with the concentrated acid, which blackens on the addition of water, whilst under the same conditions the former gires a red colour, changing to blue.Similar colorations are yielded by carbon tetrachloride solutions of the chulesterol, with the excep- tion that the yellow solution turns white instead of Black; the chloro- form solutions also exhibit analogous colour changes, Js. W. Electrolytic Reduction of Paranitro- compounds dissolved in Sulphuric acid. By ARTHUR A. NOYES and JOHN J. DOREANCE (Ber., 1895, 28, 2349-2352 ; compare Abstr., 1893, i, 406 ; also 1894, i, 503).-A large platinum electrode is fitted closely to. the side of a small beaker, in which is placed a porous cylinder containing a small platinum electrode ; 20-30 grams of t-he nitro-compound is dissolved in two to three times its weight of concentrated sulphurie acid, and transferred to the beaker, whilst the porous cell, originally filled with concentrated sulphuric acid, is replenished from time to time with dilute acid.A current of 1 or 2 amperes is employed during 40-50 hours. Paranitraniline yields paradinmidobenzene sulphate, paranitro- phenol giving rise to paramidophenolsulphonic acid, which is also formed when parachloronitrobenzene is reduced. The paper contains a short summary of the result,s hitherto obtained. Action of Aniline on Mercurous Iodide. By MAURICE FRAN~OIS (Compt. rend., 1895, 121, 253--256).-When mercurous iodide is mixed with excess of aniline in the cold, metallic mercury separates, and diphenyldimercurammonium iodide, HgI,,'LNH,Ph, is formed and dissolves.At the boiling point of the aniline, the change takes place verj rapidly. With aniline in smaller proportion, but still in excess, some of the mercurous iodide remains unchanged, and if mercuric iodide is dissohed in its own weight of warm aniline, and mercury is added, a small quantity of mercurous iodide forms on the surface of the metal. Itl follows that the action is, to a certain extent, rever- sible, and the author finds that when equilibrium is established a t the boiling point of aniline, there are 26.35 parts of mercuric iodide No analysis is given. M. 0. F.0 ROAN10 CHENISTRY. 23 in every 100 parts of the solution. The result is the same, whether the original substances are aniline and mercurous iodide, or aniline, mercuric iodide, and mercury.The quantity of mercuric iodide in solution when equilibrium is established varies with the temperature, but an exact determination was only made at the boiling point of the aniline. A solution of mercuric iodide in aniline containing 26 parts of the salt in 100 parts of solution, does not decompose mercurous iodide at 182O, but dissolves it in considerable quantity, and the mei-curous salt separates in crystals when thc liquid is cooled, whilst the undissolved mercurous iodide, if the latter is in excess, is also €ound to hare become crystalliue. C. H. B. Halogen Additive Products of the Anilides. By HEKRY L. WHEELER (Amer. Chem. J., l895,17,612--619).-Meta~iitracetaniZide dibromide, C8HRNZOSBr2, is prepared by acting on metanitracetanilide in nitrobenzene with bromine, washing with light petroleum, and crystallisiDg from chloroform.It forms stellate, yellow prisms, and melts and effervesces a t 143'. Water removes hydrogen bromide from it, yielding pcirabromometanitracetanilide, which crystallises in yellow needles, and melts at 1 4 3 O . Bromonitraniline, [NH, : NOz: Br = 1 : 3 : 41, is obtained ..:hen parabromometanitracetanilide is boiled with alcohol and strong hydrochloric acid. It crystallises in slender, yellow needles, and melts at 131'. The author shows that in the above dibromide the bromine atoms are probably attached to the benzene nucleus, not to the nitrogen of the aiiilide group. Its hydrocltloride and sulphate are described.A. G. B. Behaviour of Ethers of Azophenol on Reduction with Stannous Chloride and Hydrochloric acid. By PAUL JACOBSON (Annnlen, 1895, 287, 97-147; compare Abstr., 1893, i, 327; and 1894, i, 26).-The paper forms an introduction to the matter brought forward in the following abstracts ; it is divided into three portions, dealing respectively with the results of the investigation, their theo- retical bearing, and the methods which have been adopted in the course of the work. 'l'he changes involved when ethers of azophenol are reduced, folIow three alternative courses, resulting in the formation of orthosemidine bases, parasemidine bases, a i d scission bases, the quantity in which bases of each class is produced being influenced by the nature of tho azophenol derivative erriployed, a n d by the position in the molecuio occupied by the substituent.The author has, therefore, collected in 8 table the quantitative results obtained on reducing various deriva- tives of benzeneazopheneto'il. M. 0. 1'. Reduction of Ben zeneazo-orth ocresetoil and Ben zene azo- metacresetoil. By PAUL JACOBSOX, F. K. FmrrscH, FRED. MARSDEN, and G. SCHKOLSIK (Annalen, 1895, 287, 147--160).-Benzeneazo- orthocresetoll yields the orthosemidine base, 2 : 4 : 5-amidoethoxy-24 ABSTRACTS OF CHEMIOAL PAPERS. rnefhyldiphenyZamine, NH2*C6H2Me( OE t,).NHPh, which crystallises in lustrous leaflets, and melts at 94-95' ; the hydroc7doride is crystal- line. The aziinide, C,,H,,N,O, is obtained by the action of nitrous acid on the base, and crystallises in colourless needles melting at 118' ; the methenyl derivative, C16H16N20, formed on treating the base with boiling formic acid, crystallises from petroleum, and melts ah 102", whilst the nitrate and hydrochloride crystallise in needles.The thiocar- benyl-compound, C16H16N20S, is obtained by heating the base with carbon bisulphide and alcohol ; i t crystallises in small needles, softens at 225', and melts a t 238-240'. The stiZba.zoniu~n base, C,,H,,N,O,, is obtained by condensation with benzile ; it. forms lustrous, lemon- yellow leaflets, and melts at 136'. Monaizilidotoluquinone is obtained by oxidising the orthosendine base with ferric chloride, and is also formed in preparing the azimide by treatment with uitrous acid ; i t crystallises from alcohol i n lustrous, violet-red needles, and melts at 148".Dianilidotoluquinone is produced when the foregoing substance is treated with aniline in alcoholic solution ; it separates from glacial acetic acid in the form of a crystalline powder, and does not melt below 300'. The orthosemidine base is not the sole product of reduction of benzeneazo-orthocreseto'il, a small quantity of a parasemidine base, 4-amido-4' : 3'-ethoxyrnethyldiphenylamine, NH2*C,H,*NH*C6H,~~e*O~;t, which crystallises from petroleum in lustrous, colourless needles, and melts at 110-111' being obtained ; the acetyl derivative crystallises in rosettes of needles, and melts at 173'. From 10 grams of benzene- azo-orthocresetoil, 4.95 grams of the orthosemidine base were obtained, the yield of the parasemidine base amounting to 2.1 grams, whilst 2 grams of scission bases were also formed.Benzeneazometacresetoil, 0 E t-C,H,Me*N,P h, crys tallises in ornnge- red needles, and melts at 51.5" ; the chief product of its reduction is the parasemidine base, 4-anzido-4 : 2'-ethoxymethyldiphenylamine, which crystallises from petroleum in pink prisms, and melts at 61'. The nzonacetyl derivative of this base melts at 97-98' ; the diacetyl derivative at 153'. The thiocarbamide crystallises in nacreous leaflets, and melts at 181.5'. 4.7 grams of the parasemidine base were obtained from 10 grams of benzeneazometacresetoyl, 4.1 grams of mixed aniline and metacresetidine being formed at the same time. 31. 0. F. Reduction of Ethers of Tolueaeazophenols. By PAUL JACOB- SON, FR. D~~STERBEHN, J.KLEIN, and G. SCHKOLNIK (Annalen, 1895, 287, 161-183) .-Reduction of ort.hotolueneazopheneto'i1 gives rise t o the parasemidine base 4 : 3 : 4'-amidomethylethoxydiphenylamine (D. R. P., 75,292), which crystallises from petroleum i n colourless needles, and melts at 82' ; the hydrochloride dissolves in cold water with extreme difficulty, and crystallises in leaflets. The diazoiodide is formed when a solution of the diazochloride is poured into aqueous potassium iodide, and crystallises in reddish-yellow needlee. The monacetyl derivative melts at 15G0, and the diacetyl derivative at 180-181" ; the benzylidene derivative and orthohydroxybenzylidene derivative melt at 86-87" and 12k125' respectively. 4 : 4' : 3-Chlor-ORGAN10 OHESIISTRT. 25 et~x?l~?zethyEdi~he~2yEamine is obtained from the parasemidine base by Sandmeyer's reaction, and melts at 77-78' ; the nitrosamine melts at 49-50', From 10 grams of orthotolueneazophenetoyl, 5.1 grams of the parasemidine base were formed, 3.6 grams of a mixture of ortho- tolnidine and phenetidine being formed at the same time.Metatolueneazophenetozl, C,H4Me*N,*C6H4.0Et, crystallises from alcohol in orange-red prisms, and melts at 65O ; ou rediiction, i t yields approximately equal quantitiefi (26-28 per cent.) of orthosemidino and parasemidine bases. The hydrochloride of the former, 2 : 5 : 3'- arnidoethoxyinethyldi~he?zylami~ze, was isolated, but the base has not been obtained in the crystalline state; the azirnide forms colourless needles, and melts a t 110-111', and the stilbazoizium h s e crystallises in lustrous, yellow needles, and melts at 176".The methenyl com- pouud was obtained in the form of the nityafe, which crystallises in needles. The parasemidine base, 4 : 4' : 2-anzidoetho~ymethyldiphenyl- nmine, crystallises in long, colourless needles, which rapidly become blue when exposed to air, and melts at 92-93' ; the hydrochloritle ci*ystallises from hot water in colourleas leaflets, and the monacet:yZ derivative melts at 112-113O. An attempt has been made to obtain this base by synthetical means. 4' : i2-~thoxymeth?yldiphenylnmirze was prepared by the action of ethylic bromide and sodium ethoxide on hydroxymethjldiphenylamine ; it separates from petroleum in pale yellow crystals, and melts at 81-82", boiling under atmospheric pressure at 354' (uncorr.).The nitrosamine melts at 71-72', but the transformation of this derivative into the parasemidine base has not been effected in a satisfactory manner. Reduction of paratolueneazophenetojil, which is first converted into paratoluenehydrazophenetoyl, gives rise to an ortliosemidine base, which is either 2 : 5 : 4'-arnidoethoaymethylcliphenylamine, or 2 : 4' : 5-amidoethoaymethyld~phe~zylamine, in quantity amounting to 18 per cent., a mixture of paratoluidine and paraphenetidine being also produced to the extent of 69 per cent. Neither the hydro- chloride nor the base has been analysed; the azirnide, however, crystallises in colourless leaflets, and melts at 117-118", and tho stilbazonium base crystallises from alcohol in yellow needles, sinters at 141', and melts at 144-146'.When the isobntyl ether of paratolueneazophenol is reduced, 72 per cent. of the material employed, is obtained as a mixture of para- toluidine and the isobutjl ether of paramido phenol, the products of the semidine transformation not having been, in this case, examined. The benzyl ether of paratolueneazophenol yields paratoluidine and poramidopheqlic benzylic ether, which crystallises in silky leaflets, and melts at 56" (Abstr., 1893, i, 330); the acetyl derivative melts a t 139'. The mixture of these bases amounts t o 78.5 per cent. of the material employed. M. 0. F. Reduction of Tolueneazocresetoi'ls. By PAUL JACOBSON, E. HEBER, F. HENKICH, and c. SCHWARZ (Annulen, 1895, 287, 183- 211).-Orthotolueneazo-orthocreseto~l crystallises in red, transparent aggregates, and melts at 35-37" ; the difficulty with which i t solidi- fies accounts for the observation of Noelting and JVerner (Abstr.,26 ABSTRAOTS OF CHEMICAL PAPERS.1891, 214), who describe this substance as a red oil. On reduction, i t yields the orthosemidine base, 2 : 5-amidoethox~-2' : 4-dimetI~yEdi- ph,enylamine, which crystalhes in flat prisms, and melt8 at 78'; the hydro- chloride is an oil which rapidly solidifies. The thiocarbenyl-compound, C,,Hl8N2OS, melts at 2-53', and the stilbazonium base crystallises from alcohol in small, yellow iieedlea, and melts at 153'. Oxidation with ferric chloride converts the orthosemidine base into orthotolu- idotoluqinone, which crystallises in dark, lustrous leaflets, and melts a t 145-146'.The parasemidine base, 4 : 4' : 3 : 3'-amidoethoxydi- metjLZlldiphenylamine, is also formed on the reduction of orthotol uene- orthocresetoil ; it crystallises in colourless leaflets, becomes red when exposed to air, and melts at 86'. The snonacetyl derivative melts a t 1 4 3 O , the thiocarbaniide at 17Y--18O0, and the diformyl derivative at 146-147'. The ortho- and pam-semidine bases are obtained in quantities amounting to 29 and 36 per cent. respectively, the re- mainder of the product consisting of scission bases. Metntolueneazo-orthocresoZ, CsH~Me*N2*C,H,Me*OH [N : Me : OH = 1 : 3 : 41, is obtained by bringing together diazotoluene chloride and orthocrssol in molecular proportion ; it crystallises from benzene in lustrous, golden yellow needles, and melts at 115'.Metatolueneazo- orthocreseto21 crystallises in reddish-yellow plates, and melts at 4 6 4 7 ' . When this ether is reduced, the orthosemidine base, 2 : 5-amidoethoxy-3' : 4-dii)2ethyldipl~enylamine, is produced in quantity amounting to 43 per cent. of the material employed ; it crystallises from petroleum in aggregates of colonrless needles, and mclts a t 91-92-3". The azimide crystallises from petroleum in leaflets, and melts at 83--84* ; the stilbazonium base melts 137*5-140', and the solution in alcohol exhibits grecnish-yellow flu.orescence. Oxidation with ferric chloride converts the orcthosemidine base into metatohhido- tolupuinone, which forms purple-red needles, and melts at 142'. The parasemidine base, 4 : 4' : 2 : 3'-amidoethoaydimethyldiphenyl- amine, is also formed when metatolueneazo-ort hocresetoil is reduced, the yield amounting to rather more than 5 per cent. It crystallises from petroleum in long needles, and melts at 99-looo.Reduction of paratolueneazo-orthocresetoil gives rise to the ortho- semidine base, 2 : 5 : 4 : 4'-amidoethoxydimethyldiphenylamine, which crystallises from dilute alcohol in small, white needles, which become violet when exposed to light or air, and melt a t 76". The azimide crystallises in colourless leaflets, and melts at 131', the thiocarbenyl- cornpound at 205-206O, and tho stilbazonium base at 146-149'. The yield of the orthosemidine base amouuts to 50 per cent., 21 per cent. of mixed bases being also obtained. ~rthotol~ceneazometacresoE crystallises in orange-red plates, and melts at 112" ; the sodium derivative crystallises in lustrous, yellow leaflets.. ~Ietaci.esolbisazo-ol.t~iotoluelte, ( C6H4Me.N2),C6H,Me*OH, is formed during the preparation of t h e phenol, and melts a t 188'. 0rthotoZueneazu7,Letac?.esetoi'Z crystallises from alcohol in deep red, lustrous needles, and melts at 64" ; when this substance is reduced 4.3 per cent. of the parasemidine base, 4 : 4' : 3 : 2'-amidoethoxydi- methyldiphen!llnmilze, is formed, 53 per cent. of other bases being pmduced at the same time. The base crystallises in white leaflets,ORGAN10 OEEMISTRT. 27 and melts at 86'; the sdphate ci:yst.allises from alcohol in long, colourless needles, and the mmacetyl derivative and dictcetyl derivativo melt a t 144' and 115" refipectively.Met atoliieneazonzet awesol crys tall ises in orange- yello w, rh ombic plates, and melts at lOS-lOiO ; during its preparation metacresozbis- a.zo?netatolzhe?ze is formed, crystallising in long, reddish- brown needles, and melting at 1 0%--103'. lMetatolzceneazo~netaci-esetoi'l crystallises from alcohol in red prisms, and melts at 73' ; on reduction, it yields 44 per cent. of the payasemidine base, 4 : 4' : 2 : 2'-amidoethoxydimethyl- diphenylamine, which crystallises in co!ourless prisms from benzene to which petroleum has been added ; it melts at 95-96', the monacetyl derivative at 116", and the thiocndamide at 70-72'. Paratolueizeazoi~~etuc~~esol crystallises from benzene in orange-red prisms, and meits at 135" ; metacresolbisazoparutoluene is formed at the same time, and melts at 107".Paratolueneazometacresetoi'l cry- stallises from alcohol in orange-red, four-sided plates, and melts a t 64'; on reduction, it yields 24 per cent. of an orthosemidine base. The stilbazonium base crystallises in long, canary-yellow needles, and melts 178-179'. M. 0. F. Reduction of Metaxyleneazophenetoil. By PAUL JACOBSON and G. SCHKOLNIK (Annalen, 1895, 287, 212-212).-3~etaxyleneazo- phenol crystallises from benzene in brown prisms, and melts at 134'. 2lfetaxyleneazophenetoi:l crystallises in red needles, and me1 ts at 97". On reducing this substance, 74 per cent. of mixed bases is obtained, consisting of xylidine and phenetidine. Reduction of Azophenetoile. By PAUL JACOBSON and FRIEDRICH MEVER (Annalen, 1895, 207, 212-220).-Orthop?~eaetoi'lazopara- phenol, OEt*C,H,*N,.C,H,*OH, is obtained by adding a solution of diazotised phenetidine to a well-cooled solution of sodium phenoxide containing 1 gram of phenol to 25 grams of water ; i t crystallises from benzene in lustrous, reddish-brown leaflets, and melts at 151".Ortho- phenetoalazopara~henetoi'l crystallises from alcohol i n brown leaflets with a golden lustre, and melts at 77-78". When this substance is reduced, the parasemidine base, 4 : 3 : 4'-a?~ziaodiethozydiphien!/la,nine, is obtained ; this crystallises from petroleum in lustrous, feathery lerrflets, and melts at 84.5" ; the hydrochloride forms aggregates of colourless needles, which rapidly become blue. The thiocarbamide melts at 154.5-135'. The parasemidine base is obtained in quantity amounting to 5 1 per cent.of the material employed. ~Ietaphenetoi'lazopn~aphenol melts at 105-106', metaphe~ietoi'lpara- plzenetoil a t 70-7 Lo ; on reduction, the latter yields 69 per cent. of a, mixture consisting of ortho- and para-semidine bases. Paraphenetoilazoparaphenol melts at 125-126', and not at 204*5" as already stated (D. It. P., 48,543). On reducing the ethyl ether, 95 per cent. of paraphenetidine was obtained. M. 0. F. By WrLLrAnr NCPHERSOK (Ber., 1895, 28, 2414-2418).-Two views have been held with regard to the constitution of the hydroxjazo-compounds ; N. 0. F. Constitution of the Hydroxyazo-compounds.28 ABSTRAOTS OF CHEMIOAL PAPERS. one that their constihtion is that denoted by the name, the other that they are in reality qiiinone-derivatives. Benzoquinone reacts with phenylhydrazine and its alkyl derivatives to form quinol, free nitro- gen, and other products.With /3-benzoylphenylhydrazine, however, it reacts like a ketone, yuinonemonophenylbenzoylhydrazone, C6H40:N*NPhBz, being formed. This substance ci*ystallises in yellowish needles, or in groups of flat prisms, which melt at 171’. It is quantitatively con- verted by zinc dust and acetic acid into benzanilide and paramido- phenol ; this reaction is exactly similar to that shown by many of the acetic and beiizoic derivatives of the orthohydroxyazo-compounds. Q uinonebenzoylhgdrazone explodes when i t is brought in contact with phenylhydrazine, aud even in alcoholic solution a vigorous ac- tion, accompanied by evohtion of nitrogen, takes place.Quinone- benzoylhydrazone, which from its properties and the method by which it is obtained, must have the formula given above, is entirely different in its properties from the benzoate of parahgdroxyazobenzene (Ber., 43, 56l), which is hydrolysed by concentrated sulphuric acid or alco- holic potash into benzoic acid and parahydroxyazobenzene, and there- fore appears to have the formula OBz*C6H4*N:NPh. This true hydroxyazo-compound is converted by zinc dust and acetic acid into a, dihydrogen derivative, which is probably the corresponding hydrazo- compound. Quinonebenzoylhydrazone, like the benzoate of parahydroxyazo- benzene, is converted by sulphuric acid or alcoholic potash into benzoic acid and parahydroxyazobenzene, so that the two isomeric benzoic derivatives yield, on hfdrolysis, only one compound (compare Nef, Annalen, 287, 354).These results seem to show that parahydroxyazobenzene really has the constitution indicated by its name, and is a true hydroxy-deriva- tive and not a quiiionc derivative. The research is being extended to the naphthalene derivatives. A. H. Rules controlling the Formation of Azo-colouring Matters. author points out that the formation of azo-colouring matters may be well compared with the bromination of aromatic hydroxy- aud amido- compounds. Such differences as are noticeable may be traced to the closer relationship of the amido-group t o the azo-group than to the hydroxyl-group, and to the smaller acidifying power of the azo-group as compared with that of the bromine atom, as well as iu the spacial relationship of the azo-group towards the bromine atom.It must further be noted that bromination takes place in acid solution, whilst the formation of azo-dyes is generally effected in alkaline or neut,ral solutiom, seldom in the presence of acids. WILHELM TTAIJBEL (J. pr. Chem., 1895, [el, 52, 284--288).--The A. G . B. Symmetrical Dibenzylhydrazine (Hydraziphenylmethane). By THEODOR CGRTIUS and E. QCEDENFELDT (Ber., 1895, 28, 2345- 2347 ; compare Abst>r., 1889, 393).-Syrnmetriral diteirz2/Ehyr~r.a,-ine, CH,Ph*NH*NH*CH,Ph, is obtained by reducing benzglideneazine inORQANIO OHEMISTRY. 29 alcoholic solution with sodium amalgam ; it crystallises in large, lustrous plates, and melts at 65'. On remaining exposed to the atmosphere, i t becomes converted into a colourless oil. The base is indifferent towards alcohol, water, acids, and alkalis, and does not reduce Fehliiig;'~ solution ; it reduces zl cold, ammoniacal silver solu- tion however.The ?nonohydrochloride is not decomposed on exposure t o air ; i t crystallises in colourless prisms, and melts a t 153'. The picrote is insoluble in water, but ci*ystallises from alcohol in long, golden-yellow prisms, and melts at 130'. The acetyl derivative crys- tallises in colourless needles, and melts at 78" ; the benzoyl derivative melts at 87", and the nitroso-derivative, which crystnllises from alcohol in large, yellow prisms, at 89". When the nitroso-derivative is treated with reducing agents, ammonia is formed, together with dibenzylhydr- nzine or benzylamine, according as reduction is mild or energctic.Oxidation of dibenzjlhydrazine in alcoholic solution with mercuric oxide, leads to the formation of a compoi~nd which crystnllises from alcohol in colourless prisms, and melts ah 152'; aJthough having the em- pirical formula of azobenzyl, its molecular weight is found to be twice CH2Ph*r*T*CH,Ph CH2Ph*N.N*CH,Ph' as great, and it prcjbably has the constitution Benzylideneazine tetrabroniide, CHBrPh*NBr*NBr*CHBrPh, is ob- tained by adding bromine to a chloroform solution of benzylideneazine ; it forms orange-red crystals, and melts a t 134'. On dissolving it in acetone, a colourless liquid is obtained, bromacetone and the dihydro - bromide of benzylideneazine being formed. Liberation of nitrogen takes place when benzylideneazine tetrabromide is dissolved in alcohol : the reaction proceeds quantitntivclg, mineral acids and boiling water producing the same effect.hi. 0. P. Tautomerism. By WILLY MARCBWALD (Annalen, 1895, 286, 343-368 ; compare Abstr., 1895, i, 347).-The author is of opinion that the amidines are tautolneric compounds, and that the hypothesis of pseudomerism cannot be applied t o them. Derivatives of this class would he expected to behave consistent,ly with having both the structures NHR'*CR:NR" and NR':CR.NHR" ; this is actually the case, and where contradictions have occurred in the apparent exis- tence of two isomerides, repetition of the experiments in question has established their inaccuracy. The author criticises von Pechmann's views regarding the constitution of formazyl-compounds (Abstr., 1894, i, 456), and discusses the subject of tautomerism at some length.In the formul3e given below i t is to be understood that the taiito- meric formula is also implied in each case. Orthopal.aditoEylcLcetamidi?ze, C6H4Me*N:CMe-NH*C6HJMe, is ob- tained from ethylisothioacetorthotoluidide and paratoluidine, or from ethylisothioacetoparatoluidide and orthotoluidine (Wallach and Wus- ten, Ber., 1883, 16, 148). It crystallises from alcohol i n needles, and melts a t 144-145'; the same product is obtained from both sources, and the previous investigators were mist,aken in recognising two modifications.30 ABSTRACTS OF OHEMIOAL PAPERS. Phenylparatolylbenzamidine (von Pechmaun, Abstr., 1895, i, 347) is obtained from benzauilide imidochloride and paratoluidine, or from benzoparatoluidide imidochloride and atdine; the two forms originally described by von Pechmann are identical, as he, himself, has since shown (Zoc.cit.), and both preparations, when recrystallised, melt at 1:31-132' t o a turbid liquid, which becomes clear a t 1:B'. The nitrate forms small, white crystals, and melts and decomposes at 144' ; the hydrochloride melts at 237O, and the picrate a t 195'. Diphenylparatolylguanidine, C6H4Me*N:C( NHPh),, is formed from aniline and phenyltolylcyananiide ; aniline, phenyltolylthiocarbamide, and lead oxide ; paratoluidine, diphenyl thiocnrbamide, and lead oxide, or from paratoluidine and diphenylcyanamide ; Huhn, by means of the first two methods, obtained products which he believed to be different from one another (Abstr., 1886,1036).Tho baQe separates from alcohol in white crystals, and melts at 128-129'; the hydrochloride melts at, 221-222', and the ylatinochEoride becomes brown at 230°, but does not melt at this temperature. Tetyap henglpara to1 y ldiguanide, NHPh-C (NPh)*N( C6H4Me)*C(NPh)*NHPh, is obtained as a bye-product in preparing the foregoing compound from diphenylcyanamide and paratoluidine ; it crystallises from absolute alcohol, and melts at 150'. It is prepared by allowing the latter substance to remain in alcoholic solution with the former (2 niols.) for one day. The hydrochloride melts and decomposes at 1 5 6 O , and the platinochlwide melts at 136'. Pentaphenyldiguanide, NHPh-C (NPh)*NPh*C (NPh) *NHPh, is a bye-product in the preparation of triphenylguanidine ; it is also pre- pared by allowing an alcoholic solution of aniline and diphenylcyan- amide to remain for one day a t the ordinary temperature.It melts at 160°, and when heated with aniline yields triphenylguanidine. The hydrochloride melts at 213O, and the ptatinochloride is amorphous. PhenSldiorthotolyl,uanidine, NPh:C(NH*C6H4Me),, was described by Huhn, who obtained a product melting at 102O from diorthotolyl- cyanamide and aniline, and from diorthotolylthiocarbamide, aniline, aiid lead oxide, whilst a preparation from phenylorthotolylcyanamide and orthotoluidine, or from phenylorthotolylthiocarbamide and ortho- toluidine by the action of lead oxide, melted at 112'. Making use of these four methods, the author has been able to isolate one form only of phenyldiorthotolylguanidine ; this separates from alcohol in we1 1- formed, colourless crystals, and melts at 97-98' ; the hydrochloride nielts a t 197', and the r7itl.de melts and decomposes at 183'; the piutinochloride forms minute orange-yellow crystals, and melts a t 213-214'. When the base is prepared by either of the methods irldicated, tritolylguanidine (m.p. 130-131O) is formed at the same time ; its hydrochloride melts above 250°, and the nitrate decomposes and melts at 204'. The action of carbon bisulphide on phenpldiortho- tolylguanidirie affords evidence of the tautomeric nature of this sab- stance; if its structure is to be represented by the tautomeric forrnultx NPh:C (NH*C6H4Me)*NH*C,U4Me and NHPh*C (NH*C6H4D/I e) :N*CsH,Me,ORGAN10 CHEMISTRY.31 a, mixture of diorthotolylthiocarhamide and phenylthiocnrbimide with phenylorthotolylthiocarbamide and ortliotolylthiocarbimide should be formed under the influence of carbon bisulphide, whilst a substance having a rigid strncture would yield only one thiocarbamide and one thiocarbimide. Experiment shows that the former alternative takes place, irrespective of the source from which the base is derived. Uiphenylorthotolylguanidine, C6H,Me*N:C (NHPh),, is the sole pro- duct of the action of orthotoluidine on diphenylcFanamide ; i t separates from alcohol in white crystals, and melts at 112'. The nitrate melts at 1 7 2 O , and the plutinochloride a t 210'. Tetraorthotolylphertyldiguanide, C6H4Me*NH*C ( N*C6H&fe) *NPli*C (N* C6HB,hle)*NH*CGH,Me, is obtained by the union of aniline with diorthotolylcyanamide (2 mols.) ; it ciytallises from alcohol in white needles, acd melts -at 111O.The hydrochloride and the platinochloride are sparingly soluble i n water. M. 0. F. Mixed Amidines and Tautomerism. By HANS VON PECHMANN (Bey., 1895, 28, 2362-2374 ; compare Abstr., 1895, i, 347).-Former cAxperiments have dealt with the tautomerism of the types NX:R*NHY and NHX*R:NY, in which X and Y represent chemically similar radicles ; i n the present series, the radicles are dissimilar, and it is found in consequence that tautornerism does not occur. N e t h y 1 benzaniide imidocNoride, C PhC 1 :NMe, is obtained by the action of phosphorus pentachloride on methylbenzamide ; i t is a, colourless, mobile liquid which has an irritating odour, and boils at 124O under a pressure of 60 mm., undergoing. slight decomposition.13- Napht h ylanzido5enzeii~~lmeth~l imidine, NMe:CPh*NH*C,,H7, is ob- tained by allowing p-naphthylamine to act on the foregoing sub- stance dissolved in ether, or from /3-benzonaphthalide imidochloride and methylamine. It separates from much boiling alcohol in lustrous crSstais, and niel ts at 204'. The crystalline form is monosymmetrio, a : b : c = 1.8456 : 1 : 0.70848 ; /3 = 81-39'. The picrate crystallises i n sulphur-jellow prisms, and melts at 166.5O. NMe:CPh*NMe*C,oH7, is obtained by mcthylnting the foregoing substance, and is identical with the amidine obtained from methylbenzamide imidochloride and p-methylnaphthylamine ; it is an oil which readily forms the picrate, crystallising in orange-yellow plates, melting at 155.5O.is formed when diniethylamine remains in contact with benzonapli- thalide iniidochloride ; the hydriodide crystallises from ether i n colourless prisms, and melts at 215O, whilst the picrate forms bright yellow prisms, and melts a t 150'. Phcnylumidobenzenylm ethy limidisze, MeN:CP h*NHPh, is obtained by the action of aniline on methylbenmmide imidochloride, and of methylamine 011 benzanilide imidochloride ; it crystallises from alco- hol in colourless needles, and melts at 234'. Thepicmte melts at 1 6 9 O , and the hydriodide at 190". p-Naphthylmethy lamidobeiizenylmetJ/ ybimidine, Dimet hylumido benzm y 1 - P-rLap ht h y h i d ine, SIe,N*C P h: NC I0H7,32 ABSTRACTS OF CHEMIOAL PAPERS.Met 1, y 111 hen y 1 amido benzeu y lm et 1, y l i n d ine, MeN : C P h*NMe PI], is produced on methylating the foregoing substance ; i t crystallises from petroleum, and melts a t 56". The hydriodide is colourless, and melts at 190' ; the picrate melts at 174". Dzmeth yZarnidobe?ue?a ylphen ylimid ine, Me,N*CPh :NPh, is o b tai D ed from henzanilide imidochloride and dimethylamine ; it melts at, 73-74". The hydriodidc forms lustrous prisms, and melts a t 196" ; tbe picrate melts a t 126". Pheiaylamidobenze~zyla.lailimidine. NHPh*CPh:N*NHPh, is obtained by heating a mixture of benzariilide imidochloride and phenylhydra- zine on the water bath ; it cr~-stallises in yellow prisms, and melts a t 119'. Ferric chloride develops a red coloi-ation in the alcoholic solution ; i n coucentrated sulphui*ic acid, the same coloration is developed by potassium dichromate, whilst ferric chloride produces no change.Pehling's solution is slowly reduced on boiling. The hydrocldoride is sparingly soluble, and crystallises in needles, and the picrate melts and decomposes a t 202". A~zilamidobenzen~lphe?z~limidir~e, PhN:CPh*NH*NHPh, is produced by heating a solution of benzophenylhydrazide imidochloride in ben- zene with aniline, and also in the preparation of the foregoing base ; it crystallises in lustrous needles, and melts at 174-175'. Ferric chloride develops a brown coloration i n the alcoholic solution, and a violet coloration in concentrated sulphuric acid solution ; E'ehling's golution is reduced on boiling.The hydrochloride is readily soluble, and crystallises in needles; the picrate melts and decomposes at 175". M. 0. F. Action of Phenylic Isocyanate on some Acids and Ethereal Salts. By ALBIN HALLER (Compt. reud., 1895, 121, 189-193).- Phenylic: isocyanate and cyanacetic acid, in molecular proportion, react at the ordinary teniperat ure, and jield cyanacetanilide, CN*CH,*CO*NHPb, which crystallises from alcohol in nacreous white plates melting a t 199O. Methylsalicylic acid and phenylic isocyanate at 120' yield methyE.salicyEaniZide, which melts a t 62O, and is not affected by water or by boiling aqueous potash. Anisic acid, on the other hand, at 120°, yields anisic anhydride, identical with that obtained by the action of phosphorus oxychloridc on sodium anisate ; a t 180-1903, however, it yields anisanilide.Anisic acid, therefore, behaves in the same manner as benzoic, toluic, phthnlic, camphoric, and other acids (Sbstr., 1895, i, 679). Phenylglycollic acid yields only phenylglycollamide, OHCHPh*CO*NHPh, melting at 145-146°. Benzoylbenzoic acid and p henylic isocyanate, in presence of ether or light petroleum, yield unstable crystals, which readily split up into their proximate constituents when dissolved in any hot neutral solvent. If, however, the two compounds are heated a t 100" i i i the absence of any solvent, symmetrical diphenylcarbamide and benzojlbenzoic acid are formed ; the latter crystallises from alcohol in transparent, lozenge-shaped crystals melting a t 140-141°, and is identical with the anhydride obtained by von Pechmann by heatingORGANIC CHEMISTRY.33 acetylbenzoj-lbenzoic anhpdride at 200'. this product rneltiug at 140-14l0, and not a t 120'. as stated by Pechmann. At 140-1.50", beuzoyl benzoic acid and phenylic isocyanate seem to yield be:ixoylbenzanilide, but the lattei. could not be isolated. It follows that benzoyl benzoic acid behaves both as a lactone-alcohol, CO<06~>CPh*OH, C H and as an acid ketone, COOH*CsH,*COPh. Ethylic tartrate and p henylic isocyanate, in presence of dry benzene, at 130" yield the compound CO OEt C (OH) (GO NHP h).C (OH) (C: 0 NHP h) *GO OE t , which crystallises from benzene in white needles melting at 164', and, when dissolved in chloroform, has a molecular rotatorF power [ajD = -61.56'. C. H. B.Action of Bensoic Chloride on Urethane. By HAKS VOK PESHMANN and LUDWIG VANISO (Bey., 1895, 28, 2383-2384).- Benzoyl~ret~haue is obtained by heating a mixture of urethane, benzoic chloride, and pyridine, in molecular proportion, for 10-12 hours in boiling water ; the mass is agitated with caustic soda and ether, and the alkaline liquid acidified. A solution of the product in alcohol deposits ethylic benzoyZaZZophanate, COPh*NH*CO*NH*COOEt, which crystallises in silky needles, and melts at 179" (compare Kretschmar, Bw., 1875, 8, lop), whiht benzoylurethane (m. p. 110") crystallises from the mother liquor. When ethylic benzoylallophanate is heated above its melting point, it solidifies at 200-205°, phenylic cyanide distilling over ; the residue crystallises from alcohol in lustrout; leaflets, and melts at 223".M. 0. F. Syntheses with Sodamide Derivatives. By CARL BLACHEK (Bey., 1895, 28, 2352-2360; compare Abst,r., 1895, i, 289).-The author has continued his study of sodamide derivatives, and included sodium succinimide and sodium phthalimide in the investigation. Sodium succinimide yields benzylsuccinimide when heated with excess of bcnzglic chloride for four hours in a reflux apparatus; sodium acetanilide gives rise to acetobenzylanilide. Benzoic anhy- dride and acetic anhydride yield with sodium benzamide, dibenz- nniide and acetylbenzamide respectively ; diacetanilide is formed =hen acetic anhydride acts on sodium acetanilide. The action of sodium or potassium ethylic sulphate on sodium benz- amide and sodium phthalimide leads to the formation of ethylbenz- amide and ethylphthalimide respectively.M. 0. F. Ethereal Imidocarbonates and the so-called Normal Ethereal Cyanates. By ARTHUR R. HANTZSCH and LGDRIG MAI (Ber., 1895, 28, 2466--2472).-The authors agree with Nef (d?znaZeii, 287, 310) in stating that the ethereal salts of cyanic acid described by Cloez (Annulen, 102, 355) have no existence. The products of the reac- tion between cyanogeii chloride and sodium alkyloxides consist mainly of the ethereal salts of imido-carbonic acid (as much as VOT,. LXY. i. d34 ABSTRAOTS OF CHEMICAL PAPERS. 92 pel- cent.), together wit.h small quantities of etheral salts of cyan- uric acid. Phen ylic imidocarbonate, NH:C( OPh),, is most readily obtained by the action of cyanogen bromide (1 rnol.) on a mixtuine of sodium phenoxide (1 mol.) and phenol (1 mol.), dissolved in ether.It forms a hard, white mass, melts at 54O, and readily undergoes decomposi- tion even a t the ordinary temperature, yielding phenylic cjanurate and phenol. The decomposition takes place much niore rapidly wlren the solution of the phenylic imidocarbonate in light petroleum is heated for several hours. By no alterations in the methods of pyocedure, were the authors enabled to obtain normal phenylic cyanate. Parabromop hen ylic irnidocarbonnte, NH:C ( O*C6H4Br)2, is readily ob- tained by the action of parabromophenol (2 mols.) on cjanugen bromide (1 mol.) ; it melts at 129O, is sparingly soluble in ether and cold alcohol, and is also more stable than the corresponding phenylic salt.Ethylic imidocarbonnte is very stable, and is only decomposed into alcohol and ethylic cyanurate when heated in sealed tiibes at 200' for several hours. Aqueous solutions OF the imido-ether, when treated with an alkaline solution of bromine, give a precipitate of ethylic brminzidocarbonnte, NBr:C(OEt4)2 ; this is readily soluble in ether, and crystallises in needles, which melt a t 4?. No trace of ethylic cyanate could be obtained by the action of cyanogen bromide on sodium ethoxide, nor yet of methylic: cyanate from sodium methoxide. The chief product was always the imido- ether, together with s.r)all quantities of the cyanurate. Sodium phenoxide and also sodium parabromophenoxide cause the condensation of phenylic isocjanate into phenylic isocyanurate.The polymeride of phenylic isocyanate obtained by Hofmann (Annalen, 1, 37) differs from this cyanurate, and is shown to be LZ &molecular iso- cyanate, whereas the isocyanurate is a tri-molecular compound. Benzazide (Benzoylazoimide). Acid Azides of the Fatty Series. By THEODOR CCRTICS (J. pr. Chen2., 1895, [el, 52, 210- 226 : compare Abstr., 1895, i, 32).-Benzoylazoimide (benzazide) (Abstr., 1891, 56) is best purified by dissolving it in acetone, from which i t crystallises in large, colourless tables melting a t 32'. Its behaviour with water, with alcohol, with bromine, and with aniline has been described (Abstr., 1894, i, 331 ; 1895, i, 32). Dimetanitro- diphenylcarbamide melts at 24i--250G, not at 233" as heretofore stated. When reduced by means of sodium amalgam in alcohol, benzoyl- azoirnide is converted into etliylic benzoate and sodium azoimide ; when alcoholic ammonium sulphide is the reduciug agent, benzamide and ammonium azoimide are the prociucts, hydrogen sulphide being liberated.When zinc dust and glacial acetic acid are used, benz- amide can alone be isolated ; but when caustic soda is substituted for acetic acid, sodium benzoate and sodium azoimide are formed, unless the solution is very dilute, when nitrogen is evolved and dibenzoyl- hydrazine (m. p. 233'), NHBz-NHBz, produced (compare Zoc. cit.). J. J. S .ORGANIC: CHEMISTRY. 35 Phenglazoimide, PhN3, can be similarly reduced to hydrazobenzene, SHPh-NHPh, by sodium amalgam in alcohol. dzccciny Inzoimide, C2H4( CO*N3)2, is prepared by graclually adding sodium nitrite (2 mols.) to a well cooled, concentrated aqueous solu- tion of auccinylbydrazine hydrochloride (Abstr., 1895, i, 264) , and shaking with ether.It crystallises in long prisms, and explodes when heated. It is easily soluble in alcohol, sparingly so in ether, and insoluble in water. Under water, it melts nt 30". Boiling water decomposes it with evolution of carbonic anhjdride and nitrogen, and formation of ethyleiiecarbaniide. Boiling alcohol decomposes it, with formation of ethylenediurethane (ni. p. 110'). Attempts to prepare oxalylazoimide, N3.CO*CO*N,, have not been successful ; treatmenc of oxalylhydrazide (Zoc. cit.) in the manner descrilwd in the preceding paragraph, yielded hydr*azioxnZyZ, ?o*NH*NH'?o which is a white solid, insoluble i n all solvents.CO*NH*NH*CO' JI&?zylaZoimide, CH2( CO*N3)r, prepared by diaaotising malonyl- hydrazine (Zoc. cit.) in the manner described for succinylhydrazide, is an explosive oil which is converted into a yellow oil when heated with alcohol ; the reactions of tlie yellow oil prove it to be methylenedi- urethane. GlycoZylazoirraitle, 0 tl*CH2*CO*N3, is easily obtained by diazotising glycol~lliydraziiie (Abstr., 1895, i, 331) hydrochloride ; it crystallises in double pyramids, and explodes feebly. Boiling alcohol coriverts it into the wethtme, OH*CH,*NH.COOEt, wliich melts at 189'. A. G. B. Azides (Azoimides) of Substituted Benzoic acids. By A. STRL-VE aiid RUDOLF RADENHAUSEN ( J . pr. Chem., 1895, [ a ] , 52, 227- ~ 4 2 ) . - ~ I e f a n ~ t ~ o b c ~ ~ z ~ y l a z o ~ m ~ d e , N0,*C6H4*CO*N,, is prepared by dis- solving metanitrobenzoylhydrazine in dilute nitric acid, and adding the calculated quantity of sodium nitrite.It crystallises in white lamince, melts at, 6S0, and dissolves e:tsily in ether, benzene, alcohol, and glacial acetic acid, but not in water. It is also the main product of the action between diazobenzene sulphate and metanitrobenzoyl- hydrazine. When heated with much water, it is converted into di- me tnnitrodiphenylcarbsmide melting at 234' (compare preceding abstract). Tef ~~nizit~~odiphenylca~ba~~zide crystallises in jellow needles. When metanitrobenzoylazoimide is boiled with alcohol, it yields meta- 12itroluhenyZuretha?ze, N02*C,H,*NH*COOE t, which crystallises in yellow needles, melts a t 56", and dissolves easily in alcohol and ether ; strong hydrochloric acid at 120' decomposes it into carbonic anhydride, alcohol, and me tan it raniline. 01.thonitrclheiizoyZazoirnide is similarly prepared ; it crystallises in y e h w prisms, melts at 36", and dissolves freely in ether, chloroform, aiid benzene, but only sparingly i n light petroleum.Parani~i.obeiizoyln~oi~~~ide crystallises in coloui~less laminae, melts at 69", and resembles the meta-derivative in solubility. Hot water con- verts it into d~p:pnralzitl.odiphenylcur.~a?nide, CO ( NH.C6H4.N02),, which ci*ystallises in lemon-yellow needles, melts above 260°, and is insoluble in water ; hydrochloric acid at, 130' decomposes i t x i t b formation of d 236 ABSTRACTS OF CHEMICAL PAPERS. paranitraniline, but the change is more difficult to accomplish than in the case of the meta-derivative.Hot alcohol converts paranitro- benzoylazoimide into paranitrophenylurethane (Abstr., 1885, 149). Orthobromobe?azoy Zhydraziize, C6H4Br*CO*NH*NH2, from ethylic orthobromobenzoate and hydraziiie hydrate, crystallises in colourless needles, melts at 153'. and is only sparingly soluble in water, but freely so in alcohol and hot benzene. Metnhydroxy benzoy Zh yd?*azine, OH*C,H,*C 0.NH*NH2, from et hylic metahydroxybenzoate and hydraziiie hydrate, forms white crystals, melts a t 150°, and dissolves in water and alcohol, but not in ether, chloroform, or benzene. When its aqueous solution is shaken with benzaldeh yde, benzylidenenzeta hydro~:?lbeizzoylhyd,.uziiae, separates ; it melts at 205'.Metahydroaybenzoylazoimide, OH*06H4*CO*N3, prepared by diazotis- i n g the hydrazine, forms small, nearly colourless crystals, melts a t 95O, and dissolves easily in alcohol, ether, and chloroform, but only sparingly in light petroleum ; when heated with water, it yields tli- metahydroxydiphe?iyZcarbamide, CO(NH-C,H,*OH),, which forms colourless crystals, and melts at 280". Parahydro~benzoylhydrnzi?ae, prepared like the meta-derivative, crjstallises in white laminae, melts at 260°, and dissolves in hot water and alcohol. The corresponding benzylidene derivative forms white crystals, and melts at 218'. Pnraltydroaybenzoylazoimide crys- tallises in white needles, melts a t 132", and dissolves in ether, alcohol, benzene, and chloroform, but not in water.When it is heated with alcohol, it yields a crystalline compound which melts at 105-l1Oc, and is converted by hot water into diparnhydroxydi- pheny Icnrbanzidc ; thi? crystallises in colourless ncedles, and decom- poses, without melting, at 230". Ortholi ydroxybenzoylh ydrazine, prepared from methyiic salicylate at id hydrazine hydrate, crystnllises in colourless lamine, and melts at, 145". The corresponding benzylidene derivative forms small, colourless crystals, and melts a t 230". Orthohydroxybenzoylazoinzide crystallises in large, colourles~, rhombic plates, melts at 2 7 O , and has a powerful, tear-exci ting odour. Diort hoh!/di*oxydipheu ylcnrb- nilside crjstallises in white needles, and melts at 125'. Meta??zic7obeizzoylhydl.uzine, NH,*C,H,CO-NH*NH,, is prepared from ethylic metamido benzoate and hydrazine hydrate.It forms colour- less crjstals, melts a t 77", and is 1-ery soluble in cold water and in alcohol ; the iLydrochloi*ide, ~H2.C6HJ*CO*N.IH3,2HCI, melts a t 265". The benzylidene derivative, PI'HI,.C,H,.CO*PITH*N:CHPh, melts a t 180". ~fetnniidobeirzoylazoinside, NH2*C6HI*CO*~\r3, is precipitated by adding sodi urn acetate to a mixture of metamidobenzoylhgdrazirie and diazo- benzene sulpliate in aqueons solution ; it ciytallises in yellow needles, melts a t 85", and dissolves in ether, benzenc, and light petroleum. OH* C,H,CO *NH *N: CH Ph , A. G. B. Hydrazide and Azoimide of Hippuric Acid. By THEODOR CCRTILS (J. p a . Cheric., 1895, [Z], 52, 243-2'il).-The author describes in detail the prepaiation of hippurplhydrazine (-4bstr.,ORQANIC CHE3IISTRY.37 1891, 56; 1802, 112; 189.5, %2) by the action of hydrazine hydrate on (1) ethylic hippurate, (2) hippuramide, (3) hippurylazoimide, (4) ethylic hippurylglycolats. Hippirylhydrazine hydrochlode, NHBz*CH,*CO*NH*NHz,HCI, forms colourless crystals. The pZafinosocILloride, ( NHBz*CHz*CO*NH*NH?),PtC I:, crystdlises in slender needles. Hippurylbeiizylidenehydrazone has pi-evionsly been described (Abstr., 1891, 56). H~~pziryZcinnn??aylidene- hydrazine, ?JHBz*C H,* C 0 *NH*N: C: H*CH: C H P h, cry st allises in y el- lowish pi*isrns, and melts a t 201.5". S?yminetrical acetytkippIiry2lLydra- zine, NHBz*CHz*CO*NH~NHAc, is formed by the iiiteraction of acetylbydrnzine (Abstr., 1895, 263) with hippurylazoimide in ethereal solution; it crystallises in colourless needles, melts at 18G0, and dissolves easily in alcohol.Syinmet&nl hippiIryZ~hen~l!Z7Lydraxine, NHBz*CH2*C0.NH*NHPh, from phenylhydrazine and hippuryhzo- imide, crystallises in si1ver.y lnmiiize or needles, melts at 182*5O, and can be distilled nearlF unclecomposed when quickly heated ; it dis- solves in hot alcohol, but not in water or in ether; it does not reduce hot Fehling's solution. 1~~L'tro.sohi~~'lC).l!lphenylhy~).atine, N BBz*CH2*C0.NH-NPh*N 0, prepared by treating the last-named compound in glacial acetic acid solution with sodium nitrite, forms a yellow, crystalline powder, me1 ts at 128-12Y0, and dissolves in alcohol, but not in water; hot water decomposes it into phenyl- azoimide and hippuric mid.Acetylhippurylphenylhydrazine, N HBz* CH2* CG*NH*NPhAc, prepared by digesting hippurylphenylhydrazine with acetic anhyd- ride, forms a white, crystalline powder, melts at 15.io, and dissolves in water and alcohol, but not in ether. l)i7Lippz~rylhydrazine, (NHBz*CH,*CO)~N,H,, can be prepared by heating a mixture of hippurylhydrazine and ethylic hippurate in molecular proportion ; it forms small, silvery crystals, melts at 268--f169", and is insoluble in boiling alcohol, boiling water, and etLer ; i t is a feeble acid. Hippii~ylazoimide, NHRz*CHz*CO*N3, the product of the aztion of sodiuni nitrite and acetic acid on an aqueous solution of hippuryl- hydrazine, has been previously described :IS a nitrosohippurylhydra- zine (Abstr., 1891, 571, and as diazohippurarnide (Abstr., 1892, 113) ; new analyses have now established its identity.It does not give Liebermann's reaction, as prsviously stated, neither does it give a p1.e- cipitate with silver nitrat.e in alcoholic solution until some time has elapsed, when silver azoimide sepamtes. With alkalis, hippurylazo- imide yields the alkali azoiniide and the alkali hippurate, but as an intermediate product R salt is obtained which has a blue fluorescence (compare Zoc. cit.). With acids, hippurylazoimide is hydrolysed into hippuric acid and azoimide, whilst with ammonia it yields ammo- nium azoimide and hippuraniide. This reaction with ammonia is typical of the behaviour of hippury lazoimide with aniline, para- toluidine, and metatoluylenediamine ; the following new compounds have been prepared by such reactions.Hippiimnilide cyystnllises in long, lustrous prisms, melts at 208*5O,3s ABSTRACTS OF CHEMICAL PAPERS. and dissolves easily in hot glacial acetic acid and hot alcohol, but only sparingly in cold alcohol or ether, and not at all in cold watei.. Nit,.osollippuraniZidc, XHBz*CB,*CO*NPh*NO, obtained by the actiou of nitrous acid on the anilide, is a yellowish, crystalline powder, 'which darkens below loo', and melts between 195" and 197". H~ppzLropal.atoZuicJz'de, N H Bs C B p*C O*NH*C6H4Me, cry s t all i ses i u colourless needles, and dissolves freely in hot alcohol and hot glacial acetic acid, biit only sparingly in water, cold alcohol, or ether. Hippur-oparatoluylenedinmide, NHBz~CH,*C0.NH~C6H,Rle~NH,, crystallises iii pale yellow, lustrous Inmine, melts a t 205'.and slloms a similar solubility t o that of hippuroparatoluidide. The behaviour of hippui-ylazoimide with hjdrazine and acid hjdra- zides has already been indicated (Abstr., 1895, 34), and the products of these reacticris will be described in n future communication. In discussing the behaviour of hippurazide with water, alcohol, and halogens (compare Abstr., 1894, i, 331 ; 1895, 32 ; this vol.! i, 34)) the author adopts the name hippenyl for the radicle NHBz.CH,-. Dih~~~enylcartamide, (KHBZ*CH,-KH)~CO, is obtained when liip- purylazoimide is boiled with water, carbonic anhydride and ni trogeii being eliminated. It forms microscopic, colourless crystals, melts at 246', and is nearly insoluble in water, but, dissolves to some extent in hot alcohol and gJacial acetic acid.Hydrochloric acid. at 120", coriverts it into benzoic acid, ammonium chloride, carbonic anhydride, and formaldehyde. When the hot filtrate from the dihippenylcarb- amide is cooled, a compound, probably iiippenylcndanil, R'HBz*C H,*N:C 0, or a polynieride thereof, separates in the form of colourless crystals, which melt at 233" ; dilute acids readily decompose it into beiizoic acid, ammonia, formaldehyde, and carbonic anhydride. A third compound, C9H6N20, is left as an oil when the mother liquor from the carbanil is evaporated; it is soluble in alcohol and in glacial acetic acid, from which it is precipitated in the form of crystals ; it melts a t 98'. The same substnnce is produced when hippurylazo- imide is heated either by itself 01% in an indifferent medium.Hippnrylazoimide reacts with alcohok at their boiling points to form the correspondiiig hippenylurethanes ; these are hydrolysed by hydrochloric acid, a t loo', iuto benzoic acid, ammonia, formaldehyde, carbonic anhydride, and the parent alcohol. Hippenylethy Zzcrethaue, NHBz*C HZ*NH-C 0 OE t, cry stallisea i n aggregates of colourless needles, melts a t 162', and dissolves easily in hot alcohol, benzene, and glacial acetic acid, but only sparingly in hot water. It behaves as a base, and can be distilled almost unchanged. Hippenylnzethyl- urethane, NHBz*CH2*NH*COOM e, crystallises like the ethyl com- pound, and melts at the same temperature (162'). HippenyZbeizzyl- urethane, NHBz*CHZ*NH.C00.CH,Ph, crystallises in felted needles, which become highly electrified by friction; i t also melts at 162'.Both the last-named compounds resemble the ethyl compound in properties. Alkylic haloyd salts react with moist hippurylazoiniide, when warmed therewith, to form the corresponding hippenylurethane, withORGANIC CHEMISTRY. 39 liberation of hydrogen halo'id. I n this reaction, the author sees evidence that moist hippurylazoimide has the constitution NH B z* C H2*C O N €3. IT2* 0 H. By treating hippurylazoimide with a halogen in ethereal solution, nitrogen is eliniinated, and a di'nalo'id hippenylcarbanil is formed. In this way, compounds which are assumed to be dib).onsoh.ippe,rylcai.b- anil, NHBz.CH2*NBr2:C0, and d i i o d o l i i p ~ e i ~ ~ l c ~ ~ ~ ~ b a n i l have been crys- t a1 li sed. Heactions of hippurylazoimide with hydrogen chloride, aldehyde, and acid amides, are briefly mentioned, but their elucidation will receive further attention. A.G. B. Appendix to recent Publications (Benzoylhydrazines). BJ- THEODOR CURTIUS ( J . pr. Chem., 1895, [2], 52, 272--276).--1n describing carbohydrazimine, Curtius and Dedichen (Abstr., 1895, i, 29) have overlooked the fact that Angeli (Abstr., 1894, i, 149) had previously prepared the same compound. The compounds described as hjdrazimines i n the same paper arc wroi~gly named ; they contain two fewer hydrogen atoms, and are identical with Pinner's isocli- hydrotetrazines (Bcr., 1889, 22, 3274). The author thinks Pnrgotti's claim for priority (Abstr., 1895, i, 27) cannot be allowed. Ethylic benzoylh~~rnzc)ilclacefoclcrtate, COPh-KH-N:CMe*CH2*COOEt (compare Struve, Abstr., 1895, i, 3 4 ) , has been prepared by heating benzoylhydrazine with ethylic acetoacetate ; the crude material melts at about 60°, but when its solution in alcohol is diluted, i t separates as an oil, which is still liquid at -15'.The preparation of ethylic metanitrobenzoylhydrazoneacetoacetate (Abstr., 1895, i, 276) is detailed. A. G. B. Metallic Bisulphite Compounds of Aldehydes. By A. FAGARD (J. Phawz., 1895, 6, [2] , 145-148).-Benzaldehyde lithium hydroge9L szclphite, CiH60,LiHS03 + *H20, is prepared by passing sulphurons anhydride into an aqueous suspension of lithium carbonate, into which benzaldehyde is slowly dropped. The product is evaporated to crystallisation, preferably under low pressure.The sulphate crys- talliaes i n small, colourless prisms, and appears to resemble the analogous sodiuni compound. Acetone bin~izirn h y d ~ o g a u szclyhite, 2C3'E-T60,Ba( S03H)z,Hz0, is made by passing sulphnrous anhydride into a mixture of barium hydroxide, water, and acetone. The baryta gradually dissolves, with evolution of heat, and the additive cornpound separates on cooling. It crystal- liscs in s111a11, brilliant plates, resembling those of boric acid. The corresponding strontium compound is anhydrous, and forms small needles, or twinned prisms. JN. w. Resolution of Benzaldehy dacyanhydrin by means of Alkalis. By CARL GLUCKSYASX (Chem. C'entr., 1895, i, 8i3-274, from Yhamz. Post., 27,573-574 and 585-588 ; compare E. Utescher, Abstr., 1893, i, 419) .-The fact that benzaldehyde combines with40 -4BSTRACTS OF CHEMICAL PAPERS.hydrocyanic acid in dilute solution has no bearing on the question of' the hydrolysis of benzaldehydecyanhydrin, since this is treated successively with alkali, acid, and silver nitrate. The action of magnesium hydroxide is, like that of potash, direct; it is not dependent on the formation of silver oxide, and the hydrolysis is completed more rapidly. Parahydroxybenzaldehyde. By CARL PAAL (Ber., lE'9.5, 28, 2407-2414) .-The monobromo- and moniodo-derivatives of para- hydroxybenzaldehyde described by Herzfeld (Ber., 10, 2196) are in reality disubstitution products. Bromine converts parahydroxy- benzaldehyde, when dissolved in dilute alcohol, directly into the dibromo-derivative, whilst if chloroform be used as the solvent, metnbromoparahydroxybenzaldehyde [CHO : Br : OH = 1 : 3 : 41 can readily be obtained.It crystallises from hot water in white plates, melts at 124', and decomposes when distilled. The sodium and silcer derivatives orystnllise in needles. JIetabyomoparahydroxybenz- aZdo.cime crystallises in druses of white needles, melting at 133". ,lIetabrornoparahydroxybenzylideneaniline forms flat needles, melting at 135'. Metabromoparahydroxjybenzoic acid is formed by the oxida- tion of the aldehyde with alkaline permanganate ; it crystallises in concentric groups of:white, flat, needles, melting at 148', and is soluble in hot water. Jletiodoparahydyoxybenzaldehyde is found in the mother liquors obtained in the preparation of the di-iodo-derivative.I t crystallises in white plates, biit has not yet been obtained quite pure. Metanitroparnhydroxybenzaldehyde can be readily prepared by dissolving the hydroxybenzaldehyde in acetic acid and adding nitric acid. A. H. By HEINRICH LIMPRICHT (Amden, 18'35, 288, 306- 342).-The ketones described in the following abstracts were pre- paTed by mixing the chloride employed with a slight excess of the hydrocarbon, adding several volumes of carbon bisulphide, and heating the liquid with alnminium chloride in a reflux apparatus for 8-12 hours. The ketone is obtained as a resinous cake, and, after being washed with water, is crystallised from alcohol. The carbonyl group in these ketones occupies the para-position with respect to the methyl of the tolyl residue.Metanitrophenyl Paratolyl Ketone. By HEINRICH LIIIPRICHT and M. LENZ (Annalen, 1895, 286, 307-321).-31etanitrophenyl paratolyl ketone crystallises in white leaflets, and melts at 111" ; in small quanti- ties, it may be distilled without undergoing decomposition. The ketone is readily soluble in organic solvents and hot alcohol, but is sparingly soluble in cold alcohol and 50 per cent. acetic acid. The dichlo7eide is obtained as a brown oil by heating i t with phosphorus penta- chloride ; the ketone is regenerated on treating this substance with alcoholic ammonia or aiiiliiie. The monochloro-derivative is formed when chlorine gas is led into the ketone at 150" ; it crystallises from alcohol in long, brittle needles, and melts at 96". The monobromo- derivative crystallises from alcohol in long, white needles, 2nd melts a t 116".~~~etanitrophenyl-par~tol~b-lteto~~es:zil~hoizic acid is obtained by J. B. T. Ketones. 31. 0. F.ORGANIC CHEllISTRY. 41 dissolving the ketone in several volumes of fuming sulphuric acid ; it crystallises from water in large, rhombic plates containing 3H20. The substance effloresces in the atmosphere, and melts a t 140" with effervescence, but if heated for eight hours in the vapour of boiling toluene it becomes anhydrous, and then melts at 215' ; the barizcrn salt crystallises from water in colourless prisms, and contains 3Hz0. Diniirophmyl paratolyl ketone formswhite scales, and melts at 125"; the tyinitm-derivative cry s t a k e s in minute, six-sided prisms, and melts at 165'.Azoxyphenyl paratolyl ketone is prepared by dissolving the nitroketone in alcoholic potash ; i t separates from alcohol in yellow crystals, and melts a t 145'. The ketozime, obtained by heating the alcoholic solution of the ketone with hydroxylainine hydrochloride and sodium carbonate, crystallises from alcohol in white, lustrous needles, melting at 111'; if caustic soda is employed, the kefozime of the azoxy-derivative is formed, occurring in two modifications which melt at 235' and 243' respectively. SIetanzidophe?tyl paratolyl ketone is obtained by reducing the nitro- ketone in alcoholic solution with stannous chloride ; i t crystallises from alcohol in amber-coloured prisms, melts at ill', and may be distilled in small quantities without undergoing decomposition. The hydrochloride crystallises in needles, and melts at 198'; the szdphate separates from water in aggregates of needles, and melts at 142O.The szclphonic acid of the amido-ketone forms small crystals which decrepitate when heated ; it melts at 300", and effervesces and blackens. The acetyl-derivative crystallises in small, white prisms, and melts at 139'. On adding sodium nitrite to an aqueous solution of the amidoketone sulphate, the diazo-compound is formed : gas is evolved when the diluted liquid is boiled, and the slender, white needles which the cold solution deposits melt a t 120°, and consist prob- ably of hydroxjphenyl pamtolyl ketone. Phenyl paratolyl ketone is obtained from the amido-ketone by adding a concentrat4ed aqueous solution of sodium nitrite to a solution of the hydrochloride in absolute alcohol, and treating the liquid with 6nely divided copper.The keloxiine of amidophenyl parat oyl ketone crystallises in minute, white prisms, and nielts R t 146' ; the amido-ketone is regenerated on heating i t with concentvated hydrochloric acid for four hours. Xetanitropnmbenzo yl beizzoic acid, N 02- CsH,* C 0- C,H,*CO OH, is ob- tained by oxidising the nitro-ketone, in glacial acetic acid solution, with chromic anhydride ; it crystallises in rhombic tables, melts a t 242', and sublimes a t higher teuiperatnres, forming white crystals. The potas- siziin salt crjstallises in white needles, and the barium salt, cmtain- ing lHzO, foiams leaflets ; the chloride melts at 94', and the nmide at 2 0 4 O . Jletaniidoparabemoylbenzoic acid is obtained by reducing the foregoing nitro-compound with stannous chloride ; it crystallises from alcohol, and contains 1H20, which is lost at 145", when the sub- stance melts ; the b a ~ i z m salt is anhydrous, the hydrochloride crys- tallises in long, slender needles, melting above 250", and the szdphnte contains 2H20.When the chloride of nitrobeiizoglbenzoic acid is heated with toluene and aluininium chloride, metanit~ophenyZpa~atoZyZ- phe?z!/Zene diketone, N0,*C6H4*C0.C6H,*Co*c6H~~~e, is formed ; it crystallises in colourless leaflets, and melts at 210". When oxidised42 ABSTRACTS OF CHEJnCXL PAPERF. with chromic anhydride in glacial acetic acid solution, i t yields a2etn- nitro~nl.nbenzoylpa,.abcnzoyEbenzoic acid, which melts at 276' ; the sodiicm salt crystallises i n nacreom scales.M. 0. F. N02*CGH~*CO*CGH11CO*C~H~*COOH, Paranitrophenyl Paratolyl Ketone. By HEIXRICH LTJI PR IC HT and E. SAMreirz (Annulen, 1895, 286, ;3'21-332).-Yal.aizit,.oyhelzyl paratolyl ketone crystallises in white needles, and melts a t 122-124". I n small quantities, it may be sublimed without undergoing decom- position ; the ketone is soluble in organic solrents and in concentrated sulphuric acid. Dinitrophenyl paratolyl ketone melts at 127', and tri- nitrophenyl paratolyl ketone at 159'; both these compounds have been obtained by Milne (Ber., 1874, 7, 983), and they appear to be icien- tical with the dinitro- and trinitro-ketones described in the foregoiug abstract. P(rz.a?nidophe?zyl paratolyl ketone is obtained by reducing an alcoholic solution of the nitro-compound with stannous chloride ; it separates from benzene in well-formed crystals, and melts a t 179'.The szdphate forms nacreous leaflets, and melts and decomposes at 210-216' ; the ncetyl derivative melts a t 155'. On adding sulphuric acid and sodium nitrite to an alcoholic solution, the amido-ketone becomes diazotised ; copper powder is then added, and on filtering the liquid into water, separation of pheiiyl paratolyl ketone (m. p. 52") takes place. Dinmidophenyl pnratolyl Jcetone is obtained by reducing the dinitro-compound, and melts a t 178" ; the s d p h a t e becomes dark, and decomposes above 240'. !l?rinrnidophenyl parcttolyl ketone crystallises from water i n white needles, which becotne brown on exposure to air ; it melts at 199".Parahytlroxy~henylpa?-atolyl ketone is obtained by boiling an aqueous solution of the diazotised amido-ketone ; it crystallises i l l long, white needles, and melts at 160O. Ilronzophenyl p n m t o l y l Eetoue is prepared by treating the diazo-compound with hydrogen bromide End copper powder; it crystallises in small, white needles, and melts at 139". The ketozime of paranitrophenyl paratolyl ketone crystallises in aggre- gates of needles, and melts a t 145' ; the phenyllqdrazone crystdlises in lustrous, scarlet needles, and melts a t 1.54". The phenyZlLydyazmJ of tho amido-ketone forms Iiistrous, brownish-red, rliombic ci*~stals, andmelts at 163". ParaIzityopa?.atrenzoylbenzoic acid is obtained by oxidising paranitro- phenyl paratolyl ketone with chromic anhydride in glacial acetic acid solution ; it melts at 255".The sodiu?72 salt crystallises in small, an- hydrous leaflets ; the chloride melts at 124". Pa?.n7,2iJopara~e?azo.~~- benzoic acid crjstallises i n bright yellow needles, and melts at 211' ; the sulphate is colourless and anhydrous. Paraiiitropheql para f olylph eiay lei1 e diketone, NO,*Cg H,* CO'C~HA'C O*C~HIMEL is obtained from toluene and the chloride of paranitropnrabenzoyl- benzoic acid by treatment with aluminium chloride ; it melts a t 236'. Paranitropnrabenzo yl~nrnbeiazoylbenz~ic acid crysta llises in 1 ust rous leafleh, aud melts a t 306-308" ; the S o d i u i i L salt dissalves sparingly in water. Jf. 0. F:ORGAN I C C HE M I ST K I-. 43 Metanitrophenylxylyl Ketones.By HEISRICH LIAIPKICHI and H. FaLKKsst; KG (Anualen, 1895, 286, 3~3--542).--7Ie~nrLilt.ophc-)zyl ?netuxylyl ketoue crystallises in lustrous yellow leaflets and melts at 64'. The ~1.initI.o-deri~-ative crystallises from alcohol in yellow needles and melts a t 138-139'. Xetamidopheti yl metazylyl ketone is obtained by reducing the nitro- conipound with stannous chloride ; it forms brownish crystals 2nd melts at Ll8'. The hydrochlo~ide crystallises in needles and the szblphcrte in lustrous nodules. The sulphoizic acid of metanitrophenyl metaxlyl ketone crystallises from water in long, white, lustrous needles; the barium salt contains 2H20, which is lost a t 13G'. Azox!lphenyl nzetaxylyl ketone is preFared by treating the nitro-ketone with boiling alcoholic potash ; it separates from petroleum in small, red needles and melt,s a t 134".The ketozime of metanitrophenyl met'axylyl ketone fornis small, white crystals, and melts between 131' and 149O. Two ~netaiaitrobenzoylmetatolzLic acids, N02.C6H4.C O*CsH3Me*COOH, are obtained by oxidisi ng the nitro-ketone with chromic anhydride i n glacial acetic acid solution, melting a t 173" and 152-153" respec- tively. The barium salt of the former is anhydrous, and crystallises in yellow needles and the silcw salt! forms minute white prisms, becoming violet when exposed in the moist state to light ; the chlo~ide is an oil, and the amide forms yellowish-brown crystals and melts a t 2 2 6 O . Xeta?zitrophe:Lyl orthnzylyl ketone crystallises in yellow plates belonging to the rhombic system, and melts a t 100'.Jletamidophcuyl orihoxylyl ketone is very soluble in alcohol and ether; the sdphate crystallises in pale-red nodules, and the lr ydTochZoride forms white needles. X e t unit 1.0 beizzo y lo~tlzo to l u i c acid forms small, ye1 lo wish crystals aucl melts at 191' ; the b a r i u m salt crystallises i n jellow needles, and the silrer salt is also crystalline, becoming violet when exposed t o light in the moist condition. illetanitriphenyl p a r a x y l y l ketone forms white, silky crystals, and melts a t 97-98'. ilIetall,idopheri y l pamxlyl 1;etone was not obtained in the crystalline state ; the sulphnte forms reddish crjstals, and t h e hydrochZoride crystallises in yellowish needles. b~eta~iitroph.e~zy1paratolz~ic acid crystallises from glacial acetic acid i n lustrous, brownish needles, and melts a t 189'; the bariunt salt fornis small, yellow crystals, and the moist silcei.salt is decomposed by light. M. 0. F. Resacetophenone. By GEOKG GREGOI{ (Monatsh., 1895, 16, 619-629 ; compare Nencki and Sicber, Abstr., 1881, 591 ; Wechsler, Abstr., 1894, i, 521, and Gliicksmaiin, Abstr., 1892, 38).--Wlieii diethylresacetophenone (1 mol.) is suspended in water and oxidised by the gradual addition of a solution containing potassium permanganate (1 mol. K2R/Inz08) and potassium hydroxide (2 mols.), 2 : 3-dietlzo.zy- benzoylformic acid, C6H3(OEt),-CO*COOH, is formed. It is insolxble in cold water but dissolves in hot water, and more readily in alcohol and ether ; from the solution in benzene, it separates in small crjstals44 ABSTRACTS OF CHEMICAL PAPERS.which melt at 1'27'. It forms an osime, C12H14@1:NOH, which crystal- lises from benzene and melts and decomposes at 130°, R silver salt, Cl2HI3AgO5, which is amorphous, cz sodiicnz salt, Cl2Hl3NaOS + 6H,O, which crystallises in scales, and a crysta.lline barium salt, (C12H1305)zBa + 8H2O. On reduction with sodium amalgam, the rtlcoholic acid, Cl2HI6O5, is formed. This crystallises from benzene, melts at 115', forms the silver salt, C12H15Ag05r and is oxidised by permanganate in dilute acid solution to an acid identical with the product of oxidation of Tiemann and Lewy's diethylresorcylaldehyde, which is therefore un- symmetrical diethoxybenzoic acid, OEt.C<cH- CHoC(oEt)\. C.COOH. -CH> The author therefore concludes that resa,cetophenone has the constitu- G: T.M. Constitution of Fisetin. By SmNtsrlbus VON KOSTANECKI and JOSEF TAYBOR (Be).., 1895, 28, 2302-2309 ; compare Abstr., 1894, j, 93) .-Two constitutional formulae are possible for fisetin, which is converted by fusion with potash into resorcinol, glycollic acid and pro- tocstechuic acid, C6H,(oH)<o-~*C6H3(oH)2 , [OH:O:CO=1:5:6 013 1 : 3 : 43. When tetraethylfisetia is boiled with alcoholic potash, i t yields diettiylprotocatechuic acid and diethyl fisetol ether, which, if fisetin have the second of the above formulae, must have the formula, O~;t*C6H3(OH).C0.CH,*oEt [ = 1 : 3 : 41, according to which it is an ethoxy-derivative of monethyl resacetophenone ether. On oxidation, diethyl fisetol ether is converted into ethyl-p-resorcylic acid (Herzig, Abstr., 1891, 1386).The authors have now shown that ethyl resacetophenone ether yields exactly the same product and have thus confirmed the accuracy of the view that the second of the above formula represents the constitution of fisetin. When resacetophenone is t.reated with alcoholic potash and ethjlic iodide, it yields a mixture of the two ethers. Diethyl resacetophenone ether crystallises in quadratic prisms melting at 74-75'. E t h y l res- acekphenoxe ether, OEt*C6tZ3(OH)C0.CH2*oEt, separates from dilute alcohol in white plates melting at 49'. On oxidation, the latter of these compounds is coiiverted into ethyl-S-resorcylic acid, ideiiticnl with that obtained by Herzig from diethyl fisetol ether, and with that prepared by the authors from p-resorcylic acid.Benzoylrcsorcinol differs from resacetophenone in its behaviour to wards alcoholic potash and meth ylic iodide, bemoylmet hy lresorcinol, C6H2XeBz(OH)2, being forrnecl. This substance crystallises in faintly yellow lustrous plates, melting at 176' ; i t does not contain a methoxyl group, and yields a diacetate, melting at 120', and a diben- zoate, melting at 149'. The benzoylmetliylresorcinol is accompanied byv bcnzoyZmrt7i ylresorciiiol methyl ethey, O&Ie*C6H2MeBz-OH, which crystallisea in rliombic tablets, melting at 125'. The ?nonacetate melts at 86". A. H. COOOHORGANIC CHEMISTRY. 45 Action of finely divided Silver on Ethglic Phenylbrom- acetate. By CARL HELL and S. WEISZWEIG (Bey., 1895, 28, 2445-- 2454) .-Phenylbromacetic bromide was prepared by the action of phos- phorus pentabromide (2 mols.) on mandelic acid (1 mol.), and was then converted into the ethylic salt by dissolving it in ethylic alcohol.The authors find t,hat the yield is just as good when one-half or eyen one-quarter of the theoretical quantity of pentabromide is used ; this is due to the fact that the hydrogen bromide which is formed duriny the reaction also acts on the mandelic acid. The ethylic salt boils at 175' under a pressure of 25 mm., and small quantities may be dis- tilled at ordinary atmospheric pressure mi tliont undergoing decom- position. Finely divided silver acts on the ethylic salt at the ordinary temperature, but the action is greatly accelerated by heating the two together in an oil bath at 170-180'. No product of low boiling point could be isolated, butl the ethereal extract yielded a mixture of u- and P-ethylic diphenylsuccinates(compare Reimer, Abstr., 1882,200 j, together with a small quantity of some oily ethylic salt which could not be obtained in a state of purity.Both a- and /3-salts, when hy drolysed with alcoholic potash, yield Reimer's a-diphenylsuccinic acid, whereas when hydrolysed with hydrobrornic acid they both yield the p-acid. The action of silver 011 ethylic phenylbromacetate is thus similar to its action on a-brominated fatty acids generally, and we may suppose the two isomeric ethereal salts to he formed according to the two general reactions previously given (see this vol., i, 10). J. J. S. Reduction of Phenolcarboxylic acids.By ALFRED EIXEIORN and JOHN S. LLXSDEK (AnizaZeiz, 1895,286, 257--277).-The authois' experiments shorn that whilst metaphenolcarboxylic acids are con- verted by reduction into yhydroxyhexamethylenecarboxylic acids, the ortho-derivatives generally yield dibnsic acids of the pimelic series. Pimelic acid is formed when salicylic acid is reduced with sodium and amylic alcohol (Abstia., 1894, i, 246). The quantity of this acid, which is formed on reducing ethylic salicylate 01- its ethyl ether, is extremely small, and probably arises from hydrolysis ; the main pro- duct of the action consists of hexnhydrobenzoic acid. By the action of sodium on ethylic pimelate moistened with alcohol, Dieck- mann obtained ethylic /3-ketohexamethylenecarboxylate (Abstr., 1894, i, 173), which is converted into ethylic liexahydrosalicylate on reduc- tion.The authors have treated ethylic P-ketohexsmethylenecarbosy- late dissolved in amylic alcohol with sodium, and obtained pimelic acid. This acid is also formed when guaiacolcarboxylic acid is reduced. Phen ylenuceticpopionic acid, C OOH*CH,*C,jH,*C Hz.CHz*C 0 0 EL, is obtained by reducing 2 : 3-hydroxpaphthoic acid (m. p. 216') in the manner indicated ; it is also formed when 2 : 1-hydroxyiiaphthoic acid (m. p. 156') is reduced, a mixture of ac- and ar-t,etrahydro- /&naphthol being prodnced a t the same time. It crystallises from water in colourless, hexagonal prisms, and melts at 159" ; it dissolves46 ABS'1'RACTS OF CIHEMICAL PAPERS, readily in ether and alcohol.The calcium and barium salts are anhy- drous, the silcer salt darkens slowly in daylight, and the copper salt is bright green ; the ethylic salt is a viscous oil, which has an agree- able odonr, and boils a t 210-212' under a pressure of 40 mm. ~iti.ophenylenacetic~l.opioizic acid crystallises from water in oolourless, lustrous leaflets,and melts a t 172"; i t is sparingly soluble in cold water, but dissolves more readily in hot water, and is very soluble in alcohol and ether. The calciunt salt is anhydrous, and the silver salt explodes readily when heated. When the calcium salt is submitted to dry distillation, p-ketotetrahydronxphthalene (Abstr., 1894, i, 419) is formed ; if the latter is slowly added to boiling dilutc nitric acid, phenylenediacetic acid is produced.31. 0. F. Isomeric Bromocinnamic acids and Cinnarnic acids. By Emr, ERLEMIEPER (,4.nnalen, 1895, 287, 1-25).-The author's experiments show that Glaser's a- and p-bromocinnamic acids are geometricallv isomeric modifications of a bromocinnamic acid having the halogen in the a-position. By the reduction of G laser's 13- bromocinnamic acid, in alcoholic solution, with zinc dust, an acid has been obtained which resembles Liebermam's isocinnamic acid in every respect except crystallo- graphic form; it belongs to the monoclinic system, a : b : c = 1.146 : 1 : '2.344 ; p = 79" 59'. On other c)cc:Lsions, reduction of this acid gaye rise to a mixture of cinnamic and allocinnamic acids, whilst the exclusive product of Glaser's cr-bromocinnamic acid was ordinary cinnamic acid.Transparent crystals of the new isociiinamic acid (m. p. 44') rapidly become opaque, and then melt, a t 68' ; this indicates the spontaneous transformation of the substance into allocinnamic acid. Aniline converts both modifications of isocinnamic acid into allocinnamic acid ; a n d the aniline salt, of isocinnamic acid (Liebermann, Abstr., 1890, 1417), when treated wiih alkali, yields allocinnamic acid. Treatment with concentrated sulphuric acid at 50' for 15 minutes converts allocinnamic acid and both modifications of isocinnamic acid into ordinary cinnamic acid. When allocinnamic acid (0.5 gram) is dissolved in alcohol (5 c.c.), treated with zinc bromide (0.7 girtrn), and allowed to remain for several days at the ordinary temperature, dilution with 20 C.C.of water causes the separation of an oil which solidifies to crystals, con- sisting of isocinnamic acid. It seems probable, therefore, that when Glaser's p-bromocinnamic ticid is reduced in alcoholic solution with zinc dust, a mixture of allocinnainic with ordinary cinnamic acid is first produced, the former being transformed into isocinnnmic acid under the influence of zinc bromide. Glaser has already shown that the cc-bromocinnamic acid of low melting point is converted into the other modification when heated ; the author's experiments prove that between the /?-bromo- cinnamic acids the converse change takes place. The author confirms the description already given by Xichael and Browne of the treatment of phenylpropiolic acid with hydrogen bromide (compare also Abstr , 1892, $49).ORGANIC CHESIISTRY.47 The discovery of a second isocinnamic acid introduces a fourth An attempt is made to explain t,he isonieric phenylacrylic acid. relatiollship which exists between these four modifications. Condensation of Glyoxylic acid with Amido-acids. By CARL B@ErrTIS(;ER ( A ~ c h . Phamz., 1895, 233, 199-209).-The amidobenzoic acids condense with glyoxylic acid in alcoholic solution to acids of the composition COOH*C6H~*XCHz*C00H These are yellow sub- stances ; they dissolve in alkaline carbonates, and form di-sil.z;er salts : the 1 : 2- and 1 : 3-compounds readily lose carbonic anhydride, but the 1 : 4-compound is more stable. No well-defined product was obtained by the action of glycocine on glyoxylic acid. The oxnlates of the three amidobenzoic acids are described.M. 0. F. C. F. B. Benzenesulphonamides and Mixed Secondary Amines. By OSCAR HINSBERG and A. STRUPLER (ilnnalen, 1895, 287, 220-230 ; compare Abstr., 1893, i, 168). - Diphen~ls.zc~honethyEelzedia~nine, C,H4(NH*S0,Ph),, is prepared by warming ou the water bath a mixture of benzenesulphonainide, concentrated aqueous potash, and ethylenic bromide ; it crystallises from alcohol in colourless needles, and melts at 168". D~hen.ylsulphcnediet~i ylethylenedianziiae is obtained from the fore- going compound on treating i t with potassiiini hydroxide and ethylic bromide or iodide ; it separates from alcohol in minute crystals, and melts a t 152.5'. Dietl~yZ~!t?Lylenediamine, CJJ,(NHEt),, is formed when the sulphonc derivative is he&ed with concentrated hydrochloric acid at 160° (Hof- niann, Juhresbericht, 1859, 386) ; the hydrochloride crystallises in colourless needles.Di~hen~~l.su~hoiaeo~~tl~op1~ e n y 1 enediamine, C,H, (NH* S 0,Ph ) ,, is ob- tained on agitating ortliophenylenedianiine with benzenesulphonic chloride and excess of potash ; i t crystallisee from glacial acetic acid i n slender needles, and melts a t 186'. Y e t rciphen,qldisulp 11 oti eort hopl~eny lenediamiir P , C6H,[ N( SO,Ph),],, is obtained from phenjlsulphoneortliophenylenediamiiie (LeIlmann, ,innale;z, 221, 17) by the protracted action of benxenesulphochloride and soda ; i t dissolves with difficulty in ordinary solvents, and melts a t l5O-15lo. Dipheu ylsdphoue~net h y leneo 1 s t hophenplen ediu nz ine, is preparLd by adding niethgleiiic iodide to a solution of diphenyl- sulphonephenylenediamine a d sodium ethoxide in alcohol, a n d heat- ing the mixture until it is neutral ; i t melts a t 147-148', and is ~011- verted by hydrochloric acid at 160" into phenylic bisulphide.Dipheny lsulph oneth yleneort1LopJi e q leizediamine separates €1.0 in gla- cial acetic acid in colourless crystals, and melts at 180'. EthyZenephe?ayle~ze~~um~~i~ (tetrahydroquinoxaline) is obtained from the foregoing derivative by ti-,?al,ment with concentrated hydro- chloric acid at 160-170" (ccmpaie Xei-z mid Ria, Abstr., 1887, 722).48 ABSTRACTS OF OHEMICAL PAPERS. The dinitroso-derivative cr-ystallises in minute, yellow needles, and melts and decomposes a t 168". ~ i p h e n y l s z ~ l ~ ~ o i z e t r i ~ a e t ~ ~ yleneplienyltzizedian~~ne, separates from glacial acetic acid in colourless crystals, and melts at 204-205".T~imethyZenephenyle?zediamine, CJ& < NH,C NH*CH2 H,> CH2, is obtained from the foregoing derivative by tieeatment with concentrated hydrochloric acid a t 170"; it melts a t 10So, boils a t 290-300°, and reduces an ammoniacal silver solution when heated with it. ' Ferric chloride develops a violet-red colour with the base. The diiiitroso- derivative melts at 120". Dipl~enylsuIpho~temetapheizyc!enediamine crystalliaes from alcohol or glacial acetic acid, and melts at 194'. When the sodium derivative is treated in aIcoholic solution with ethylenic bromide (1 mol.j, a compound of the formula C2,,H,,N2S20, is formed; it melts at 190-195".M. 0. F. Parabromanilinesulphonic acids : A New Method of Prepar- ing Benzoicsulphinide. By HARS KREIS (Annulen, 1895, 286, 377-388) .-Parabromanilinemetncsulphonic acid [ Br : HSOs : NH2 = 1 : 2 : 41 is prepared by dissolving parabromacetanilide (30 grams) in fuming sulphuric acid (200 grams) containing 15 per cent. of sul- phuric anhydride, and heating the liquid a t 140-150" in an oil bath ; effervescence takes place, and when this has ceased, the liquid is poured on to 600 grams of ice. The sulphonic acid crystallises from water in slender, white needles containing the solvent, which is eliini- uated on exposure to air ; the barium salt is anhydrous. When para- bromanilinemetasulphonic acid is reduced with caustic soda and zinc dust, anilinemetasulphonic acid is formed. Parabromanilineorthosulphonic acid is obtained by heating para- bromacetanilide (20 grams) with sulphuric acid (10 grams) at 170-180" for one hour ; it crystallises in anhydrous leaflets, and in needles containing 1H20.Parab?.o?izocyaizoEenz~ia~o~thosul~~o~a~c acid is obtained from the fore- going substance by means of Sandmeyer's reaction ; the sodium and potassium salts crystallise i n colourless, silky needles, and contaic 1+H20. The szdphonic chloride separates from a mixture of benzene and petroleum in lustrous crystals, and melts a t 90", and the szdphonamide is a white powder which melts above 250" ; it crystallises from pyri- dine in leaflets which contain the solvent. Parabromobenzoicsnlphinide is obtained by heating the sulphon- amide with aqueous caustic soda; it melts a t 227.5" (compare Remsen and Bayley, Bey., 1886, 19, 835).Anilineorthosulp honic acid is obtained by eliminating the bromine from parabromanilineorthosulphonic acid by means of caustic soda and zinc dust ; from this substance the author has prepared several com- pounds which hare been already described (Abstr., 1S93, i, 715), andORGANIC CHEJIISTRY. 49 records the production of benzoicsulphinide by heating orthocyano- benzenesulphonnmide dissolved in 25 parts of vater with one mole- cular proportion of sodium hydroxide. >I. 0. F. Formation of Indigo by the Action of Sunlight. BY CARL ENGLER and K. DORANT (Rer., 1895, 28, 2497-2501 ; compare Be?.., 3, 885, and Abstr.,l895, i, 231).-An alcoholic solution of orthonitro- acetophenone readily condenses with benzaldehyde, in the presence of dilute sodinm hydroxide solution, to form benzlllideneorthonitroaceto- pheizone, N0,*C6H,*CO*cH:CHPh ; this crystallises in long, colour- lees, silky needles? melts at 124', and forms a hydrazone which melts at 146-147O.When the ketone is spread on a shallow plate and exposed to bright sunlight, i t is rapidly decomposed into indigo ant1 benzoic acid, owing to the oxidising action of the nitro-group ou another part of the molecule. No action takes place i n the dark, and the rate at which the ketone is converted into indigo depends on the nature of the rays, being greatest when a blue glass plate is interposed between the substance and the sun. Similar intra- molecular oxidations have been previously observed by Baeyer (Abstr., 1881, 274 ; 1883, 341) and by Friedlaender (Abstr., 1895, i, 543).Bt.rLzylidelleol.thonnzidoacetop~~enone is formed when the nitro-ketone is reduced with stannous chloride. It crystallises in prisms which melt at 147", nnd its salts are deep red ; the ricetyl derivative melts a t 165*, the hydrnzoize at 154", and a bronzo-derizative at 159-160". Ferric chloride oxidises the nmido-ketone to a snbstance which melts at 214-216'; other products are also formed. When the nitro- ketone is reduced with zinc dust and boiling water, it substance melt- ing at 68" is formed together with the amido-compound. This pro- duct is being further examined, as i t does not give the reaction of the expected hydroxylamine derivative.J. J. S. Sulphonephthale'ins. By JOHN WHITE, jun. (Amer. Chem. J., 1895, 17, 54.5-556 ; compare Abstr., 1889, 7lO).-When sulphone- fluoresce'in is treated with bromine, a dibromo-substitu tion product is chiefly formed, and with phosphorus pentachloride a tetrachloro- derivative, which appears to he produced by the displacement of the two hydroxyl groups and the anhydride oxygen in the sulphone- fluoresce'in. It is not possible to prepare sulphonefluoresceh by the action of resorcinol on orthosulphobenzoic acid, but when an action between these compounds occurs, either four or six residues of resorcinol enter into combination according to the conditions of experimentation. No pure compounds are described in the paper. Sulphonephthalei'ns' from Orthosulphoparatoluic acid.B y WALTER JOXES (Amer. Chem. J., 1895, 17, 556-569) .-An~mon'i7~~n paranaet hyldih ydroa.ybenzoy1 benzenesulyhonate, A. G. B. VOL. LXX. i. eis prep are d by h eating am rn onium 11 y c3 rogen o rthosul pho paratolua te (Abstr., 1S91, 1225) with resorcinol ; it forms colourless crystals, and its aqueous solution yields an insoluble basic lead salt, with 12H20, when boiled with minium; t,he corresponding acid is obtained by decomposing the lead salt with hydi*ogen sulphide, and forms colour- less crystals, with 4H20. The barium salt (C,,H,,sO6),Ba + 5H20, the normal lead salt, with 7&0, the caZci?inr, salt, with 6H20, the zinc salt, with zH20, and the silzer salt, with 2H20, n w descrihed. Attempts to substitute other acid radiclcs for the phenolic hydroxjl groups i n paramethyldihydroxybenzoylbenzenesulphonic acid provetl unsuccessful.When the acid is heated at 170°, it yieldspnramethyl- szLZ~honeJluorescezti, O<C6H,(oH C,H,(OH) >>C<" C HMe 0" ->SO,, orthosulpho- paratoluic acid, and water ; treatment of this fluorescein with phospliorus pcntachloride, produces a tetravhloro-derivative, and treat- ment with excess of bromine, produces a dibromo-substitution product which fluoresces like eosin. Two other sulphonepb thale'ins can he derived from orthosulphopara- toluic acid, by treating it with resorcinol ; one containing four and t h e other six resorcinol residues. A. G. B. Allofluorescein. By BROSISLAW P ~ w r ~ ~ w s ~ r (Bey., 1895, 28, 2360-2362 ; compare Abstr., I &95, i, 219) .-AlZoJluorescei'?i, is obtained by heating resorcinol with phthnlic chloride alone or in solo- tion, on the water bath ; the red or yellow product is then treated with ncetic anhydride €or several hours at 3.50-1 SO", and, after evaporating the liquid, the residue is repeatedly extracted with glacial ncetic acirl and with alcohol.The colourless, amo~.phous substance melts at, 140". and is almost insoluble in the niajority of organic solvents ; it dis- t-olves to some extent in boilirig glacial acetic scid, and to a greater degree in acetic anhydride and ethylic acetate, separatiny frorii solution in the amorphous state. 'l'he freslily prepared substanccb dissolves readily in alkalis and alkali cai-borintes, the liquid exhibiting strong fluorescence ; the dried or fused substance, however-, dissolves in concentrated alkalis with great difficultj. The flaorescence 0:' solutions in ammonia o r barium hydroxide is green.The paper contains a detailed comparison of allofluorcscein witli the ordinary modification. Relation of the Indulines to the Safranines. By OTTO FISCEIKK and EDuARD HEPP (Ber., 1895, 28, 2283--2289).-Phenosafra- nine belongs to the samc group of compounds as the mauvejiiies, indulixies, arid indazines. On treatment with :ilkalis, i t yields safran~], Or l,Sdl.oxS"posah*anonc, which only contains one hydroxyl-g~*oup, su tlint phenosifranine must itself be free from Avitter, a t all events a t 100". Al)osafranine, which is obtained from phenosafrnnirie by the rcrtloval of the amido-group, therefore, is t o be looked on :is the &implest meso-pheiiJ1 derivative oE the series, corresponding with M.0. P.ORGANIC 0HER.IISTRT. 5 i YH :CH*y--”.$! :CH* EH The NH: C-CH : C *NP h* C : CH* C H’ rosinduline, its formula being f)lcts, which, previously, were apparently at variance with this view, heve now been more accurately investigated. The free .base itself is free from water, like phenosafranine (Abstr., 1895, i, SOS), and the beirzoyl derivative is also anhydrous. This substance crystallises from benzene i n dark violet plates, which contain 1 mol. of benzene; it is strongly basic, and forms yellow salts. The relation between apo- safranine and the simplest benzene-induline, appears to be precisely similar to that bet ween aposafranone and the simplest benzeneindone.When aposafranone is heated with aniline and aniline hydrochloride, i t is converted into the substance previously termed benzeneindone (A?rnaZen,, 1884, 226,254), and formulated as C,,H,,N,O. The forma- tion of this substance from aposafranoiie now shows that its true for- mula must be CZ1HliN30, and i t is, therefore, anilidoajposufr~?zo,ze. When it is boiled with 75 per cent. sulphuric acid, it is converted into 7~lldl.ozyaposafraiior~e, C18H14N202, which was previously described as benzeneindonehydrate. Hpdroxyaposafranone is also fsrmed when ;iposafranone is boiled with alcoholic potash. Anilidoaposafranone may be reconverted into aposafranone by boiling with 60 per cent. acetic acid and zinc dust. I n the same way, the simplest induline derived from aposafranine, which is known a s anilidoaposafranine (Kehrmann) may be reconverted into aposafrauine.l’henylinduline, which is derived from benzeneindone by the dis- placement of a single atom of hydrogen by the mil-group, must now receive the formula C30H22N0, instead of that previously assigned to it, and all the indulines must be classed as anilidosdranines, their formula being altered in accordance with this relationship. A. H. Action of Alkalis on Paranitrotoluenesulphonic acid. By OTTO FISCHER and EDUARD HEPP (Ber., 1895,28,2281-2283 ; compare Abstr., 1893, i. 697). The authors, in reply to Bender’s criti- cism (Abstr., 1895, i, 287), maintain the accuracy of the results obtained by them i n the reduction of parani trosostilbenedisulyhonic acid by means of ferrous sulphate, and its oxidation by chromic acid, new experiments having given the same results as the ones previously quoted.A. H. Synthesis of Bidiphenyl and its Identification as Benzery- threne. By ARTHC“: A. NOPES and ROLE’E M. ELLIS (Amer.Chem. J., 1895, 17, 620-622) .-ParabidiphenyZ, PhCGH1*C6H4Ph, was pre- pilred from parabromodiphenyl by boiling an ethereal solution of it with sodium ; the solid matter was separated, washed with water and henzene, and sublimed. I t forms large, crystaliiue lamina+ melts a t 31‘i0, and distils at 428’ (18 mm. pressure) ; i t is insoluble in boiling alcohol, ether, chloroform, and carbon bisulphide ; boiling benzene dissolves it sparingly. The compound termed benzerythrene, CZ4HJ8, by Schmidt and Schultz (Amden, 1880, 203, IS), and ob- tained by the action of heatt on benzene, melted a t 308O, and was iusoluble i n alcohol, but slightly soluble in boiling benzene.Tlie e 252 ABSTRACTS OF CHEMICAL PAPERS. author2 conclude t,hat beiizerythrene is identical with pambidi- phenyl. A. G. B. Reduction Product of Xanthone. By G. GUR(;ESJASZ and STAXISLAUS VON KOSTAN~XRI (Be?.., 1895, 28, 2310--231l).-When xanthone is boiled with acetic acid and zinc dust, i t is converted into dixanthylene (te trap henyleneet 11 ylenedioxidc) , This crystallises from benzene in long, thick, almost white needles, which melt at 315'. The solution i n benzene has a bluish-green fluorescence. 4 : 5-Dimethylxanthone is converted by similar treat- ment into 4 : 5 : 4' : 5'-teti-anzef7i?i?dixanthyZene, which does not melt below 360'.2 : 7-Dirnethylxanthone yields 2 : 7 : 2' : i"-tei~amethyL xn?athyEene which sublimes without decomposition at 275-277'. A. H. Benzylidene-p-dinaphthylic Oxide. By E. MERCB (Chew .. Centr., 1895, i, 431; from Ber. u. d. Ju~w., 1894, 21-22).-Thc. residue obtained dnring the preparation of henzoyl-&naphthol con- tains benzylidene-p-dinaphthyl oxide (m. p. 188-191') ; i t must have been formed from benzaldehyde or benzylidene chloride contained in the benzoic chloride employed. Synthesis of Phenanthridine. Ry AMB PICTET and A. HIJIXI~T (Chem. Cedr., 1895, 432-433 ; from Arch. sci. phys. Qenire, 1894: 32, 493-504) .--The method employed consists in the condensation, by means of zinc chloride, of acidyl orthoamidodiphenyl derivativrs, IrtNH*C6H4Ph.Orthoamidodiphenyl is most readily prepared by Graebe and Rateann's method (Abstr., 1894, i, 529). 2-FornaylamidorliphenyZ, COB.NH*C6HoPh, crptallises in colourless needlep, melts at 75', and, when heated with zinc chloride ( 5 parts) at 280-300', yields phennnthridine. Mesometkylpher~anthridine, C6H4<i6g>CMe, is formed in a similar manner a t 320' from acetyl- amidodiphenyl ; i t crystallises in small, colourless needles, and melts at 85'. The hydrochloride and mercwochloride are colourless, and melt at 285' and 247' respectively. The picrate and inethiodide are yellow, and melt at 233' and 263' respectively. The platinocldoride ;C,4H,2N)2PtCl6 4- 2H20 (m. p. 272') is flesh-coloured ; the dz'clzronzute is orange-yellow, and darkens at 150'; thc aurochloyide (tn.p. 163-164') is pale yellow. All these derivatives crystallise in needles. 2- Prcvpio.layln?nidodi~henyl crptallises in colonrless, lustrous needles ; it melts a t cis', and yields mesoethy Zphenanthridine, J. B. T. which is deposited from light petroleum in small, colourless needles melting a t 54-55'. The following derivativcs crystallise i n needles.URQASIC CHJCMISTRY. 53 The hydroch1o?.ide and mercwochloride, melting at 205" and 214" i-espectively; the dichromate is golden yellow; the picrnte is pale yellow, slowly decomposes when heated, and melts a t aboixt 2 1 0 O ; the pZatixochloride, ( C,,Hl3N)2,HJ'tCI, + 2H20, and the au~*ochZoride, are yellow, and melt at 241-242' and 149' respectively. a 2-Be?~zo~ZanaiJod~p~~~zyZ, NHBz*CsH,Ph, crystallises in pearly, lus- trous plates, melts at 85-86', and at 300-360' yields nzesophenylphen- anthridine, c6H4 <c6H4>CPh, which is also formed by heating st mix- ture of amidodiphenyl, benzoic aci2, and zinc chloride; it crystal- lises in iridescent, transparent, quadratic plates, melts at log', boils above 360°, is a feeble base, and dissolves in dilute mineral acids with a violet fluorescence.Its salts are only stable in presence of acid ; they are decomposed by water. --N The hydrochloride, CI9H,,N,HCl + E20, crystallises in yellow prisms melting at 95-96' ; the anhydroub: com- pound forms pale yellow needles, and melts at 220'. ThepZatino- chloyide crystallises with ZH20 in yellow needles, and decomposes :it about 300'. Orthodip hen y Zwethane, C6H4P h*NH*C 0 0 E t, prepared from orthamidodiphenyl and ethylic chlorocarbonate crystdlises in colourless needles, melts at 186', and, when heated with ziric chloride, yields phenanthridone.J. B. T. Orientation in the Terpene Series. By AUOLF vos BAEYEB and FMTZ BLAU (Be?.., 1895, 28, 2289-2297 ; compare Abstr., 1891, i, 252).-l-B~om0-A"~-ter~ene is formed when Wallach's terpene tri- bromide is dissolved in a mixture of alcohol and ether, and treateil with zinc-dust ; it forms compact rhombic prisms, iiielting at 34-- 350 . Hydrogen bromide converts it into dipentene dihydrobromide, along with a11 oily substance. When bromoterpene is treated with sodium nitrite and hydrobromic acid, the uitrosobromide is formed in blue crybtals, which melt at 44', but could.not be obtained quite pure.A'*8-Terpenol acetate also jields a ~titrosobromide, which crystallises iii blue needles, and melts a t 81-42'. The two nitroso-bromides just descrihcd yield the same prodnct when they are treated with a solution of hydrogen bromide in acetic acid, bromine being in both cases set free. This product crystal- lises in thin, quadratic plates, which melt at 182-184', its constitu- tion being most probably expressed by the formula, I t reduces silver salts and Fehling's solution. When this substance is dissolved in water, and potash or ammonia added, 2 mols. of hydrogen bromide are removed, and a base, CloH18NOBr, is obtained, which crystallises i n indefiuite forms, and melts at 100-106'. This base also reduces Behling's solution, aud probably has the constitution, C M e B i ~ < C , ~ : ~ ~ z ~ C * C M e z * ~ H * O5 4 ABSTRACTS OF OBEMICAL PAPERS.Kitrous acid converts it into a nitroso-compound, C10H17B~N202, which crystailises in serrated, rhombic t:) blets, melting a t 138-139". This substance may be obtained by ;L similar series of reactions fronl (lac11 of the three compounds, the nitrosobromide of brornoterpene, the nitrosobromide of terpcnol, and the nitrosochloride of terpeiiol wetate, a fact which confirms the f o r m u l ~ proposed. The product of the action of hydrogen bromide on the nitroso- chloride of terpenol acetate has the formula, CloHJ!TOClIlr2, and crystallises in almost rectangular tablets melting a t 179-180". The hydroxylamine derivative, CloHIJVOBr, which is formed from the nitrosobromide by the action of hydrogen bromide, is converted hy the action of bromine into the original nitrosobromide, so that t h e action is a reversible one.Trihydrozyterpane, ClOHPoO3, is formed by the action of dilute potassium permariganate solution on A*.'-terpenol. It forms crystals which contain 1 mol. water, arid melts a t 95-96'. The anbydrous substance melts at 110-112', and boils at 200' (pressure = 20 mm.) almost without decomposition. Hydrobrbmic acid converts it into TVallach's tribromide. A considerable amount of a substance which melts at 127-128', aud has the formiila of dipentene tetrabromide, is formed during the preparation of the tribromide from dipentene dihydrobromide. From Pinene to Carvacrol. By JOHN L. MEAD and EDWARD KREMERS (Anzer.Chem. J., 1895,17, 607-61l).-Urban and Kremers have already shown that " nitrosopinene " is really an oxime, and that i t yields an oil, ClaHlrO, on hydrolysis (Abstr., 1894, i, 468). It is now shown that this oil is carvacrol (compare von Baeyer, Abstr., 1895, i, 379). A. G. B. A . H. Ethereal Oils. By EDUARD GILDEMEISTER (A&. Phnrm., 1895, 233, 174--189).-The oil expressed from the xind of sweet limes (Citrus Linzettn Risso), growing in South Europe, was found to con- tain limonene with possibly :I little phellandrene ; aIso, in smaller amount, linalyl acetate, together with a little linalool ; it thus re- sembles oil of bergamot, which contains dipentene in addition. The sample exanlined was brownish-yellow, had the sp. gr. = 0.872 at 15', and [ajD = +66" 52'.Linalool was identified by oxidisiiig it wit,li chromic mixture to geranaldehyde, and converting this, by Doebner's method (Abstr., 1894, i, 261), into citryl-/3-naphthocinchoninic acid, melting at 197". Four samples of oil of origanum from Smyrna were examined: their exact botanical origin was unknown, perhaps they were ob- tained from Origanum sn~~i*naic~irn. The sp. gr. was 0.916-0-932 a t 15"; the rotation in a length of 100 mm. -7' 52' and -8' 44' in two of the samples ; the percentage of phenols (by shaking 10 C.C. of the oil with 50 C.C. of 5 per cent. soda, and noting the volume of t h e residual oil) 32.47 ; all the samples dissolved in 2$ parts of alcohol of 70 .per cent. strength by volume. The oil was found to consist mainly of linaliiol ; cymene is also present, and possibly an " olefinic rerpene " (compare Semmler, Abstr., 1591, 655, and Cliapltiau,ORGAN10 CHElllISTRT.5s Trans., 1895, .5%) ; the phenol present is rnninly carvncrol, but therc is a small quantity of a phenol that gives a violet coloui- with ferric chloride. C:wvacrol was identified b y means of its plienylic cyanate derivative (Goldschmidt, AbLti.., 1895, i , 723) ; cymene by oxidising it with potassium dichromnte and dilute sulphuric :icid 011 the water bath to hydroxyprop3lbenzoic acid, melting a t 15G--158", and con- verting this by boiling with fuming liydrocliloric acid into isopropenyl- benzoic acid, melting at 25.5 - 260" (\\';tllach, Annulen, 264, 10). c. F. B. Oil of Lignaloes. By PHILIPPE; DARIUER and Lours I~OUVEAUI;~~ (Compt.rend., 1895, 121, 168--170).--Oil of lignaloes coirtains, ilk 1000 parts, 1 part each of a biv;ilent terpene, a quadrivalent terpeuc, and methylheptcnone, 20 part,.; of licarhodol, 30 parts of a sesqui- terpene, and 900 parts of licsreol. The sesqniterpcne, C15H24, boils at 135-136' under a pressure of 10 m n . , has a faint, pleasnilt odour, and combines with 4 atoms of bromine ; its proportion w r i e s con- siderably in difFerent specimen? of the oil. The methyllieptenone is always present in the oil, and is identical with the Iriethylhepteiioiic: obtained by Wallach by I he decoinpositioii of cinole'ic anhydride ; it. is isomeric with that, found in oil of lelrion-grass (Ahstr., l&%k, i, 4l11). and, when heated with zinc chloride, is converted into dihydrometa- xylene, C,H,,, boiliug a t 134".h sniall part of the licai*eol is present in the oil in combination with acetic acid and higher acids of the same series. C. H. B. Oxidation of Inactive Campholenic acid. By AUG WTE B ~ I A I , (Ccmpt. wnd., 1895, 121, 213-216 j.-When oxidised with nitric w i d of sp. gr. 1.27, inactive cnmpholenic acid jields hydroxycam- I'horonic acid, melting at 167-16&@, isobutjric acid, and t w o dibasic acids, C7H,,04 and C6Hl?04. The acid CiH1204 is very solnble in water, benzene, or ether, crystallises from a mixture of benzene aud light petroleum, and melts a t 83.5'. l l s c2ilcium salt, C7H,,04Cn + 3H,O, crystallises in flattened, orthorhoiiibic prisms. The m h y d n 2 e melts at 38*5O, and boils at 270"; in prgsence of benzene, it reacts with aniline, auci yields the compourd Cc,til102*CO*N.HPh, which crystallises from d i l u t e alcohol, melts a t 146', and, when distilled with water, is con- CO verted int,o tlie irnido-compound, C5Hlo<Co>NPh, which nielts at 121.5O.The acid C,H,,O, seems to be a glutaric derivative; i t s ethylic salt boils at 235-238°. The acid C,H,,O, melts a t 144O, and is very soluble in water ; i t s ethylic salt boils a t about 230", aiid its unhi,LZride a t about 920' ; the plze?zlllaiiiido-derirative melts at l 8 5 O , and the pl~e;zylirnido-deriva- tive at &Go. C. H. B. Action of Nitric Peroxide on Campholenic acid. By AUGGSTE BEHAL and VICTOR Br,AtsE (C'ompt. 9-end., 1895, 121, 256- 259).-W hen nitric pcroxide is passed over inactive campholeiiic acid until the latter has absorbed n, molecular proportion of it, a, blue liquid is formed, and when this is treated with a cold saturated56 ABSTRAOTS OF UHEMlCAL PAPERS.solution of potassium hydrogen carbonate, a blue oil remains undis- solved and soon solidifies. When this product is dried and crystal- lised from alcohol of BOO, cer.1LZeonitrosocnmyhoZenoZide, CloHl5PYTO3, is obtained in thin lamelltle, which melt at 134.5', and have a blue colour similar to that of copper sulphate. It has a neutral reaction, and is insoluble in alkali hjdrogen carbonates. If an alcoholic solu- tion is exposed to diffused light €or some days, a white, amorphous iiiodification, Zeuconitrosocanzplolenolide, separates. Unlike the blue compound, it is insoluble in ordinary organic solvents, but when heated with them, or alone, it is reconverted into the blue modifica- tion, of which it seems to be a polymericle, although its molecular \\eight could not be determined.C eruleoni t rosocam ph ol enolide, when treated with aIco h 01 ic po tauh, jields R red azo- or azoxy-derivative, which is decolorised by sodium amalgam, and regenerated by oxidation with mercuric oxide. The product of yeduction by the amalgam reduces Fehling's solution in the colci. When boiled with tin arid acetic acid, the ceruleonitroso- c:impholenolide yields an unsaturated lactone, wliich melts at 31.5", aud an amine acetate, which melts at 9i'. Excess of nitric peroxide converts campholenic acid into the compoiind ClnH,,NO,, which melts at 175O, and has been described by several previous obsei-vers as nit~rocampholenic acid.It has, 1 owever, no acid function; it is neutral to litmus, and does not. decompose alkali hydrogen carbonates. When boiled with potas- sium hydrogen carbonate, i t yields didehydrocampholenolide, CI,,kil,02, :L crystalline compound, wbich melts at 31*5', and boils a t 193' under :I pressure of 17 mm. When boiled with alkali hydroxides, it is con- verted into dihydroketocampholenic acid, C1nH1603, which crystallises Irom benzene or dilute alcohol i n prismatic needles, and melts a t 1%' if heated rapidly, or at 112' if kept at this temperature for some time, It begins to change into a lactone abore 1W0, and a t 150', it yields the original lactone. The acetate of the amine, obtained bj- reduction of so-called nitrocampholenic acid, crystallises well from absolute alcohol, and melts at 97".It would seem that the so-called nitrocampholenic acid is really R nitrocampholenolide ; it has SL .lactonic function, and the NO, group seems to exist in two forms, which are probably tautomeric: the constitution of the lactone and amine being analogous, although the position of the ethylene linking is somewhat uncertain. The ketonic acid probably has the constitution COOH*CH,*CHR'*COK, and cerrleoaitrosocampholenolide the coiistitution 9 0 -0-C; R-N 0 CHZ-CHR' * C. H. B. Campholic acid. By GUEHSET ( A m . Chin2. Phys., 1895, [7], 4, 239-365).-The greater part of the work contained in this paper has previously been pi1 blished (compare Ahstr., 1894, i, 254 ; 1895, i, 61, 240, 295, and 383.Also Errara, Abstr., 1892, 1345; 1893,ORGANIC UHEMISTRY. 5 i i, 108). It is shown that carnpholic acid is practically not acted 011 by hydrochloric or hydrobromic acid at 20U'. Campholene hydriodide (Abstr., 1894, i, 234) melts a t about 5.2" when rapidly heated. The nitrosochloride (Bhhal, Abstr., 1895, i, 240) forms an indigo- blue crjstalline mass, and melts at 25' when rapidly heated. The author thinks most of his results support the hydroxyketone formula of campholic acid suggested by Friedel. By OTTO HELM ( A ~ c h . PhaTm., 1895, 233, 191-199 ; compare Tschirch and Aweng, Abstr., 1895, i, 384). -Gedanite does not contain free succinic acid, although Aweng states that i t does; the dealer had, doubtless, sent him as gedanite what was really a specimen of succinite (ordinary amber).Gedanite further differs from succinite i n that i t contains 2-3 per cent. more carbon and about as much less oxygen; i t contains some sulphur, but less than succinite does. A much larger proportion o€ gedanite dissolves in various solvents than is the case with succinite; it is evrn entirely soluble in linseed oil. There is a variety of succinite knowii as " soft " or "friable amber " (" m i i ~ b e ~ Succinit "), which is intermediate in its properties between gedanite and true succinite. C. F. B. J. J. S. Gedanite, Succinite, &c. Opoponax from Burseraceae. By A. Bhult (Arch. Pharnz., 233, 209--252).-The substance once known by this name had a rather un- pleasant odour, and was probably derived from a Persian member of the T/mbeZZifei-l;e.The substance now known as opoponax contains a pleasant smelling ethereal oil, which is used as a perfume ; the samples examined by the author contained plant lixngments which showed them to bc derived from some member of the genus B ~ l s ~ n t o d e n d r o n , order Buwei*acece-probably from U. KafaZ. It contains 19 parts per cent. of resin, 6.5 of ethereal oil, and 70 of gum, besides plant fragments. The resin contains ~~-pnnax-~e~se?z, C32H540J, soluble in light petroleum ; /3-pmaz-.l-ese.r~, C%LHjZ05, insoluble in light petroleum, but soluble in ether ; and ~nnaresisiotannol, CuH5008, iiisoluble iii light petroleum, and only slightly soluble in ether, but soluble in alcohol, and also, unlike the preceding two, in alkalis.These are yellowish-brown bubstances, which can be powdered when coId, but arc plastic when warm ; it was riot found possible to hydrolyse themt nor could well- characterised substances be obtained from them in any way. The echereal oil possibly contained a terpene ; the portion of higher boil- ing point yielded, when hgdrolysed, an alcohol, Cj6HgS0, boiling at 2.50-255' (uncorr.), and, apparently, a fatty acid (? butyric). This oil is obtained from the drug by treating it witli superheated steam ; the residue then coutains a new substance which is not present in the original drug. This is cI~i?*o~zoZ, C28H480, a white, crystallised sub- stauce, soluble in ether. and hot alcohol, and melting a t 176' (uncoi~.) ; it yields crystallised mwmcefyl and ~noizolei~zoyl deyivatires, melting respectively a t 196' and 186' (uncorr..), and is oxidised by per- manganate in hot acetic acid solution to chil-ouolic acid, C,,H,,O,, il white, amorphous substance, which me1 ts a t 1 U O -108', dissolves in alkalis, but not in water ; and, in alcoholic solution, reddens litmus58 ABSTRACTS OF OHEJlIOAL PAPERS.paper. Opoponax also contains an alkaloid, which could not, horn- ever, be obtained crystallised. Unlike the oils from Persian Umbel- tverce, it contaifis 110 umbelliferone and no S L I ~ P ~ U ~ * . 3Iecctt balsain also contains resins resembling those of opoponax in character ; resins, that is, that cnmot be hjdrolysed, and so cannot have the constitution of et,lierenl salts. To “ indifferent ” resins, which have the charactel.neither of ethereal salts, acids, nor alcohols, Tschirch has given the name of “ resens.” C. I?. B. Sagapen. By 31. HOHENADEL ( A ~ c h . Pharm., 1895, 233, 259- 286).--Tliis substance is obtained fisom the stems and fruits of a Persian species of Ferula, order Umbellkferm, as was shown by an examination of the plant fragments contained in the drug, The sample examined by the nnthor contained resin, 56.8 ; ethereal oil, 5.8; water, 3.5; gum, 23.3; and impurities 10.6 per cent. The purified resin is yellowish-brown, and is brittle when cold, plastic when warm, melting at 74-76’; it yields a sublimate of umbclli- ferone when heated, and, when hydrolysed by boiling with sulphuric acid, i t is decomposed into umbelliferone and sagaresinotannol, of which two substances it is the ethereal salt. Sagaresinotannol, C?4H2BOS7 is a brown substance soluble in alkalis, and yielding a pre- cipitate with ferric chloride : it yields monncetyl and iizonohenzoyl tlericatives, and is oxidised by nitric acid t o styphnic acid (trinitroi-esor- ciriol).The 56.8 parts of purified resin contains 40 of sagaresinostznnol, 15.7 of combined, and 0*11--0.15 of free urnbelliferone. The ethereal oil contaiDs 9.7 per cent. of sulpliur. and probably contains an ethereal salt of ralcric acid; the bluish fraction boiling at 210-270° W R S found to resemble, as regards its absorption spectrum, the similar bluish or greenish fractions, of much the same boiling poixit, obtained from the oils of galbanurn, asafetida, chamomile, valerian, Japanese valerian, millefoil, absinth, and Itlula Helenium.The substance con- tained in it, ‘L azulene,” is not, however, present in the original oil, but is formed during the process of fractionation. Digitalin. By HEIKRICH KILTANI (Arch. Pharnz., 1895, 299- :3!0).-“ ‘l’he glucosides ohtained from the seeds of Digitalis pwpiirea consist. to the extent of a t least one-half, of digitonin, which can easily be obtained crystallised ” by digesting Digitalinum pur. pub. geymmzic. with four times ita weight of 85 per cent. alcohol. ‘“l’hey contain Digifalinunz z’erum (digitalin) as the essential constituent, to which alone their action on the heart is due ; the existence of ’ d gitalein ’ is, to say the least, doubtful. In addition they contaiii a, weil-crystallised organic compound containing calcium and potassium.Digitonin and Digitalinum ver?m, are both, when pure, very sparingly soluble in water. The ready solubility of the mixture of glucosides (Digitalinum pur. p z h . ) is due solely to the presence of 1-esinous amorphous substances, in addition. Digitogenin was not detected in Nerck’R samples. It is certain that the crystals, which Schmiedeberg described as digitin, were nothing but digitonin.” The author has worked o u t the following method, by means of which Digitalinurn vemm is now prepared on the large scale :- C. F. B.ORCISSIC C BESIISTRT. 5!, L L One part by weight of Digilaliizri~z pi*. pri1r. is dissolved, bar means of a gentle heat, in four of 95 per cent. alcohol. The cold solution is stirred or shaken, and five parts of ether (sp.gr. 0.72) are, mean- \vhile, added, and the whole allowed to remain for 24 hours in a, vlosed vessel. The alcohol-elhereal solution is then clmwn off, weigtieci o r measured, and the weight of solid matter in i t (= A) (letermined by evaporating R portion. The ether. and most of the ;~lcohol are tlien distilled off under reduced pressure nntil the mciglit of t h e residual solution is 1.6 A ; 2.4 A parts of water are then added, and the mixture is allowed to stand for 24 hours iri a closed vessel. Tho crude digitalin which has separated is now broaght on to a filter, nllowed to drain without snction being applied, wnslied with 10 per ceilt. alcohol, and, finally, with water, and dried on poroiis plates or i i i a vacuum. The dry substance is then ‘recrystallised’ from 95 per cent.alcohol, with the addition of animal cbarcoal.” T t is thus obtained in white granules. C. F. B. p-Digitoxin. By HE~SRICH Kr r,IAxr (Arch. P~CLWL., 1895, 233, 311--320).-The leaves of Iligitalis pwpiirea contain neither digi- tonin nor digitalin, but a new glucoside, /j-digitoxiii,, Cz,K,sOlo + 5&0, can be obtained from them by successive extraction with water and 50 per cent. alcohol. This is contained more largely in the alcoholic extract; the total yield of the pure substance was about 1 gram per kilo. of the leaves. It forms white crystals, which, when anhydrous (From chloroform-alcohol solution), are still unmelted at 240°, but otherwise (fiBom 85 per cent. alcohol) soften a t 145-150°.When hjdrolysed with alcoholic: hydrochloric acid, it yields p-digitogenin, CzlH,,Or, and a substance, difgitoxose, which crystallises after the manner of glucose, but was found, unexpectedly, to liarc the com- position C,H,,04. Schmiedeberg’s “ digitoxin ” was probably an impure specimen of the substance described above ; the author proposes to call it, pro- visionally, a-digitoxin, distinguishing his own cornpoiitid by t,he prefix p. C. F. B. Quassole, a Substance accompanying Quassin. By E. MERCK (Chem. Ceirtr., 1895, i, 435 ; from Ber. u. tl. Jahr., 1894, 19- iW).-Q&z~assoZe, CdoHi,,O + H,O (?), is obtained from crude quassiu by extraction with ether ; i t crysttillises in colourless plates, and melts at 149-151”. I n R mixture of ether and chloroform [alu = - 4 2 * 6 O , and in chloroform alone = --Go.In alcoholic solution, it gives a pale vellow coloratioii with ferric chloride ; in chloroform solution, a deep Eed coloration with concentrated sulphuric acid, and differs from quassin by its absence of taste. Quassole dissolves i n fuming nitric acid, b u t the orditiary concentrated acid is apparently without actiotl. Arternisin, a Substance accompanying Santonin. i 3 ~ E. MERCK ((Jlrenz. Centy., 1893, i, 436 ; from Ber. ii. d. JLrhr., 1891, 3-6). --.-1~tentisin, C,,tf 1804, is obtained from the last mother liquors i n the technical treatment of the seed of Arfernisia nzaritima. It is freed from saritorkin by recrystallisation from chloroform, being deposited J. B. T.60 ABSTRACTS O K Ckl1EJllGXL PAPgEHS.in combination with 1 mol. of the solrent, which is evolved at 90". It me1t.s a t 200°, gradually turns yellow in the air, and is more readily soluble in water and dilute alcohol than santonin; [a]= = -84-3c. The ferric chloride reaction is not characteristic ; when heated with soda (10 parts) and water (40 parts), a fugitive carmine-red colorn- tion is produced, and, like santonin, it gives the same colour with alcoholic soda. Physcihydrone and Protophyscihydrone. By OSWALD HESS E (Anizalen, 1895, 286, 376 ; compare Abstr., 1895, i, 300).-Physci- liydrone bas t,he composition ClsHl404, and protophyscihydrone the formula C15Hiz04. M. 0. 3'. Artemisin is apparently a hydroxysantonin. J. B. rr. Phenylcoumalin and Pseudodicotoin. By O~WALD HESSE (Be,.., 7895, 28, 2507--2509).-1n reply to Ciamician and Silber (Abstr., 12395, i, 554), the author states that he was the first to show that." dicotojin " is a compound of cotoin and phenylcournalin. The melt-- ing point of phenylcoumalin is still given 3s 61°, whereas Ciamiciaii and S i l k give 65'. The investigation of Tod's pseudo-dicotoiii cannot be continued for lack of material. J. J. S. Derivatives of Cinchorneronic acid. By SIEGFRIED BLUNEK- FELD (Jlonatsh., 1895, 16, 693--729 ; compare Meyer, Abstr., 1894, i, 425, and Pollak, Abstr., 1895, i, 39L).--DiethyZic cinchomeronate, CjNHs(COOEt), is coiivenieiitlg prepared by the further ethylation of Strache's ethylic hydrogen cinchomeroiiate (compare Abstr., 1890, 1157). It is a colourless, odourless oil, having a burning taste and turning yellow on cxposure to light, ; it decomposes when distilled under ordiiiarg pressure, boils at 172.1' (cow.) under a pressure of 21 mm., and does not solidify at -660".:It mixes with alcohol, ether, benzene, xyleiie, and light petroleum i l l all proportions, gives a platinochluride, 2C,NH,( COOEt),,H,PtCl,, which crystallises in small, yellow iieedles, and melts and decomposes at 14%--144". I t forms alkyl additive products, which, on hydrolysis with silver oxide, yield the ethylbet aiue of cinchomeronic acid, CgHgNO,, a compound analogous to apophyllenic acid (compare Roser, Annuleu, 1886, 234, 119), and from which the silrei. salt, CgH,AgN04, crystallising in lonq? slender, colourless needles, a.nd t,he hyd?*ocliioride, C9HgN04,HC1, melting with decomposition at 214-216', may be formed.Ci.izc/iomeronamide, C,NH,(CONH&, obtained in quantitative yield by the action of ammonia on diethylic cinchomeronate, is insoluble in benzene aaid ether, dissolves in water and etliylic alcohol, melts with evolution of gas a t 163-165", again solidifies, and finally melts and decomposes ;it 225'. With potassium hSpobromite, cinchomeronamide yields both /3- and r,-amidopy;.idiiiecarboxylic acids i n addit,ion t o a11 intermediate product. The hydrochlorides of these carboxylic acids are resolved by the action of lieat int,o p- and yttmidopjridine respectively. G. T. B!. Collidinepiperidine. Bay PEYER KXKDSEN and RICHARD WOLYFEN- S'I'EIN (Ber., 1695, 28, 'L.Li5-2276).-Bromocollidine readily reactsORGAN10 CHEMISTRY.61 with piperidine to form coZ?idi?zeplpe7.idine, C1?HzoNr, hrdrogen bromide k i n g also formed. The new base boils at 279-2532", and forms a hychochloridc, C13HlllN2,2HC1. Coniine reacts i n a similar manner, the corresponding derivative bcinq formed. The pZat;no- chloride of collidineconiziie, C,,H26N,,BHzPtC16, crystnllises in small, red prisms, and melts and decomposes a t 244-245". The authors assume that the bromine remores the hydrogen atom combined with Quinoline Derivatives substituted in the Nitrogen Ring. By ALFRED KINI~ORN and PESOYER SHERVAS (AnnaZeu, 1895, 287, 26-49 ; compare Abstr., 1891, 8;J).-2'-Quinolylacrylic acid is the substance emplojed in the prepamtion of those compounds described i n the present paper ; its barium salt crystallises in white needles, with 2Hz0, the szlcer salt darkens when exposed to light, the ethplic salt melts at 73', and the aniide at, 175-176'.2'-Quinolylpropionic acid melts at 122-123', and not at 115" as previously stated (Zoc. cit.); the calcium salt is anbpdrous, the platinochboride melts and decomposes at 19'7O, and the aiilide melts at $-QuinolyZpropylic alcohol, C9NH6*CH,*CH2*CH2*OH. is obtained by reducing 5Y-quinolylacrylic acid with sodium amalgam in alkaline solution, or by means of tin and hydrochloric acid ; it crystnllises from petroleum in lustrous needles, and melts at 115'. Oxidation with potassium permanganate gives rise to 2'-quinolyl propionic acid. 2'-QuinolyZglyceric acid, C9NH6*CH(OH)-CH(OH)*COOH, is ob- t ained by oxidising 2'-quinolylacrylic acid with potassium perman- ganate; i t crystallises from dilute alcohol in white leaflets which contain 3H20, and in this condition melts between 100' and 130°, slowly losiag water, and becoming bIack.The au?*ochZoricZe crystal- lises in yellow prisms, and melts at 174O, the barium salt is anhy- drous, the ethylic salt mclts at 107--105O, and the methylic salt at 140-141O. 2'-Quinolylacetic acid has been already described (lop. cit.) ; the ylatiiiochloride is dimorphous, the ?wthyZic salt melts a t 72", and the ethylic salt, a t 6 i 0 . Much evidence is adduced to shorn that the product of condensn- tion between 2'-quinol~lacetnldehyde and orthamidobenzaldehyde is identical with Weidel's 2'-3'-diquinolyl. By LEOPOLD RGGHEIMER (,4nnalen, 1195, 287, 50-97 ; compare Abstr., 1889, 2*32, and 1894, i, 55)..-!i'he authoy prefaces the description of his experiments with a discussion of the constitution of liippurotlavin and its derivatives ; the structural jarmula already put forward (Zoc.cit.) continues to be adopted, and attention is drawn to the quinonic character of the substance. Hippuroflavin (dibenzo~lisop~~aziizeqz~inone), C18H10NZOl, has been already described in some detail (Zoc. cit.) ; the following clerivatives have been prepared for the first time. Dih?ldrol~i~~urOJEavindianilitie (DianilidodihycEroxydibe,lzoyl-nn-di- Ijydropymxine), CJoH24N,0A, is obtained by heating hippuroflavin on the nitrogen of the reduced pyridinc base. A. H. 149-1 50'. 11. 0. F. Hippuroflavin.62 ABSTRACTS OF CHEXICAL PAPERS. the water bath with excess of aniline and glacial acetic acid ; it melts and decomposes at 158-160', and does not dissolve in common solvents, purification being effected by converting i t into the potas- siqinz salt, which is tlien decomposed by the addition of water t o the alcoholic solution.When caustic soda is added in small quantities to dianilidohippuro. flavin suspended in warm water. the amidanhydride of dibenzylamido- diaiiilidosuccinic acid, , is formed; the solid product obtained on acidifying the filtered liquid i s dissolved in ammonia, and treated with calciiim chloride, in order to remove the acid as calciiim salt. The amidanhydride cqstallises from alcohol in small needles, and melts with effer- 1 escence a t 266--227O ; the calcium salt forms slender, colourless needlcs, containing 3H20, and precipitates are formed when a neuti*al solution of the ammonium salt is treated with solutions of uetsllic salts.(dinzethy lanilidodih ydroxydi- benzoyl-nn-dihyd?.op~~a~i~e), (&!H?,SN~O~ is obtained from hippuro- flavin and methylaniline ; it melts a t 2 3 8 O , previously becoming dark y el I ow. HippwoJEaz.iu bismetliglnnilide, C,,H2,N4O4, is obtained from the foregoing substance by the action of boiling nitrobenzeue ; i t melts at 233-234O. Dill yclrohippuro~a~ind;o1.t7~otolziidide (diorth otoluidobenzo?lldihy~?.~x~- ~ ~ n - d i h y d r o ~ y , . a z i r , e ) , C32H28N404, is colourless, and melts at 2:35--238O. y i el d ing ort ho to1 ui (3 in e and hipp?wojaz.inort h o toluiclid e, C26H,9N30,, which crystallises from benzene in stellate aggregates of needles, all4 inel t s a t 208- 209'.Hippui.olllr.ritryu1.afo77tidide, C2,H1,N,O4 and hjpr)ZC,.oJEaz:inxylidille melt at 246" and 223-225' respectively. D i h ydrohip~?L1.oflaz.i?2dia micle (dial i t i d od ibewzzo y 1 dih y d roxy -nn- dih y dyo- p!p.nzine), Cl8HI6NJO4, is ohtained by the action of ammonia on hip- proflavin; it melts at 240°, and begins t o darken at 220-225". Hilz~puroJla.r.iiidiamz'ne, C,,H,,N404 is obtained by treating the fore- going compouiid with alcoholic ammonia in sealed tubes at 105O, for four hours ; it melts a t 237-233'. Two new Bases in the Urine of the Insane. By MARTIN KRCGEE (Chem. Centr.., 1895, i, 292-293 ; from Du Bois-lieynzoud's Awh., 1894,553-555).-l'he one base, CIOH13NY02, is, from its reseni- Llance to guanine, termed epiguaniiie, and crjstallises from water i n slender needles, aiid from highly dilute ammonia in silky, lustrous prisms ; it dissolves in acids, in sodiiim carbonate solution, and in soda; from the last solvent, lustrous, broad needles are deposited, which probably consist, of a sodium derivative. The nitrate forrtis polyhedral crystals ; the chi*omate is deposited i n 1 ustrous prisms, the p l a t i w - c/i Zoi-ide in long, orange-i*ed prisms.The picrute and aui-ochloride c~ystallise in needles. 'I'he base gives precipitates with ammonia, silver nitrate, copper sulphate, and sodium hydrogen snlphite, but not with mercuric chloride, normal, basic, or ammoniacal lead NHBz*v(NHPh)*F (NHPh)*COOH co - NBz Dih ydrohippzirofZaz.inbismcth ylanil ide M.0. F.ORGANIC CHEMISTRY. 63 acctate. from t h e mother liquor of epiguanine. The secmd base was obtained onl:, in very sinall quant,ity J. B. T. Hydrogenation of Quinine. By I’;DUAI:D LIPP?,:ANN and F n ~ s z FLEISSXER (AIounts7~, 1895, 16, 630--6:37).-When dissolved in abso- lute alcohol arid treated with rnetallic sodium, quinine yields a reduc- tiou product which is appareritly a t.ctmhydroquinine. It is an amorphous, brittle mass, which is sparingly (lissdved by water, but is exceedingly soluble in alcoliol, benzene, and chloroform. The bascs has f,he odour of quinoline, yields fluorescent solutions when dissolved in sulphuric acid and nitric acid, and gives t h e quinine reactioti with ammonia and chlorine water. With a feebly acid solutioii, ferric.chloride gives an intense green coloration, which o n further additioii of t h e reagent turns reddish-brown. These colour reactions arc’ characteristic of t h e base, which also forms t h e following nnstablc salts : a normaZ kydi-ochloride, C20H2eN202,HCI + H20, a n czciii! hydro- chloride, a nomzal sulphate, a n ucid sulphate, and a plat inochlode, C,,H,,N,O,,H,PtCi,. On heating with excess of acetic anhydride, only one acetyl group entew t h e molecule, t h e compound C,,H,,AcO,N,, being formed a s a viscous mass. Tetrahydroquinine therefore contains only one lijdroxyl group, and from its behaviour with hj-drochloric acid, whereby hydrochlorohydroapoquinine is fornied, i t would appear that the double liitkage existing between t h e carbon atoms in quinine is not broken away during the addition of the four atoms of h j d rogen.IIydroquiuine has a powerful toxic effect, small doses causing sus- pension of respiration with ~ O S S o l voluntary and reflex movement, and ultimately convulsions aiia deiith. G. 1’. 11. Merochinine. By WILHLLM KOENIGS (Bey., 1895, 28, 1986- 1991).-Merochinine, which is obtained, a s already described by tlie author (Abstr., 1894, i, :392,477), by tho hjdrolytic decomposition of cinc’uine and chinine, and by the direct oxidation of cinchonine wit11 chromic acid, is converted into 3 : 2-metliSlethylpyridinL. by heating with hydrochloric acid and mercuric chloiide at 250”. As i t also contains t h e inlido-group, i t is in all probability the carboxylic itcicl of a liydropyridine base of t h e formula C8H,,N.All attempts to convert i t irito the ccwresponding pyridinecnrboxylic acid by removal of hydrogen or by elimination of hydrogeii bromide from bi.omome1.o- chiiiiiie have been unsuccessful, as the carboxyl group is i n all cases simul tR neously eliuiinated. When oxid ised with p t a s a i u n i pet-mit~i - ganate, i t is coiiverted into cinclioleuponic acid, and t h o carboxj 1 group must therefore occupy the same position as one of t h e carbox3-1 groups of the latter compound. From his researches, Skraup has concluded t h a t i n the so-called “ second reaidue ” of the cinchona alkaloids, a viiijl group is combined \\ i th one of t h e carbon atoms of the hydropgridiiie ring, and this con- olusioii has been supported by voii Miller and Rvhde (Abstr., 1895, i, A:%>) ; in that case, rrierocliinine, wltich is obtained from tbis second residue, would also coutuin t h e vinyl group, probably in combination witl: tlie 2-carboil atom of the pyridine group.The presence of this64 ABSTRACTS OF CHEMlOA L YAFKHs. group in cinchonine is borne out by the following results. The author and Comstock have shown (Abstr., 1887,281) that ciuchonine readily combines with 2 atoms of bromine, and on treatment \rith boiling alcoholic potash the product loses 2 mols. of hydrogen bromide, forming dehydrocinchonine, which must therefore either contain two ethylene linkages or an acetylene linkage. S o direct proof of the presence of the latter has been obtained, but it is found that, 011 oxidation, one carbon atom of dehydrocinchonine is eliminated as carbonic anhydride, with formation of cinchotenine.The lattel- has been also obtained by Skraup by the oxidation of cinchonine ; i t is ft saturated compound, aiid contains a carboxyl group, in addition to the hydroxyl group of the cinchonine, and therefore the dehydro- cinchonine, from which it is prepared, cannot contain two ethylene linkages, but must contain an acetylene linkage, which is formed from the vinyl group of cinchonine by removal of hydrogen. Bromomerochinine hydrohomide, CgNHlpBr02,HBr, is obtained by the action of bromine water on merochinine, and is identical with the compound obtained by Comstock and Koenigs by the action of bromine water on the bFe-products of the oxidation of quinine and cinchonine with chromic acid, and to which they at that time ascribed the formula C,NH,,Rr20 + $H20.It forms rhombic spheno'ids, melts and decomposes at 248-250°, and is reconverted into niero- chinine by treatment with zinc dust and sulphuric acid, all attempts, however, to convert it into n pyridine or lower hydropyridine deriva- tive were without success. When bromomerochinine hydrobromide is boiled wi t,h water, i t readily loses one atom of bromine, and on long-continued boiling the second bromine atom is eliminated, hydrozymerochinine, C,NH,,O,, being formed, On adding ether to a solution of this compound in methylic alcohol, it crystallises out with 1H20 ; this is evolved at 110', the anhydrous substance melting and deconiposing a t 254'. The hydyochloridc, C,NH,,O3,HC1, forms stellate groups of needles me1 ting at 208-210O ; the ~~Zatinoc7~Zoride small, lustrous, orange-yellow crys- tals melting and decomposing a t 240' ; and the aurochloride needles melting and decomposing a t 181'. The acetgl derivative is very soluble in water and alcohol, aiid yields an azwochloride which melts a t 2 1 4 O , with evolution of gas.It is only oxidised by alkaline potas- sium permangannte on warming, whilst merochinine and bromomero- chinine are oxidised in the cold, and whereas merochinine readily undergoes etherification when hydrogen chloride is passed into i t s solution in methylic alcohol, the bromo- and hydroxy-derivatives can only be etherified with difficu1t.y in this way. Higher brominaked derivatives of merochinine may be obtained by heating bromomerochinine hydrobromide with bromine a t looo, o r by the action of bromine on the hydrochloride of merochinine ethy lic ether in chloroform solution.One of these is a colci~rless, crystalline compound melting aiid decomposing a t 184", and is the hydro- bromide of either a tribromomerochinine, or of a monobromomei-o- chinine dibromide. H. G. C.ORQAKIC CHEMISTRY. 65 New Methods for the Preparation of Tropinic acid. B~RICHARD WILLST;~~L.TER (Eer., 1895, 28, %277--3380).-L)ih~droxytropidine, CH -C H (OH).CH( OH j --CH, contains two hydroxyl groups, which aiy united to adjacent carbon iltoms; and when treated with c*li1+omic acid, it is c o n v e r t d into tropinic acid, identical with that, obtained by ttie oxidabion of tropine.This proves t h a t two adjacent carbon atoms of dihjdroxytropidine, and therefore also of t,r.Ipine, serve t o form the two carboxyl groups of tropinic acid, C0OH.C E3 <(J NMe*C H, . c H, H'>CH*COOH. Tliis is in agreement with the above formula proposed for ths acid by Melaling (Abstr., 1832, 358), whilst it is inconsistent with Ladenburg's formula for the same sub- stance. A. H. Scopoleines (Ethereal Salts of Scopoline), By E. MERCK (Chenz. Centr., 1895, i, 434-435 ; from Bcr. 2. d. Julzr., 1894, 15- 18).-The only sccpolei'ne found in nnt,nre is scopolamine, the scopo- lc'ine of tiwpic acid, which occurs in ScnpZicc ,j(tpi~zicu and S. atro- p vides, a 1 i d i s id e n t i c'al w i t.h h y o sci 11 e . A c et Isoc~p o 1 e iue, C, B ,?N 02Ac, forms white crystals melting a t 250" : the m~?-ochlwide melts at 1%-197".Renzoy l s c o l ~ o l ~ i ' i ~ e , C,H ,2NOrBz, is c r j s t.al line, aud me1 ts at 68-70"; the 1Lytlrochloricle melts and decomposes a t 849-250' ; the hyd7dromitle crystallises in ctolonrless p r i b r n s melting at 245- 247' ; t h e i~ili-trte, pltrtiizocliloride (m. p. 200--201'), azwochloride ( i n . p. 188"), niercwochloride (m. p. 14fi--I42'), and p i c m t e (m. p. %UO-20lo) have also been prepared. CSH,,NO,*CO*CH:~BPI~, slowly becomes crystalline ; its nitrate melts at 172-173° ; the hydro- bromide has also been prepared. By E. MEKCK (Cheiiz. CeTLtr., 1893, i, 434 ; from Ber. ii. d . Juh7-., 1894. ?-ll).-l'he object of this investigation was the deteruiinatioii of the physiological action of the fatty acid deriva- tives of trope'ine.The majtrrity have 110 special influence; lactyl- tropei'ne exercises a well-marked effect on the heart, but it is not a mydriat.ic. AcefyZtwpri'?Le, C8H,NOAc, is a pale yellow syrup, boiling a t 235-237" ; the azwocldoi*ide melts a t 19:3O. Lactyltropei',ce, CBH,,NO-CO*CHMe*OH, cr-ystallises in colou~~lcss needles, and melts at 74-75O ; its lz!ld~ochloride, hydriodide, nitrate, sdphatr, arid uuro- chloride (m. p. 143-14fj0) have been prepared. Succi?zyltmpez?te, ~!,H,(CO.C,B,NO),, yields a JLydrotronz.ltle and a n azcrochloride; ttie forrrler is colourless ; the latter cryst,allises in yellow plates. The same derivatives of walyl-, tartryl-, and hipptlrgl-tropei?ie have also been prepared ; the a~~roc/,lor-~des melt a t 203-204", 2:3:j0, and 1:10--l!M' respectively.Tartryl tropejine is c*oloui*less and crystal- I I nc. Parameth y ihommr tropiue, C,H,,N 0.C O.CH( OH).CB H ,&, pre- p;hi-ed b y tlie action of dilute hgdrochloiic: acid on tropiiie para- ulcthylmandelate, is c Y j ~ b t a l l i i i C ; its Ul/.rUcILl~Jritlr: iiiclr,s at 192-1 gS0. ,N Me --- C H,, \c H,-- --CH,' Cis~~ianzo~lscopolezne, J. B. T. Tropeines, J . B. 1'. YOL. I . X X i. f66 ABSTRACTS OF CHIEMIOAL PAPERS. Angostura Alkaloids. By HEINRICJI BECKL-RTS ( A d . .PhRr?)t., 1895. 233, 410--423).--The alkalo'ids cuspwine, cuspai*ndine, gnlipine, and gnlipidine are obtained together from the ethereal cxtract of the bark of Cic.cparia trllfoZi/rtn, Eiigler (Galipen qtjicinali.9, Hancock) (Abstr., 1892, 642).Derivatives of cusparine only are described in the preserit communication. The purification of this compound from traces of galipine is exfremely dit€icult, and is hest accomplished by repeated recrystallisation from light petro- leum; criteria of its purity are i t s melting point (89") and t h e formation of coloiirless salts with acids. The alkaloid gives the following colour reactions. With concentrated sulphuric acid, a dull red, changing to cherry colour. Fuming nitric acid produces a yellow solution ; t h e residue, after evapomtion and treatment with potash, becomes orange. Frohde's reagelit Kives a brown solution, which changes Kuccessively to violet, bluish-green, and deep blue ; when warmed. t,he blue colour is obt,aimd more readil?, and it, is pro- duced immediately with the concentrated reagent,. Sulphuric acid c'o titaining titanic.aiihjdritle and fnrf tirnldehyd e respectively gives a reddish-brown and a bi-owlish-red solutiou. I3v t8he tiction of bromine water on cusparine hydrgbrornide, the riibromide, C.,,H ,?YO,.HBr,Br,, is formed as a pale yellow, amorphous powder nieltiiig a t 11 i o ; when t.reated with alcohol, hard yellow prismatic needles are obtained ; they melt at 23tjo, and probably consist of cwspwine dibromidc, C,,,H,,NO,,Br,. The platinochloride crystallises with C;H,O. Cmpa- Tine ?nethocl~ZoriLJe, C,,H19N0,MeCI, preparcd from the methiodide (Zoc. cit.), ci*yst,allises in lemon-colon~~ed needles 2nd melts a t 1 90". I t s platinochloride, (C20Hl,N0,R~e)2PtCI,, is deposited i n lustrous golden needles melting a t 210' ; the auru~l;lori~?e forms reddish- brown needles and melts at, 152-153'.MethyZcmpa?*ir,e, C,,,H,,N 0,Me + -!jH,O, is prepared by the action of potash o r silver oxide on cusparirie niethiodide ; it crystallises from dilute a,lcohol in colourless nredlea, from water in pearly lustrous plates, and me1 ts at 190'. The kydwdwomide crystallises with 10H20 in slender, lustrous, yellowish-green plates. The hydro- chloride crystallises n i t h 2*5H20 in hard, dxllate needles. The p7atii~ochZoritJe, ( C2,H1,NO,Me),,B2Pt,Cl~, forms golden, lustrous needles and plates nielting at 210'. l'he methiodide, C,,,H,,NO,Me,MeI, CTFS- tdlises in slender, jellow, lustrons needles ; i t melts at I%', darkens on exposill-e to light, and has a n intensely hitter taste. Caspari.iie stlr.iodide, C2,,H,9N9:I,EtI, is depcxited in yellow, lustrous needles, darkens when exposed to light, and melts at 201'. The chloride crystallises in lemon-colonred needles melting a t 156". l'he pZn/inr.chZo7*ide is deposited in golden, st el late, rhombi c prisms me1 ti it g- at 178'. I ~ t I ~ ~ Z c z r s ~ / r . ~ . i ~ i ~ , ~ ~ , , H , ~ N 0 ~ 1 1 : t, prepared by the action of sod:% 011 the cthiodide, c i ~ y ~ t ~ l l i ~ e ~ in coIou~~lc'ss, transparent prisms, a n d melts at 1 90--101.0. Tlic snine coniponnd, together with tlie ?iyd7~.tr, C,,H,,NO,I<t + HzO, i s fornicd by t h e interaction of tlie ethiodide and silver oxide ; i t crjstallises in lustrous plates, and melts a t 114--115". By H. PnhlMEI;F:lIKF: (A~71. Phaiw., 18'35, 233, 1.'7-174).--'l'lie pulverised ~ , o o t of h'ei*be, is ,I. B. rr. Alkaloids of Berberis Aquifolium.ORGANIC OHEMISTRY. 67 aycifoldum was repeatedly extracted with water containing a little ;icetic acid, the extract was concent,rated and filtcred from berberine acetate and other substances, and from t h e filtrate, by saturating it wit,h sodium sulphat.e, oxyacarithine WAS eventu:illy obtained, whilst berbamine was ohtained by snturtting tlie filtrate from the oxyacan- thine with sodium nitrate. These two alkalo'itls wei'e then purified by crjstallisation of their hydi*ochlorides from water. New experi- ments were made with them, and some hitherto tloubt,ful points finw.lly decided. Some properties cf berberine, as t o which contra- dictory statements exist, were also re-examined. Ozyncanthine.-This substance Ilas the composition C,,H2,N03 ; ih is a monacid base, and is identical in composition and properties with t h e product obtained by Hesse from B. zzdgnris. It, van be oh- tained A S a white, amorphous precipitate, which me1t.s at l~0-16U0 ; or, bg crIstallisafioii from 90 per c+ent,. alrohol, in coloui*less crjstals which melt at 208-21d0. I n alcoholic solution a t ZOO, i t has the specific rotation [a],, = + 1 7 4 O 5', amd i t forms a well ci-ystallised compoiirrd with l ~ v o - , but not with dextro-, rotatory t-nrtarrc acid. It contains an hpdroxyl group, for, altliough acetic: chloride and aretic anhy- dride seem to exercise a dehydrating actim on it, j e t bensoic chlo- ]aide converts it into a mo?tohcnzoyl dtriraiiw. of which the platim- chloride, wit.h 8 H20, and niirocliloride, with 2H,O, were prepared. I t probably contains 2 met,hoxyl groups ; t h e numbeis obtained by Zeisel's method point, curiouslg enough, t o I$. It reacts as a tertiary base with naethglic iodide, yielding a n additice compound, C ,,H,,NO,,MeI + 2H,O ; 1i:ilf of the water is lost at looo, t h e rest a t 110'; it melts when mliydrous at 248-250°, and can be converted by means of silver oxide int,o au alkiiline quaternary ammonium base, the plntinochloridc, with 5Hz0, and aurochloride, with H,O, of which were prepwed. Oxyacanthine gives the usual alkaloid reactions. The following snlta were prepared and analysed :-Hydrochloride, specific rotation [ a ] D = + 163' 49', ~?.yiIr-o2,i.(,,r,idc, hydriodirle me1 ting a& 256-25Y0, nif?wtt., all with 2H20 ; normal sujphnte, anrochloride, both with 4H,O ; platinochloride with 3H,O. I>'erbnnziize.--This has the composition ClRH,9K03, a s was shown by the analysis of i t s hydi*ocJiZoridc, with 2H,O, and platiuochloridc, with 5H20. It was obtained in small quantity only, and appears to contain 1-2 methoxyl groups. Berberiue.-This nlkalo'id yields a normal $ulphate, with 3Hz0, i n addit,ion to t h e hydrogen sulphate ; i t also forms a st,able hydrogen carbonate, CZOHliNOJ,H2COS + 2H20, and a, stable hjdrocyaniclcb. Metliylic, ethglic, and amylic iodides form additive corripounds wit,)) 1,a*hei~;ne, Ltit t1ie.e qnateimary animortiuin dei-ivntives Are not v t ~ y st:tblt: ; they do nota yield the corresponding chioi-ides when t,reated with silver chloride, bcrberine hydrochloride being formed instead. C. F. 13. Identity of Baptitoxine and Cytisine. By PIICTER C. PT,L.(;GE (:lwh. /'harm., 1895, 233, 89.I.-~9!)).-H;tt)tiL9xine, obtdincd by ~ ' 0 1 1 Sjclii.ocder froin the root uf fiaplisia fi?Lc/oi-;a,'is shown to be identical68 ABSTRACTS OF OtlJ3MlC;XL PAYERS. with cytisine. The seeds afford a better source of the alkalo'id ; those of B. uustralis contain 2.85 per cent. of cytisiue, and those of L'. tinctoria probably an equal amount. Estimation of Alkyl Groups attached to Nitrogen. By JOSEF HERZIG aiid HANS NEYER (Mouat.sh., 1895, 16, 5!49--608 ; compare Abstr., 1894, ii, 2l!j ; lE95, i, SlO).-The autliom have previously (loc. cit.) described a, method for the detection and estimation of alkyl groups attached to nitrogen, and have shown that, by a modi- fication of the process, the meLhox:l and ethoxyl groups present can also be determined. A large number of suhstances have now been examined, and the results obtained i n part agree with accepted con- stitutions, amd in other. cases contradict them. The alkalo'ids, harmirie and harmaline, each contains one methoxyl group, but 110 meth.y1 attaclled to nitrogen (cornpare Fischer, Abstr., 1889, 730, and Fischer and Tauber, Abstr., 1885, 829). Sparte'ine contains no methyl group attached to uitrogen (compare Ahrens, Abstr., 1888, 6111, and Ahrens' norspartehe is only an impure form of sparte'ine. Pilocarpine contains oril;y one methyl group attached to nitrogen and no ruethoxyl group, the authors theiefore coiiclude that either Hardy and Calmel's to1 mula, which gives three methyl groups directly attached to nitrogen must be incorrect, o r that their method bf estimation is unsuited to t h i s compound. The methyl derivative of the met.hylbet;i'iile of papaverinic acid, which melts ai 126', conttiins foni. niethoxjl groups (raompare C. F. B. Scliranzhofei., Abstr., 1894, i, 59 and 151). G. 'r. M. Pauqine. By E. MERCK (C'heni. Ceiztr., 1895, i, 4t-14, from Ber. u. J. Juhr., 1SY4, 11-15)6-l'au~ine, C,,H,,N,O, + ti*,SH,O, is the alkslo'id of the " pnuc;o nut,:' the fruit of Pentaclethra mac?*oy?iyZZa; i t crystallihes in golden plates, melts a t 12t;", is insoluble in ether and chlorofoi-m, and a por*t,ion is decnrnposed when i t is reci-ptallised from wnt er. The h!idwchZoritle, C2,H3,N5O3,2HCI + 6H,O. melts a t 245-247'. The plathiochloride, Cz7H3,Nb05 H2PtCI, + 6H,O. is brownish-red, c q stalline, and irlelts at 145'. The pic?*ccfe crgstallises in ga.r.net,-red prisms melting a t 22b". Bx the actioii on pauqine, of potash, or of concenti-ated hydrochloric acid, at I&', dimethylamilie is eliminated. J. B. T. Matrine, the Alkaloid of Sophora Angustifolia. By PIETER C. P L U G ~ ~ E (Arch. P~AYUI., 1895, 233,441-443).-Kag:ni has receritly published, in Japanese, n coniniunicat.ion on the alksloiid in the root of h'ophom ang?ts/,$oliu, whivh he terms rnatyijle, C,,H,,N,O ; it melts tLt. about SO', is, in aqueous solution, dexti.ogjrate, and gives precipi- h t w , wliich are fr*equeiltly crystalline, wit.11 t,he usual alka.lo'id re- tig~ii ts. l'h e y lut LuucliZor~ d e , c 16 H,,N,O :H2P t C Is, and tli e u i ~ r o c h l ~ ~ t ? e , (~,,H,,N,O,HAiiCl,, ha\ e been prepared by PITacEti? and tlie author has obtained R crystalline j i ~ , ompri7d/>. The lethal dose of matrine is l'tiger than that of cgtisihe, aiid the conipouiids differ in phpsio- logical uctiori. 3 . l3. T.