97 Organic Chemistry. Action of Bromine on Propylic Bromide in presence of Aluminium Bromide. By A. MOUNEYRAT (Compt. rend., 1898,127, 273-276).-The author has applied t o propylic bromide the method already used in the case of ethylic bromide (this vol., i, 1). One hundred grams of the substance t o be brominated was heated with 20 grams of aluminium bromide and the calculated quantity of bromine. I n this way, he has readily prepared propylenic bromide, CH,* CHBr*CH,Br, from propylic bromide, and tribromopropane, CH,. CHBr* CHBr,, from the propylenic bromide. I n the formation of the tribromo- propane, which is accompanied by small quantities of its isomeride, CH,Br*CHBr*CH,Br, and a tetrabromopropane, it is probzbble that the propylene bromide loses hydrogen bromide, and is converted into bromopropylene, which at once combines with bromine, or possibly with hydrogen bromide.Z'et~abromoproparze, CH,Br* CHBroCHBr,, is obtained in a similar way from either of the derivatives CH,* CHBrGKBr,, or and, in its turn, yields pentabromopropane, CHBr2* CHBr*CHBr,. CH2Br CH Br-CH2Br, C. H. B. Action of Acetylene on Mercuric Nitrate. By KARL A HOFMANN (Bey., 1898, 31, 2783-2787. Compare Abstr., 1898, i? 635).-H. Erdmann and Kothner (this vol., i, 21) describe a substance obtained by the action of acetylene on a hot solution of mercuric nitrate as a double compound of mercurous carbide and nitrate, HgCiCHg,HgNO,+ H,O. I t is not an acetylide, however, for it gives no acetylene when heated with hydrochloric acid, but aldehyde instead. Neither is it a mercurous compound, for, when it is digested for hour with dilute hydrochloric acid, 83.8 per cent.of mercuric chloride is formed, but only 2.3 per cent. of mercurous chloride, and this, no doubt', on account of the reducing action of the aldehyde simultaneously formed ; further, potassium cyanide solution dissolves the compound without deposition of mercury, and ammonia produces no black coloration. The substance analysed by Erdmann and Kothner contained a little mercury ; af ter removal of this by digestion with dilute nitric acid, the analytical numbers agree with the formula NO,*Hg*C( :Hg,:O) *CHO, that of a substituted aldehyde, The compound is best prepared by dissolving yellow mercuric oxide (20 grams) in dilute nitric acid (70 C.C. of 30 per cent.acid and 500 C.C. of water), filtering, and passing a fairly rapid current of acetylene for 2 hours through the solution a t a temperature of 189 The precipitate is then collected, digested three times with 8 per cent. nitric acid (150 c.c.) at the ordinary temperature for 6 hours, filtered, washed with alcohol and ether, and dried under diminished pressure over sulphuric acid. C. F, B. VOL. LXXVI. i h98 ABSTRACTS OF CHEMICAL PAPERS. Acetylene Tetrabromide and Tribrornethylene. By KARL ELBS and J. NEWMANN (J. p'. Chern., l89S, [ii], 58, 245--254).-1n preparing acetylene tetrabromide from acetylene generated from calcium carbide, the gas is best purified from hydrogen phosphide by passing it through a solution of mercuric chloride acidified with hydro- chloric acid.The pure tetrabromide is an almost colourless liquid boiling a t 124-126' under a pressure of 15 mm. When reduced with zinc dust and acetic acid, or zinc dust and sodium ethoxide in alcoholic solution, the principal products are acetylene di bromide and tri- bromethy lene, and small amounts of ethylene dibromide. Aluminium amalgam reduces the tetrabromide so rapidly and completely to ace- tylene dibromide that it may be used as a means of preparing that substance. Attempts to replace bromine in acetylene tetrabromide by iodine or acetyl groups proved unsuccessful ; the action of aniline, dimethyl- aniline, or alcoholic ammonia causes the production of t r i bromethylene. When the tetrabromide is heated with bromine and aluminium in sealed tubes a t 90-95", hexabromethane is produced.Bromine acts readily on tribromet hylene, producing pentabrom- ethylene ; iodine reacts but slightly, whilst chlorine gives rise t o chlorotribromethylene, crystallising in coIourless needles melting a t 3 5 O (compare Denzel, Abstr., 1880, 228), and uniting with bromine to form chloropentabromethane melting at 170". Zinc dust acts on tribromethylene, producing acetylene ; concen- trated sulphuric acid gives rise to pentabromethane ; fuming sulphuric acid decomposes the substance completely ; and nitrous anhydride produces tribromonitroethybne as a heavy, pale yellow liquid, with penetrating odour, boiling a t 108-110" at 21 mm. (compare Scholl and Brenneisen, Abstr., 1898, i, 345) Chlorine acts on pentabromethane a t 200-205", with production of chlorotribromethylene, whilst antimony pentachloride gives rise to hexachlorethane.A. W. C. Hydrocarbon, C,H,, a Secondary Product of the Decompo- sition of Barium Pyromucate. By PAUL FREUNDLER (BUZZ. SOC. Chim., 1897, [iii], 17, 614-616).-The hydrocarbon, C,H,, obtained when barium pyromucate is distilled (see this vol., i, l20), has a some- what aliaceons odour, and precipitates an alcoholic solution of mercuric chloride, but not ammoniacal cuprous chloride or silver nitrate. When treated with bromine, i t yields a small quantity of a dibrmide boiling a t about 50" under reduced pressure, but the chief product is a tetrabromide, C,H,Br,, a liquid boiling a t 162" at 20 mm. pressure. This compound has not been obtained pure, as it is extremely hygroscopic, and as it is not identical with allylene tetrabromide, it is probable that the hydrocarbon has the constitution CH2<rH.CH J. J. S. Action of Ammonia on Zinc and Mercuric Cyanides, and on Haloid Double Salts of the Latter. By RAOUL VARET (Ann. Chin2. Phys., 1897, [vii], 10, 5-18. Compare Abstr., 1896, i, 3, 633, ii, S8, 149, 513; 1897, i, 685, ii, 38, 9'3).-l'he conzpou?adORGANIC CHEMISTRY. 99 Zn(CN),,2NH3,H,0, obtained in transparent, prismatic crystals is produced by the action of ammonia on aqueous solutions of zinc cyanide ; the compound Zn(CN),,.2NH3, is formed in alcoholic am- moniacal solutions, or by the action of dry ammonia on the heated cyanide. Both these substances are very soluble in aqueous and alcoholic ammoniacal solutions, and rapidly decompose on exposure t o the air. The compound 2Hg(CN),,4NK3,H,0 separates in white, prismatic needles when a saturated solution of mercuric cyanide in concen- trated ammonia is cooled in a freezing mixture; the compound 2Hg(CN),,2NH3,H,O is obtained when a saturated solution of mercuric cyanide in less concentrated ammonia is allowed t o crys- tallise at 0'; both substances are very unstable, and are completely resolved into their constituents when heated to 100".The compound Hg(CN),,2NH3 results from the employment of alcoholic solutions ; it separates in transparent, prismatic needles, which decompose rapidly on exposure to air. The cornpound Hg(CN),,NH,, produced in an aqueous ammoniacal solution of mercuric cyanide in the presence of excess of the salt, separates from the filtrate in hard, granular crystals; it is more stable than the preceding compounds, but is completely decom- posed on heating a t 100'.No definite compound results from the action of dry, gaseous ammonia on warm mercuric cyanide. The double salt, Hg(CN),,HgCl,, when treated with alcoholic ammonia, is resolved into its components; mercuric chloride gives rise t o an insoluble compound, 2HgC1,,3NH3, whilst mercuric cyanide yields the substance Hg(CN),,2NH3. A greyish-white su6stance, 2Hg2(CN),C1,,3NH,, is obtained by the action of dry ammonia on gently heated mercuric chlorocyanide. The chlorocyanide, when treated with aqueous am- monia, gives a precipitate of mercuric ammonium chloride, NH,HgCl ; if zinc cyanide be added to the mixture, the precipitate redissolves, and on concentrating the solution the double salt, 2Hg(CN),,ZnC12,4NH,, is obtained in nodular crystals ; this compound is also produced by the action of aqueous ammonia on the double salt, 2Hg(CN),,ZnC1,,7H20.The latter method is employed in preparing the following series of analogously constituted double salts. 2Hg(CN),,ZnBr,,4NH3 ; 2Hg(CN),,CuCl2,4NH3 ; 2Hg(CN)2,CuBr2,4NH, ; 2Hg(CN),,CdBr2,4NH,,2H20 ; 2Hg(CN),,CdBr,,4NH3 ; 2Hg(CN)2,Ud12,4NH3. These compounds are crystalline, and the copper and cadmium derivatives do not evolve ammonia when heated to 100'. Action of Chlorine on Secondary Alcohols. By ANDRB BROCHET (Am,. Chirn. Phyg., 1897, Lvii], 10, 134-144).-This paper gives a detailed account of the ultimate action of chlorine on iso- propylic alcohol and methylhexylcarbinol ; the results obtained have already been published (see Abstr., 1895, i, 259 ; 1897, i, 4). G.T. M. G. T. 3%. Action of Chlorine on Primary Alcohols. By ANDRJ~ BROCHET (Am&. Chz'm. Phys., 1897, [ vii], 10, 289--380).-This paper contains a very detailed account of work which has already been published. The theory of the chlorination of ethylic alcohol is fully discussed, and the work of previous investigators compared with the results h . 2100 ABSTRACTS OF CHEMICAL PAPERS. obtained by the author with other primary alcohols. The action of chlorine on methylic alcohol (Abstr., 1895, i, 637, and 1896, i, 276), on propylic alcohol (Abstr., 1896, i, 114), and on isobutylic alcohol (Abstr., 1892, 1292; 1894, i, 484; and 1897, i, 3, 4) has already been made known.When chlorine acts on any primary alcohol, except methylic alcohol, the first product of reaction is a dichloro-derivative, CnH2,C1*CHC1*OH ; this either passes into a monochloraldehyde, CnH2nCl*COH, by loss of hydrogen chloride, or condenses with another molecule of alcohol to form an unsymmetrical dichloroxide, C,H2,C1*CHCl*O*CH2*CnH2n+l. This statement has been verified in the case of ethylic, propylic, isobutylic, and isoamylic alcohols (Abstr., 1898, i, 549). I n the case of methylic alcohol, the initial product is chloromethylic alcohol, which, by elimination of water, is converted into symmetrical dichloromethylic oxide. G. T. M. By ANDRI~ BROCHET (Ann. Plys. Chim., 1897, [ vii], 10, 381-387).-Chlorine has no action on cold dimethylethylcarbinol in diffused daylight, but at the boiling point of the alcohol, it is rapidly absorbed without evolution of gas. The products of the reaction are fractionated ; the lowest fraction contains tertiary amylic chloride (2-methyl-2-chloro- butane), CMe2C1* CH,Me, and chloramylene (2-methyI-3-chlorobutene), CMe2:CMeC1.This mixture is treated with bromine and sub- sequently steam distilled, wheu amylic chloride is obtained in the distillate and chloramylene dibromide remains in the residue. The higher fractions contain some unattacked alcohol and higher chlorinated derivatives of isopentane (2-methyl butane), dichloriso- pentane, CNe,Cl* CHMeC1, and trichlorisopentane, have been isolated. The latter boils at 176", its sp.gr. = 1.215 a t 15'/4", and its index of refraction nD= 1.472 a t 21'. The chief product of the action of chlorine on the cold alcohol in the presence of sunlight is the above-mentioned dichlorisopentane. When the gas is passed into a boiling mixture of the alcohol and water, the chief product is trichlorisopentane ; chloro-derivatives of higher boiling point, acetone, acetic, formic, and carbonic acids are also formed, but no amylic chloride could be detected. The first action of chlorine results in the formation of CMe,Cl* CHMeCl, this substance loses hydrogen chloride and forms CMe2:CMeCl, addition of chlorine t o the chloramylene produces CMe2C1* CMeCl, ; the amylic chloride is produced by a secondary reaction between the hydrochloric acid liberated and the unattacked alcohol. By PHILIPPE BARBIER and GEORGES LESER (BUZZ.Soc. C h k , 1897, [iii], 17, 590--596).-When pure licareol (boiling a t 86-88" under 10 mm. pressure) is heated with its own weight of acetic anhydride during 8 hours at 150-160' and the product rectified under a pressure of 10 mm., three fractions are obtained. The first passes over between 50' and SO', and consists mainly of terpenes ; the second, passing over between 80" and 105", consists mainly of unaltered licareol, and the third, boiling at 105-130", when further fractionated with the aid of a dephlegmator, The author puts forward the following generalisation. Action of Chlorine on Tertiary Amylic Alcohol. G. T. M. Dextro-licarhodol.ORGANIC CHEMISTRY. 101 yields a colourless liquid boiling at 11 9-1 20' under 10 mm.pressure ; this has the composition C,,H,,* OAc. The higher fractions contain an ether, (C,oH,1)20, boiling at 145-150° under 10 mm. pressure. The acetate is hydrolysed when the theoretical quantity of alcoholic potash is run in at the ordinary temperature, and the mixture then heated to 100' for an hour. The alcohol, Cl0H,,O, licarhodol, thus obtained boils a t 1 1 2-1 14' under 9 mm. pressure, has an agreeable odour, sp. gr. at Oo= 0.904, and rotatory power [ a],, = + 4' 8'. The yield is about 800 grams from 5 kilos, of licareol. When oxidised with perman- ganate, licarhodol gives dimethyl ketone, terebic acid melting a t 174", and levulinic acid. When oxidised with chromic mixture, the products are methylheptenone, CMe,:CH*CH,*CH,Ac, a small quantity of geranial-citral, and an acid, C,H,,O,, probably methyl- heptenonecarboxylic acid.The following is the constitution suggested for licarhohol, CH,:CMe* CH(CH,OH)*CH,* CH:CMe,. Action of Neutral Salts on Glucose at a Higher Tempera- ture. By H. C. PRINSEN GEERLIGS (Chem. Centr., 1898, i, 712; from ds.ch. Javasuikerindustrie, 1898). - The author finds that, not only do the salts of weak organic acids bring about the inversion of sugar in presence of glucose, but that at looo they also act on the glucose, converting the dextrose into levulose, or when the latter is in excess, inversely converting it into dextrose; the same change is effected by the alkali salts of strong mineral acids (see following abstract), but t o a very much smaller extent.The amount of change is proportional to the time during which the action has proceeded and to the concentration of the solution of the salt. A portion of the glucose is converted into organic acids, and it is these acids which sometimes interfere with Romijn's test for dextrose with iodine solution containing borax (Arch. Xuikerindustrie, 1897, 1001) by absorbing iodine and forming iodoform. The feeble rotatory power of molasses containing much invert-sugar is due to the fact that the raw sugar molasses contain considerable quantities of salts of organic acids. E. w. w. Inversion of [Cane] Sugar by Neutral Salts in Presence of Glucose. By H. C. P~INSEN GEERLIGS (Chem. Centr., 1898, i, 71 1 ; from Arch. Suikerindustrie, 1898).-The quantity of sucrose inverted by neutral salts in presence of glucose (see Arch.Xuikerindusti+e, 1895) is approximately proportional to the time during which the action takes place and to the amount of glucose originally present; the quantity of salt (sodium chloride) has only a very slight influence on the action. The action of the glucose is due to the liberation of a very small quantity of acid by the formation of a glucosate of the base, but when calcium carbonate or a salt of a weak organic acid is added, the inversion is retarded or prevented. The more easily dissociated salts are the more active, thus magnesium chloride and the chlorides of the alkaline earths are more effective than the chlorides of the alkalis. Tho acids contained in the salts also have a great influence; the following salts of potassium are arranged in order of decreasing activity : chloride, bromide, nitrate, sulpha te, J.J. S.102 ABSTltACTS OF CHEMICAL PAPERS. chlorate, oxalate, and succinate. Since Ohe monosaccharides, dextrose, levulose, galactose, and lactose act like glucose, whilst the alcohols and the di- and tri-saccharides are inactive, the presence of an aldehyde group may be necessary t o bring about the reaction. E. W. W. Inversion ,of Saccharose by Water. By BOHUSLAV RA<MAN and OTTOKAR SULC (Chem. Centr., 1898, i, 608-609 ; from Zeit. 2ucL.- Tnd. Bohrn., 22, 233-248. Compare Abstr., 1898, i, 34S).- Saccharose is inverted by water at temperatures above l l O o , but when acid is added the change takes place a t a lower temperature. When extremely pure water is used, 10 per cent.and weaker solutions of saccharose are not affected by boiling for some hours, but when the water has a considerable conductivity, the action com- mences ; generally speaking, the more concentrated the solution is after boiling, the more quickly inversion begins. When platinum vessels are used, the action occurs more rapidly, no matter how small the conductivity of the water, and in vessels of other metals inversion takes place with varying rapidity. The action of the metals of the platinum group in powder was investigated ; of these, palladium induced the most rapid change, iridium alone retarded the action, and in many cases a faint acidity of the solution could be detected by Congo-red. When metallic vessels were used, this acidity was only apparent in the cases of copper and silver.The author ascribes the influence of metals partly to a hydrolytic action and partly t o the formation of acids from the sugar; like acids, the metals are supposed to increase the chemical activity or “ionisation” of the water. The acid compounds are formed by a process of migration of the oxygen atoms analogous to certain reactions of sugars with alkalis and water. The oxidation of hydroxy-aldehydes and hydroxy- ketones is explained by a process of successive dehydration and hydration, whereby the groups CH,*OH and CH*OH become CH, and CH, respectively, and the terminal carbon atoms either form carboxyl groups, formic acid, or carbonic anhydride. At the same temperature, increase of pressure diminishes the inversion effected.E. W. W. Hydrolysis of Polysaccharides by Yeast Enzymes. By AKUSCIIAWAN KALANTHAR (Zeit. physiol. Chem., 1898, 26, 88-101). -The author has studied the hydrolytic action of yeasts from various wines and beers, and from the Russian beverage ‘‘ kissly-schtschi ” and the Armenian beverage ‘6 mazun ’) on the polysaccharides. Pure cultures were prepared in each case, and both fresh and dried cells and aqueous extracts were employed. The polysaccharides experimented on were cane-sugar, maltose, lactose, melibiose, trehalose, melitriose (raffinose), melicitose, and a-methylglucoside ; 10 per cent. solutions were submitted to the action of the yeast, a little toluene being added to prevent alcoholic fermentation. The amount of monosaccharide produced was determined either by titra- tion with Fehling’s solution, or in the case of those polysaccharides which themselves reduce Fehling’s solution, by ascertaining the amount of osazone produced with phenylhydrazine ; the resultsobtained are tabulated, and they indicate that the dried yeast and the aqueous extract possess a greater hydrolytic action than the fresh cells.Cane-sugar and rafinose were readily hydrolysed by all the forms o€ yeast employed. Maltose and a-methylglucoside were usually decomposed to the same extent, but in one or two cases the latter compound appeared to be more readily attacked. Although melibiose and lactose are formed from t,he same components (d-glucose and d-galactose), they behave somewhat differently towards enzymes ; the amount of the former hydrolysed varied with the temperature, only oiie wine yeast being capable of hydrolysing it a t 25’, but in every case negative results were obtained with lactose.Trehalose was hydrolysed by all the yeasts in the dried condition (compare Abstr., 1895, i, 441), except in the case of an orange-red yeast from ‘‘ mazun ’’ ; fresh wine or distillery yeast also induced appreciable hydrolysis. Melicitose was hydrolysed by all the beer yeasts, with one exception. The author adds a description of the preparation of “mazun” from milk. This beverage contains, besides bacilli and micrococci, nine species of yeast cells; seven of these have been isolated by Lindner and the author, and a table showing their hydrolytic action on maltose, a-met hylglucoside, trehalose, lactose, and cane-sugar is included in the paper.Q. T. M. Formation of Furfuraldehyde from Starch and its Derivatives. By FAUSTO SESTINI (L’Orosi, 1898, 21, 109-113).- Furfuraldehyde, t o which the odour of new bread is partly due, is produced by the simple heating of all varieties of bread, the crumb requiring to be heaOed to 140-160°, whilst for the crust, which has been already more strongly heated in the cooking, a temperature of 110-115° is sufficient. The aldehyde does not exist ready formed in the bread, since none is obtained from i t by steam distillation, and its production must be attributed to the decomposition of pentoses derived from the bran, or t o that of the starch and allied carbohydrates. Dry starch of various kinds was found to yield furfuraldehyde when heated to lSOo and upwards, whilst if previously moistened with a minute quantity of sulphuric or hydro- chloric acid, even a temperature of 100’ was sufficient for its produc- tion.Nageli’s ‘‘ starch granulose,” deprived of every trace of free acid, .evolves furfuraldehyde at 100’ or a few degrees higher, and the different varieties of dextrin behave in a similar manner. Fur- furaldehyde may be obtained from pentoses without the aid of acids, as various kinds of gum were found to yield this substance when heated in the dry state to 180-200°, and also, if slightly moistened with water, at 120”. Two specimens of purified rice starch, when distilled with hydrochloric acid of sp. gr. = 1.06, yielded respectively 1.16 and 0.44 per cent. of furfuraldehyde, quantities far greater than could be derived from traces of pentoses possibly present in the starch and which, moreover, could not be detected therein.It follows from these results that the amount of furfuraldehyde obtain- able from starch and allied carbohydrates is by no means a neglige-108 ABSTRACTS OF CHEMICAL PAPERS able quantity, and this fact must be taken into account in estimating pentoses by the furfuraldehyde method. Derivatives of Bromethylamine and Bromopropylamine. By SIEGMUND GABRIEL and ERNST LEUPOLD (Bey., 1898, 31,2832-2839). -Orthohydroxybenxylidenebromethylamine, OH-C,H;CH :N*C,H, Br, formed by the condensation of bromethylamine hydrobromide with salicylaldehyde in presence of an alkali, crystallises in yellow needles, melting at 56-57'.Ethylenepseudothiocarbamide is converted by nitrous acid into N. L. ?H2* S CH;N >CPh; the picrate crystallises in lemon- p-phenylthiazoline, yellow needles, which s:ften a t 165' and melt at 173--174', whilst the dichromate, (C,H,NS),,H2Cr207, forms orange-yellow needles. The formation of this compound favours the supposition that ethylenepseudothiocarbamide contains a n amido-group, and has the YH2* S constitution CH2,N>C* NH,. The thiazoline derivative is accom- panied by a substance crystallising in flat, yellowish needles which melt and decompose at 203-204". This compound is probably nitroethylenepseudothiocarbamide, but has not been obtained in suffi- cient quantity for further examination. FHMe S p-Phen y l-P-me t hyl t hiazoline, CH,--N >CPh, is obtained from propylenepseudot hiocarbamide, and ?s identical with that previously obtained from thiobenzamide (Gabriel and von Hirsch, Abstr., 1897, i, 1 20).Nitropopylenepseudothiocarbamide, C4H7NS*N0,, cry stallises in flat, oblique needles, which melt and decompose a t 166". Mercaptothiazoline is decomposed by hydrochloric acid at 155" with formation of amidomercaptan. Mercaptomethylthiazoline, when treated in a similar manner, yields c~midopropyZ-/3-mercaptan hydrochloride, SH*CHMe-CH,*NH,,HCI, which crystallises in microscopic tablets and melts at 87-88"; the picrate crystallises in com- pact, rhornbic tablets melting at 143-144' ; on treatment with iodine, it yields diamidopropylic P-bisulphide, the hydrochloride of which, C6Hl,S2N212HC1, melts at 213-214', the picrate forms short, thick prisms melting at 162-163'.Chemical Activity of Organic Ammonium Salts. By WOLFGANG BRENDLER and JULIUS TAFEL (Ber., 1898, 31,2683-2686. Compare Tafel, Abstr., 1898, i, 47 l).-T~irnethylacetonylammonium bromide, COMe*CH,*NMe,Br, obtained on passing trimethylamine into an ethereal solution of bromacetone, crystallises in well-formed, colourless needles when the alcoholic solution is exposed t o an atmos- phere of ether; it melts at 190°, and a t 195' gives rise t o a yellow distillate and tetramethylammonium bromide. The phelzylhydraxone is a crystalline substance which dissolves more readily in water than in alcohol ; Fehling's solution precipitates a yellow oil which is volatile in steam. Bromacetonyltrimethybmmoniurn bromide, C,Hl,NOBr2, obtained by the action of bromine on trimethylacetonylnmmonium bromide, A.H.ORGANIC CHEMISTRY. 105 crystallises from alcohol. If bromine water is employed instead of the undiluted halogen, a reddish-yellow, crystalline precipitate is formed having the properties of an ammonium tribrornide ; when an attempt is made to dry this substance, hydrogen bromide is elimi- nated, and bromacetonyl trimethylammonium bromide is formed. The aqueous solution of the last-named substance yields trimethyl- amine when heated. M. 0. F. Propylnitramine and its Alkyl Derivatives, and the Probable Existence of a New Glass of Neutral Nitramines. By HERM. UMBGROVE and ANTOINE P. N. FRANCHIMONT (Rec. TTUV. Chirn., 1898, 17, 2 70-2 86).-DipropyZdinitroxa~ide, C,O,( NPr *NO,),, prepared by leaving dipropyloxamide in contact with six times Its weight of concentrated nitric acid for 48 hours, and pouring the product into ice cold water, crystallises from alcohol in large tables, and melts a t 44".When dissolved (65 grams) in concentrated aqueous ammonia (150 c.c.), oxamide separates, whilst the ammonium derivative of propylnitramine remains dissolved ; on adding dilute sulphuric acid to the clear solution, nearly the theoretical quantity of propylnitramine is obtained. Etl~~Z~opyZnitram~ne, prepared by boiling a mixture of the potas- sium derivative of ethylnitramine (26 grame), propylic iodide (32 grams), and methylic alcohol (100 c.c.) during 30 hours, is a colourless liquid with a characteristic odour ; it boils a t 108" under t~ pressure of 22 mm., and has a sp.gr. = 1.028 at 15". It dissolves in concen- trated sulphuric acid without evolution of gas, giving rise, apparently, t o nitrosulphuric acid and a substance possessing cupric-reducing power, which is probably a hydroxylamine or an imine. From the lower fractions obtained in purifying the crude ethylpropylnitramine by fractional distillation, a substance isomeric with the latter was isolated, differing from it in boiling point (65' under a pressure of 20 mm.) and i n its behaviour with concentrated sulphuric acid. On heating ethylpropylnitramine with 10 per cent. aqueous potash for 9 hours at 150-160°, it is decomposed into propylamine, nitrons acid, and acetaldehyde; tliis is in accordance with van Erp's views (Abstr., 1895, i, 590 ; and 1897, i, 6) regarding the action of alkalis on mixed aliphatic nitramines.It appears that, in this decomposition, the heavier radicle separates combined with the amido-group, and the lighter in the form of an aldehyde. The principal product formed on leaving the silver derivative of propylnitramine (82 grams) in contact with ethylic iodide (60 grams) dissolved in ether (500 grams) during 12 hours in the dark, and sub- sequently heating the mixture during 6 hours a t 50", is iso-ethylpropyl- mitrumine ; this distils unchanged at 58.5" under a pressure of 16 i-nm., has a sp. gr. = 0.9755 at 15', and does not give a colorat-ion with an acetic acid solution of a-naphthylamine, either alone or in presence of zinc. It differs in this respect from an isomeric substance formed simultaneously, which decomposes when distilled into nitrogen, water, acetaldehyde and propaldehyde ; together with this unstable iso- meride, a small quantity of ethylpropylnitramine is also formed.On heating iso-ethylpropylnitramine with 10 per cent. aqueous potash,106 ABSTRA(!TS OF CHEMICAII PAPERS. nitrogen is evolved, and propaldehyde appears to be formed, although this immediately polymerises, giving a resin. ~ s o ~ r o ~ ~ l e t h y l n i t r c ~ ~ ~ ~ i ~ e , prepared by acting on the silver derivative of ethylnitramine with an ethereal solution of propylic iodide, boils at 65' under a pressure of 20 mm., and has a sp. gr.=0*9783 a t 15'; at the same time, propylethylnitramine is formed, together with an isomeric substccnce, which decomposes when heated, giving nitrogen and propaldehyde.When isopropylethylnitramine is heated with 10 per cent. aqueous potash, it gives rise to nitrogen and acetaldehydo, in accordance with van Erp's rule (Zoc. cit.). Isopropylmethylnitramine, prepared by leaving the silver derivative of methylnitramine in contact with propylic iodide dissolved in ether during 5 days at the ordinary temperature, boils a t 51' under a pressure of 18 mm., and has a sp. gr. = 1.012 a t 15' ; altbough no gas is evolved when i t is heated at lOO', it gives a marked coloration with an ace t'ic acid solution of a-naphthylamine. When decomposed by aqueous potash, i t apparently gives rise to formaldehyde. W. A. D. Action of Sulphuric Acid on Aliphatic Nitramines and their Isornerides. By ANTOINE P.N. FRANCHIMONT and HERM. UMBGROVE (Rec. Trau. Chim., 1898, 1'7, 287-295).-Concentrated sulphuric acid acts in the same manner on the silver and mercury derivatives of methylnitramine as on methylnitramine itself ; in each case, nearlythe theoretical quantity of nitrous oxide is evolved, no other gas being formed. From ethylnitramine, however, and its potassium derivative, a small quantity of an inflammable gas, probably an olefine, was also obtained, and the same is true of propyl- and butyl-nitramine. The behaviour of ethylpropylnitramine with concentrated sulphuric acid has been dealt with in the preceding abstract ; the action is the same, but slower, when 40 per cent. sulphuric acid is employed, partial decomposition only taking place.The isodialkylnitramines are, however, rapidly decomposed by this mid a t the ordinary tempe- rature, giving nitrous oxide and two alcohols, that formed by the alkyl radicle directly attached to the nitrogen also giving rise, as a rule, to an olefine, except in the case when the radicle is methyl. This behaviour was verified in the case of iso-ethylmethyl-, isomethylethyl-, isodiethyl-, iso-ethylpropyl-, isopropylethyl-, and isopropylmethyl- nitramines. The ease with which the isodialkylnitramines undergo de- composition when treated with 40 per cent. sulphuric acid is explained by attributing to them the general formula NKNO*OR ; or, assuming that the acid nitramines have the general formula O<,->o THR (Briihl), by giving the neutral isonitramines the general structure W.A. D. K N . TR OR' Neurine and its Derivatives. By WL. GULEWITSCH (Zeit. physiol. Chem., 1898, 26, 175-188).-The author describes the ap- pearance, as seen with the un3rsisted eye and with th9 microscope, ofORGANIC CHEMISTRY. 107 precipitates obtained with dilute solntions of synthetically prepared neurine hydrochloride and the usual reagents for alkaloids. These precipitates obtained with dilute solutions of neurine are far less soluble than those from choline. Contrary to Brieger's observation, the author finds that phosphotungstic acid gives a precipitate with neurine hydrochloride which is distinctly visible even in solutions containing only ,$aBth of the base. Neurine picrate forms golden-yellow needles melting at 263-264O ; it is very insoluble in cold water and alcohol. Neurine platino- chloride melts a t 195.5-19S0, contains no combined water, and differs in its crystalline form from the corresponding choline salt. The aurichloride, C5H1,NAuC14, forms golden-yellow needles melting at 228--232O, and contains no water of crystallisation.On the addition of mercurous chloride to an alcoholic solution of neurine hydrochloride, two double sults are precipitated ; the less soluble, C5H12EU'C1,6HgCl,, forms colourless, tabular crystals and melts at 230*5--234O ; the more soluble, C,H12NCl,HgC1, crystallises in aggregates of narrow prisms and melts at 198*5-199-5°. Dilute solutions of neurine are not decomposed on boiling, but concentrated solutions give off trimethyl- amine. Neurine hydrochloride, when recrystallised from water, has no tendency t o take up one molecule of the solvent and become trans- formed into choline hydrochloride.G. T. M. Constitution of Ornithine and Arginine. By ERNST SCHULZE and ERNST WINTERSTEIN (Zeit. physiol. Chem., 1898, 26, 1-14. Compare Abstr., 1898, i, 2Sl).-Ornithine, C,H,,N,O,, was originally discovered by Jaffk (Abstr., 1878, SSS), who suggested that its consti- tution might be that of a diamidovaleric acid ; i t does, in fact, closely resemble the diamidopropionic acid prepared synthetica.lly by E. Klebs (Abstr., 1894, i, 439). A rginine, C,H,,N40,, prepared either from the seedlings of Lup'nus luteus 013 by heating albumin with hydrochloric acid, yields ornithine and carbamide when hydrolysed with baryta water.Ornithuric acid, the dibenzoyl derivative of the former base (JaffC., Zoc. cit.), is obtainedfrom the crude product of reaction by the Schotten-Baumann method ; this compound is hydrolysed by con- centrated hydrochloric acid, first into a monobenzoyl derivative, and then into ornithine, the yield of benzoic acid aiid ornithine dihydro- chloride being almost theoretical. Ornithine, on treatment with nitrous acid, loses the whole of its nitrogen, but the hydroxy-acid which should be formed has not been investigated. Phenanthraquinons gives no quinoxaline derivative with ornithine, and the authors there- fore suppose that the amidogen groups are not attached t o contiguous carbon atoms. If ornithine be assumed to be a diamidovaleric acid, then arginine might have the following constitution, which resembles those of glycocyamine and creatine.The yield of ornithine from arginine is only 40 per cent. of the theoretical quantity. This may be due, as in the case of creatine, t o the fission of the molecule taking place in two ways, but no other well- characterised product of hydrolysis has yet been isolated. NH:C(NH,)*NH*CH,-CH,*CH,*CH(NH,)*COOH, G. T. M.108 ABSTRACTS OF CHEMICAL PAPERS. The So-called Nitroazoparaffins. By EUGEN BAMBERGER (Be+*.., 1898, 31, 2626--2635).-1n accordance with modern views, the ‘‘ nitroazoparaffins ” of Victor Meyer must be regarded as hydrazones containing the grouping *C(NO,):N*NH*, and, therefore, as true nitro- compounds, whilst their salts must be looked on as derived from the tautomeric isonitro-azo-compounds, the above group having become *C(NOOH) *N :No.When L nitroazoparaflins ” are subjected to alkaline hydrolysis, they are decomposed v i t h production of acidylhydrazines and nitrous acid. Thus ‘‘ phenyl-nitroam propane," or nitropropionalde(pheny1)- hydrazone,” as the author prefers to term it, when heated on the water-bath, with a 1 per cent. solution of soda, is almost quantitatively converted into /3-propionylphenylhydrazine, probably iu accordance with the equation, NO,*CEt:N*NHPh + H,O = COEt-NH-NHPh + HNO,. NitroacetaZde(phenyZ)hydraxone, NO,*CMe:N*NHPh, is produced in nearly theoretical amount by the foregoing process. Nitroethane (10 grams) is quickly dissolved in an ice cold solution of soda (5.2 grams) in water (3 grams) and mixed at once with an ice cold solution of the diazonium acetate made by dissolving aniline (12 grams), concentrated hydrochloric acid (30 grams), sodium nitrite (9.4 grams), and crystallised sodium acetate (44.4 grams) in water (2 litres).The sub- stance separates quickly as a yellow oil, which soon solidifies ; it does not exhibit either Meyer’s or Konowaloff’s reaction, and cannot, there- fore, be the ‘‘ iso-” form, NOOH:CMe*N:NPh. It crystallises from alcohol in golden-yellow, and from benzene in orange-red, leaflets, and melts a t 141-142’. It decomposes slightly when kept in a closed vessel, and then has an odour of acetic acid; in one instance, it decomposed, giving nitrous and acetic acids and diazobenzene nitrate. When nitroacetalde(pheny1)hydrazone is warmed with a dilute solu- tion of soda in dilute methylic alcohol for 2 hours, it is decomposed, giving an appreciable quantity of an isodiazotate, ammonia, phenyl- hydrazine, and a neutral oil, but the principal product is P-acetyl- phenylhydrazine. Nitropropionalde(pheny1) hydrazone, NO,*CEt:N*N HPh, prepared by a method similar to that used in the case of the acetaldehyde compound, forms hard, orange-yellow crystals, and melts a t 98-5-99.5’ (com- pare Meyer, this Journal, 1876, ii, 93).It does not, as stated by Meyer, give an immediate violet-red coloration when treated with strong suIphuric acid, but a fiery-red, the violet tone being a later development ; a similar statement holds true in the case of the acetalde- hyde compound. Nitropropionalde( pheny1)hydrazoa e, is, as hasalready been mentioned, almost completely converted into nitrous acid and P-propionylphenylhydrazine when warmed with dilute soda.Nitrovaleralde(phenyl)hydraxone, C,H,: C(N0,) :N*NHPh, is obtained when nitropentane is treated with the diazonium acetate ; it exists in two forms. The P-modijkation obtained by crystallising the substance from alcohol, separates in golden-yellow leaflets having a bronze-like lustre, and melts at 92-5-93’, dissolves readily in acetone, and decom- poses when kept for a long time in a closed vessel ; its solution in sulphuric acid is a t first fiery red, but gradually becomes violet-red * The author omits the “phenyl ” in his paper.-[EDITORS.]ORGANIC CHEMISTRY. 109 spontaneously, and at once on the addition of dichrornate.The u-rnod.2- cation obtained from the former by boiling it with heavy petroleum, separates from the solution on cooling in long, silky needles, which are orange-red by reflected and golden- yellow by transmitted light, and have a metallic-blue reflex; it has the same composition as the u-form, but melts at 51*5-52", and is very readily dissolved by light petroleum ; it may be converted into the P-modification by dissolving i t in boiling alcohol, and if the melted substance is allowed to solidify, it melts once more a t 86-87', indicating a more or less complete conver- sion into the /3-form; a similar change is found to have occurred when its solution in alkalis is precipitated by means of an acid. By trent- ment with alkali, p-nit rovaleralde(pheny1)hydrazone is .converted into P-valerophenylhydrazide ; the latter melts at 112-112.5° and not at 101' as stated by Autenrieth (Abstr., 1888, 251).A. L. Formhydroxamic Acid.-By JOHN U. NEF (Ber., 1898, 31, 2720-2721).-1n view of the paper recently published by Schroeter (Abstr., 1898, i, 623), the author points out that investigations on form- hydroxamic acid and its derivatives are in progress in his laboratory. The ethers of this acid can be obtained by heating formic acid with a-alkylhydroxylamines. Benzylhydroxamic acid, for example, can readily be prepared in this way, and is a thick oil with strongly acid properties. A. H. Action of Semicarbazide on Formaldehyde. By JOHANNES THIELE and JAMES BAILEY (Annalen, 1898, 303, 91--93).-When a 4 per cent. solution of formaldehyde is added to aqueous semicarbazide hydrochloride, a gelatinous precipitate is formed, and this compound, after being washed with water and dried at 95", has the composition C,H,,N,O, + $.H20 ; it is, therefore, a hydrated condensation product of semicarbazide (2 mols.) with formaldehyde (3 mols.).H. Thoms (Ber. deutsch. Pharm. Ges., 7, 5 ) has recently obtained a normal pro- duct of condensation. The substance dissolves in 60 per cent. hydro- cyanic acid, yielding a compound which crystallises from dilute acetic acid, and melts a t 12'7.5"; no definite formula has been assigned to it. M. 0. F. Aldehyde-ammonia. By ROBERT DE FORCRAND (Compt. rend., 1898, 126, 248-250).-The author's calorimetric experiments con- firm those by which Delepine (Abstr., 1898, i, 462) demonstrates that aldehyde-ammonia in the solid state consists of the more or less polymerised hydrate of ethylidenimine, and that, when dissolved in water, a gradual change into the simple form takes place.Two series of calorimetric determinations were made on the heat developed by the action of dilute sulphuric acid on solutions of alde- hyde-ammonia which had been kept for different periods of time. In one case, the aldehyde-ammonia solution was prepared by adding weak ammonia to a dilute solution of aldehyde, and in this series of determinations the heat effect at first decreased until a minimum was reached after 8 days, and then increased until the end of 50 days. When the solution was prepared by dissolving solid aldehyde- ammonia in water, the heat developed by the action of the acid was110 ABSTRACTS OF CHEMICAL PAPERS.least after 7 minutes, aiid gradually increased until the end of 50 days. I n the first series, there is a rapid change of aldehyde-ammonia into polymerised ethylideniminc, and, at the same time, this polymeride slowly passes into the simple form; in the second series, the poly- meride gradually dissociates into the simple imine. G. T. M. Amidoaldehydes. By EMIL MA ASS and RICHARD WOLFFENSTEIN (Ber., 1898, 31, 2687-2692. Compare Abstr., 1898, i, 44).-For reasons which are discussed in the original paper, the authors regard those amidoaldehydes which are convertible into piperidine deriva- tives as capable of acting in accordance with the tautomeric formula, :C,H,*NH:O; from this point of view, they belong to the group of oxides obtained by the action of hydrogen peroxide on 1-alkylpiperidine bases (Wernick and Wolffenstein, Abstr., 1898, i, 536).The facts which have led to this conclusion are as follows. The benzoyl derivative of orthamidomethylphenylacetaldehyde (Abstr., 1898, i, 44) yields benzoic acid on oxidation with potassium permanganate. Benzoic acid is also produced by the oxidation of the benxoyl derivative of 8-amidovaleraldehyde (Abstr., 1892,1484), which melts a t 66O; the other product is a hygroscopic syrup which is also formed when piperidine is oxidised with potassium permanganate. Carbon bisulphide converts 6-amidovaleraldehyde into the dithio- carbamate of piperidine (m, p. 169-171°), and by its action on amido- valeropropaldehyde, gives rise to the dithiocwbamate of coniine, which melts at 58-61".I n the behaviour of amidovaleraldehyde towards nitrous acid, however, i t resembles ordinary amidoaldehydes. M. 0. F. Action of Water on Acraldehyde Dibromide. By CORNELIS A. LOBRY DE BRUYN (Rec. Y'yav. Chim., l898,17,259--262).-Although acraldehyde dibromide is converted into bromacraldehyde when boiled with a 50 per cent, aqueous solution of sodium acetate (Piloty and Stock, Abstr., 1898, i, 402), it apparently gives rise to glyceraldehyde when left in contact with water, either a t the ordinary temperature, or, better, at that of the water-bath. On removing the hydrobromic acid from the solution by successive treatment with lead carbonate, hydrogen sulphide, and moist silver oxide, and subsequently concen- trating in a vacuum, a syrup is obtained which reduces Fehling's solution, and gives rise to glycerosazone when mixed with a solution of phenylhydrazine acetate.[NOTE BY AssTRAcToR.-since the original paper was published, Wohl (Ber., 1898, 31, 2394) has prepared glyceraldehyde from the acetal of acraldehyde, in the form of a white, crystalline powder.] W. A. D. Acetylrnethylheptenone (2 Methyl-2-nonene-6 : 8-dione). By PHILIPPE BARBIER and GEORGES LESER (Bull. Xoc. Chim., 1897, [iii], 17, 748--751).-Nstural methylheptenone (Z-methyl-2-heptene-6-one) readily reacts with ethylic acetate in the presence of sodium, with the formation of ci,cRt~li,znthyZl~e~~e~~o~ze, CMe,:CH*CH,*CH,*CO*CH,* COMe. The latter is purified by conversion into its copper derivative, a paleORGANIC CHEMISTRY.211 blue, crystalline powder melting a t 132-133', from which it is regenerated by the action of dilute sulphuric acid. Acetylmethyl- heptenone is a colourless liquid of powerful aromatic odour and having a sp. gr. = 0.954 a t 0'. It boils at 114-115' under a pressure of 15 mm., and at 233-234', with slight decomposition, a t the ordinary pressure. Treatment with the theoretical quantities of hydroxylamine hydrochloride and sodium carbonate converts it into the oxaxole, CMe,:CH*CH,*CH,*C< CH:(?Me, which boils at 118-119' under a pressure of 14 mm., whilst the dioxirne, a crystalline substance melting at 109-llOo, is also formed. N-0 Ace tylme th y lhep tenone Forms a sodium derivative, CMe,: CH-CH,*CH,*CO CHNa COMe, which, when warmed for some hours with ethylic monochloracetate, is converted into a mixture of the ethylic salts of 2-methyl-2-hexenoic acid, levulinic acid, and 2-methyl-2-nonene-6-onoic acid.The first two of these compounds are formed by the action of alcohol, and the third by the action of water, on the normal product of the reaction, which would have the composition CMe,: CH*CH,*CH,*CO* CH( COMe) CH, COOEt. Ethylic 2-methyZ-2-hexenoate, CMe2:CH.CH;CH2*COOEtj, is a colour less liquid of agreeable odour which boils a t 182-184' and has a sp. gr. = 0.928 at 0'. On hydrolysis, it yields 2-methgl-2-hexenoic acid, which is a colourless liquid boiling at 216-218". Ethylic 2-methyZ-2-nonene-6-onoate boils a t 152-1 54' under a pressure of 14 mm. and has a sp.gr. =Om988 a t 0'. The corres- ponding acid cry stallises from light petroleum in colourless needles melting at 57". The ethylic salt forms a phenylhgdraxone, which melts at 93' and boils at 235-240" under a pressure of 15 mm. The sodium derivative of acetylmethylheptenone reacts with ethylic iodide to form acetylmet?Lylethylheptenone, which boils a t 133-135' N. L. Conversion of Ketones into Diketones. 111. By MICHELE FILETI and GIACOMO PONZIO (J. pr. Chena., 1898, [ ii], 58, 362-367).- Further investigations have confirmed the conclusions already arrived a t (Abstr., 1897, i, 317). Ethyl butyl ketone yields a mixture of two diketones, acetylualergl and propionyZbwtg?*yl, and two dinitrohydrocarbons ; of the former, the mixture of dioximes was so far separated by fractional crystallisation from dilute-alcohol t h a t fractions melting at 168-170'and 141-144' were obtained ; as regards the dinitrohydrocarbons, potassiodinitro- ethane is more soluble than the corresponding butane derivative.Ethyl amyl ketone behaves in a similar manner ; acetylhexoyl and propionyl- valeryl are the diketones ; the dioxime and osazone of the latter melt at 139-141" and 96-97' respectively ; as regards the dinitrohydro- carbons, potassiodinitroethane is more soluble than the corresponding pentane derivative. Ethyl isoamyl ketone yields acetylisohexoyl and dinitroethane only ; the dioxime of the former was also prepared from ethylic isoamylacetoacetate. Ethyl isohexyl ketone yields under a pressure of 15 mm. acetylisoalnylacetyl and dinitroethane only. c.F. 6,112 ABSTRACTS OF CHEMICAL PAPERS. Acetylation with the help of Sulphuric Acid. By ZDENKO H. SKRAUP (Monatsh., 1898, 19, 458-460).-The author points out that Franchimont (Abstr., 1880, 159) was the first to draw attention to the value of sulphuric acid as an addition to acetic anhydride in acetyl- ating (compare Thiele, Abstr., 1898, 469), and the method has long been employed in the author's laboratory. The reaction is liable to become uncontrollable unless precautionary measures are taken. By the action of acetic anhydride containing Less than 1/100 per cent. of its weight of sulphuric acid on mucic acid, tetracetylmucic acid is easily produced in amount equal to 79 per cent. of that theo- retically possible. By the usual method of heating the acid with acetic anhydride and anhydrous sodium acetate, only amorphous products are obtained. With smaller quantities of sulphuric acid ( l / l O O O O per cent.), the reaction still goes on, but is probably in- complete.The method of estimating acetyl used by Wenzel (Abstr., 1898, i, 234) was published 6rst by Franchimont (Ber., 1879, 12, 1940), and modified later by the author (Abstr., 1894, i, 15). By DIOSCORIDE VITALI (L' Orosi, 1898, 21, 114--117).--0ne hundred parts of dry sodium valerate and 117 parts of crystallised zinc sulphate are separately dissolved in the smallest possible quantity of hot water, the solutions mixed, the liquid evaporated t o dryness at a temperature not exceeding 70°, and the finely powdered residue extracted with 95 per cent.alcohol. On concentrating the alcoholic extract by evaporation a t 70°, zinc valerate is obtained in a very pure crystalline condition. This process is simpler and more economical than those commonly employed. A . L. Preparation of Zinc Valerate. N. L. Wax of the Humble Bee. By ERNST E. SUNDVIK (Zeit. physiol. Chern., 1898, 26, 56-59).-Samples of wax taken from the nests of Bombus musca!runz and B. lapidarius have the same chemical proper- ties. The mixture of wax and pollen, freed from eggs and larvse, and extracted with ether or chloroform, yields a crude wax of brownish- yellow colour, melting at 35-40', and having an agreeable odour resembling honey. This substance still contains fat and colouring matter. The principal constituent of the wax is an alcoholic sub- stance, which is freed from glycerides by treating the partly purified product with weak potash on the water-bath.After repeated crys- tallisations from alcohol, the unaltered residue melts at 74-75', and its composition agrees with the formula C,,$,,O ; it forms flexible, woolly needles which can be easily kneaded into a pale yellow cake. A berhzoyl derivative, C3,H,,0Bz, obtained by heating the substance with benzoic anhydride a t 150-1 60', crystallises from alcohol, benz- ene, and petroleum, and melts a t 55'. Ethylic P-Isopropylacetobutyrate and Stereoisomeric Di-isopropylbutenedicarboxylic Acids. By PHILIPPE BARBIER and V. GRIGNARD (Compt. rend., 1898, 126, 251-253).-Ethylic isobutylideneacetoacetate and ethylic malonate suffer condensation in the presence of potassium ethoxide, yielding a liquid which, when G.T. M.ORGANIC CHEMISTRY. 113 distilled, first under ordinary and subsequently under reduced pressure, gives rise to two substances; the chief product, a colourless liquid boiling a t 170' under atmospheric pressure, consists of ethylic p-isol3?.opylacetobutyrate, CH2Ac*CHPrN2H,* COOEt ; the product obtained in less quantity is an unstable intermediate com- pound, COOEt*CHAc*CHPr~*CH(COOEt),, boiling at 189-191' under a pressure of 10 mm., which passes into the preceding substance by the loss of two COOEt groups. When ethylic P-isopropylacetobutyrate is treated with sodium ethoxide, two molecules of the former coalesce, and condensation takes place, accompanied by the elimination of two molecules of acetone.The ethereal salt, C,,H,,O,, which is obtained, boils at 156' under a pressure of 10 mm., and on hydrolysis furnishes a mixture of two isomeric di-isopro~yl6utenedicurboxylic acids, having the formula COOH- CH,* CPrp:CPrP*CH,*COOH ; one crystallises in needles melt- ing at 156-15S0, and the other in colourless plates melting a t 11 7-1 19'. The stereoisomeric relationship of these isomerides has not yet been determined. G. T. M. Syntheses with Ethylic Cyanacetate. By TIMOTH~E KLOBB (Ann. Chim. Phys., 1897, [vii], 10, 145-214).--EthyZic isovaleryl- cyanacetate, CHMe,. CH,. CO*CH(CN)*COOEt, produced by adding an ethereal solution of isovaleric chloride to an alcoholic solution of ethylic cyanacetate in the presence of sodium ethoxide, separates in white needles when the oily product is cooled to - 36'; it melts at +21°, boils at 138-140' under a pressure of 21 mm., at 144-148' under 31 mm., and decomposes when distilled at the ordinary pressure ; its specific gravity = 1.030 a t 24'.The substance is a strong acid, not only decomposing carbonates, but its alcoholic solution dissolves the metals, magnesium, zinc, iron, aluminium, copper, cobalt, and nickel, with the evolution of hydrogen ; silver, bismuth, and antimony are not attacked. The mag?zesiurn, ferrous, and coppel. derivatives obtained in this manner by the displacement of the hy- drogen in the CH group are described. Methylic isovalerylcyanacetate, prepared like the ethylic salt, crys- tallises in rhombic plates melting a t 41-42', and boils without decom- position a t 171-172' under a pressure of 100 mm.; its sodium, cal- cium, 6arium, and silver derivatives are crystalline. Both ethereal salts are insoluble in water, but dissolve easily in the usual organic solvents. When boiled with aqueous potash, they undergo hydrolysis, am- monia, the potassium salts of carbonic, acetic, and isoyaleric acids and the corresponding alcohol being produced ; long continued boiling with water results in the formation of tarry products and a small quantity of a compound having the formula C,,H,,N,O, and crystallising in white needles melting a t 133-134'. The preparation of the alkylic derivatives of diphenacylcyanacetic acid (PP-dibenzoylcyanisobutyric acid) is given in detail ; the propylic salt, obtained by the action of bromacetophenone on ruethylic cyanacetate, dissolved in propylic alcohol, in the presence of sodium propyloxide, crystallises from alcohol in nacreous leaflets and melts at 114'.The isobutylic salt could not be obtained by this method ; the VOL. LXXVI. i. i114 ABSTRACTS OF CHEMICAL PAPERS. methylic and ethylic salts have been previously described (see A.bstr,, 1894, i, 592; 1897, i, 531). Phenylhydrazine gives rise to no definite hydrazones with these ethereal salts. On hydrolysis with boiling alkalis, they yield diphenacylacetic acid (PP-dibenzoylisobutyric acid). The preparation of the alkylic phenacylcyanacetates (a-cyano-/3-benz- oylpropionates) is described at some length; an account of these com- pounds and of the free acid has already been published (see Abstr., 1896, i, 126).P-Benzoylpropionic acid is the final product of the action of potash on these ethereal salts. The syntheses based on the displacement of the hydrogen of the group CH in the above ethereal salts have already been studied (Abstr., 1896, Zoc. cit., and 1897, i, 419 ; 1898, i, 586) ; the prepara- tion of the methylic, ethylic, and benzylic substitution products are fully described in the paper. Ethylic and methylic a-cyano- P-acetylpropionates have already been described (Abstr., 1896, Zoc. cit.). G. T . M. Constitution of Tetric Acid and of the Lactone of 7-Hydroxydimethylacetoacetic Acid. By MAX CONRAD and RICHARD GAST (Ber., 1898, 13, 2726--2731).-Methylic monobromo- dimethylacetoacetate, which has been previously described (Abstr., 1897, i, 321), boils a t 225-230" under atmospheric pressure, under- going slight decomposition.When the acetate prepared from this compound by means of potassium acetate is kept for some months at the ordinary temperature, it yields methylic acetate and the lactone of y-hydroxydirnethylacetoacetic acid (2 : 2-dimet hyl-3-butanone-4-oloic acid, CMe,<CO,O , which is a coIourless oil of sp. gr. = 1.147 at 18'/15O, and boils at 208-212' without decomposing. The dilute alcoholic solution gives no reaction with ferric chloride. Bromine converts the lactone into a monobromo-derivative, which is decomposed by water with formation of the lactone of dihydroxydimethylaceto- acetic acid. Aniline converts the original lactone into a derivative, C,,H,30,N, which crystallises in compact, lozenge-shaped crystals melting a t 88' and boiling at 300-310"; this compound, which is decomposed by aqueous baryta and by platinic chloride, probably has the constitution CMe,<~&~~>CH,.The lactone readily reacts with hydroxylamine hydrochloride to form an oximidolactone, OH N:C<CMe2. CO' which melts at 134", and gives no coloration with ferric chloride ; the corresponding phenylhydraxone melts at 131", and is sparingly soluble in light petroleum. Methylic tetrate, CO*QH, CH,--F) CB2-0 OMe*CGCMe. bo, prepared by the action of methylic iodide on silver tetrate, is a colourless liquid boiling at 215-220"; it is isomeric with the lactone just described, but does not yield derivatives with hydroxylamine or phenylhydrazine, whilst acids reconvert it into tetric acid.The fact that the lactone of y-hydroxydimethglacetoacetic acid is soORGANIC CHEMISTRY. 115 dissimilar from tetric acid both in chemical behavionr and boiling point renders it improbable that the latter is the lactone of y-hydroxy- methylacetoacetic acid, having the formula CO-0 CHMe<(J*.&,' A. H. Reduction of Aconic Acid to Paraconic Acid. By HANS REITTER (Ber., 1898, 31, 2722--2725).--Aconic acid is readily con- verted into paraconic acid when it is treated with glacial acetic acid and zinc dust, although Fittig (AnnaZen, 1883, 216, 97) was unable t o effect this reduction by means of sodium amalgam. The ready formation of paraconic acid affords further evidence in favour of the formula COOH*C< CH-? for aconic acid proposed by Fittig.CH, CO A. H. Syn thesis of Terebic Acid. By EDMOND E. BLAISE (Compt. vend. , 1898, 126, 349--351).-Ethglic bromosuccinate and acetone are mixed together in the presence of a copper-zinc couple and the mixture is occasionally shaken during 24 hours. The double zinc compound pro- duced is decomposed by dilute sulphuric acid, and the ethylic terebate is extracted by means of ether and hydrolysed by aqueous potash. The acid is liberated by hydrochloric acid and purified, first by conver- sion into its soluble barium salt, and subsequently by recrystallisation from water and alcohol ; it melts a t 174", and is furthur identified by conversion into methyl-2-pentanolide. The yield of terebic acid from ethylic bromosuccinate is 10-12 per cent., that from pinene is less than 2.G. T. M. Tautomeric Forms of Ethylic Isaconitate and of Ethylic Dicarboxyglutaconate. By MAX GUTHZEIT (Ber., 1898, 31, 2753--2758).-Ethylic isaconitate is a thin, colourless liquid which boils at 178-180' under a pressure of 20 mm. and has the sp. gr. = 1.1291 at 20°/200. This constitutes the enolic form of the compound, and gives a deep blue coloration with ferric chloride, whilst it also forms a copper salt, and is a t once coloured deep yellow by sodium carbonate. This form is always obtained by the ordinary methods of preparation, but changes very slowly, if kept, into the ketonic or true form, which is also produced in a few hours when a small amount of piperidine is added t o the enolic form. The ketonic form is a very viscid, deep yellow oil which cannot be distilled without undergoing decomposition, and has a sp, gr.= 1.1432 at 20°/200. It gives no colorittion with ferric chloride, does not yield a copper salt, and is only slowly coloured yellow by sodium carbonate. When it is dissolved in alcoholic sodium ethoxide and the solution acidified, the enolic form is regained. Both forms ham the same molecular weight as determined by the boiling point method. The two forms of this compound probably have the following constitutions, COOEt*CH:CH*CH(COOEt), ; COOEt*CH:C H*C(COOEt):C(OH)*OEt Ethylic dicarboxyglutaconate appears also to exist in two forms, the enolic form being that which has previously been described, whilst the i 2116 ABSTRACTS OF CHEMICAL PAPERS. ketonic or true form, which is produced by the action of piperidine and is also formed when the enolic form is kept for along time, crys1,allises in monosymmetric crystals melting at 101-102'.The latter have only been obtained in very small amount, and are being further in- vestigated. A. H. Condensation of Ethylic Malonate with Aldehydes under the Influence of Ammonia and Organic Amines. By EMIL KNOEVENAGEL (Be?., 1898,31, 2585-2595. Compare Abstr., 1894, i, 570, &c.)-Methylenebispiperidine and methylenebisaniline react readily with ethylic malonate when heated with i t on the water-bath, yielding ethylic methylenebismalonnte. When aniline is added to ethylic malonate mixed with formaldehyde, no action takes place a t the ordinary temperature, and methyleneaniline does not react with ethylic malonate t o form ethylic methylenebisrnalonate. The best method for the production of the latter substance is to add a small quantity of an amine, usually piperidine or diethylamine, to a mixture of formaldehyde and ethylic malonate mixed in the requisite pro- portions. Ethylic ethylidenebismalonate, prepared in a manner similar t o the above, boilsat 208-209' under a pressure of 17 mm.; it is accom- panied by ethylic ethylidenemalonate. The derived P-methylglutaric acid melts at 87", and its anhydride a t 47".Ethylic isobutylidenebis- mazonate boils at 198' under a pressure of 12 mm., and /3-isopropyl- glutarir: acid prepared from it melts at 96-5-97' (Schryver, Trans., 1893, 1345, gives 99-looo), and affords a silver salt, C',H1204Ag2, which is sparingly soluble in water.Ethylic P-isopro~ylglutarcLte is a thick oil having a pleasant odour, and boils a t 250' under atmospheric pressure. Ethylic &soamyZidenebismcllonate, C19H3208, boils at 204' under a pressure of 15 mm. P-&obutylghtaric acid crystallises in long, white needles, and melts at 48'; it is very soluble in ether, alcohol, glacial acetic acid, and water, and somewhat readily in carbon bisulphide and light petroleum; its copper, zinc, and lead salts are insoluble in water, and the silver salt, C,Hl,04Ag2, is a white, curdy precipitate. Ethylic cenanthylidenebismalonate, C21H3608, boils at 195' under a pressure of 16 mm. ; the corresponding P-liexylgluturic acid was obtained in very small amount, and melted at 215-236O. Aromatic aldehydes and ethylic malonate condense in molecular proportion under the influence of amines.Ethylic benzylidene malonate is easily obtained by treating a mixture of benzaldehyde (1 mol.) and dry ethylic malonate (1 mol.), with a little piperidine or alcoholic ammonia. [With F. GIESE.]--Ethy&c cumylidenemalonate, C17H2204, i s a light yellow oil, and boils at 205-208' under 15 mm. pressure. [With H. HoFFMANN.]-E~~,Y~~c pcbranitrobenxylidenemaZorzate, CI4H,,O9N, forms colourless needles and melts at 94'; it dissolves readily in hot alcohol, light petroleum, and benzene, but only sparingly in ether. F(CO0Et):CH CO O>'GH49 is made by Ethylic coumarincarboxylate, the condensation of salicylic aldehyde with ethy lic malonate by meansORGANIC CHEMISTRY. 117 of piperidine or ammonia; it forms crystals, and melts at 94"; coumarincarboxylic acid melts at 185-1 87".[With A. G~oos.]--Ethylic ccnisylidinemalonate, Cl5HI8O5, boils at 200-211° under 14 mm. pressure, and melts at 38-40' ; It dissolves readily in ether, benzene, and alcohol. Ethylic rnethylsalicylidene- rnalonate, C,,H,,O,, boils at 193-195O under a pressure of 14 mm., and could not be soldified. [With F. GIESE.] -Ethylic piperonylidenemalonate boils a t 2 16-219' under a pressure of 11 mm., crystallises from alcohol in beautiful, colourless prisms, and melts at 63' ; it is readily soluble in cold benzene and aceticacid, and in warm ether and alcohol, and is sparingly soluble in light petroleum. Et hylic f urfurylidenemalonate, which may be produced in several different ways by the condensation of furfuraldehyde and ethylic malonate, is obtained in small amount by merely warming the com- ponents together on the water-bath, but the yield is greatly augmented by the addition of a little piperidine. Uric Acid and the Murexide Reaction.By DIOSCORIDE VITALI (L'Oposi, 1898,21, 73--80).--The fact that the presence of small quantities of iodides in urine cannot be directly demonstrated by the usual methods has been attributed to the oxidation of organic compounds, especially uric acid, by the iodine at the moment of its liberation, with simultaneous formation of hydriodic acid. The pro- duction of the latter is shown by the immediate liberation of iodine on adding iodic acid, and by means of this reagent traces of iodine in the form of iodides may readily be detected in urine.I f , moreover, a solution of iodine be gradually added to a solution of potassium urate mixed with a little starch paste, no blue coloration appears until a considerable amount of iodine has beon absorbed; the liquid a t the same time becomes acid from the production of hydriodic acid, and deposits a crystalline precipitate of ixric acid. A por- tion of the latter is simultaneously oxidised to carbamide and alloxan, as was proved by the isolation of urea oxalate and by the fact that the liquid gave the murexide reaction when evaporated to dryness and gently heated. This formation of murexide (ammonium purpurate) is probably due t o the action of the ammonia, produced by the decomposition of the carbamide, on the alloxantin formed by the reduction of the alloxan by hydriodic acid.Instead of iodine, chlorine, bromine, iodic acid, and nitric acid may be used. In the last case, the necessary reduction in the latter phase of the reaction is, perhaps, brought about by nitric oxide or nitrous acid, but the action of chlorine is not easily explained. The use of bromine or iodine instead of nitric acid in the murexide test for uric acid is recom- mended as giving more certain results, with less liability to failure from excessive heating. Hypoxanthine, xanthine, theobromine, and caffeine, when subjected to successive oxidation and reduction under the same conditions as uric acid, also yield murexide, and the absorp- tion of iodine by urine is partly due to the presence of the two first- named compounds. It is found, in fact, that the elimination of the uric acid and urates from urine does not wholly obviate the difficulties in the detection of traces of iodides therein, N.L. A. L.11s AI3STRACTS OF CKEMICAI, PAPERS. Nitrobiuret and Amidobiuret. By JOHANNES THIELE and EMIL UHLFELDER (AnnaZen, 1898, 303, 93--107).--Nitro6izlret, NO,* NH* CO *NH* CO *NET,, prepared by adding biuret in small portions to a mixture of concen- trated nitric and sulphuric acids, separates from water as a white, crystalline powder, which melts and decomposes a t 165'; it does not develop colour with alkali and copper sulphate, but gives the nitramine reaction with ferrous sulphate and sulphuric acid, and is resolved by boiling water into carbonic anhydride, nitrous oxide, and carbamide. Tbe potassium and silver derivatives are anhydrous.Dinitrobiuret, NH( CO *NH*NO,),, produced when the finely divided nitro-derivative is added t o fuming nitric acid cooled with a freezing mixture, crystallises from methylic alcohol in white needles, and explodes a t 124'; it gives the nitramine reaction, and is resolved into nitrous oxide, carbonic anhydride, and ammonia under the influence of boiling water. The potccssium derivative crystallises from water in colourless, rhombic plates, Benxylidenearnidobiuret, CHPh :N*NH* CO *NH* CO *NH,, obtained on reducing nitrobiuret, and treating the product with benzaldehyde, crystallises from alcohol in small, white needles, and melts a t 202". Amidobiuret hydrochloride is formed when the benzylidene derivative, moistened with alcohol, is heated with concentrated hydrochloric acid on the water-bath ; i t crystallises from alcohol in plates, and melts a t 185'.It dissolves readily in water, and is gradually resolved into ammonium chloride and hydrazodicar bonimide (urazole) when the aqueous solution is boiled ; i t reduces cold, ammoniacal silver nitrate and. hot Fehling's solution. The nitrate crystallises from boiling alcohol in beautiful needle^, and melts a t 165' ; i t is best prepared by the action of concentrated nitric acid on the acetone (P-propylidene) compound, CMe,:N*NH* CO-NH* CO-NH,, which crystallises in white needles and me1t.s a t 1 8 9 O . The picrate melts at 175'. CN*CMe,*NH.NH*CO*NH*CO*NH,, prepared by the action of hydrogen cyanide on the acetone compound of amidobiuret, crystallises in prismatic plates and melts a t 146'; oxidation with potassium permanganate converts i t into allophanyl- axoisobutyronitrile, (2" CMe,*N:N* CO *NH* CO *NH,, which crystal- lises from benzene in yellow, rhombic plates, and melts and decomposes at 127".A ZZopharLyZhydraxoio~utyronitriZe,~ N N AZZophanaxide, NH,* CO *NH* CO *N<r I , obtained by the action of nitrous acid on amidobiuret, melts and decomposes at 195'; i t is insoluble in water, but dissolves in aqueous ammonia and in alcohol, undergoing decomposition. Silver nitrate precipitates, from the alco- holic solution, a white, highly explosive substance, which dissolves in ammonia and nitric acid. When the azide is heated with boiling alcohol, diazoimide is eliminated, and ethylic allophanate produced.Z'etwret, NH(C0 *NH*CO *NH2)2,. prepared by the action of am- monia on allophanazide, crystallises in colourless, rhombic prisms, and AlZophC~il~ll is the name given by the authors t o the: radicle NH,*CO*NH*CO.ORGANIC CHEMISTRY. 119 melts at 186" ; copper sulphate and alkali develop a deep violet colora- tion, more intense, but less red than the biuret reaction. M. 0. I?. Nitrodicyanodiamidine and Amidodicyanodiamidine. By JOHANNES THIELE and EMIL UHLFELDER (Annalen, 1898, 303, 107-1 14).-Nitrodicyanodia~~aidine, N02*NH* CO *NH* C(NH,):NH, prepared by adding :dicyanodiamide to a mixture of concentrated nitric and sulphuric acids, forms a microcrystalline powder soluble with difficulty in water and in alcohol; i t is neutral in reaction, and when heated with water, becomes alkaline, with elimination of nitrous oxide and carbonic anhydride, guanidine carbonate crystallising from the liquid.The silver derivative decrepitates when heated. Amidodicyanodiamidine dihydrochloride forms white needles and melts at 181"; the picrate becomes brown at 1 9 8 O , and melts at 336". The benzylidene compound forms a hgdrochloride, which crystallises from alcohol in white prisms and melts a t 226". Acetoneamidodicyanodiamidine hydrochloride, CMe,:N*NH* CO *NH* C(NH,):NH,HCl, crystallises from alcohol in small, white leaflets and needles, and melts at 206". Guanidinecarboxylazide hydrochloride, N,. CO *NH* C(NH,):NH, HCI, prepared by adding cold, aqueous amidodicyanodiamidine hyd Po- chloride to chloroform saturated with dried nitrous anhydride, melts at 157", and explodes when heated on platinum foil.Boiling alcohol eliminates diazoimide, and yields the compound C,H,,N ,05, which crystallises in elongated, thin prisms and melts at 187". &I. 0. F. Chemistry of Acetylene. By GEORG SCHROETER (Annalen, 1898, 303, 114-132. Compare Abstr., 1898, i, 614).-Acetaldehydedi- sulphonic acid, COHO CH(S0,H)2, produced by the action of concen- trated sulphuric acid on acetylene, has not been obtained crystalline, but forms a syrup which dissolves in alcohol. The bayium salt con- tains 2H,O, and the basic barium salt, which is less readily soluble, crystallises from water in needles containing 4H,O ; the potassium sait contains 1H,O, and when treated with potassium hydrogen sulphite, yields the potassium hydrogen sulphite compound of potassium acetaldehydedisulphonate, already obtained by Rathke from chloral and potassium sulphite.The sodium salt dissolves in water more freely than the barium and potassium salts, and contains 1H,O ; the silver, copper, and lead salts are also readily soluble, and the basic lead salt contains 1H,O. Acetaldoximedisulphonic acid, NOH:CH* CH(SO,H),, forms a potassium salt which crystallises from water in lustrous needles con- taining 1 H,O. Acetaldehydephenylhydrazonedisulphonic acid, NHPh*N:CH- CH(SO,H),, forms a barium salt which crystallises from water in leaflets contain- ing 2H20. Acetalazinetetrasulphonic acid, N,[ :CH* CH(SO,H),],, forms a barium salt which contains 6H20 ; the hyclraxine salt contains 2H20, and decomposes a t 200O.The SuZplzates of acetaldehydedisulphonic acid, S,O,H* CH(OH)CH(SB,H),, and SO,[* O*CH(OH)*CH(a03€T).L]2,120 ABSTRACTS OF CHEMICAL PAPERS. are also produced when fuming sulphuric acid is saturated with acetylene. M. 0. F. 1 : 2-Acetylfurfuran ; and its Occurrence in Wood Tar. By LOUIS BOUVEAULT (Compt. Tend., 1897, 125, 1184--1186).-This com- pound is produced synthetically by heating together on the water- bath ethylic pyromucate and ethylic acetate in the presence of sodium. The product, after treatment with dilute hydrochloric acid, yields 1 : Z-ethylic pyrornucylacetate, C,OH,* CO*CH,* COOEt, which boils at 142-143' under a pressure of 10 mm. and has a n odour resembling that of ethylic acetoacetate.7H:CH CH:CAc 2-A cet ylfitifuran, >O, produced by the hydrolysis of the preceding compound with 25 per cent. sulphuric acid, boils a t 67" under a pressure of 10 mm., solidifies to a mass of crystals melting at 29*5", and has an odour recalling that of acetophenone. The oil boiling between 150-200°, obtained by the distillation of beech- and oak-wood after removal of the phenolic and basic sub- stances, is rectified under reduced pressure. The fraction boiling between 60" and 70" under a pressure of 10 mm. is treated with excess of hydroxylamine ; the product distilled under the same pressure yields a mixture of oxirnes boiling at 105-115". The distillate yields a crop of crystals melting a t 127-128', and consisting of the oxime of methylcyclopentenone, C,H,O, a compound already obtained from wood tar.By warming the oxime with acetic anhydride, a n acetyt derivative, C,H,N* OAc, is produced, which boils a t 123" under a pressure of 10 mm., and crystallises in needles melting a t 73'. The greater portion of the rectified oximes remains liquid, and on treatment with acetic anhydride yields the acetyl derivative of 1 :2-acetylfurfuranoxirne which boils a t 135' under a pressure of 10 mm., and crystallises from ether in needles melting a t 96'. 1 : 2-Acet~lfwfurunoxirne is obtained by bydrolysing the acetyl corn- pound with alcoholic potash ; i t boils at 110-1 11' under a pressure of 10 mm., and crystallises from ether in well-defined prisms melting a t 104". When the oxime is hydrolysed with 25 per cent.sulphuric acid, 1 : 2-acetylfurfuran is regenerated. G. T. M. Decomposition of Pyrornucates of the Alkaline Earths. By PAUL FREUNDLER (Bull. #OC. Chirn., 1897, [iii], 17, 609-612).-The author has prepared furfuran by Limpricht's method (Annulen, 1873, 165, 281), namely, by heating barium pyromucate with soda-lime. It is not advisable to use more than 100 grams of the barium salt at once, and the yield is extremely poor, only some 4-6 grams of furfuran being obtained from 100 of the barium salt. A considerable amount of gas is evolved during the reaction, and this consists of equal volumes of an unsaturated hydrocarbon, C,H, (this vol., i, 98), and of carbonic oxide, or hydrogen when an excess of soda-lime is employed. No better yield could be obtained by employing the calcium in place of the barium salt.Experiments have also been made by heating the barium salt with barium oxide under reduced pressure, and also byORGANIC! CHEMISTRY. 121 heating the barium salt alone, both under atmospheric and reduced pressures; the products obtained in all cases mere furfuran (10-12 per cent., hydrocarbon, C,H, (5-6 per cent.), carbonic oxide (3-4 per cent.), hydrogen and the ketone, (C,H,O),CO (1-2 per cent.). J. J. S. A New Series of Cyclic Ketones. By AUGUSTE BEHAL (Compt. rend., 1897, 125, 1036--1038).--The heavy oil obtained by the distillation of wood t a r consists of a mixture of acidic, basic, and neutral substances; the new ketones are separated from the neutral portions by extraction with concentrated hydrochloric acid, in which they are soluble. The acidic extract, diluted, and subjected t o distillation with steam, yields a distillate containing the ketones in the form of a supernatant, yellow oil having an odour of menthol, and boiling between 180' and 205'.The ketones differ in their solubility in hydrochloric acid, and a partial separation may be effected by the use of various strengths of acid. The greater portion of the mixture is dissolved by a solution of dilute acid (1 : 2), and this portion, when rectified, distils a t 190-192'. The ketones in the distillate are converted into oximes, and these into their benzoyl derivatives. The latter can be separated into two distinct substances, the one less soluble in benzene, alcohol, and ether, and melting at 167O, the other far more soluble in these solvents and melting at 128-129'.The oximes are regenerated by the alkaline hydrolysis of the two benzoyl derivatives, that derived from the less soluble benzoyl derivative (m. p. 1G7°):melting a t 121*5', and that from the more soluble compound (m. p. 129') a t 102.5'. The parent ketones are obtained by distilling the oximes with 20 per cent. hydrochloric acid. The oxime of higher melting point yields a ketone which boils at 192' under a pressure of 760 mm., and is soluble in water and the ordinary organic solvents. This ketone can be obtained in crystals and melts a t 12'; its sp. gr. =Om9866 at Oo. Another ketone, which also boils a t 192O, is furnished by the oxime of lower melting point ; i t does not solidify when cooled to - 27'; it is soluble in water and the ordinary organic solvents, and its sp.gr. =0*9539 a t 0'. The quantity of these ketones in the heavy oilof wood tar amounts to 16 per cent., and they belong chiefly to the tetrahydrobenzene series. G. T. M. Action of Potassium Hydrosulphide on Orthocyanobenzylic Chloride. By SIEGMUND GABRIEL and ERNST LEUPOLD (Bey., 1898, 31, 2646-2654. Compare Abstr., 1890, 1249)-When orthocyano- benzylic chloride is treated with potassium hydrosulphide, a compound, C,H,NS, is produced, which may be regarded either as orthocyano- benzylic mercaptan, CN- CGH,* CH,. SH, or as thiophthalimidine, N-rI --UH, C6H4<C(NHPS. The continued action of potassium hydrosulphide . I CH produces dithiophthcclide, C6H4(CS$S, which crystallises in reddish, flat plates melting a t 68'; this substance again is converted by excess of the snlphide into a sparingly soluble compound, C,,H1,S,, which122 ABSTRACTS OF CHEMICAL PAPERS, crystallises in needles with a green reflex, and probably s ti t u t ion CH,<CF>C: C<-">CS.acid, this compound is converted into dithiodiphthalyl, On oxidat ion 6 4 C6H4 has the con- with nitric which crystallises in loni, greenish-ydlow needles, and melts at 332-333O (uncorr.). Fuming nitric acid converts dithiodiphthalyl into diphthalylic acid, C,,H,,O,,. and i t s constitution is thus established. When this is boiled with alkalis, i t yields a salt of the corresponding hydroxy-acid, which is decomposed by acids, with formation of the dilactone. When a solution of dithiodiphthalyl in alcoholic sodium methoxide is treated with methylic iodide, the tetramethylic derivative SMe* CO*C,H,* C(OMe):C(OMe)*C,H,* CO*SMe, of this acid is pro- duced, which crystallises in yellow, six-sided tablets melting at 160-161° ; on reduction, this methylic derivative is converted into two isomeric compounds, Cl6H1,O4, one of which is an acid, and the ot'her an indifferent substance.The former crystallises in oblique prisms and melts a t 228-229', whilst the latter forms snow-white needles melting at 255-257'; the constitution of these two com- pounds is shown by the fact that they are both formed when deoxy- benzoinorthodicarboxylic acid, COOH. C6H4* CH,. CO-C,H,* COOB, is heated, and are reconverted into this acid when they are heated with alkalis.The indifferent substance is, therefore, an inner anhy- dride of deoxybenzoindicarboxylic acid, whilst the acid is a lactonic acid, the exact constitution being still uncertain in both cases. A. H. Electrolytic Reduction of the Nitro-group. BY WALTHER LOB (Zeit. Elektvochem., 1898, 4, 428. Compare Abstr., 1897, i, 331 ; and 1898, i, 14).-The author's object was to isolate intermediate reduction products by adding a substance which will combine with them, and so withdraw them from further reduction. When a mixture of 10 grams of nitrobenzene, 35 grams of fuming hydrochloric acid, 25 C.C. of water, arid 70 C.C. of alcohol is placed in a porous cell containing a lead cathode, and this is immersed in dilute sulphuric acid (1 : 10) contain- ing a platinum anode, aniline is practically the only product obtained with E.M.F.'s from 2.5 to 6 volts, and temperature from 20'to 80'.When the 25 C.C. of water is replaced by 25 C.C. of 40 per cent. form- aldehyde solution, and the electrolysis conducted with 5 volts and 2 amperes, a t 45-60", a polymeride of pa,ranhydrohydroxylamino- benzylic alcohol, (OH* CH,* C6H,-NH* OH - H,O),, is obtained. This compound is also formed by the interaction of phenylhydroxylamine and formaldehyde i n presence of hydrochloric acid. It is a red, amorphous powder, which yields paraleucaniline with aniline and aniline hydrochloride, whilst with nitrous acid a diazo-derivative is formed which yields parahydroxybenzaldehyde on boiling. Its hydro- chloride dissolves in warm, concentrated hydrochloric acid, and the free base is obtained by pouring this solution into dilute ammonia.The base decomposes a t high temperatures without melting, may be boiled with caustic soda without decomposition, is iasolnble in mastORGAN 1C CHEMISTRY. 123 solvents, slightly soluble in chloroform, and more so in aniline and concentrated sulphuric acid. When the electrolysis is carried out with 2.8-3 volts at 30°, methylenediparanhydroamidobenzylic alcohol, HN* C,H,* CH, CH2<HN* C,H,* CH,>09 is the only product. This substance has not previously been described, and may be obtained by the direct interaction of aniline and formalde- hyde. The hydrochloride and platinochloride were analysed. The base is a pale yellow, amorphous powder, soluble in dilute acids, chloroform, and aniline, less soluble in alcohol and glacial acetic acid, insoluble in water, ether, alkalis, and light petroleum.Its solutions in acids are yellow or red. When nitrobenzene (10 grams), 40 per cent. formaldehyde (10 grams), alcohol (10 grams), and fuming hydrochloric acid (35 grams) are gradually treated with zinc dust (20 grams) a t 50°, paranhydro- hydroxylaminobenzylic alcohol is formed almost quantitatively. I n order to prevent the reaction of the formaldehyde with the hydrogen atom in the para-position to the nitro-group, experiments were tried with paranitrotoluene. Paranitrotoluene [(lo grams), alcohol (100 c.c.), water (4 c.c.), and sodium hydroxide (5 grams) were electrolysed as above described with 1.3 amperes and 5-6 volts, A quantitative yield of paraxotoluene was obtained.Paranitrotoluene (10 grams), suspended in fuming hydrochloric acid (100 c.c.), and electrolysed with 5 volts and 1-7 ampi?res, gave a, quantitative yield of paratoluidine. Paranitrotoluene (10 grams), alcohol (80 c.c.), water (35 c.c.), and fuming hydrochloric acid (35 gra,ms) electrolysed with 1.5 amperes and 4 volts, also gave an almost quantitative yield of paratoluidine. I n the last case, when the water was replaced by 40 per cent. form- aldehyde, two substances were obtained in nearly equal quantities, namely, paradime t hyl t oluidine and paradimet hylenedi t oluidine, C,H,Me*N<CH2>N* C,H,Me. The latter is formed almost quantitatively by the action of formalde- hyde on paratoluidine in acid solution? and crystallises from dilute alcohol in slender needles melting a t from 119-125'; it cannot be reduced, either chemically or electrolytically, to paradi- methyltoluidine, except in presence of formaldehyde, when the reduc- tion proceeds perfectly smoothly, yielding paradimethyltoluidine and paratoluidine.T. E. CH2 Reduction of 2-Nitro-3 : 5-dimethylphenylnitrornethane [ ~-2-Dinitromesitylene]. By EUGEN BAMBERGER and MAX WEILER (J. pr. Chena., 1898, [ii), 58, 333-361).-When ~-2-dinitromesitylene, NO2* C6H2Me2* CH2-N02 (Konowaloff, Abstr., 1896, i, 674), is dissolved in 95 per cent. alcohol, and reduced with 4 per cent. sodium amalgam at - loo, 2-amido-3 :5-dirnet?~ylbenxaZloxinze, NH,* C,H2Me,* CH:NOH, is formed ; this melts a t 170-171°, dissolves in dilute mineral acids and caustic alkalis, forms a clibenxoyl derivative melting a t I42--142*5O9124 ABSTRAC'TS O F CHEMICAL PAPERS.and a yellow compound melting a t 179-180°, when mixed with meta- nitrobenzaldehyde in dilute hydrochloric acid solution. When boiled with dilute sulphuric acid, i t yields 1-amido-3 : 5-dimethylbenxuldehyde, NH,* C,H,Me,* CHO, identical with a product obtained from mesitylene in the manner described below ; this is yellow, and melts at 48-49'; with phenylhydrazine, it yields a substance melting at 142-143", and possibly not a normal hydrazone, as it is not soluble in acids. When the oxime is boiled for a short time with acetic anhydride, i t forms 2-C~cetcLmidomesitylenolnitrile, NHAc* C,.H,Me,* CN, together with a sub- stance that melts at about 150"; the nitrile melts at 196*5-191.5", and is insoluble in dilute acids and alkalis, but when warmed with these it is converted into a substance that melts at 271.5-272.5"; the latter has the properties of a quinazolone (Weddig&, Abstr., 1885, 661 ; 1887, 1044), and must, therefore, be trimethylpuinazolone, C,H,MO,<~& Me ; its orange-yellow platinochloride is still un- melted at 345O.When the oxime is dissolved in a mixture of acetic acid and anhydride, and the mixture is saturated with gaseous hydrogen chloride at 0" and allowed t o remain (Beckmann's mixture), the product, which melts at 166*5--168O, has the properties of an acetylisindazole (Auwers, Abstr., 1892, 186 ; 1896, i, 504), and con- CO *NH CH sequently must be acetyldimethylisindccxole, CGH2Me2<NAc>N ; it is soluble in cold, dilute hydrochloric acid, but not in cold, aqueous caustic potash; when boiled with the latter, it dissolves gradually, and f r m the solution acetic acid precipitates a substance melting at 19 1 *5-192*5", which possibly may be 2-acetamido-3 : 5-dimethyl- benzaldoxime.When the amidodimethylbenzaldoxime is diazotised in hydrochloric acid solution with sodium nitrite, the product is . dimethylindiaxone oxinae, C~H,Me,<C(NoHN)>N --- ; this is yellow, melts and decomposes at 181*5-182.5", and dissolves in cold, dilute mineral acids and alkalis, but is decomposed by these on boiling, the products being, when acid is used, hydroxylamine ; amidodimethylbenzaldehyde (see above) ; dimethybulicylccl~ehyd~, which solidifies at about 1 5 O , and forms an oxime, OH* C,H,Me,*C'H:NOH, melting at 138-5-139.5O ; and a substance which forms an oxime melting at 99--100*5O and is devoid of acid character.If w-2-dinitromesitylene is dissolved in commercial absolute alcohol and reduced with 4 per cent. sodium amalgam at - 5' to O", the pro- ducts then obtained are a resin ; mesitylenic acid ; amidodimethylbenz- aldoxime ; a base, ( C,HI,NO\,, possibly C,H,( OH),(CGH2Me,*NH,),, which melts at 260" ; another buse, or mixture of bases, which melts at 133-147*5", and has the composition C, 70.2-72.0; H, 8.26-8.51 ; N, 9.15 (these last two bases are insoluble in alkalis); and a small quantity of a n acid containing nitrogen. 2-Amido-3 : 5-dimethylbenzaldehyde was prepared from rnesitylene by oxidising it t o bimethylbenzaldehyde with chromyl chloride in carbon bisulphide solution ; or, better, by converting it into mesitylic bromide and oxidising this with chromate or lead nitrate, nitrating the aldehyde with a solution of potassium nitrate in strong sulphuricORGANIC CHEMISTRY.125 Bromopropionate . . . Bromophenyl- acetate ............ Bromobutyrate . . . . . . Bromisobutyrate . . Bromisovalerate . . . acid cooled by a freezing mixture, and reducing the 2-nitro-3 : 5-di- methylbenxddehyde, NO,. C,H,M:e,* CHO, which melts a t 102-1 03", with ferrous sulphate and ammonia. Hydrolysis of Ethanedicatechol 1 Dicatechol Acetylenic Ether]. By CHARLES MOUREU (Compt. Tend., 1898,127, 276 -278).- The compound C,H,O,, obtained by boiling dicatechol acetylenic ether with dilute sulphuric acid, is orthohydroxy~J~enoxyacetic m i d , OH* C,H,* O-CH,.COOH. It is acid to litmus, phenoIphthalein, methyl-orange, and the blue-C4B, gives an intense blue coloratiori with ferric chloride, and reduces ammoniacal silver nitrate in the cold, but gives no coloration with rosaniline hydrogen sulphite. Its phenyl- hydrazone crystallises in white, rectangular scales which melt and decompose at 193'. When heated, it forms a lactone which crystal- lises in large, elongated prisms melting a t 54-56', and when boiled with water is reconverted into the acid melting a t 130-131". The same acid is obtained by heating sodium monochloracetate with monosodium catechol and treating the product with hydrochloric acid. It is probable that when the dicatechol acetylenic ether is boiled with the dilute acid, the first product is a compound, C,H,: 0,: CH* CHO, which, by hydration, is converted into OH* C,H,* O*CH(O€I)* CHO, and the latter, being unstable, changes by intramolecular migration of an oxygen atom into the acid OH*C,H,*O*CH,*COOH.C. H. B. By PIERRE H. BAYRAC (Ann. Chim. Phys., 1897, [vii], 10, 18--79).-This paper gives full details of work which has already been published (see Abstr., 1895, i, 412, 416; 1896, i, 605, 606). Formation of Chains. XXVII. Benzylaniline. XXVIII. Diphenylamine. By CARL A. BHCHOFF (Be?., 1898,31,2672-2677, 2678-2683. Compare Abstr., 1898, i, 182).-Chain formation occurs less readily in the case of benzylaniline and of diplienylamine than with the secondary bases discussed in the preceding papers; this is indicated by the numbers in the following table, which give the approxi- mate extent in percentages of the theoretical maximum to which action takes place between the amines and ethylic salts there tabulated. C.F. B. Preparation of Paraquinones from Indophenols. G. T. &X. At A t At At 100". 110". 120". 100". Nil 29.2 50.9 1 1 40.3 ' 27.0 14.0 1 Xi1 Nil ~ Ethylic salt. Benzylaniline. Diphenylamine. At A t At 110". 120". 170-175". Nil 36.1 33'5 42'0 4'4 8.3 9'1 3'0 At 195-200". 55.8 The following new substances were prepared in the course of the Phenylbe.nxylgZycine, CH,Ph-NPh*C H,* COOH, prepared from investigation.126 ABSTRACTS OF CHEMICAL PAPERS. benzylaniline, chloracetic acid, and sodium acetate, crystallises from alcohol in needles, and melts a t 121-123" ; it decomposes on exposure to light and air, when an intense odour of benzaldehyde becomes perceptible.a-Bromopropionobenzylc~nilide, CH,Ph*NPh*CO*CHMeBr, formed by the action of a-bromopropionic bromide on benzylaniline, separates from alcohol in crystals belonging to the rhombic system and melts at 7 8'. a-Bromo but yro benx ytanilide, CH,Ph *NPh CO CH E t Br, is d e- posited by dilute alcohol in colourless crystals and melts at 50-54" ; a-b~-omisobutyrobenxylaniZide, CH,Ph*NPh*CO*CMe,Br, is an oil. a-BromisovaZerobenxyZaniZide, CH,Ph*NPh*CO*CHBr*CHMe,, crystal- lises from 96 per cent. alcohol in aggregates of colourless prisms and melts at 95-96'. a-BromopopionodiphenyZamide, NPh,*CO*CHMeRr, separates from hot alcohol in colourless, transparent crystals belonging to the monoclinic system and melts a t 109".a-BromobutyrodipT~enykcmide, NYh,* CIO*CHEtBr, is deposited by alcohol in large, lustrous crystals and melts a t 85" a-B!romiso6utyrodip~enyZa~~ide, NPh,*CO*CMe,Br, crystallises from alcohol in plates, and melts a t 82". a-B!romisovalerodiphenylcwnide, NPh,*CO*CHBr*CHMe,, crystallises in colourless, four-sided plates, and melts at 110.5". By AUGUSTIN BISTRZYCHI and FRITZ ULFFERS (Ber., 1898, 31, 2788-2790. Compare Abstr., 1894, i, 181, and Kay, ibid., 77).-Phenacetine, OEt*C,H,*NHAc, is boiled for several hours with a large excess of acetic anhydride in a reflux apparatus, moisture being excluded by means of a calcium chloride tube; the acetic acid formed and some of the anhydride is distilled over ; the residue is boiled again with more acetic anhydride, the product distilled under 15 mm.pressure in an oil bath at 180°, and the residue poured out. I n this way, diacetopJhenetidide, OEt*C,H,*NAc,, is obtained ; it melts a t 53-5-54", and boils a t 182' under a pressure of 12 mm. ; when kept in stoppered bottIes, it is decomposed very slowly by the moisture of the air, acetic acid being formed ; its physiological action is similar to that of phenacetine, and the same effect is sometimes obtained, although i t is commonly less lasting, with a smaller dose, than in the case of phenacetine. M. 0. F. Peracetylation of Phenacetine. C. F. B. Potassiodiphenylamine. By CARL HAUSSERMANN (J. p-. C'hem., 1898, [ii], 58, 367-368).-Diphenylamine (30 parts) is melted in a strong, round-bottomed flask in a boiling water-bath, potassium (1 part) is added little by little, and as soon as the violent action has ceased, the flask is exhausted of air and the heating is continued for 3-4 hours until the potassium has disappeared, after which un- changed diphenylamine is removed by digestion with absolute ether, The product, presumably NPh,K, is a yellow, sandy powder, which absorbs oxygen from the air, turning black, and unites with dry car- bonic anhydride to form potassium dipJienyZthiocurbamate, NPh, *COOK, a white powder which is decomposed by water into diphenylamine and potassium hydrogen carbonate. C.F. B.ORGANIC CHEMISTRY. 127 Nitroso-derivatives of Aromatic Amines. By CAMILLE MATIGNON and DELIGNY (Cornpt.Tend., 1897, 125, 11 03-1 lO5).-The authors have made a comparative study of the heats of combustion of the following nitroso-compounds of aromatic amines : diphenylnitros- amine, nitrosophenylaniline, and paranitrosodimethylaniline. They find t h a t the introduction of a nitroso-group into the aromatic nucleus lowers the heat of combustion by 15 calories, whereas its attachment t o the nitrogen of the side-chain lowers this by 9.8 calories. This difference explains the readiness with which the nitroso-group migrates from the nitrogen atom into the nucleus. Provided that the molecules originally contain a sufficient number of atoms, the introduction of a new radicle produces the same change in the heats of cornbustion if the entering group becomes similarly attached in each case.G. T. M. Behaviour of Substituted Amidonitriles towards Aromatic Aldehydes inpresence of Alkali. By WJLHELM YON MILLER and JOSEF PLOCHL (Bey., 1898, 31, 2699-2717).-Substituted amido- nitriles yield alkylideneamides with aromatic aldehydes, just as they give rise to amides under the influence of water. [With BR. BRUHN.]-The compound C,,H,,N,O, obtained by the action of benzaldehyde on benzylideneaniline under the influence of alcoholic potassium cyanide, is also produced gradually in absence of benzaldehyde ; it crystallises from atiiylic alcohol or nitrobenzene in microscopic needles and melts a t 249". The isonaeride, formed a t the same time, crystallises from alcohol in pale yellow prisms melting a t 208" ; i t is accompanied by a small quantity of a substance which crystallises i n pink leaflets and melts at 151".The compound C,,H,,N,O, is also produced ; i t melts and decomposes a t 194' and is distinctly acidic in character. The three compounds are formed when alcoholic potassium cyanide acts on the nitrile of phenylanilidoacetic acid and benzaldehyde, and they are all resolved into benzaldehyde, ammonia, and phenylanilidoacetic acid under the influence of boiling dilute hydrochloric acid. The less readily fusible isomeride is converted into that melting a t 208' by the action of boiling alcoholic potash, and of boiling glacial acetic acid ; the action in each case is reversible. [With LUDWIG GE~N~~oss.]-~rorn phenylanilidoacetonitrile and cuminaldehyde dissolved in alcoholic potash, two indifferent, isomeric compounds, CzaH2,N20, are obtained melting at 226" and 198" respectively ; they are also produced by the action of cuminaldehyde on benzylideneaniline, along with an acidic compound, C,,H,,N,O,, and the nitrile, C25H,,N,0, which melt at 208" and 256' respectively.The indifferent compounds are interconvertible, and, like the acid, yield cuminaldehyde, ammonia, and phenylanilidoacetic acid with boiling hydrochloric acid ; phenylhydrazine gives rise to cuminphenyl- hydrazone. Cumelnykanilicloacetonitrile, CI7Hl8N2, from cumylideneaniline and hydrogen cyanide, cry stallises from alcohol in lustrous, monoclinic prisms and melts a t 86". Cumenylanilidoc~cetamide, C,7H,oN,0, obtained by the action of concentrated sulphuric acid on the nitrile, forms colourless prisms melting at 1 5 9 O , and yields a nitroso-deriva-128 ABSTRACTS OF CHEMICAL PAPERS.tive which melts a t 132'. Curnenylanilidoacetic acid, Cl7Hl0NO2, crystallises in small aggregates of needles ; it melts and decomposes at 158'. [With P. SCH~r~z.]-~enxylideneparanisidine, C,,H,,NO, crystallises in leaflets and melts a t 72"; hydrogsn cyanide converts i t into the nitrile of phenylparanisidoacetic acid, which melts at 85', whilst the amide melts at 120'. Phenylparanisidoacetic acid, C,,H,,NO,, melts and decomposes at 184'. The two indifferent compounds, C,,H2,N,0,, obtained from the nitrile with benzaldehyde and alcoholic potash, melt at 222' and 193' respectively ; the acidic compound, C,,H,,N,O,, melts at 1 9S', with effervescence, and the corresponding nitrile, C,,H,lN,02, melts at 233'.[With R. LUPPE.]-Anhydroformaldehydeaniline with benzaldehyde and potassium cyanide, or anilidoacetonitrile with benzaldehyde and alcoholic potash, yields two indifferent compounds, C,,H,,N,O, melt- ing at 219' and 169' respectively, along with an acidic compound, C,,H,,N,O,, which melts and effervesces a t 239' ; when the com- pound melting a t 169' is recrystallised from alcohol, it is in part con- verted into the isomeride, the change being complete on exposing the substance to a temperature of 170" during some hours. Boiling 20 per cent. hydrochloric acid resolves tLe substance into benzaldehyde, ammonia, and anilidoacetic acid. [With WILHELM SIEBER.]-T~~ indifferent compounds, Ci,Hl,N20, obtained from anhydroformaldehydeparatoluidine with benzaldehyde and potassium cyanide, melt a t 245' and 168' respectively; the acidic compound, CI7Hl8N2O3, melts a t 228'. Paratoluidoacetic acid, C,H,Me*NH*CH,*COOH, obtained by hydrolysing with 20 per cent.hydrochloric acid the compound which melts at 245', crystallises from light petroleum in large, lustrous, monoclinic plates, and melts at 132" (compare Bischoff and Hausdorfer, Abstr., 1892, 1335) ; the nitrile melts and decomposes a t 61", and the amide, which melts a t 16S3, yields a nitroso-derivative melting at 158'. [With J. H~b~~u~~E~].-Ethylideneaniline, with benzaldehyde and potassium cyanide, yields a n indifferent compound, C,,H,,N,O, which melts a t 203', and an acidic compound, Ci7HlSN20,, melting at 220'. [With W.Ko~~~ao~s~~.]-Benzylidenemethylamine, with benz- aldehyde and potassium cyanide, yields a n indifferent compound, C,,H,,N,O, which melts at 152', and an acidic compound, Ci7Hl,N,0,, melting at 179'. Hydrolysis resolves these substances into benz- aldehyde, ammonia, and phenylsarcosine. M. 0. F. Stereochemistry of Quinoneoximes. By FRIEDRICH KEHRMAWN (Annalen, 1898, 303, 1-33. Compare Abstr., 1894, i, 460).-The two modifications in which both the benzoyl and methyl derivatives of metachloroquinoneoxime are produced have been regarded by the author (loc. cit.) as stereoisomerides ; further evidence in support of this view has been derived from a determination of the molecular weight of the two isomeric acetyl derivatives, and from an examina- tion of the behaviour of parachlorotoluquinone towards hydroxylamine hydrochloride.It being exceptional for the meta-halogen derivatives of toluquinone to yield isomeric oximes, the author concludes that itORGANIC CHEMISTRY. 129 is only in the case of a slight difference in the stability of the two forms that the phenomenon is noticeable; when the difference is great, one form only is produced. [With HUGO GRAB.]-T~~ stable modification of the acet$ deriva- tive of metachloroquinoneoxime crystallises from benzene in amber- coloured, four-sided prisms, and melts a t 166-167'; the labile compound dissolves more readily in benzene, from which it crystallises in yellow leaflets, and melts a t 136-137'. Both forms give normal figures for the molecular weight in glacial acetic acid, and yield 4 : 6 : 2-chlorodinitrophenol and 6 : 4-chloramidophenol on oxidation with nitric acid, and on reduction with stannous chloride and hydro- chloric acid respectively. The isomerism consequently meets with explanation on the hypothesis of Hantzech and Werner.When metachloroquinoneoxime is heated with alcoholic hydroxyl- amine hydrocliloride in a reflux apparatus, it yields metachloro- quinonedioxime ; the diacetyZ derivative of this substance occurs only in one modification, which crystallises from benzene in colourless prisms and melts a t 171--172". Oxidation and reduction of the dioxime lead to 1 : 3 : 6-chlorodinitrobenzene and 2 : 1 : 4-chlorodiamido- benzene respectively. ParadiciLZorozuinoneoxime, C,H,C1N02, separates from benzene in two crystalline forms, and melts indefinitely a t 155-160'; it is uncertain whether the dieerence in crystalline structure represents stereoisomerism.The acetyl derivative crystallises from benzene in amber-coloured prisms, and melts at 149". [With MICH. TICHYINSKY.]-T~~ oxirne of 4-chlorotoluquinone occurs in two modifications, which are separated by a method described in the original paper. The more sparingly soluble isomeride crystallises from alcohol in lustrous, brownish-yellow prisms, and decomposes a t 170" ; the ucetyl derivative melts at 158-159'. The more readily soluble modification crystallises from alcohol and from toluene i n aggregates of slender, pale yellow needles, and decomposes a t about 165" ; the acetyl derivative crystallises in long needles from the benzene mother liquor of the isomeride, and melts a t 141-142'.Chloramidocresol [Me : NH, : C1: OH = 1 : 2 : 4 : 51, obtained by re- ducing either modification of the oxime with stannous chloride and hydrochloric acid, forms colourless leaflets and melts at 204-205' ; the diacetyl derivative crystallises f r o p benzene in colourless needles and melts a t 162'. Chlorodinitrocresol [Me : (NO,), : C1 : OH = 1 : 2 : 6 : 4 : 51, produced by the action of dilute nitric acid on either modification of the oxime, crystallisus from alcohol in yellow leaflets and melts a t 108". [With CARL RUST.]-~-B'/'O~ZO~O~U~U.~~O~~ [Me : 0, : Br = 1 : 2 : 5 : 41, prepared by treating toluquinone with fuming hydrogen bromide and oxidation of the product with chromic acid, crystallises from alcohol in large, yellow plates and melts at 105".The oxime occurs in two modifications, the more sparingly soluble forming brownish-yellow needles which decompose at 186', whilst the more readily soluble crystallises from toluene in slender, pale yellow needles and decom- poses a t 178--180"; the acetyl derivatives melt a t 166-167" and 131-1 32" respectively. The corresponding benxylic ethers melt at VOL. LXXVI. i. 7,.130 ABSTRACTS OF CHEMICAL PAPERS, 95-96' and 80--81° respectively ; the latter crystallises in the asymmetric system, and has the axial ratio a : b : c =; 1.7562 : 1 : 1.1580. B~omnlzz,icZo~~~etccc~csoZ [Ne : NH, : Br : OH = 1 : 2 : 4 : 51, prepared by reducing either oxirrie, forins silvery leaflets, and decornposes at 205 -208' ; the dicccetp? derivative crystallises from toluene in colourless prisms and melts at 17 1-1 72'.Bro.nzoclinitrometcccresoZ [Me : (NO,), : Br : OH = 1 : 2 : 6 : 4 : 51, ob- tained from both modifications of the oxime by the action of moderately concentrated nitric acid on the water-bath, crystallises from petroleum in sulphur-yellow octahedra and melts at 115-116' ; trinitrocresol, which melts a t 106-107', is produced along with it. M. 0. F. Ethers of Toluquinoneoxime and their Bearing on the Space- isomerism of Nitrogen. By JOHN L. BRIDGE and WILLIAM C. MORGAN (Amer. Chem. J., 1898, 20, 761-776).-Toluquinoneorth- oxime, which is readily prepared by the action of nitrous acid on metacresol, melts at 155", not at 145-150°, as stated by Beilstein; toluquinonemetoxime, prepared similarly from orthocresol, melts at 134'.The silver derivative, C7H,N0,Ag, of the metoxime, when freshly prepared, is a light reddish-brown powder, which slowly decomposes on exposure to the air, and when thoroughly dry ignites spontaneously on being heated above 60'; when shaken with methylic iodide dissolved in light petroleum, it is partially converted into the corresponding methyl derivative, C,H,NO, ; this can be better obtained, however, by adding the calculated quantity of methoxylamine hydrochloride to toluquinone dissolved in a large quantity of water. The product in either case, after being recrystallised several times from light petroleum, melts indefinitely between 55' and 70°, and appears t o consist of a mixture of two stereoisomerides; one more sparingly soluble in light petroleum, can be isolated by fractional crystallisation and melts at 73-74', but the second modification cannot be separated.The Corresponding ucetyl derivat,ive, C,H,NO,,. formed in small quantity on adding acetic chloride to the silver derivative suspended in ether or light petroleum, is resolved by fractional crystallisation from the latter into two stereoisomerides; one of these melts a t 112-113', and crystallises in thick prisms, whilst the other forms spherical aggregates of minute crystals and melts at 85-87'. The benxoyl derivative, C1,HliNO,, prepared by acting on the sodium salt of toluquinonemetoxime prepared from orthocresol, is identical with that obtained from the oxime prepared from toluquinone and hydroxylamine hydrochloride ; both products are mixtures of two stereoisomerides, one crystallising in bright yellow needles and melting at 193", the other separating in thick prisms, and melting probably at 142-144", although fractions were obtained melting at 129'.No trace of the orthoxima could be detected in the product obtained from toluquinone. On adding bromine t6 a chloroform solution of the benzoate of the metoxime, the dibromide, C14HllBr,N0,, is obtained ; it crystallises from glacial acetic acid in white prisms, melts and decomposes a t 165", and is converted by boiling alcohol into a mixture of two stereoisomeric be72xoccte,~, C,,H,,BrNO3, of bromotoluquinonemetoxime ; the crudeORGANIC CHEMISTRY. 132 product melts and decomposes at 155-1 70", hut after fractional crystallisation from alcohol melts and deconiposes a t 174".The silve?. derivative, C,H,NO,Ag, of toluquinoneorthouiiue closely resembles the corresponding meta-derivative, but is much more stable than the latter. The ntethyl derivative, C,H,N02, obtained from it crystallises from light petroleum in long needles, melts at 6 9 O , and appears to exist only in one form; when the calculated quantity of bromine is added to its solution in chloroform, the clibyomide, C,H,Br2N0,, is obtained which crystnllises from light petroleum in white prisms and melts at 112'. The same acetyl derivative as was prepared by Wurster and Riedel (Abstr., 1880, 109) from acetic anhydride and toluquinoneorthoxime is formed in small quantity by acting on the silver derivative of the latter with acetic chloride.The corresponding benxoyl derivative, C14H11N0,, crystallises from alcohol in flat, brownish-yellow prisms, and melts and partially decomposes at 177" ; the dibromide, C,,Hl1Br2NO3, crystallises from glacial acetic acid in stunted orthorhombic prisms, and melts and decomposes a t 159'. I n discussing his results, the author emphasises the fact that, whereas the preparation of derivatives of toluquinonemetoxime gives rise to two stereoisomerides, the corresponding derivatives of the orthoxime exist only in one form; it is suggested, as tt possible explanation, either that, in the latter case, the proximity of the side- chains prevents the formation of a space-isorneride, or that isomeric substances exist which cannot be distinguished by the ordinary methods.Since no trace of the orthoxime is formed on treating toluquinone with hydroxylamine hydrochloride, Kehrmann's rule (Abstr., 1889, 243) concerning the influence of side-chains in quinones on the position taken by the entering isonitroso-group is confirmed ; the latter's views of the space-isomerism of the quinoneoximes also explain the existence of stereoisomeric modifications in the cases dealt with above. W. A. D. Beckmann's Transformation. By KARL AUWERS and H. CZERNY (Bey., 1898, 31, 2692-2698).-The production of indazole derivatives by the action of glacial acetic acid with acetic anhydride and hydro- gen chloride on the oximes of aromatic orthamidoketones (compare Auwers, Abstr., 1896, i, 503), suggested the possibility of obtaining analogous indoxazenes, C6H4e:>N, from the oximes of aromatic orthohydroxyketones.Contrary t o expectation, however, the oxime of unsymmetrical orthohydroxymetamethylbenzophenone, OH* C,H,Me*CPh:NOH, undergoes the Beckmann transformation, yielding benzenyl-3-amido- paracresol, C,H,Me<z>CPh, and the anilide of 4-hydroxymeta- toluic acid. I n addition to Beckmann's mixture, zinc chloride, phos- phorus pentachloride, phosphoric anhydride, and anhydrous copper sulphate induce this change, which also occurs when the substance is distilled under ordinary and reduced pressures ; the action of copper sulphate gains in interest from the fact that i t has, hitherto, been k 2132 AESTRACTS OF CHEMICAL PAPERS employed when transformation of an oxime is to be avoided.The result of heating the oxime of orthohydroxymetamethylbenzophenone gives support to Beckmann's opinion that the transformation of oximes into amides is an instance of catalytic action (Abstr., 1894, i, 240). The oxime of unsymmetrical orthohydroxymetamethylbenzophenone, OH* C,H,Me*CPh:NOH, crystallises from glacial acetic acid in small, white needles, and melts at 126-128.5". action of Beckmann's mixture, melts a t 104" ; concentrated hydro- chloric acid at 150-160° converts it into benzoic acid and 3-amido- paracresol. The dibenxoyl derivative of S-amidoparacresol, NHBz*C6H,Me*OBz, crystallises from alcohol in white leaflets and melts a t 190-191O; hydrochloric acid precipitates from the solution in caustic soda the benxoyl derivative, NHBz- C,H,Me*OH, which crystallises in nacreous leaflets and melts at 191".When either of these compounds is boiled during a few minutes, i t yields benzenyl-3-amidoparacresol. The anilide of 4-hydroxymetatoluic acid, obtained by the action of zinc chloride on the oxirne of orthohydroxymetamethylbenzophenone, melts at 158-159", and not at 5S0, as stated by Bargioni ; the hychogen phosphate melts a t 18'7-189'. M. 0. F. Action of Alkylic Salts of ,&Ketonic Acids on Paraphene- tidine. By ERNESTO FOGLINO (Chem. Centr., 1898, i, 501 ; from Ann. Chim. $'arm., 26, 535-541).-By the action of paraphenetidine on ethylic benzoylacetate a t 120-130°, alcohol and benzoylacetophene- tidine, OEt*C9H,*NH* CO*CH2Bz, are formed ; the latter crystallises from alcohol in white needles, melts a t 139-140°, and is insoluble in cold water.With the ethylic salts of acetoacetic, methylacetoacetic, diethylacetoacetic, benzoylacetoacetic, and acetylsuccinic acids, para- phenetidine at 140---150" yields alcohol, a ketone, and Wenghofer's paradiphenetoilcarbamide, CO(NH* UGH,* OEt),. The last compound is also formed by the action of benzoylacetoacetamide on paraphene- tidine. E. W. W. Action of Piperidine on Carbonates Derived from Phenols : Formation of Aromatic Urethanes. By PAUL CAZENEUVE and MOREAU (Compt. rend., 1897, 125, 1107-1109). -When piperidine acts on carbonates derived from phenols, urethanes alone are produced, there is no formation of carbamide derivatives. Piperidine and phenylic carbonate, when simply mixed together, form a urethane, C,H,,N*COOPh, which melts at 80°, and dissolves in the ordinary organic solvents ; it is hydrolysed by caustic potash into phenol and piperidine.The urethane, C,H,N* COO*C,H,* OMe, from guaiacol carbonate and piperidine, crystallises from alcohol in white prisms, melts at 44O, and boils at about 330'. The corresponding P-napl&ylic uq*ethane, produced by mixing together /3-naphthylic carbonate and piperidine, crystallises in needles and meltsORGANIC CHEMISTRY. 133 at 107". The a-naphthylic compound has not yet been obtained crys- t alli n e. When treated with concentrated sulphuric acid, these urethanes yield piperidine sulphate and a sulphonic acid of the corresponding phenolic compound. G. T. M. By PAUL CAZENEUVE and MOREAU (Conzpt. ?*end., 1898, 126, 481-483.Compare preceding abstract).-Conicine and phenylic carbonate, when heated together for 1 hour, form the urethane, C,H,,N*COOPh, a viscous liquid boiling a t 325" ; its rotation in alcoholic solution is [ a3j + 3-66'. The urethane, C,H,,N* COO*C,H,* OMe, is obtained in similar manner from guaiacol carbonate; i t forms a viscous liquid boiling a t 277". The a- and P-naphtlLyl urethanes, C,H,,N* COO*C,,H7, are very viscous liquids boiling above 300". All these substances are hydrolysed by caustic potash at 150°, and are decomposed by concentrated sulphuric acid with evolution of car- bonk anhydride. G. T. M. Aromatic Urethanes of Conicine. Pseudophthalimidine and Orthocyanobenzylamine. By SIEG- MUND GABRIEL and WILLY LANDSBERGER (Bey., 1898, 31, 2732-2740).-Kiel (Inuug. Diss. Bonn., 1896) has shown that pseudophthalimidine probably has the constitution, NH:C<-'A>CH,, which was formerly assigned by Graebe to phthalimidine. The authors have examined the molecular weights of these compounds in order to ascertain whether they both correspond with this formula. Pseudo- phthalimidine itself is not adapted for this purpose, since it cannot be purified by distillation, and the corresponding nitro-derivative was, therefore, substituted for it. Orthocyanobenzylic chloride is converted by nitration into 5-nitro-2-cyanobenxylic chloride, CH,Cl* C,H,(NO,)*CN, which forms yellowish crystals and melts at 94". When heated with hydro- chloric and acetic acids a t 140-150", i t is cwverted into 5-nitro- phthalide, a reaction which indicates the constitution of the corn- pound.The nitro-compound can readily be converted by hydrolysis with sulphuric acid into o-chZoro-5-nitro-ort?~otoZuamide, CH,Cl* C,H,(NO,)* CO*NH,, which crystallises in matted, snow-white needles melting at 228O when rapidly heated. When heated for some time a t l l O o , it is con- C H verted into 5-nitropsezcdopl~thcLlimidine. NO,* C,H,<-CH2->0, which C(NH) crystallises in needles melting a t 158". The hydrocldoride decomposes in aqueous solution, forming ammonium chloride and nitrophthalide. The picrate melts at 158", whilst the platinochloride crystallises in narrow, orange-yellow prisms and decomposes at about 120°, and the auyichloride crystallises well, This compound and phthalimidine itself have the normal molecular weight, determined by the boiling point method.Hence it appears that phthalimidine has the constitution C,H,<-"->NH, whikt CH2134 ABSTRACTS OF CHEMIICAI, PAPERS. pseudophthalimidine receives the formula assigned to it by Kiel. When orthocyanobenzylphthalimide is heated with hydrochloric acid at 190--200°, a small amount of phthalimidine is formed. I n former experiments, this was isolated as nitrosophthalimidine, the formation of which was, however, ascribed to the action of the nitrous acid on the orthocyanobenzylamine which is also present in the product. Renewed experiments have, however, shown that orthocyanobenzyl- amine is not attacked by nitrous acid, but that it is converted into phthalimidine by the continued action of acids, This formation of phthalimidine affords further evidence in favour of the formula ascribed to it above.Orthocyanobenzylarnine is best obtained by heating orthocyanobenzylphthalimide with alcoholic potash. The hydrocldoride decomposes at about 2 0 7 O , whilst the picrate melts and decomposes a t about 219". Alcoholic potash cannot be employed for the preparation of other amines from their phthalimide compounds ; benzylphthalimide, for example, when treated in this way, does not yield the amine, but is converted into benx~lphthalccminic acid, C,H,*NH* CO*C,H,* COOH, which crystallises in needles and melts and decomposes a t 154", benzylphthalimide being again produced. A. H. Diazomethane and Nitroso-acidamides. By HANS VON PECFI- MANN (Ber., 1898, 31, 2640-2646).-When nitrosomethylurethane is decomposed by alcoholic potash, only half the theoretical yield OF diazomethane is obtained, and this is due t o the fact that the re- mainder of the urethane is decomposed by the potash in the following mays.I, Formation of nitrous acid and urethane, NO *NMe*COOEt + H,O = HNO, + NHMe* COOEt ; 2, formation of carbonic acid, nitrous acid, and methylamine, NO *NMe* COOEt + 2H,O = OH* COOEt + HNO, + NH,Me. Nitrosoethylurethane, nitrosobenzylurethane, and nitrosobenzoylbenzylamine are decomposed in a similar manner., whilst it has been found that benzylamine acts as an alkali in the same way as the potash. Nitrosoethylurethane, prepared in the same way as the methyl derivative, is an oilfwhich boils at 90' under a pressure of 42 mm. and has a sp.gr.=1*0735 a t 15'/15'. When treated with alcoholic potash, 20 per cent, of the theoretical amount of diazoethne is produced; this is very similar to diazomethane, but its solution in ether is of a darker colour. When nitrosoethylure- thane is treated with benzylamine, nitrogen is evolved and benzyl- urethane produced, the diazoethane, which is, no doubt, the first product, being immediately decomposed. Benxylwethccne crystallises in colourless plates melting a t 44O, and is converted by nitrous acid into nitrosobenxylurethane, which is a reddish-yellow oil, and cannot be distilled; when this is treated with alcoholic potash, it yields stilbene and benzylic methylic ether. Nitrosobenxobenxylamide crys- tallises in pinkish prisms, melts a t 46-47O, and gradually decom- poses when kept, yielding nitrogen and benzylic benzoate.When heated with alcohol, i t decomposes in all the ways already described in t,he case of nitrosomethyluretliane : (1) into benzoic acid and phenyl- cliazomethane, which appears in the product partly as benzylic ethylic othcr, and partly as benzylic benzoate; (2) into nitrous acid andORGANIC CHEMISI'HY. 135 benzoylbenzylamine ; and (3) into benzoic acid, nitrous acid, and benzylamine. Attempts to bring about the direct elimination of nitrogen from diazomethane by heating it, and by the use of powdered copper, platinum black, &c., proved unsuccessful. A. H. New Representatives of Primary Disazo-dyes of the Benzene Series. By CARL BULOW and HANS WOLFS (Ber., 1898,31,2775-2783, Compare Abstr., 1898, i, 308).-The following additional colouring matters have been prepared; they have the general formula NMe,.C,H,(OH)(N,R) *N2R "Me, : OH : N,R : N2R' = 1 : 3 : 4 : 61, and the groups tabulated under 4 and 6 are the groups 11 and 12' respec- tively; the method of preparation is t h a t already indicated. 4. Ph l-CI0H7 1-C1,0H7 PI1 2-CloH7 2-C10H7 1-C10H7 2-CloHV 1-C10H'7 2-C,0H7 1-C10H7 2-C10H7 2-C,H4Me 2-C,H4Me 4 - C,H4Me 4-C6H,Me 2 : 4-C6H,Me, 2 : 4-C6H3Me, 6. CoIour. ' Melting point. 1 Dark red Violet-red Dark brown Claret -red Brown Brown Black Dark green Dark brown Dark green Green Dark brown Red Dark green Dark red Dark red Red Dark green 178" 176 180-181 176 196 154 185-1 86 132 182 187 182 153 180 141 175 154-155 , 147-148 171-172 C. F.B. Ketochlorides and Orthodiketones of Phenylazimido- benzene and Phenyl-$-aeimidobenzene. By THEODOR ZINCKE and E. PETERMANN (J. pr. Chein., 1898, [ii], 58, 234-244. Compare Abstr., 1898, i, 537).-The paper contains a preliminary account (without experimental details) of experiments with phenylazimido- benzene and phenyl-$-azimidobenzene, carried out on similar lines t o those already described with azimido benzene (Zoc. cit.). Like the latter substance, they can be converted into ketochlorides and ortho- diketones, possessing a strong analogy t o those derived from azimido- benzene. The analogy is not complete, however, for the presence of the phenyl group, and the difference in constitaution of the nitrogen ring, exert an influence on the results. For example, the phenyl group of the azimido-derivative does not react mit'h chlorine, whereas substitu- tion tnkcs placc in the phenyl group of the $-derivative.A. w. c'.136 ABSTRACTS OF CHEMICAL PAPERS. Hydrazides of Meta- and Para-bromobenzoic Acid. By THEODOR CURTIUS and EDUARD PORTNER (J. pr. CJLem., 1898, [ii], 58, 190-205. Compare preceding a bstract).-Metabromobenxhydraxide, C,H,Br-CO *NH*NH,, prepared from hydrazine hydrate and ethylic metabromobenzoate according to directions already given (J. pr. Chem., [ii], 50, 295), forms long, glistening, silken needles, melts at 151", is soluble in alcohol, but almost insoluble in ether, chloroform, and benzene, and reduces Fehling's solution and ammoniacal silver nitrate in the cold. The hydrochloride forms small leaflets melting and giving off gas a t 248' ; the sodium salt, small plates ; and the cccetyl deriva- tive colourless, silken prisms melting a t 169".Benxylidenernetabromobenzhydraxine, CHPh :N*NH* CO *C6H4Br, pre- pared by the action of benzaldehyde on the hydrazide, crystallises from alcohol in beautiful, long, colourless needles melting at 105" ; boiling dilute mineral acids decompose it into its components. The cor- responding ortJhohydroxybenxylidene compound forms tufts of colour- less needles melting at 192", and the acetone [P-propylidene] deriva- tive, small needles melting at 88.5". Dimetabromobenxhydrazidu, (NH*CO*C,H,Br),, obtained by the action of iodine on the bromo- benzhydrazide, crystallises from glacial acetic acid in small, glistening needles melting at 265'.When boiled with dilute mineral acids, it is converted into bromobenzoic acid and a hydrazine salt. Metabrornobenxaxide, CGH4Br*C0 *N3, obtained by the action of nitrous acid on bromobenzhydrazide, is a colourless oil with a n un- bearable odour producing tears, and explodes violently when heated in a test tube. Metadibrornodiphentjlcarbarnide, CO(NH* C6H,Br),, prepared from the azide by boiling with water, forms long, colourless, silken prisms melting at 262". It is volatile without decomposition, sublimes in small needles, and, when boiled with acids, is decomposed into meta- bromaniline and carbonic anhydride. E'thylic rnetabromophenylcarbamate, CGH,Br *NH* COOEt, obtained by the action of absolute alcohol on metabromobenzazide, is a thick, colourless oil boiling a t 193-194" under a pressure of 17 mm., and is decomposed into its components by concentrated acids.The cor- responding methylic salt is a colourless oil boiling at 165-16'7' under a pressure of 75 mm. The following corresponding para-compounds are also described. Bromobenxhydraxide, long, colourless prisms melting at 164" ; i t s hydrochloride, small, glistening needles melting at 262" ; acetone- [P-propylidene]bromobe~x~h~dr~~~ide, long needles melting at 194.5" ; benxylidenebi.omobenxJhydraxide, colourless, silken prisms melting at 235" ; brornobenzazide, colourless plates melting a t 46" ; ethylic bromo- phenylcarbamate, long, white needles melting at 81" ; the corresponding metJLylic salt melts at 81" ; dibrornodipJienyZcarbamide, clusters of nacreous needles melting at 2'74' ; and bromophenylbi*omobenxoylsemi- carbaxide, C,H,Br *NH* CO *N,H,- CGH4Br, microscopic plates melting at 248". When parabromobenzazide is dissolved in carbon tetrachloride, and bromine added, a colourless, crystalline substance, probably dibromo- carbanil, is obtained. A.W. C.ORGANIC CHEMISTRY. 137 P henylsernicarbaxide. By THEODOR CURTIUS and ADOLF BURKHARDT (J. pr. Chem., 1898, [ii], 58, 205-233. Compare Abstr., 1896, i , 647).--In continuance of the researches of Curtius and Hof- mnnn (Zoc. cit.), i t is now shown that phenylcarbamazide does not undergo rearrangement, as do ordinary acid azides of the type RCON,. When heated with water in sealed tubes, i t is completely converted into carbonic anhydride, diphenylcarbamide and hydrazoic acid ; alcohol decomposes it into hydrazoic acid and phenylurethane ; aniline produces the cnrbanilide, and bromine gives pccrabrorno~lzeIayZcnrbam- axide, C6H,Br*NH.CO*N3, separating from alcohol in rhombic crystals melting at l26', which are acted on by water, with produc- tion of paradibromocarbanilide. The solid, microcrystalline product formed on adding sodium nitrite to a n aqueous solution of oxalhydrazide hydrochloride is not a product of the rearrangement of the oxazide, but the dihydrazide of oxalic acid, produced by the oxidation of the hydrazide.Phenylsemicarbazide may be obtained by the action of hydrazine hydrate on ( a ) the phenylurethanes, NHPh*COOR + N2H,0H = NHPh*CO*NH*NH, + ROH + H,O ; (6) on mono- or di-phenylcarb- amide,CO(NHPh), + N,H,*OH = NHPh*CO*NH*NH, + NH,Ph + H20; ( c ) on phenylcarbirnide.The best yields are obtained from diphenylcarbnmide, all the other reactions being more or less compli- cated, and the isolation of the base difficult. Phen ylsemicarbazide hydrochloride forms colourless, transparent prisms melting a t 215'; the sodium compound crystallises in yellowish needles, and the acetyl derivative in colourless needles melting a t 169'. EthyZic phenylsenzicarbaxideacetoacetute, NHPh- COON H*N:CMe* CH,* COOEt, formed by the interaction of ethylic acetoacetate and the semicarb- azide, crystallises from alcohol in small, colourless needles melting at 151". HydrcLxidicarbonanilide, N HP h* GO NH NHGO *NHPh, obtained by the action of iodine or of heat alone on phenylsernicarbazide, crystallises from glacial acetic acid in long, colourless prisms melting at 245O, without decomposition, is with difficulty soluble in the ordinary organic solvents, and possesses basic properties.When heated with hydrochloric acid in sealed tubes, a t 180-200°, it is completely converted into carbonic anhydride, aniline, and hydrazine hydr ochlor- ide. Bromine acts on it in glacial acetic acid solution, forming a tetrabromo-compound, C,,H,,N,Br,, crystallising in needles and melting at 215-218O. Axo-dicarbonanilide, N2( C'O*NHPh),, produced by the action of nitric acid on hydrazidicarbonanilide, crystallises from acetone in bunches of dark red needles melting a t 182-183'. On rubbing, the substance becomes strongly electric, and is reconverted into hydrazidicarbon- anilide by boiling with acids, alkalis, or tin and hydrochloric acid.Phen?lZca,i.bamirtccxide, NHPh*CO*N,, prepared by the action of138 ABSTRACTS Ok' CHEMICAL PAPERS. sodium nitrite on an aqueous solution of phenylsemicarbazide hydro- chloride, crystallises in colourless leaflets melting at 103-104°. A. W. C. Catecholglyoxal. By CHARLES MOUREU (Compt. rend., 1898, 127, '324-326).-The compound, C,H,O,, obtained by J. Hesse by boiling with dilute sulphuric acid the product, C,H,:O,:CH*CH(OEt),, prepared by the action of dichloracetal on disodiumcatechol, is identical with the hydroxyphenoxyacetic acid obtained by the author under similar conditions from dicatecholacetylenic ether. It is clear that, although the aldehyde catecholglyoxal has not been isolated, it must be the first product of the hydration of the compound C,H,:O,:CH*CH(OEt),, and hence may be assumed to be an intermediate product in the hydration of catechol acetylenic ether, since the final product is the same in both cases (compare this vol., i, 125).Beneoyl Derivatives of Acetonitrile and Paratoluoylaceto- nitrile. By 0. SEIDEL (J. pr. Clzem., 1898, [ii], 58, 129-159).- Benzoylacetonitrile (cyanacetophenone) is best obtained by the action of concentrated hydrochloric acid on benzacetodinitrile. Obregia (Abstr., 1892, ii, 324) obtained from it, by the action of phenylhydrazine, a yellow, crystalline substance melting at 134-135°,whereas Burns (Abstr., 1893, i, 314),by the action of phenyl- hydrazine on benzacetodinitrile, obtained yellow needles melting at 121", although the reaction should give the same substance as that obtained by Obregia.The author now shows that the twosubstances are identical, and must be regarded as the phenylhydraxorze of cyan- acetophenone melting a t 146-147", the difference in the observed melting points being accounted for by the fact that, on warming, or on exposure to air, or by repeated crystallisation from dilute alcohol or chloroform, it is partially converted into an isomeride, 1 : 3-dipheng1- 5-inaidopgraxoZine, C,,H,,N,, crystallising in white, rhombic plates and melting a t 129.5"; this cannot be reconverted into the phenylhydr- azone, than which it is much more stable, and possesses basic properties. The hgdrochloride is not stable in air, and the platinochloride crystal- lises in large, prismatic needles melting and decomposing a t 191".Both isomerides, when treated with acetic anhydride, give the same nzonacetyl derivative, crystallising from benzene in beautiful, white needles melting at 149". When the phenylhydrazone is treated with nitrous acid in ether, benzene, alcohol, or chloroform solution, nothing but tarry products are produced, but when dissolved in acetic acid, whereby it is converted into its isomeride, two substances are formed which can be separated by the difference initheir solubilities in acetic acid or benzene; the one is the true nits.oso-clerivative of diphenylimidopyrazoline, C1,H1,N,O, crystal- lising from benzene in dark red, glistening prisms melting at 207", which, when heated with concentrated hydrochloric acid, is converted into 4-isonitroso-1 : 3-cliphenylpyrazolone (compare Knorr a i d K lot z, C.H. B.ORGANIC CHEMIS'MiY. 139 (Abstr., 1887, 1121), and the other, of the composition C30HZRNp crystallises from glacial acetic acid in canary-yellow needles, melting a t 317'. It is not acted on by concentrated sulphuric acid or hydro- chloric acid when heated with it in sealed tubes a t 160', and is pro- bably formed by the condensation of 1 molecule of the red substance with 1 molecule of the iinidopyrazoline. Phenylhydrazine reacts with paratoluacetodinitrile, forming :% phenylhydraxone crystallising in yellow needles and melting a t 153". When heated, or dissolved in acetic acid, it is converted into the isomeric l-phenyl-3-paratolyl-5-imidopyrazoline, from which, by the action of nitrous acid a ?wed substance, C,,H,,N,O, melting a t 2 3 2 O , and a yellow substance, C,,H,?N,, melting a t 212', are produced.Burns (Zoc. cit.) and Obregia (loc. cit.) have stated that cyanaceto- phenoneoxime is only stable in the form of its isomeride phenylisox- nzoloneimide, whereas Pro bst believes the oxime of paratolylacetodini- trile t o be a true oxime. The author cannot substantiate Probst's conclusions, and regards the substance as 7-paratolylimidoisoxazoline. C z1 H, ?N R, obtained by the action of diphenylhydrazine on an alcoholic solution of cyanaceto- phenone, crystallises from dilute alcohol in yellow prisms melting a t 148'; it cannot be converted into an isomeride either by the action of heat or by dissolving i t in glacial acetic acid.3-Phenyl-5-imidopy~axoZine, C,H,N,, produced by the action of hydrazine sulphate on cyanacetophenone, forms white crystals melting at 125'. The hydrochZoq*ide crystalliscs in small needles, and the platinochloride forms large, yellow prisms melting and decomposing a t 225'. 1 : 3 : 5-Tripl~enyl-4-cyanopyrccxoZe, C,,H,,N,, obtained by the inter- action of dibenzoylacetonitrile and phenylhydrazine hydrochloride, crystallises from alcohol in white needles melting at 189", is insoluble in potassium hydroxide, is not attacked by hydrochloric acid when heated with it in sealed tubes at 160°, o r by sulphuric acid, in which it is soluble, and does not form a platinochloride; when hydrolysed, it is converted into 1 : 3 : 5-triphen~l-4-~y~u~oleca~~~oxyZic acid, which crystallises in white needles melting a t 23S0, and when heated alone, is changed into 1 : 3 : 5-pyrazole, with loss of carbonic anhydride.When the silver salt of dibenzoylacetonitriie is treated with methylic iodide, the methylic salt is obtained in small, yellow needles melting at 117-118"; it is neutral, and is readily decomposed by water into dibenzoylacetonitrile and methylic alcohol. Tq.i6enxoyZcccetonitriZe, CN*CBz,, or CN*CBz:CPh*OBz, obtained from the above silver salt by the action of benzoic chloride, forms compact, white crystals melting a t 13S0. Alkalis decompose it at once into dibenzoylacetonitrile and benzoic acid ; aniline gives the corresponding ccnilide crystallising from alcohol in silken needles melting at 165", and phenylhydraziiie proclwes 1 : 3 : 5-triplienyl-4- cyanopyrazole.During the original reaction (benzoic cliloride and acetonitrile), a substance, C17H,,N,0, is also produced, crystallising in golden needles melting a t 204'; it could not be obtained in quantity sufficient for Cyanccce tophenone diphenyllb y draxone, complete investigation. a. w. c,140 ABSTRACTS OF CHEMICAL PAPERS. Condensations with Phenylacetone [Benzyl Methyl Ketone]. 11. By GUIDO GOLDSCHMIEDT and GUSTAV KNOPFER (Monatsh., 1898, 19, 406-436. Compare Abstr., 1898, i, 31).-The ketone, C1,H1,ClO, obtained by t h e action of hydrochloric acid on a mixture of benzyl methyl ketone and benzaldehyde, may be made t o yield stilbene by distillation with lime, It dissolves gradually in cold, strong sulphuric acid, giving a colourless solution, which becomes yellow and finally brown when warmed.When heated with a n alcoholic solution of hydroxylamine hydro- chloride, chlorobenzylphenylacetone, a s the author terms the above ketone, yields a n oxime, CI,H,,NO, which crystallises in beautiful, colourless, silky needles, melts at 153", and is insoluble i n alkalis or acids; when boiled with acetic anhydride, i t affords a substance, possibly an acetyl derivative, which crystallises from alcohol in beautiful, white needles, and melts a t 92". When chlorobenzylphenylacetone is warmed, in alcoholic solution, with an equal weight of potassium cyanide, a compound, C17Hl,NO, is produced which crystallises from alcohol in needles and melts at 193' ; i t sublimes without decomposing, and dissolves in strong sulphuric acid, giving a yellow solution which, when warmed, exhibits a feeble violet fluorescence.It was not possible t o obtain the correspond- ing acid by hydrolysis. The ketone, C1,H,,O (m, p. = 53", Zoc. cit.), yields a thick oil on dis- tillation with lime, but stilbene could not be detected in it. The ketone dissolves in sulphuric acid, giving an emerald green solution, which assumes a bluish-violet fluorescence when warmed. It is at once destroyed by permanganate solution, but is not appreciably affected by potassium hydroxide, or dilute alcoholic hydrochloric acid. It does not yield a crystallisable additive product with bromine. The ketone, C,,H,,O (m. p. = 71'), comports itself towards perman- ganate and on distillation exactly like its isomeride.Its solution in sulphuric acid is lemon-yellow, and, when warmed, becomes red, exhibiting a strorig green fluorescence. It evolves the odour of benz- aldehyde when warmed with alcoholic hydrochloric acid, and the solu- tion on cooling, especially after dilution, deposits oily drops and crystals of the unaltered substance. The dibromide, C,,H,,OBr,, made by adding bromine to a solution of the ketone in chloroform, crystallises in beautiful, silky needles, melts at 93', and dissolves very readily in ether and benzene, but only sparingly in alcohol and light petroleum. Triphenyltetrahydro-y-pyrone, when warmed with alcoholic hydro- chloric acid, is decomposed into benzaldehyde and the ketone melt- ing at 71"; the inverse change is effected by shaking a mixture of benzaldehyde and the unsaturated ketone with aqueous potash during 48 hours ; the saturated ketone does not afford the pyrone derivative under these conditions ; under certain circumstances, the substance melting at 175" is also formed by this process of condensation (Zoc, cit.). The analysis and molecular weight of the latter compound points to the formula C41H3803,.hence its formation from benzyl methyl ketone and benzaldehyde is probably effected in similar manner t o that of dibenzylidenetriacetophenone, by the condensation of aceto- phenone and benzaldehyde ; its constitution is probably, therefore,ORGANIC CHEMISTRY. 141 Para ........ .... dOMe*CPh(CHPh*CHPh*COMe),. Benzylidenetriphenylacetone dia- solves in strong sulphuric acid, and forms a lemon-yellow solution, which darkens spontaneously and becomes ruby-red when warmed.When hydrogen chloride is passed into a n imperfectly cooled mix- ture of benzyl methyl ketone and benzaldehyde, a substance, C25H220, is sometimes obtained ; this forms yellowish crystals, melts a t 140°, and may be distilled without decomposing. It is probably pro- duced by the condensation of an intermediate 1 : 5-diketone in the usual manner, being, therefore, 1 -metlql-2 : 3 : 4-triphenylcycZo-A'- hexenone-5, CMe<:EPh' cHl$>CHPh. It gives an oxime, C,,H,,NO, which forms aggregates of crystals, melts a t 204", and dissolves sparingly in alcohol, but readily in other media. Dibenzyl ketone and benzaldehyde condense in presence of dry hydrogen chloride, forming a substance which has the composition C,,H,,C10, and is, therefore, the hydrogen chloride additive product of benzylidene dibenzyl ketone ; it melts a t 143', and, on distillation, yields phenylacetic chloride and stilbene.Of the above isomeric ketones, C1,H,,O, t h a t melting a t 53" is saturated and produced by a ready elimination of hydrogen chloride from the substance C,,H,,ClO, and is, therefore, in all probability a cyclic compound, 1-phenyltetrahydro-P-naphthenone, CHPh* $JHz C6H4<CH2--co 9 whilst the isomeric unsaturated ketone (m. p. = 71") probably has the constitution CHPh:CPh*COMe. The hydrocarbon melting a t 120°, which was obtained from benz- aldehyde and benzyl methyl ketone by the use of sulphuric acid (Zoc.cit.), turns out t o be stilbeno (compare Miller and Rohde, Abstr., 1S90, 978). A. L. By ARNOLD F. HOLLE- MAN (Rec. 2"yav. chirn., 1898, 1'7, 247--258).-The following table gives the solubilities of ortho-, meta- and para-nitrobenzoic acids in water, chloroform, and absolute alcohol a t temperatures of 1 5 O , 25", and 35'; the numbers represent grams of acid dissolved in 100 grams of the solvent, except in the case of alcohol, when they represent gram-molecules per litre. Solubilities of the Nitrobenzoic Acids. 0*0213 1 0.0235 0'0419 0.088 1 Nitrobenzoic acid. A bs 01 tit e Water at 11 Cliloroform at 1 I The solubility in water of a mixture of the para-acid with either the ortho- or meta-acid is approximately equal to that calculated142 ARSTRACTS OF CKEMTCAT, PAPERS.frorri Nerust's t)ieory of the diniinntion in solubility of one substance i n presence of another haviug ;iu ion in conimon with it. An increase of solubility of the three acids occws, however, when they are all present simultnneously in solution ; and the same is true of a mixture of the ortho- and meta-acids. To explain this anomaly, combination is assumed t o take place between the substances present together (compare Le Blanc and Noyes, Abstr., 1891, 388); this would eluci- date the difficulty experienced in separating ortho- and meta-nitro- benzoic acids by crystallisation from water. W. A. D. Piperonal Derivatives. By S. BAUDE and ALBERT REYCHLER (Bull. SOC. Chim., 1897, [ iii]) 17, 616-618).-EthyZic methylenedioxy- cinnumute, CH2<O>C,H,* CH:CH* COOEt, obtained by the action of metallic sodium on a mixture of piperonal and ethylic acetate, crys- tallises in needles melting at 65-68", is soluble in alcohol and ether, and distils, with slight decomposition, at about 317'.Its dibromide forms colourless plates melting at 84O, and is readily soluble in ether or alcohol, but insoluble in light petroleum. CiC*COOH, ob- 0 Methylenedioxyphenylpopiolic acid, CH,<O>C,H,* 0 tained when the dibromide is repeatedly boiled with alcoholic potash, crpstallises from dilute alcohol i n pale yellow needles, turns brown at 145", and melts and decomposes at 166". Met?~yle~dioxy~?~en~Zc~~etyZene, obtained by heating the above acid with tlhree to four times i t s weight of dry aniline at 150-160°, is a yellow oil.J. J. S. Condensation of P h t h a l a l d e h y d i c Acid with Acetone and Acetophenone. Ey ARTHUR HAMBURGER (Monatsh., 1898, 19, 427-455. Compare Goldschmiedt, Abstr., 1S92, 179, and Hemmel- mayr, Abstr., 1893, i, 181, and 1894, i, 151).-Phthaldehydic acid and acetone condense readily a t 40-60" i n presence of dilute soda ; the liquid, after remaining for 24-48 hours, is acidified with hydrochloric acid, when the mixture acquires a milky appearance, and a gelatinous precipitate slowly forms. This is separated by filtration, washed, and dissolved in alcohol, from which, on cooling, di~~?~t?~aZidedimet?ayl ketone, (CO<??:>CH* CH,),CO, crystallises in the form of white, felted needles which melt at 156-157". On evaporating the filtrate from the above precipitate, or extracting*it with ether, it yields R much larger quantity of a second substance, p?At?Lalidedimethyl hetone, CO<"G"~CH* CH,.CONe, which crystallises from water i n quad- ratic plates of considerable size and melts at 67-68", dissolves readily in water, alcohol, ethylic acetate, and benzene, and more sparingly i n chloroform and light petroleum. Both compounds dissolve slowly in cold, but readily in hot, potash, giving intensely yellow colorations ; with bromine, they give substitution, not additive, compounds. l)'i1117Lt?~alitledinaf!thyZ keto:cinza, CISH1605N, is nearly insoluble in water, -0ORGANIC! CHEMISTRY. 143 :icetic acid, cthylic acetate, and benzene, atid o d y very s1)aringIy iu alcohol, nielhylic alcohol, ether, acetone, and chloroforni, but dissolves readily in cold potash, iind is reprecipitated by acids ; i t is iudistiiictly crystalline, sinters a t lSl", and melts at 197-203". When hydroxylamine acts on phtlialidedimethyl ketone, two isomeyic oxinaes, C,,H,,NO,, are formed; one of these, obtained by acidi- fying the product with hydrochloric acid, crystallises from dilute alcohol in yellowish forms arid melts a t 127-12fi0 ; i t dissolves very readily in methylic or ethylic alcohol or ether, less readily in water, sparingly in benzene and chloroform, and is more easily soluble in alkali than in water.The second oxirne is formed by dissolving the first in boiling water, from which it separates i n white, felted leaflets, or by heating it for some at 100" ; it melts a t 59-61', and dissolves readily in the usual media and in alkalis.Both oximes, when treated with the "Beckmann mixture," give an oil and an acetyl compound: Cl,Hl,N04 ; this forms slender needles, and on warming with fuming hydrochloric acid gives phthalidedimethyl ketone. Phthalidedimethyl ketone reacts with phenylhydrazine and with bromine, hydrogen bromide being evolved in the latter instanc.e ; in neither case, however, is a crystalline compound produced. Phthalaldehydic acid and acetophenone interact in presence of soda at 40" ; the product, phenylphthalidernethyl ketone, ?GH4>CH*CH2*COPh, crystallises from alcohol in long, white, felted needles, and melts at 141-142'. It dissolves instantly in warm alkalis, with a yellow coloration, and is sparingly soluble in water and ether, but dissolves somewhat readily in alcohol.Phenyl pihthalidernethyl ketoxirne, Cl6HlSNOS, forms white needles, sinters a t 1'77O, and melts a t 181-182'; a second substance is obtained simultmeously which is insoluble in soda, and decomposes, evolving gas, a t 180' and melts at 215'. The former is some- what readily soluble in alcohol, ether, and hot benzene, and is very unstable in presence of light, becoming yellow ; potash quickly dissolves it, but it is deposited unaltered on adding an acid. When subjected t o treatment with (' Beckmann's mixture," it yields coo 3-carboxyp?~enyL5-p~~en yZisoxaxoZine, C P h q N O>CH * C,H; COOH. CH, Bromine acts on phenyl phthalidemethyl ketone, hydrogen bromide being evolved, but the product is not crystalline; it is not affected when shaken with benzylic chloride and aqueous soda.When a mixture of phenylhydrazine and phenyl phthalidemethyl ketone is warmed on the water-bath, a substance of the composition -C6H4- C',,H,,N,O,, probably CO<N2Hph>CH' CH,* COPh, is formed. This crystallises from alcohol in yellowish, glistening needles and melts at 118---123O ; i t is very readily soluble in chloroform and alcohol, some- what less readily in benzene and acetic acid, sparingly in ether, and is nearly insoluble in water. When heated with strong sulphuric acid, it becomes dark-red, but quickly dissolves, forming a yellow solution which soon becomes green, especially on the addition of a drop of144 ABSTRACTS OF CHEMICAL PAPERS. solution of ferric chloride. is not affected by hot alkalis or bv concentrated hvdrochloric acid.It does not reduce Fehlingjs solution, and An isomeric Eonymnd, C22H,iN20, possibly " COOH. C,H,.CH<~~~* Gph, NPhON is produced when phenyl phthalidemethyl ketone and phenylhydrazine are heated together in sealed tubes at 170-1900 for 5 hours. It crys- tallises from alcohol in rosettes of needles and melts between 170' and 200', is sparingly soluble in benzene, but dissolves readily in alcohol, ether, glacial acetic acid, and nitrobenzene. I t s solution in concen- trated sulphuric acid is red, becoming dark blue on the addition of a, drop of ferric chloride, owing t o the formation of a sparingly soluble blue compound, and on adding potassium dichromate, a violet coloration is produced which changes successively to dark blue, red, and yellow- ish-brown ; in the latter instance, subsequent dilution of the liquid causes the separation of a red precipitate; dilute nitric acid instantly turns the substance blue; it does not reduce Fehling's solution.It. dissolves i n sodium carbonate solution, producing a liquid which readily forms a lather, and when excess of soda is used, a sodium salt is formed, which crystallises in beautiful, transparent needles. The first isomeride, when heated in a closed tube at 170°, suffers almost complete conversion into the second. When phenyl phthalidemethyl ketone is heated at 170-190° in sealed tubes with phenylhydrazine (2 mols.), a third substnnce, C2,H,,N,0, possibly CO<G$3G>CH* CH,* CYh:N*NHPh, is ob- tained, which is nearly insoluble in water, alcohol, ether, and light petroleum, but dissolves readily i n hot amylic alcohol, ethylic acetate, and glacial acetic acid, sinters at 157', and melts at 163-175'.Sulphuric acid dissolves it, forming a dark green solution in which a trace of ferric chloride, potassium dichromate, or sodium nitrite pro- duces a red coloration. It is insoluble i n boiling alkalis, and does not reduce Fehling's solution. A. L. Behaviour of Phthalide on Distillation with Lime. By HANS KRCZMAR (Monatsh., 1898, 19, 456--460).-A mixture of phthalide and lime was cantiously heated a t about 290' in a long glass tube, through which a slow stream of hydrogen was passed; the distillate contained a clear liquid and a crystalline solid. The liquid portion consisted for the most part of benzene and probably, in part, of toluene, as on oxidation with chromic acid the odour of benzoic acid made itself perceptible.The solid substance was anthracene, probably contaminated with diphenyl. A. L. Condensation of Malonic Acid with Aromatic Aldehydes by means of Ammonia and Amines. By EMIL KNOEVENAGEL [and in part FR. BAEBENROTH and 0. ~OLLWEBER] (Be?-., 1898,31,2596-2619). -When malonic acid is warmed with substituted benzylidenebisalkyl- amines or benzylidenebisdialkylamines, interaction as a rule takes place readily, and acids of the acrylic or malonic series are produced. In the case of benzylidenebispiperidine and malonic acid, the action is represented by the equation CHPh(C,NH,,), + CH,(COOH), = CHPh:CH* COOH + CO, + 2C5H,,N.ORGANIC CHEMISTRY.145 Many benzylidenealkylamines act i n a similar manner, but by using benzylidine-a(or /3)-naphthylamine and benzylidenemetanitr- aniline, no cinnamic acid was obtained. Hydrobenzamide reacts with malonic acid in a fashion which is analogous to the behaviour of other substituted benzylideneamines ; the equation is N,(CHPh), + 3CH2(COOH), = 3c02 + 3NH, + 3CHPh:CH. COOH. Salicylideneaniline and malonic acid yield coumarincarboxy lie acid, aniline, and water. It is not necessary to isolate the salicylidene- aniline, mere addition of aniline to a solution of malonic acid and salicylic acid, or of the aldehyde t o aniline malonate, being all that is required. Similar results with analogous trios of substances have shown that, in general, the order of interaction exerts only a quanti- tative influence on the product obtained.The intermediate product in these reactions, namely, the alkylidine- malonic acid, may be isolated if t h e temperature of the reaction be kept sufficiently low, the optimum point depending on the nature both of the base and of the aldehyde employed. With ammonia, the temperature at which carbonic anhydride is eliminated is lower than where aniline is the condensing agent, and, in consequence, a smaller yield of alkylidenemslonic acid is obtained. It is to be noted that the requisite proportion of base varies with the nature both of the base itself and of the aldehyde used ; it is found, moreover, that, with some bases, little or none of the desired products are obtainable. The necessary duration of the action is also found to vary; in some cases, a short time only is advisable, and in others the reverse holds true.The paper concludes with a detailed description of the experiments on which the foregoing statements are based, and the following substances are described for the first time. Anisyliclenemalonic acid is obtained when anisaldehyde (1 *3 grams) and normal ammonium malooate (1.4 grams) are covered with alcohol and the whole rapidly evaporated on the water-bath nearly to dryness, and is precipitated by means of sulphuric acid from its alkaline solution as a yellow, flocculent substance which melts and effervesces briskly at 185-189' ; i t yields paramethoxycinnamic acid when boiled with alcohol, Pi3-eron~lidenemc~lonic acid is made by warming piperonal with malonic acid and alcoholic ammouia (2 mols.) or with normal am- monium malonate.It is thrown down from i t s solution in soda, on acidification, a s a white, flocculent precipitate, which melts and eff er- vesces at 190-195°. When a mixture of furfuraldehyde and malonic acid is cooled and treated with aniline, the whole soon solidifies and, on subsequently adding hydrochloric acid, crystals of a nitrogenous substance are deposited; this is sparingly soluble in water and dissolves in alcohol, forming a red solution which deposits violet crystals having a metallic lustre. It is completely destroyed by warm soda, and when warmed with sodium carbonate solution t h e colour is destroyed, hut is restored on adding an acid. A. L. VOL. LXXVI. i.I146 ABSTHACTS OF CHEMICAL PAPERS. Condensations of Acid Derivatives of Ethylic Malonate with Ethylic Benzylideneacet oacetat e. E y EMIL KNOEVE NAGEL and W. FABER (Ber., 1898, 31, 2768--2'772).-When ethylic benzyl- ideneacetoacetate (Abstr., 1896, i, 232) and either ethylic isobutyryl- malonate (see below) or ethylic benzoylmalonate (Claisen, Annaclen, 1896,291,72), are heated with a little alcohol until a homogeneous mix- ture has been formed, alcoholic potassium ethoxide then added, and the whole allowed t o remain for several days, the product in both cases is diethylic 5-phenyl-1 : 3-diketocyclohexane-4 : 6-dicarboxylate (Abstr., 1894, i, 576), the isobutyryl o r benzoyl group being removed. "o<:%oEt ): CHPh + COOEt*CHBz*COOEt co<CH,-- CH(COOEt)*CHPh co>CH* COOEt.E:thyZic isobutyylmalonate, CHMe,* CO~CK(COOEt),, prepared from isobutyric chloride and ethylic sodiomalonate, boils at 133-1 34' under 14 mm., and at 126-127' under 10 mm. pressure. C. F. B. Condensing Action of Diethylamine. By EM IL KNOEVENAGEL and W. FABER (Bey., 1898, 31, 2773-2775).-When ethylic benzyl- ideneacetoacetate, CHPh:CAc* COOEt (Abstr., 1896, i, 232), dissolved in a little alcohol, ethylic cuminylideneacetoacetate (Abstr., 1898, i, 404), or benzylideneacetylacetone (Abstr., 1895, i, SO), is mixed with a little diethylamine and allowed t o remain, the product is ethylic benzylidenediacetoacetate, CHPh(CHAc* COOEt), (Abstr., 1896, i, 210 ; Hantzsch, Abstr., 1886, 77), ethylic cuminylidenediacetoacetate or benzylidenediacetylacetone respectively. I n the first case, a similar condensation took place, even when ethylic isobutyrylmalonate was present ; no condensation with the latter substance occurred.C. P. B. Orthaldehydophenoxy-acids. By H E R & i m N CAJAR (Ber, 1898, 31, 2803-281 l).-SodiosaZicylaldehyde, CHO*C,R,* ONa, was pre- pared by treating salicylaldehycle with sodium ethoxide in the presence of a large quantity of alcohol; it is lemon-yellow. When it is suspended i n benzene and treated with ethylic chloroformate, and the product distilled under 90 mm. pressure, a n oil comes over at 197", which is presumably ethylic orthaldehydophenylic cc~bonate, CHO*C,H,* O*COOEt. A41coholic soda appears t o hydrolyse this t o the sodium salt, but the latter is a t once decomposed by water, with formation of salicylalde- hycle ; the ethylic salt forms, however, a yellowish phenylhytlmxone melting at 101 --102', and with aqueous semicarbazide hydrochloride, a yellow product melting at 11l0, which apparently has the composition COOEt*O*C,H,* CH:N*NH* CO *N:CH* C,H,- O*COOEt ; with aqueous hydrnzine hydrate, i t yields salicylaZdehyde iiydmxone, NH,*N:CH*C,H,*OH, melting at 96' (this can also be obtained by adding a solution of hyclrnzine hydrate in dilute alcohol t o an alcoholic solution of snlicylnldehyde ; when treated with acids, i t yields Curtius and Jay's hydroxybenzalazine [Abstr., 1889, 3931) ; with salicylalde-ORGANIC: CHEMISTRY.147 liyde hydrazone, the ethylic salt yields a compound, OH* C',H,*CH:N*N:CH* C,H,* O*COOEt, which melts a t 11 4-1 15', and forms hydroxybenzalazine when treated with acids (salicylaldehyde hydrazone also forms a compound, melting at 11 3-1 14', with ethylic acetoacetate) ; with hydrazine sulphate in aqueous solution, it forms the compound N,(:CH* C,H,* 0-COOEt),, which is bright yellow and melts at 109-110'.With hydroxylsmine, the ethylic salt does not react; by warming salicylaldoxime with ethylic chloroformate in concentrated alcoholic solution, a compound melting at 69.5' is obtained, but this, probably, has the constitution COOEt- 0 *N:CH* C,H4* OH, for salicylaldehyde itself does not react in an analogous fashion. With ethylic malonate, after 3 hours heating on the water-bath, the ethylic salt forms coumarincarboxylic acid, 0--yo Stuart, Trans., 1886, 40, 366).'GH4<CH: C*COOH ( Orthaldehydophenoxyacetic acid (Rijssing, Abstr., 1885, 388) was prepared by heating salicylaldehyde (1 mol.) with monochloracetic acid (1 mol.) and aqueous caustic soda (2 mols.) of sp. gr. = 1.2 ; when boiled with 3 per cent. methyl alcoholic hydrochloric acid, it yields the rnethylic salt, CHO*C,H,*O*CH,* COOMe, which melts at 55-56', and forms a yellow hydrazone, N,(:CH* C,H,* O*CH,* COOMe),, melting a t 159-160' (the allied opianic acid yields a pseudo-salt ; compare Wegscheider, Abstr., 1 892, 1208). With hydrazine hydrate, the acid gives a yellow hydrazone, N,(:CH* C,H,* O*CH,* COOK),, which me1 t s and decomposes a t 222' (and not a phthalazone; compare Abstr., 1893,371). When heated with hydroxylamine hydrochloride in 80 per cent.alcoholic solution, it yields the ethylic salt of orthaldoxime- phenoxyacetic acid (Elkan, Abstr., 1887, 259), NOH:CH* C,H,*O*CH,*COOEt ; this melts at 80'. By P. GENVRESSE (Bull. Soc. Chim., 1897, [iii], 1'7, 599-609. Compare Abstr., 1897, i, 240).-Phenylene bisulphide, (C,H,S),, and an isomeric compound are obtained by the action of sulphur on benzene in the presence of aluminium chloride. The diphenylene bisulphide may be removed by treating with boiling glacial acetic acid until the residue gives a n emerald green colour with concentrated sulphuric acid ; the impure isomeride is then freed from excess of sulphur by washing with carbon bisulphide, and is dissolved in hot benzene, in which it is sparingly soluble and from which it separates on cooling in an amorphous condition.It melts a t 295', but begins to sublime even at lower temperatures, is sparingly soluble i n hot benzene or chloroform, and is insolnble in most other solvents. Chromic acid oxidises i t to isodiphenylene disulphone, C,H4<So2>C,H4, which has not been obtained in a crystalline form, but is colourless, melts above 360°, is non-volatile, and only sparingly soluble in benzene, and when heated with Concentrated sulphuric acid a t 200" is converted into n sitbstnnco soluble in water. C. F. B. An Isomeride of Diphenylene Bisulphide. so2 1 2148 ABSTRACTS O F CHEMICAL PAPERS. Fuming citric acid oxidises tho isobisulphide, yielding a mixture of products which have not been separated. Fuming sulphuric acid yields a colouring matter isotvioxyphenylene hisuZphide, C,S2H40?, when heated in sealed tubes at 120-125° with the isobisulphide ; this compound is readily soluble in water or alcohol, giving red solutions, but is insoluble in benzene, chloroform, &c.I n the solid state, it is brown, and with sulphuric acid gives a green solution; it may be obtained in a crystalline form from dilute sulphuric acid, but not from its aqueous or alcoholic solubions. I t s aqueous solution, when mixed r i t h a solution of sodium chloride, yields a brownish red precipitate, containing 70 per cent. of sodium chloride, and insoluble in alcohol. Sodium hydroxide turns the red, aqueous solution black, and a precipitate is slowly formed ; a precipitate is also obtained with sodium carbonate, but no evolution of gas occurs.Barium hydroxide gives a dark brown precipitate, which, on adding an excess of hydroxide, becomes white; it is sparingly soluble in hot water, and its composition is represented by the formula C,S,H,O,Ba. The dark coloured precipitate can also be obtained in a crystalline form, and has the composition (U,S2H30,),Ba. A tyiacetyl derivative, C,S,O,HAc,, is obtained when the compound is boiled with acetic anhydride, but when the acetyl derivative is boiled with barium hydroxide, only one acetyl group is removed. The acetyl derivative forms a hard, black mass, soluble in water. The brown coiouring matter gives azo-colours with aromatic amines. J. J. S. Hydrazides and Azides of Sulphonic Acids. By THEODOR CURTIUS and FERDINAND LORENZEN (J. pr. Chein., 1898, [ ii 1, 58, 160-189.Compare this vol., i, 136).-The ethereal salts of aromatic sulphonic acids, R.SO,H, are completely hydrolysed on standing in the cold with hydrazine hydrate, the hydrazine first formed taking up water, with the production of the diammonium salt of the sulphonic acid, whereas the ethereal salts of sulphinic acids are not only hydrolysed, but decomposed by the reducing action of the diamide according t o the following equation, 4PhS0,Et + 3N2H,*OH = 2Ph2S, + 4EtOH -I- 7H,O + 3N,. The hydrazides of the sulphonic acids can also be obtained by the action of hydrazine hydrate on the acid chloride; they reduce an ammoniacal solution of silver nitrate and Fehling's solution, and precipitate mercury from mercuric oxide. Iodine converts them into bisulphides and disulphoxides, but the latter could not be isolated, a similar reaction taking place when the sulphonehydrazides are heated.Like the hydrazides of the carboxylic acids, they are of a basic character, and condense with one molecule of an aldehyde or ketone, Acetic anhydride replaces one hydrogen of the hydrazine residue by an acetyl group, and nitrous acid converts them into the sulphon- azides, which, unlike the azides of carboxylic acids, are not changed by heating with water or alcohol ; neither are they acted on by bromine, and only with great difficulty by alkalis. Be.lzxeizesuZ~~~~oize~~~~~.ccsine, PhSO,*NH*NII,, crystallises from alcohol in large plates or prisms melting and giving off gas at 104-106".ORGANlC CHEMISTRY. 149 The ?qlu'rocldoriiZe separates from alcohol in fine needles melting, with evolution of gas, a t 150--152O, and the sodium salt, PhSO,*NNa*NH,, forms glistening plates.Benxyl idene benxenesulphonehydra~i~z~, SO,Ph* NH*N : CHPh, formed by the action of benzaldehyde on the hydrazide, crystallises from dilute alcohol in colourless needles melting at 110-1 12" ; the corresponding acetoiLe [P-propylidene] derivative forms glistening leaflets melting a t 143-145", and the acetyl derivative crystallises in groups of glisten- ing needles melting a t 1S3-1S4'. DibenxenesuZphoneh3draxide, SO,Ph*NH*NH*SO,Ph, produced by the interaction of benzenesulphonic chloride and benzenesulphone- hydrazide, crystallises from alcohol or water in glistening needles melting and giving off gas at 228'.It reduces Fehling's solution and ammoniacal silver nitrate slowly in the cold, and is decomposed by iodine with evolution of nitrogen, Boiling dilute sulphuric acid decomposes it very slowly, but boiling alkalis decompose it readily with production of benzenesulphinic acid. BenxenesuZphonaxide, SO,YhN,, is a yellowish oil which does not solidify when cooled, has a sweet odour, and when reduced with zinc dust and acetic acid is converted into benzenesulphonamide ; it may be obtained by the action of nitric acid on benzenesulphonehydrazide. Biamnzonium benxenesulpl~onc~te, SO,Ph*N,H,, obtained by the action of hydrazine hydrate on methylic benzenesulphonate, is a crystalline substance melting and decGmposing a t 175". When further acted on by benzenesulphonic acid, it yields the diamrnonnium salt, N,H,(PhSO,III),, crystallising from alcohol in glistening leaflets, which begin to de- compose when heated t o 250" and are not completely melted at 275".The corresponding diammonium salt of benzenesulphinic acid, N,H,(Ph,SO,H),, crystallises from alcohol in glistening leaflets melt- ing and decomposing at 139-141". P-Nap~Lt?~ylsuZp?~one7Lydrc~xicZe crystallises from alcohol in colourless needles melting and evolving gas a t 137-139', and when boiled with dilute sulphuric acid, is converted into P-naphthylsulphinic acid and hydrazine sulphate. The hydrochloride f orms tufts of needles melting at 148-150", and the sodium salt crystallises from alcohol with lEtHO in glistening leaflets, which do not melt when heated t o 275'.BenxyZidene-P-napTLt?~~Z~ulpT~onehydraxine, C,,H7* SO,* NH* XCHPh, obtained by the action of benzaldehyde on the sulphonehydrazide, crystallises in colourless needles melting and giving off gas at 150-1 52", and the corresponding acetone [P-propylidene] derivative forms glistening plates melting and decomposing at 156-158'. Aceto-P-naphthyZszc~hone~~y~rax~d~, C,,H7*S0,*NH*NHAcl prepared by the action of acetic anhydride on the sulphonehydrazide, forms colourless, glistening needles melting a t 208-209". Di-/?-naphth ylsuljd~onehydraside, ( C,,H7* SO,*NH),, formed by the in- teraction of the aulphonehydrazide with P-naphthylsulphonic chloride, crystallises from alcohol in slender needles melting and decomposing a t 2 15". Dilute sulphuric acid converts it into P-naphthylsulphonic acid and hydrazine sulphate.The sodium salt is a yellow powder, not melting when heated to 275'.150 ABSTRACTS OF CHEMIC'AI, PAPERS. p-N~~~l~tl~~lsull-'honccxicZe, Cl,H7S02*N,, crystallises in white leaflets melting at 44-46", but not exploding when heated to a higher tem- perature; when reduced with zinc dust and acetic acid, it is con- verted into P-naphthylsulphonamide. Hydrazine hydrate acts on ethylic benzenesulphinate and methylic P-naphthylsulphinate, giving respectively phenylic bisulphide and /3-naphthylic bisulphide, and not the sulphinehydrazides. A. W. C. 4 : 4-Diamidodiphenyl-3 : 3'-dicarboxylic Acid. By CARL BULOW and ULRICH VON REDEN (Ber., 1898, 31, 2574--2582).-This acid, C,,H,(NH,),(COOH),, is prepared by reducing orthonitrobenzoic acid in alkaline solution, and boiling the hydrazo-compound thus produced with concentrated hydrochloric acid. When it is dissolved in caustic soda, and the solution is shaken with benzoic chloride and kept cold meanwhile, 4 : 4'-dibenxamidodiphenyl-3 : 3'-diccc~boxyZic acid, melting at 302-304O, is formed (the ummonium salt crystallises with 2H20) ; with acetic anhydride instead of benzoic chloride, the diacet- ccmido-compound is formed ; this melts a t about 300°, and is converted into benzidine when it is boiled in glycerol solution.When the acid is dissolved in dilute hydrochloric acid and treated with sodium nitrite, and the hydrochloride formed is repeatedly dissolved in water and precipitated with a mixture of alcohol and ether, yellow 4 : 4'-tetraxodip7~enyZ-3 : 3'-dicarboxyZic acid, C12H,(N:N* OH),(COOH), + 2H20, is obtained, and this, if boiled with 1 per cent.sulphuric acid, yields 4 ; 4'-dihydroxydiphengZ-3 : 3'-dica~boxylic acid, which melts at 302--305O, and yields 4 : 4'-dihydroxydiphenyl when heated with lime. When heated with bromine in hydrobromic acid solution, the tetrazo-acid yields a perbromide from which, by means of ammonia, greyish-green 4 : 4'-disdiaxoinzidodiphenyZ-3 : 3'-dicarboxylic acid, Ci2H,(N,)2(COOH),, decomposing at 165', is obtained. Reduced by prolonged boiling with absolute alcohol, it yields diphenyl-3 : 3'-dicarb- oxylic acid, from which diphenyl can be obtained by heating with lime ; the latter acid forms a meth,yZic and an ethylic salt, melting at 100-102" and 68' respectively, when it is dissolved in the correspondingalcohol and the solution is saturated with hydrogen chloride.When reduced with sodium sulphite solution, the tetrazo-acid yieldsdiphnyZ-4: 4'-dihydraxine- 3 : 3'-dicarboxyZic acid, C12H6( NH*NH,!,(COOH),, which is greyish t o reddish-white, carbonises without melting when heated, and condenses with acetone at 40-50" to form the dark green disacetonediphenyZ- 4 : 4'-dihydraxone-3 : 3'-dicurboxyZic acid, C12H,(NH*N:CMe2)2(COOH)2, melting at 265-267". With phenol in strong caustic soda solution, the tetrazo-acid condenses to form the red 4 : 4'-disphenoZaxodiphnyZ- 3 : 3'-dicarboxyZic acid, Ci2H6(N:N* C6H,* OH),(COOH), ; with ethylic acetoacetate in aqueous sodium acetate solution, it gives 4 : 4'-disetlbyZic acetoacetate-uxodiphenyl-3 : 3'-dicarboxylic acid, C,,H,(N:N* CHAc* COOEt),(COOH), + H20, melting a t 275-278" ; with ethylic malonate in the presence of dilute alcohol and sodium acetate, it yields, after crystallisation of the C,,H,(NHBz),(COOH),, ci ,H,(OH) 2 (COOK) 2 9ORGANIC CHEMISTRY. 151 product from alcohol, brownish-yellow ethylic 4 : 4'-ilisethyZic nzesoxaltcte- clih?/drccxonedi~~~iei~yZ-3 ; S'-diccwbozylcte, C,,H,[N.N:C(COO~ti,1,(C'OOEt), + 2lI,c), which melts at 257".Parahydroxyphenylphthalide, and its Conversion into Deri- vatives of Anthracene. By AUGUSTIN BISTRZYCKI and D. W. YSSEL DE SCHEPPER (Ber., 1898, 31, 2790-2802).-The hydroxy- phenylphthalide, GO<, >CH* C,H4* OH, previously described (Abstr., 1894, i, 600), yields paramethoxyphenylphthnlide (Nourrisson, Abstr., 1886, 1029) when methylated, and so must itself be a para- hydroxy-compound ; similar conclusions may be drawn as to the con- stitution of the other substances described at the same time.When parahydroxyphenylphthalide is reduced in alkaline solution by boiling with zinc dust, it yields 4-?iyd~oxydiphen?/lmet?~ane-2'-ca~b- oxylic acid, COOH. C,H,*CH,- C,H,*OH, which melts :at 145-146' ; i t s anhydrous silves. salt was analysed. When i t is dissolved in strong sulphuric acid at a temperature not exceeding 30°, and the solution is poured into water, the product is 2-J~ydrox~acntl~mi~oZ, C. F. €3. -0- 6 4 C,H4<8EH)>c6H,* OH ; this melts at 221', and forms a diucetyl derivative melting at 141-142'; the latter, when oxidised with chromic acid in acetic acid solution, yields a product identical with P-acetoxyanthraquinone. 4-l1yd?oxy- 2-metl~yldiphenylrnetl~ane-2'-carboxylic acid, COOH- C,H4* CH,* C,H3Me* OH, melts at 168-169'; i t s anhydrous bakum salt WRS analysed.2-l~ydroxy-4-meti~yZc6nt?ri.a~aol, C,H4<bH -->C,H,Me* OH, melts at 224O, its diacetgl derivative at 172-173". 2-Acetoxy-4-methylaril.tl~ra- quinone, C6H,<co>C,K,Me* OAc, melts a t 134-1 35', is yellow, and, when hydrolysed with alcoholic potash, yields the 2-lLyds.oxy-com- pound, which is yellow and melts at 299-300°, beginning to sublime at about 200". Metacresylphthalide yields a similar series of products. C(OH) co 4 : 5' : 6'-Trinzethoxybenxoyl-2'-benxoic acid, COOH- C,H,(OMe),* CO*C,H,* OMe, formed when hemipinic anhydride is heated i n benzene solution with anisoil and aluminium chloride and the product treated with hydro- chloric acid, melts at 215-216'; its anhydrous silver salt was analysed.When reduced with zinc dust in alkaline solution, i t yields O--- paramethoxypherLyl~seudomeconine, GO<, (OISle), >CH* C6H4* OMe, which melts a.t 111-lZ3°. With zinc dust and hydrochloric acid in acetic acid solution, 4 ; 5' ; 6'-trimethoxydiphenyl.met?~mae-2'-ca~boxyl~c acid, GOOH* C6H,(OMe),* CH,* C,H,* OMe, melting at 122-124', is obtained ; strong sulphuric acid converts this into 2 : 3' : 4'-tvirnethoxy- 6 2 dihydronnthyone, C,H,(OMe),<Co->C,H,*OMe, which melts at CH2152 ABSTRACTS OF CHEMICAL PAPERS. 169-170', and is oxidised by chromic acid in acetic acid solution to 2 : 3' : 4'-trinzetI~oxyanth~aquinone, C,H,(OMe),<~~>C,H,* OMe, which is yellow, melts a t 235', and yields flavopurpurin when heated with aluminium chloride at 210'.Dinit~.oiuara~?/ds.ox~p~~eny~~~t~aZide? CO<-o->CH*C6H,(N0,),*OH [(NO,), : OH = 3 : 5 : 4, probably], obtained by treating parahydroxy phenylphthalide with the theoretical quantity of nitric acid (sp. gr. = 1.50) in concentrated acetic acid solution, is yellow, and melts at 1 87". Amido~al.cchydroxyphenl/~~~tJbaZide, CGH4 CO<igT>CH- C,H,(NH,')*OH [NH, : OH = 3 : 4, probably], is obtained" b i reducing tho corresponding nitro-corupound (Abstr., 1894, i, 600) with tin and hydrochloric acid; it is yellowish, and melts a t 229-230'. When a mixture of phthalaldehydic acid and 1-naphthol is stirred into 73 per cent.sulphuric acid at O", the product is 4-hydroxy- nc6pJ~thyl23~thcclide, CO<,&->CH* C,,H,*OH ; it melts at 322-223". An isomeric substance [OH = 2 (I)], obtained in a similar way from Electrolytic Reduction of Aldehydes and Ketones. By HUGO KAUFFMANN (Zeit. EZektvocJbem., 1898, 4, 462. Compare Abstr., 1896, i, 649).-Benzaldehyde, dissolved in alcoholic caustic soda, gives a good yield of the two hydrobenzoins when quickly reduced by means of a fairly large current. Other aldehydes and ketones behave similarly, acetophenone giving acetophenonepinacone, and the ketone, the corresponding benzhydrol. I n acid solution, the reaction takes place less smoothly, benzaldehyde giving large quantities of resinous products.Benzil (10 grams), dis- solved in boiling alcohol (150 c.c.) and 10 per cent. solution of sodium hydroxide (30 c.c.), and electrolysed for 6 hours at 70-80" with 2-3 amperes, gives, besides benzoic and benzilic acids, symmetrical tetra- phenylerythritol or benxoinpinacone, OH* CHPh*CPh(OH)*CPh(OH)*CHPh*OH, the yield of the latter being about 10 per cent. of the b e n d used. This substance melts at about 235", crystallises from alcohol in slender needles, and is most readily soluble in alcohol containing some alkali, but very sparingly in other solvents. When evaporated, the mother liquor of the benzoinpinacone deposits thick crystals which, after recrystallisation from chloroform, melt a t 175' and have the composi- tion C?8H,,03. Benzoinpinacone was also obtained by the electrolytic reduction of benzoin ; when heated at 235-240' in a vacuum, it loses 1H@, forming benzoin, With acetic chloride, it loses water and 6 4 2-naphthol, melts at 234-235'. c.P. B. CO[C6H*'N(cH3),]p - CHPh*CPh*OAc forms a diacetyl compound, probably O<CHph,&h.OAc ; this Crys- tallises from alcohol in white plates melting at 198', The substance C,,H,,@, does not undergo the pinacone decomposi-ORGANIC CHEMISTRY. 153 tion ; it forms a monacetyl compound, losing 1H,O a t the same time. The author considers that i t s constitution is probably OH CHPh*CPh(OH)*CHPh BCHPh, OH. Condensation of Mandelonitrile with Phenols. By AUGUSTI~~ BISTRZYCICI and HUGO SIMONIS (Ber., 1898, 31, 2812-2813).- a-Hydroxydiphenylacetolactone can be prepared directly from com- mercial mandelonitrile by acting on the latter with sulphuric acid and phenol, and this greatly lessens the cost of production.Neither the lactone nor the sodium salt of the acid appears to pro- duce any definite physiological effect on dogs. 7-Lactones of Phenolic Acids. By GUSTAV CRAMER (Ber., lS9S, I . Derivatives of Ort?Lo?~ydroxydipheny lace to Zactone. -Eth y lic o d m - hydroxydiphenylucetate, OH- C,H,* CHPh*COOEt, obtained by the action of alcoholic hydrogen chloride on the lactone, crystallises in stellate groups of prisms melting at 104-106O. y-Lactones of alcoholic acids, on the other hand, are usually converted into chloro- acids by this treatment. ~ r t ~ ~ o ~ ~ y d r o x y d ~ p ~ ~ e n y ~ a c e t a m ~ ~ e is obtained by the action of ammonia on the lactone, and crystallises in slender needles melting at 161-162'.When i t is heated at 180°, i t is con- verted into the lactone. OH* C6H4* CHPh*CO *NHMe, prepared by the action of methylamine on the lactone, crystallises in small needles melting a t 180-182'; the anilide, obtained in a similar manner, crystallises in lustrous, white plates melting a t 1 4 3 - 1 4 6'. OH* C,H,* CPh( NHJ-CO-NH,, is formed by the action of aqueous ammonia on orthohydroxydiphenyl- bromacetolactone, and melts and decomposes a t 150-15 1'. When it is boiled with hydrochloric acid, it is converted into the orthohydroxy- diphenylglycocine ?hydyochZoride, which melts a t 275-27s'. The cor- responding cccid crystallises in very hygroscopic needles melting a t 210-2 15',and probably has the constitution OH* C,H,* CPh<:%>O. It follows from this that the additive product obtained by the action of ammonia on the bromolactone is a true hydroxyamide and does not contain the lactone ring.Ortho~~ycl~ox~diphenyZacetcclnidoacetoluctone, NHAc*CPh<!EEj>O, obtained by the action of acetic anhydride and sodium acetate on the hydrochloride of orthohydroxydiphenylglycocine, crystallises in slender, lustrous needles melting at 225 -228'. II. Derivatives of Phenplparacresy Zucetoluctone. - PlbenyZpamcresyl- ucetamide, OH* C,H,Me*CHPh*cO *NH,, crystallises in stellate groups of lustrous prisms and melts a t 139-1 40'. PILenyZ~ccrucresyZ~rom- acetolactone, CPhBr<2Cb->0, forms well developed, tabular mono- symmetric crystals [u : b : c = 1.8482 : 1 : 2.1060 ; ,G = 85' 13'1.Phenyl- paracresylanzidoacetanaide, OH* C,H,Me*OPh(NH,)*CO *NH,, forms lustrous crystals me1 ting a t 1 4 6 - 1 4 So. I'henylpcci.acresylglycocine, OH* C,H3Me*CPh(NHz)*C00H, which is almost insoluble in any of T. E. A. H. 31, 2813-2821). The corresponding metl~ykurnide, OYt?Loh ydroxydiphen y Zanzidoacetunaide, c' H Me154 ABSTRACTS OF' CHEMTCAT, PAPERS. the ordinary SoIvents, melts st 190-102° ; the IiydrochZuride readily loses hydrogen chloride if left in n desiccator. P?Len?l~~ctracresylucet- ~lirLidoucetoluctore, NHAc*CPh<"C&->O, C H Me crystallises in lustrous needles melting at 2 14-2 16". ~hen~~ccrcccres~~ethoxyuceto~ac~one, OEt* CPh<?:_">O, crystallises in lustrous prisms melting at 1 22".Y~~en~2parucres~Zet~ox~acetic acid, OH* C,H,Me*CPh(OEt)*COOH, crystallises in slender needles melting at 131-134", and its ccmide in small needles melting a t 103-105°. 111. Beriz.atiues of Phe~~~lmetacresykcccetoluctone.-PJ~erzylmetacresy~- ucetccrnide crystallises in lustrous prisms melting at 163-1 66". PhenylnzetucresylbrornucetoZactone forms pale yellow, lustrous plates melting a t 96 -97". Pl~enyZmetcccresyZet?~oxyacetolccctone crystallises in lustrous prisms melting at 91-93". Condensation of Mandelic Acid with ,&Naphthol, Resorcinol, and Orcinol. By HUGO SIMONIS (Ber., 1898, 31, 2821-2830).- Phenyl-P-hydroxynaphthylacetolnctone is best prepared by the action of mandelonitrile on P-naphthol. The basic bccrium salt, C,,H,,O,Ba, crystallises with 3H,O in small, soluble prisms, whilst the norr.mal salt, (C,,H,,O,),Ba + 2H,O, is sparingly soluble, and crystallises in long, thread-like needles.~heny~-~-?cydroxynup?~t~~~bro~c6cetokcc~CPhBr<ygz>O, produced by the action of bromine on t h e lactone, forms well-developed, greenish-yellow, monosymmetric crystals [a : 13 : c = 1,2894 : 1 : 0.480 ; P= 91" 30'1, and melts a t 121'. Phenyl-P-hydvoxy- IztcplitlL?/Zmet~ox~ucetoZccctone, OMe* C P h < ~ ! j f Q O , obtained by the action OF methylic alcohol on the foregoing compound, crystallises in yellow prisms melting at 136". Phenyl-P-hydroxynccphthylethoxy- cccetolactone forms colourless crystals melting at 145") and is accom- panied by two deep yellow substances melting at 187" and 233" respectively. The corresponding acid forms a basic buriurn salt, C',,H,,O?Bs, as well as a norind salt, both of which are sparingly soluble in water.I'henyZ-~-I~ydrox~lmuplitl~~Zbenzylox~acetolctctone, CH,Ph* O*CPh<-~O~>O, C H obtained by the action of benzylic alcohol on the bromo-compound, forms colourless crystals and melts at 181", whilst the corresponding phenoxy-derivative melts a t 160". Mandelic acid reacts with resorcinol in presence of sulghuric acid t o form two isomeric lactones. Phe~z?~lresorcylacetolactone melts at A. H. >GO. YH:CH* E-CHPh 133", and probably has the constitution OH*C:CH -C---0 It forms tabular asymmetric crystals [a : 6 : c = 0.6007 : 1 : 0.7010 ; ~ = 7 5 " 4 2 ' ; P=11Go 19'; y=108" 16'1. The isomeric compound, isop?~enyl~esorcylacetoZuctone, melts at 125") and probably has the constitution (?HiC(oH)* f?CHPh>CO.The crystals belong t o the rhombic system [a : b : c = 0.895 : 1 : 0.7841. CH .CH---C---0ORGANIC CHEMISTRY. 155 Both lactones yield homo-derivatives, that of the normal lactone welting a t 145", and that of the isolactoiie at 142". 1)ibi,o,)Lol,~~en?/l- resol.c?lZ~6celoZactor~e, C,,H,O,Br,, is obtained from the lactone melting a t 183", and probably has the constitution CO<-, ->G6H2Br*OH. Plwzylorcyl- acetoluctone crystallises in slender needles melting at 155". The SO- lactone melts at 172". iMonobyonzophenylorcyZacetolctctone forms brown- ish crystals melting a t 185', whilst the dib?.omo-Zuctone melts a t 205". By R~OSES GOMBERG (J. Amer. Chem. Xoc., 1898,20,79O).---On mixing solutions,in benzene o r carbon bisulphide, of triphenylbromomethane and excess of icdine, a periodide, CPh,BrI,, crystallises out ; after recrystallisation from benzene or carbon bisulphide, it melts at 121-122'.The periodide may be obtained in bluish-green, iridescent, hexagonal prisms or in small needles. On .two occasions, the unusual phenomenon of the formation of hollow crystals was observed, the canal apparently coinciding with the longitudinal axis of the crystal. The author points out that all periodides hitherto described ale those of metallic salts or of bases, whereas triphenylbromomethane is not a base. CPhl3r Orcinol, like resorcinol, yields two isomeric lactones. A. H. A Periodide of Triphenylbromomethane. G. W. F. H. Tetraphenylmethane. By MOSES GOMBERG (J.Anaey. Chein. Soc., 1898, 20, 773-780),-This paper is a revision of the author's work on tetraphenylrnethane (hbstr., 1897, i, 623). Triphenylmethane is brominated, and the triphenylbromomethane produced treated with phenylhydrazine, when it yields triphenylmethanehydrazobenzene ; this, when oxidised with nitrous anhydride, gave triphenylmethane- azobenzene melting a t 110-112', which, on heating at 1 10-120°, evolves nitrogen, forming tetraphenylmethane, the yield being, how- ever, very poor. Tetraphenylmet ham crystallises from benzene in white, glistening needles. That tetraphenylmethane is really formed, is indicated, not only by the analysis, but by a cryoscopic determination of the molecular weight ; moreover, the substance is readily and completely converted into a tetranitro-derivative melting a t 275'; this does not yield ,z sodium derivative by the action of sodium ethoxide, whereas the nitro- phenylmethane derivatives, CH,[C,H,(NO,),],, N 0,.C,H,- CH,. CN, CH(C6H,*N0,),, which still contain hydrogeniattached t o the methane carbon atom, readily yield sodium derivatives. Tetranitrotetra- phenylmethane appears to be reduced by zinc dust and acetic acid to leucopararosaniline. G. W. F. H. Constitution of Phthalyl-Green. By ALBIN HALLER and ALFRED GUYOT (Compt. rend., 1897, 125, 1153-1 156. Compare Abstr., 1881, 587, and 1898, i, 483). The colouring matter produced by the condensation of phthalyl tetrachloride and dimethylaniline is identical with 0. Fischer's phthalyl-green. There are many points of resemblance between this compound and malachite-green, and the authors put forward the formula, NMe,* C,H,* COO C,fT;CCl(C!,H;NMe,) ,,156 ABSTRACTS OF CHEMICAL PAPERS.as being most in accordance with the reactions of the former sub- stance ; in other words, phthalyl-green is malachite-green containing the radicle, NAIe,* C,H; Go, introduced into an ortho-position in tbe non-substituted phenyl group. The leuco-base obtained from such a colouring matter should have the formula, ~~~e,*C,H,*CO*C~H;~H(C,H~*NMe,),, which is in agreement with 0. Fischer's analytical results. Rosenstiehl has shown that the basic colouring matters of the triphenylmethaue series containing n atoms of amidic nitrogen are capable of combining with (n + 1) molecules of hydrochloric acid t o form polyhydrochlorides, of which pararosaniline tetrahydrochloride, CCI( C,H,*NH2,HC1),, may be taken as the type.Phthalyl-green behaves like pararosaniline, and forms a tetrahydro- chloride. This compound, although containing four chlorine atoms ought not t o combine with 2 molecules of platinic chloride, since the formation of a platinochloride is due only to the presence of quinque- valent nitrogen atoms. It might be expected, however, that 2 molecules of the tetrahydrochloride mould combine with 3 molecules of platinic chloride. The platinochloride obtained by the addition of platinic chloride t o a solution of the colouring matter in concentrated hydro- chloric acid has the formula (C,H3,N30C1),,3H2PtC1,. By EUGEN BAMBERGER Bey., 1898, 31, 2624--2626).-The author has obtained with ,&naphthol results similar to those described by Dimroth (this vol., i, 54) in the case of phenol.p-H?ldrox?lnaphthyl-l-naercztric acetate, OH*C,,H,*Hg*OAc, is made by adding P-naphthol (13.2 grams) to a clear solution of mercuric oxide (20 grams) in hot acetic acid (520 c.c.) ; it separates a t once as a heavy, crystalline precipitate, and can be purified by recrystallisation from hot acetic acid. It crystallisesin white, shining needles, and, when quickly heated, melts and decomposes at 185' ; it is sparingly soluble in most of the usual media, but dissolves readily in soda, and is reprecipitated on addition of acetic acid; on addition of ammonium sulphide to its aqueous solution, a voluminous, yellow precipitate is produced which blackens when the liquid is heated, mercuric sulphide being formed.The mercury is very loosely attached to the naphthol nucleus, and the union is destroyed by the addition of soda or of diazotates, P-naphthol being formed in the first case, and phenolazonaphthols being produced in the second. G. T. M. Mercurial Compounds of ,%Naphthol. A. L. Synthetical Isoborneols ; their Identity with the Fenchylic Alcohols. By GUSTAVE BOUCHARDAT and J. LAFONT (Cow@. rend., 1898, 126, 755--757.)-Synthetically prepared dextrorotatory iso- borneol, obtained by the authors by the action of certain acids on lsvorotatory turpentine, consists of a mixture of the dextrorotatory and inactive fenchylic alcohols; these, on oxidation, give rise t o ltevo- rotatory and inactive fenchone respectively.The former is the optical antipode of the dextrorotatory fenchone obtained from oil of fennel ; both compounds have the same crystalline form and melting point, and their specific rotations are equal in magnitude but opposite in sign. The corresponding fenchone oximes bear similar relations toORGANIC CHEMISTRY. 157 each other, and when equal weights of them are mixed together, in ethereal solution, a racemoid form, melting at 154-1556', is obtained on evaporation. When lsvorotatory fenchone is reconverted into dextrorotatory fenchylic alcohol by reduction with alcoholic potash or sodium and alcohol, the optical activity of the substance is less than it was originally. G. T. 31. Beetroot-resin Acid. By KARL ANDRL~K and EMIIL VOTOCEK (Chem.Centr., 1898, i, 621-622 ; from New Zeit. RGb.-Zzcck.-lnd., 40, 39-44).-According to the authors, the substance obtained from the scum formed in the first treatment of the sugar liquors with lime and carbonic anhydride is not isocholesterol, as Kollrepp sup- posed, but a kind of resin to which they give the name beetroot-resin acid. It is prepared by treating the scum with dilute hydrochloric acid and extracting the dry, insoluble material with alcohol. The scum on the waste water of the factory, the deposits in the heating apparatus for the diffusion process, and the diffused juice also contain this substance. It crystallises from alcohol in colourless, silky needles, melts at 299-300", has a specific rotatory power [ a ] n = + 74.4" at 20°, is insoluble in water, easily soluble in boiling alcohol, amylic alcohol, and isobutylic alcohol, and less soluble in methylic than i n ethylic alcohol.It dissolves easily in glacial acetic acid, but the solution, on evaporation, does not yield the original compound. When heated above the melting point, it sublimes and partially decomposes, forming a liquid and a crystalline sublimate; the latter melts and chars a t 241'. The resin-acid bas the composition C,H,O, and crystallises with 1 H20. The colour reactions with sulphuric acid and acetic anhydride are like those of ahietic acid, vitine, ursone, gentiol, cholesterol, and many resin-acids. The sodium and potassium salts were prepared. E. W. W. Aloins. By EUG~NE LEGER (Compt. rend., 1898, 12'7, 234-236. Compare Abstr., 1898, i, 445).-TrichZoroburbaZoin, C,,H,,CI,07 + H20, obtained by the action of potassium chlorate on a solution of barbaloin in concentrated hydrochloric acid, crystallises from alcohol of 90 per cent.in monoclinic, rhomboidal tablets [a : b : c = 1.5448 : 1 : 1.38801. Unlike barbaloin, it dissolves in sodium carbonate solution, but i t does not displace carbonic acid. When heated in sealed tubes with acid chlorides, it yields tricLcet?lltricl~ZorobarbuZoin, which crystallises in very thin, microscopic, rhomboidal lamellae, and tribenxoyZtl.icl~Zorobarb- aZoin,anamorphous compoundvery solubleinacetone,but almost insoluble in alcohol. Under different conditions, barbaloin itself yields only a diacetyl or dibenzoyl derivative, but there can be no doubt t h a t barbaloin contains three hydroxyl groups, which have EL phenolic function, for i t gives a n olive-green coloration with ferric chloride, dissolves in alkali hydroxides, but not in the carbonates, and when heated with sodium hgpobromite in excess, yields carbonic and oxalic acids and carbon tetrachloride.IsobarbnZoi?A, C,,H,,07, is found in the last fractions of the crystal- lisntion of a mixture of aloins. I t crystallises from methylic alcohol in opaque nodules, composed of elongated and truncated, micro-158 ABSTRACTS OF CHEMICAL PAPERS. scopic lamelh which contain 3H20 and are efflorescent ; when crys- tallised from water, i t forms pale yellow, prismatic needles which contain 2H,O. With benzoic chloride in presence of pyridine, it yields dibenxoylisobnrbnloin, very similar to the corresponding barb- aloin derivative., Tric~lorisobarbaloi, obtained by the action of potassium chlorate and hydrochloric acid, forms brilliant yellow, prismatic needles ; when heated in sealed tubes with acetic chloride, it yields a crystallisable triacetyltrichlorisobarbaloin. Tribromiso- bcwbaloin is identical with the compound hitherto described as tribromobarbaloin. The relative proportions of barbaloin and isobarbaloin vary greatly in aloes from different localities. C. H. B. Kosin. By GIROLAMO DACCOMO and GIOVANNI MALAGNINI (L’ Ovosi, 1897, 20, 361-371).-Commercial kosin, obtained from the flowers of Hugenia a6yssiniccc, melts a t 147-149.5O, and appears to be a mixture of at least two substances, since, on fractional dissolution in, and crystallisation from, alcohol, i t yields products having melting points ranging from 105’ to 161’. The portion of highest melting point is the principal constituent of the commercial substance, and resembles in its properties the kosin described by Fluckiger and Buri; it crystallises in long, yellow needles, which are insoluble in water but more or less soluble in organic solvents, and dissolves in alkalis, yielding solutions from which it is reprecipitated unchanged on the addition of acids.Its solutions give a violet coloration with ferric chloride, reduce an ammoniacal solution of silver nitrate, and react with phenylhydrazine to forrn resinous products, and probably a hydrazone ; no reaction takes place, however, with Fehling’s solution or with hydroxylamine.This substance, to which the term ‘‘ kosin ” is properly restricted, is shown by analysis and by cryoscopic mole- cular weight determinations (found, 411 ; theory, 402) to be more accurately represented by the formula C,,H,,07, than by the formula C,,H,,O,,, proposed by Fluckiger and Buri. Triacetylkosin, C22H,, Ac,07, obtained by the action of acetic anhydride on kosin, crystallises from alcohol in small, colourless needles. The corresponding benxoyl derivative, obtained by the action of benzoic chloride on a solution of kosin in caustic potash, forms small, almost colourless crystals. The analyses of these compounds and cryoscopic molecular weight determinations are in accordance with the formula proposed for kosin by the authors. Kosin readily undergoes oxidation in alkaline solution, with the formation of isobutyric acid arid complex resinous substances.With potassium permanganate, oxalic acid is also obtained, whilst when bromine or iodine is employed, bromoform and iodoform are respec- tively produced. Kosin resembles filicic acid in many respects, but differs from i t in not reacting with Fehling’s solution or with hydroxylamine. Thc existence of three hydroxyl groups in the molecule of kosin is shown by the formation of the acctyl and benzoyl dcrivatives, whilst its behaviour with plienylhydrazine and with oxidising agents indicates the presence of a ketonic nucleus t o which an isopropyl group is probably attached. N. L.ORGANIC CHXMISTRY. 159 Strophanthin. By LEOPOLD KOIIN and VICTOR KULISCH (Monntsh., 1898, 19, 385-402.Compare Abstr., 1898, i, 326 and 327).-The strophanthin which the authors have described (Abstr., 1898, i, 329) is not identical with Feist's preparation (ibid.), The seeds from which they obtained the principle were those of Strophanthus Konzb6 or 8. hispidus, probably the former, as they appear to be identical with those employed by Feist, and the isolation of the substance was achieved by Arnaud's process (Abstr., 1888, 1310). The seeds, carefully freed from the adherent hairs, were powdered as finely as possible, washed in a Soxhlet's apparatus with light petroleum, and extracted with 70 per cent. alcohol. To the alcoholic extract, basic lead acetate and lead hydroxide were added, the lend being subsequently eliminated from the filtered liquid by means of hydrogen sulphide ; the filtrate was then evaporated in a vacuum, and the crude strophanthin so obtained purified by repeated crystallisation from water ; i t appears t o be identical with Merck's '' crystallised strophanthin," which is obtained from Strophanthus hispidus. The substance is inactive ; it is very hygroscopic and, when damp, melts a t 100'; the melting point of the anhydrous substance is very uncertain, but lies near 179'.The authors' analyses gave numbers in close agreement with those obtained by Arnaud, but it is as yet uncertain which of the formulz, C,,H,,O,, or C,,H,,O,,, represent the true composition of the substance. d trophanthin appears to contain a methoxy-group ; a determination by Zeisel's method gave a methoxyl content = 3.77-3.4 per cent., a number which points t o the second of the above formulz as being the correct one.AcetyZst?*ophanthin, C,,H,,O,(OAc),, or C,,H,,O,,(OAc),, is made by heating strophanthin with acetic anhydride and anhydrous sodium acetate, and can be purified by recrystallisation from hot alcohol ; i t forms very long, slender, colourless microscopic needles, melts at 236--238', and is insoluble in water. Strophanthidin crystnllises from hot alcohol in beautiful, slender, white needles which aggregate to form silky leaflets. It melts at 195', does not dissolve in water, but is very hygroscopic; it cannot be dried at loo", as it suffers slight decomposition a t that temperature. It has the formula C,,H,,O,, or C,,H,,O,, but, like strophanthin, its methoxyl content is too low, and is lower even than that required by the latter formula.A. L. Action of Cinnamaldehyde on Phenyltoluidoacetonitrile. By WILHELM VON MILLER and JOSEF PLOCHL (Bey., 1898,31, 2718-2720). -In distinction from the behaviour of aromatic aldehydes, which yield two indifferent isomeric compounds with anilido-derivatives or with amido-nitriles, aliphatic aldehydes yield but one indifferent pro- duct (compare this voI., i, 127). Tn order to examine the behaviour of unsaturated aldehydes under similar conditions, the action of cin- namaldehyde on phenyltoluidoacetoiiitrile has been studied. Diphenyltol yl2i9wo line, 7 C'Ph>N* C,H,Me, obtained by heating CH. CPh160 AUSTRACTS OF CHEMICAL PAPERS. phenyl toluidoacetonitrile wit h cinnamaldehyde and potash inalcobo1,crys- tallises from alcohol in lustrous prisms, and melts a t 181'; it arises from the union of the aldehyde and nitrile in molecular proportion, involving elimination of water and hydrogen cyanide, also in molecular proportion.The additive compound, CHPh:CH. CH(OH)* CPh(CN)-NH*C,H,Me, melts and decomposes at 175' ; it doubtless represents an intermediate stage in the production of diphenyltolylpyrroline, which is generated along with hydrogen cyanide when the substance is heated. 31. 0. F. Distillation of Mix:ures of Pyridine and Aliphatic Acids. By GUSTAVE ANDR~ (Conzpt. wad., 1897,125, 1187-1 189).-Chemical combination evidently occurs when formic, acetic, and propionic acids are mixed with pyridine, for a n appreciable amount of heat is developed, but when the mixture is titrated with standard baryta, using turmeric or phenolphthalein a s indicators, the acidity is found to be equal to the whole amount of acid added.After six fractionations of a mixture of propionic acid and pyridine, in molecular proportion, a distillate is obtained boiling at 150-151" under a pressure of 760 mm. This liquid has approximately the composition 2C,H,02,C,H,N, and i t boils 11" higher than propionic acid and 37' higher than pyridine. When boiled under reduced pressure, the mixtkire has no definite boiling point, and the first distillates contain more pyridine than is required by the above formula. A mixture of acetic acid and pyridine behaves in a similar manner; the least volatile portion boils at 139-140" under 760 mm., and i t s composition cori-espontls with 3C21i402, 2C,H,N.When fractionated, this portion is gradually dissociated ; ebullition always commences at looo, and the temperature rises slowly to 139--140'; when distilled under a pressure of 60 mm., it passes over unchanged a t 74", but under 20 mm. i t i s dissociated. A mixture of pyridine and formic acid, in molecular proportion, after seven fractionations, yields a distillate boiling at 148-151' (760 mm.), of the composition 5CH2O2,2C,H,N ; this mixture, when distilled under a pressure of 36 mm., boils a t 74" without dissociation. G. T. M. Ammonio- and Pyridine Salts and Hydrates of Bivalent Metals. By FRITZ RXITZENYTEIN (Zed. cmory. Chew?,., 1898, 18, 253-304. Compare Abstr., 1895, i, 121 ; 1897, i, 38O).-The author discusses the relations between the ammonium salts, hydrates, and pyridine compounds of metals.The repeated occurrence of the same type in the three series is most easily explained hy Werner's theory. The character of the acid residue which is combined with the metal becomes of more importance as the number of pyridine molecules increases ; and the influence of the metallic atom varies in the inver,*e manner. The greatest number of pyridine molecules which can be combined is six, and this occurs in the compounds with CuBr2, CdBr,, and Cdl,. The greatest number of qiiinoline moIecules is four, occurring in the compounds with CaCl, and CoCI,. Isomerides of theORGANIC CHEMISTRY. 161 formula zMeX22Py, which, according to Jorgensen's and Werner's theories, are possible, have not been obtained.The author gives a table of all the known ammonium, pyridine, and quinoline salts and hydrates, and describes the following new com- pounds. Monopyridine nickel chloride pentahydrate, NiCI,,C5H,N,5H,0, is obtained by exposing monopyridine nickel chloride to the air for 4-5 days. Nickel chloride monopyridine hydrochloride, NiC12,C5H,N,HCI, is ob- tained by treating finely divided nickel chloride with pyridine, dis- solving the product in concentrated hydrochloric acid, and evaporating the solution on the water-bath. It crystallises in flesh-coloured needles, deliquesces in the air, gives a green solution in water, and characteristic precipitates with potassiam ferrocyanide and ferricyanide. When the mother liquors obtained in the preparation of this salt are evaporated, a compound is obtained which separates in blue crystals, and is probably a tetrahydrochloride compound.Nickel chloride dipyridine hydrochloride, NiCl,,( C,H,N?HCl),, was obtained on one occasion by dissolving nickel oxide in pyridine hydro- chloride, and concentrating the solution on the water-bath, but the author was unable to obtain it again. The solution, on evaporation, first yields the salt 2NiC1,,3C,HGN, crystallising in greenish- yellow needles ; on further concentration, it yields NiCl,,C,H,N, then NiCl,,C,H,N,HCI, and finally NiC1,,4C5H,N, which crystallises from pyridine in bright blue needles. Nickel swlphate tripyridine dihydrate, NiSO,, 3C,H5N,2H,O, obtained by adding excess of pyridine to an aqueous solution of nickel sulphate, then adding alcohol and boiling, is a bluish-green, crystalline mass soluble in water, and gives a green precipitate with potassium ferro- cyanide.Cobalt chloride tetrapyridine, CoCl2,4C5H,N, is obtained by heating a mixture of cobalt chloride and excess of pyridine hydrochloride in alcoholic solution ; when dissolved in alcohol, i t yields a blue compound, probably CoC1,,2C5H,N,2EtOH, which quickly decomposes into the dipyridine compound. Cobalt chloride monopyridine pentahydrate, CoC1,,C5H,N,5H,0, is obtained as a reddish, crystalline mass by allowing cobalt chloride monopyridine to remain exposed to the air for a few days. Dicobalt chloride pentapyo*idim hydroshloride, 2CoCl,,( C5H6F,HC1),, obtained by heating the tetrapyridine compound dissolved in water with excess of hydrochloric acid, and also by the action of concen- trated hydrochloric acid on a mixture of cobalt chloride and pyridine, is a dark blue, crystalline powder, and gives a red solution in water ; when treated with silver nitrate, all the chlorine is precipitated.Cobalt chloride dipyyidine monohydrochloride, CoC1,,2C,H5N,HCI, obtained by treating the preceding compound in alcoholic solution with the theoretical quantity of silver oxide, crystallises in dark blue crystals, melts a t 1 5 5 O , is soluble in cold water with a red coloration, and, when heated in the air-bath at 150" is converted into the basic chloride, CoCl?,CoO. When treated with excess of silver oxide in alcoholic solution, it is converted into cobalt chloride dipyridine.VOL. LXXVI. i m162 ABSTRACTS OF CHEMICAL PAPERS. When cobalt chloride dipyridine is treated with ammonia and hydro- chloric acid, a salt of the composition CoC1,,(C,H,NC1,NH4C1),,3H,0, is obtained, which crystallises from absolute alcohol in bright blue needles, darkens at 120", melts a t 128-130", and when exposed to the air quickly turns red. The tetrapyridine and dipyridine com- pounds of cobalt chloride, when exposed to the air, take up water and give off pyridine in varying proportions according to the time of exposure, and compounds of the following composition were obtained, UiCl,, 2CiH,N,2H20 ; CoCl,, 1+C5H5N,3iH,0, and CoC1,.3C,H,N,3H,O. Cobalt euZphccte tripyridid' d&&te, *CoSO4,3C5H5N,2H20, ob- tained by treating an aqueous solution of cobalt sulphate with pyri- dine, separates in blood-red crystals, cannot be recrystallised from absolute alcohol or pyridine, is decomposed by warm water with pre- cipitation of cobalt hydroxide, and, when treated with barium chloride, gives a quantitative precipitate of barium sulphate.When allowed t o remain exposed t o . the air for a month, it is converted into the compound CoS04,C5H5N,2H,0. Cobalt nitrate, when heated with pyridine, yields a red compound, which can be recrystallised from absolute alcohol, smells strongly of pyridine, and is probably Co(N0,),,4C5H,:N. The author was unable to obtain a compound of ferrous chloride with pyridine in aqueous solution. When solid ferrous chloride is shaken with pyridine, the compound FeC12,3C5H,N,2H,0 is obtained ; this is a yellow, crystalline powder, has a strong odour of pyridine, is very easily decomposed, and is slightly soluble in water.Ferrous sulphate tripyridirze dihydrate, FeS04,3C,H5N,2H,0, ob- tained in brownish-yellow crystals by adding pyridine to an aqueous solution of ferrous sulphate, has a strong odour of pyridine, is easily decomposed with the formation of basic saltas, and, with barium chloride,. gives the theoretical quantity of barium sulphate. Cudmzum sulphate tripyridine dihydrate, CdS04,3C,H5N,2H,0, ob- tained in a similar manner to the preceding compound, is a white, crystalline precipitate, soluble in water. When heated a t 120" for 1 hour, or allowed to remain 35 days exposed to the air, the pyridine is eliminated and CdS04,2H,0 remains.When anhydrous copper sulphate is treated with pyridine,a dark blue, crystalline powder is obtained, which is probably 2CuS04,C,H5N,H20. It is very unstable, and cannot be obtained in a pure state. It is partially soluble in water with the formation of a basic salt, insoluble i n pyridine, and when boiled with absolute alcohol is converted into a green powder, When allowed to remain exposed to the air, it be- comes bluish-green, and thus has the composition 2CuS04,C5H5N,4H20. The compound, 2CuS04,3C5H,N, obtained by digesting anhydrous copper sulphate with absolute alcohol and excess of pyridine for some time, is a bright blue powder, which, when boiled with absolute alcohol, is converted into the compound CuS04,C5H5N, identical with the pyridine copper sulphate obtained by Jorgensen by heating copper dipyridine sulphnte, and by Lang by heating the compound CnS04,C,H5N,3H,0 at 110".OKGANIC CHEMISTRY.163 Lead chloride pyridine, PbCl,,C,H,N, obtained by boiling lead per- oxide with a solution of pyridine hydrochloride in hydrochloric acid, crystallises quickly from the filtered solution in beautiful, white crystals. Manganese tetrachloride dipyridine, MnC1,?2C5H,N, is obtained by warming freshly precipitated manganese dioxide with pyridine hydro- chloride dissolved in hydrochloric acid. On concentrating the filtrate on the water-bath, it separates in large, bright green crystals, which give a colourless solution with water; when allowed to remain ex- posed to the air, it loses chlorine and is converted into the compound MnC1,,2C,H5N.34angccnous chloride dipyridine, MnC1,,2C,H5N, obtained by adding excess of pyridine to a concentrated solution of manganous chloride, separates in brown crystals which darken on exposure, is easily soluble in warm water, and when heated at 160-165O is converted into the compound MnC1,,1 &C,H,N. Mccnganous chloride dipuinoline, MnC1,,2C,H7N, obtained by adding excess of quinoline to an alcoholic solution of manganous chloride, sepa- rates in brown crystals, is insoluble in cold water, dissolves in hot water with decomposition, and is soluble in cold alcohol. Cadmium bromide dipuinoline, CdBr,,2C,H7N, obtained by boiling cadmium bromide with excess of quinoline, separates from absolute alcohol in white prisms, and is sparingly soluble in cold water.E. C. R. Pyridine Compounds of Quadrivalent Palladium.-By ARTHUR ROSENHEIM and THEODOR A. MAASS (Zeit. anorg. Chem., 1898, 18, 331--338).-Amine bases of quadrivalent palladium have not yet been obtained. The dipalladamine chloride, Pd,CI,(NH,Cl),, described by Devilleand Debray (Compt. rend., 86, 926) is amixture consisting for the most part of ammonium palladium chloride (NH,),PdCI,, and this is the only compound which the authors were able to isolate by the action of chlorine water on palladosamine chloride in the cold. By the action of chlorine water a t higher temperatures, ammonium palladious chloride, (NH,),PdCl,, is formed, with evolution of nitrogen. The action of bromine on palladosamine chloride takes place in a similar manner.The pyridine bases of quadrivalent palladium are, however, easily obtained. Palladodipyridine chloride, Pd(C,H,N),CI2, is obtained by adding pyridine to a solution of palladious chloride; a red precipitate is obtained which dissolves when boiled with excess of pyridine, and on adding strong hydrochloric acid,, palladodipyridine chloride is precipi- tated as a bright yellow, crystalline powder. PalZadidipyridine chloride, Pd(C,H,N),Cl, obtained by the action of chlorine on the preceding compound suspended in chloroform, crystallises in small, dull, orange prisms, gives off chlorine when exposed to damp air, and is fairly stable in dry air ; when heated with potassium hydroxide, a brown precipitate of palladium hydroxide is obtained, and when the cold product is carefully neutralised with hydrochloric acid, potassium palladichloride, K,PdCl,, crystnllises out in characteristic cherry-red octahedra.When shaken with an 111 2164 ABSTRACTS OF CHEMICAL PAPERS. aqueous solution' of potassium iodide, two atoms of chlorine are eliminated, and palladodipyridine chloride is formed. Palladidipyridine dibromochloride, Pd( C5H5NBr,),Br,C12, obtained by shaking palladodipyridine chloride suspended in chloroform with bromine, is a deep orange-red, crystalline powder, and is much less stable than the preceding compound. When boiled with potassium hydroxide and then neutralised, potassium palladichloride is obtained. The authors were unable t o obtain a similar compound by the action of bromine on palladodipyridine bromide. Palladidipgridine di-iodochloridt3, Pd(C,H,N),I,CI,, obtained in a similar manner to the preceding compounds, crystallises in brown needles, and is remarkably stable on exposure to the air.When boiled with water or with potassium hydroxide, it is completely decomposed, with the formation of black palladious iodide. When, however, it is shaken with pure carbon bisulphide, it gives off two atoms of iodine, and is quantitatively converted into palladodipyridine chloride. E. C. R. Derivatives of Nicotinic Acid. By A~nb PICTET and G . SUSSDOKFF (Chem. Centr., 1898, i, 677-678 ; from Arch. Sci. phys. nat. Gedve, [iv], 5, 113--128).-An 52 per cent. yield of nicotinic acid is obtained by pouring a solution of 10 grams of nicotine in 100 C.C. of water and 20 grams of concentrated nitric acid into 250 grams of concentrated nitric acid, and heating the mixture on the water- bath until no more red fumes are evolved ; the nitrate of the acid, which is obtained -on evaporation, melts at 185'.Nicotinic acid, prepared from the nitrate by means of the copper compound or by heating with acetic anhydride or by distilling alone, crystallises in white needles and melts at 229". Ethylic nicotinate, obtained by treating the acid with alcohol and hydrochloric acid, boils a t 220-221' under a pressure of 724 mm.; the nitrate melts a t 185", and the hydrochloride at 126-127". By the action of fatty amines on ethylic nicotinate, the following amides were prepared. MethyZnicotinatmide,C5NH,.CO*NHMe, crystallises from chloroform in long needles and melts a t 104-105O ; the methiodide, C7H,N02,MeI, crys tallises in needles, melts a t 1'74O, and with silver nitrate forms the corresponding nitrate which crystallises from-a mixture of alcohol and ether in prisms, and melts at 155-156'.By treating methylnicotinamide methiodide with silver oxide, an aqueous solution of the hydroxide is obtained, which, on evaporation, decomposes into methylamine and trigonellin. Amyl- nicotinamide boils at 19 1-1 93' under a pressure of 8 mm., and is easily soluble in ether. Allylnicotinamide boils at 186--189" under a pressure o€ 8 mm., at 315-316" under the ordinary pressure, and cannot be purified by distillation. By preparing the chloride by acting on nicotinic acid with phosphorus pentachloride, removing the phosphorus oxychloride, and then treating the residue with aromatic amines, hydrochlorides of substituted aromatic amides are obtained, and these, with sodium carbonate, yield the free amides.Nicotinanilide, C5NH,.CO*NHPh, crystallises from water in needles containing 2H,O and melts at 85' ; the anhydrous compound crystallises from a mixture of light petroleum and benzene or light petroleum and chloro-ORGANIC CHEMISTRY. 165 form in needles and melts at 132'. Nicotinopu~atoluidide crystallises from water in needles and melts at 150". Attempts to introduce a methyl group into allylnicotinamide failed, but potassium-methyl- nicotinamide and allylic iodide yield meti~ykullylnicotinami~e as a viscous liquid. Attempts to remove water from the latter compound, and to obtain nicotyrine from met hylnicotinamide and allylic alcohol a t 160-170' also failed.- Piperidine nicotinute, C,NH,*COOH,C,NH,,, crystallises in long, colourless needles and melts at 122'. E. W. W. Transformation of Fatty Ketazines and Aldazines in to Bv THEODOR CURTIUS and ED. ZINKEISEN Pyrazoline Derivatives. J."p9*. Chem., 1898, [ii], 58, 31b-332. Compare Abstr., 1894, i, 348). N=QR [R:R:Me=3:5:5],are -Mahates of pyrazolines, NH<cRMe. CH, obtained by treating ketazines, CRMe:N*&::CRMe (Abstr., 1891, 1355), with maleic acid, sometimes in alcoholic solution, and purifying the product by dissolving i t in alcohol and precipitating it with ether ; the free base is obtained by treating this product with potash. Only ketazines which contain at least one methyl group, >C:N*N:CMe-, are capable of reacting in this way ; diethylketazine, CEt,:N*N:CEt,, for example, will not do so.The pyrazoline derivatives obtained distil without decomposition under diminished pressure ; the boiling point and index of refraction increase with the molecular weight, whereas the specific gravity decreases. They are stable in the presence of acids, yielding no hydrazine salt, even on boiling, but potassium per- manganate oxidises them readily, the molecule being completely broken up. They are not coloured by oxidising agents in dilute solution (Knorr's pyrazoline reaction ; probably only given by deriva- tives in which the NH-group has become NPh). Of the compounds described, only 5-methylpyrazoline resembles pyrazoline itself (Abstr., 1895, i, 24s) in other respects; the rest do not form azo-dyes, they are not coloured yellow by nitrous acid, they do not colour a pine splint yellow, and they are not oxidised to pyrazoles by bromine.3 : 5 : 5-Trimethylpyrazoline boils a t 57-59' under 14 mm. pressure; sp. gr. = 0.903 at 18', 0.907 at 10'; index of refraction nD= 1.46149 a t 10' ; when oxidised with dilute permanganate nitrogen, carbonic anhydride and pyruvic acid are formed ; when treated with bromine in chloroform solution, its own hydrobromide, which melts at 171", is the product. 5-Methyl-3 : 5-diethylpyrccxoline boils at 90-93' under 20 mm., at 78-80' under 14 mm. pressure ; sp. gr. = 0.898 a t 18'; the hydrochloride, platinochloride, picrate, methiodide, and benzoyl derivatives are oils which would not crystallise ; with bromine, an oily product was obtained that was not the hydrobromide; in the air, this pyrazoline evolves nitrogen, and yields a substance, C,H,,O, boiling at 157-1558', which forms an oily compound with phenylhydrazine, and decolorises an ethereal solution of bromine, and so is probably CEtO*CH:CMeEt, a homologue of mesitylic oxide, although it does not, like the latter, condense with hydrazine; this substance is also obtained as a bye-product in the preparation of the pyrazoline.5-Methyl-3 : 5-dipopyZpyraxoZine boils at 101-103' under 14 mm., a,t166 ABSTRACTS OF CHEMICAT, PAPERS. 113-1 15' under 20 mm. pressure ; sp. gr. = 0.884 a t 18", 0.888 at 10'; yhD = 1.46318 ; in other respects, it resembles the previous compound. 5-ilfethyl-3 : 5-dil~exylpy~axoline is not formed very readily, and was obtained only in small amount. Ethylideneccxine, CHMe:N*N:CHMe, can be prepared by shaking an ethereal solution of acetaldehyde with an aqueous solution of hydrazine hydrate, and cooling with water ; it boils a t 95-96' under 760 nim.pressure, and has sp. gr. = 0.832 at 17' ; a t 180°, it is almost unchanged, but at a higher temperature it gives off nearly all its nitrogen as gas, no butylene being formed, however ; it is fairly stable towards alkalis, but acids decompose it into acetaldehyde and hydr- azine. With maleic acid, it yields the maleate of 5-methyl'yruxoline, and this, when decomposed with caustic potash, and the product frac- tionated, yields a small quantity of the pyrazoline, together with much of a bye-product (see below).The base boils at 73' under 55 mm., at 68' under 46 mm. pressure; the benxoyl derivative melts and decomposes at 156' ; a red tolueneaxo-derivative, with green reflex, was obtained; and with bromine in chloroform solution, 5-methylpyrazole appears t o be formed. The bye-product mentioned above, C ~ ~ H ~ G N G , possibly has the constitution FH* C,N,H,Me C3N2H4Me' OMe<CH. C,N,H,Me ; its hydrochloride and picrate melt and decompose a t 148' and 142' respectively; it takes up 6Br, gives a yellow coloration with nitrous acid, colours wood yellow, and reduces ammoniacal silver solution. C. F. B. Stereoisomerism in Piperazine and Ethylenediamine Deri- vatives. By WILLEM VAN RIJN (Chem. Centr., 1898, i, 727; from Ned. Tijdsck. Plzawn., 10, 43-52.See this vol., i, 77).-DiethyZ- pipermine, prepared by warming an aqueous solution of piperazine with a n excess of potassiiim ethylic sulphate, is purified by crys- tallising the platinochloride from hot dilute hydrochloric acid. By the action of methylic iodide (4 mols.) on piperazine, the compound NHMeI<:2: ;2>NMe,I is formed ; it crystallises from water in small prisms, decomposes at 260' without melting, and, with cadmium iodide (1 mol.), forms a double salt which crystallises in small, white prisms. The compound NEt<CH,. '*2* CH2>NEt,I, cH, prepared by the action of ethylic iodide on piperaGne, &ystallises from alcohol in white needles, melts at 240°, and is insoluble i n cold water, ether, chloroform, light petroleum, benzene, and carbon bisulphide ; the cadmium iodide compound crystallises in white needles.The action of propylic iodide on piperazine is analogous t o that of ethylic iodide. Attempts to prepare an isomeride of the hydrochloride of dibenzyl- piperazine methiodide by the action of freshly precipitated silver chloride on the dibenzylpiperazine methiodide obtained from the hydrochloride by means of sodium hydroxide, resulted only in the production of the original compound. By the action of propylic iodide on methylethylethylenediamine, the mono- and di-propiodidesORCIANIC CHEMISTRY. 167 are formed, and may be separated by means of the platinochlorides. The platinochloride of the former crystallises in reddish needles, and that of the latter in reddish-yellow leaflets.No other salts could be obtained in a crystalline form. By PAUL CAZENEUVE and MOREAU (Con@. rend., 1897, 125, 1182-1 184)-Molecular pro- portions of piperazine and phenylic carbonate, when heated in alcoholic solution for 20 hours, give an almost theoretical yield of the d,iurethccne, CO0Ph.N :C,H,:N* COOPb, which forms prismatic crystals and melts a t 177--178O ; its constitution is established by hydrolysis with potash, and by decomposition with concentrated sulphuric acid. The a- and P-nuphtlbylic diurethanes, prepared in a similar manner, form white, mammelated crystals somewhat insoluble in ordinary solvents; the a-compound melts a t 190-191", the p- a t 220'. The guaiacol derivative, C,N,H,( COO*C,H,* OMe),, crystallises from alcohol in plates and melts a t 181'.Derivatives of Triasole. By JOHANNES THIELE and WILHELM MANCHOT (Annalen, 1898, 303, 33-56. Compare Thiele and Heidenreich, Abstr., 1894, i, 57).-Formamidoguanidine nitrate, COH*NH*NH* C( :NH) *NH,,HNO,, prepared by heating amido- guanidine nitrate with 90 per cent. formic acid and one drop of nitric acid on the water-bath, crystallises from water and melts a t 143'; the picrate crystallises in needles and melts at 193". Oxalylamido- guanidine, COOH. CO *NH*NH* C(NH) *NH,, obtained on adding amidoguanidine hydrogen carbonat,e to a concentrated aqueous solu- tion of oxalic acid, and boiling the liquid in a reflux apparatus, crys- stallises from water, and melts and evolves gas a t 231-232'. Ammonia is readily eliminated from amidomethyltriazole under the influence of dilute sulphuric acid at 180-190°, the other products being carbonic anhydride, hydrazine, and acetic acid; a 30 per cent, solution of caustic potash or soda, however, leaves the amido-compound for the greater part unchanged.The benxoyl derivative of amido- methyltriazole melts and decomposes at 285-290' ; the cccetyl deriva- tive crystallises from water, and remains unfused at 270". E. W. W. Aromatic Diurethanes of Piperasine. G . T. M. NH*N Met h y Ztriazoleaxodirneth y landhe, NMe,* C,H, * N,. cGN-- 8 Me, pre- pared by adding dimethylaniline hydrochloride t o a solution of diazo- tised amidomet hyltriazole, crystallises f rom alcohol, and melts and decomposes a t 238" ; reduction with stannous chloride and hydro- chloric acid destroys the colour, which is redeveloped under the influence of ferric chloride. is a red powder, with green, metallic reflex, and melts and decom- poses a t 270".The colour is destroyed by reducing agents, and is not redeveloped by ferric chloride. C'hloromethyltriaxole, CCIGN- - 8 Me, obtained by diazotising amido- methyltriazole in concentrated hydrochloric acid, and evaporating the HN*N168 ABSTRACTS OF CHEMICAL PAPERS. liquid a t tho ordinary temperature, melts at 1 4 7 O ; it is volatile in steam, and sublimes when heated on the water-bath. The silvey derivative is sparingly soluble in water, but readily in ammonia and nitric acid. NH*N Benxylidenemethyltriaxyl?tydraxine, CHPh:N*NH*CqN _- 8 Me, pre- pared by reducing diazotised amidomet hyltriazole, under special pre- cautions, and combining the product with benzaldehyde, crystallises from alcohol and melts at 263'; the ltydrochloride separates from alcohol in needles, and melts a t 256'.Amidotskcxole, NH2* C< NH'y obtained on heating aqueous N-CH' formamidoguanidine nitrate with sodium carbonate, crystallises from ethylic acetate and melts at 159' ; it closely resembles amidomethyl- triazole, but differs from the latter, which is feebly alkaline and has no reducing action, whereas amidotriazole is neutral, and slightly reduces a boiling, ammoniacal solution of silver nitrate. The nitrate melts and decomposes a t 174', and the picrate, which crystallises in yellow needles, melts and decomposes at 227-228". Axotriaxole, N2(C2H,N3),, prepared by oxidising amidotriazole with potassium permanganate in alkaline solution, dissolves in alkalis, and is pre- cipitated by acids.Hydrazotriazole Itydyochloride, which is formed when azotriazole is reduced with stannous chloride and hydrochloric acid, crystallises in white needles and melts a t 227-230", beginning to decompose before this temperature is reached. It reduces ferric chloride and ammoniacal silver nitrate, and aqueous solutions readily undergo oxidation when exposed to the air. ~riaxoleaxo~i~aethylccniline, produced on adding dimethylaniline hydrochloride t o a solution of diazotised amidotriazole, crystallises from alcohol, and melts and decomposes at 250'. NH.8 ChZoroti*iaxole, CClGN_ H, prepared by diazotising amidotri- azole in concentrated hydrochloric acid, crystallises from benzene in slender needles, and melts at 167'; it sublimes when heated, and is volatile in vapour of benzene.It yields salts with acids, and also forms metallic derivatives. obtained by NH.8 Amidotriaxolecarboxylic acid, NH2* C< N- C-COOH ' heating oxalylamidoguanidine (2 mols.) with sodium carbonate on the water-bath, melts a t 182' with elimination of carbonic anhydride and production of amidotriazole ; it dissolves readily in alkalis, and is pre- cipitated by acids. The picrate melts at 176', and the hydrochloride melts and decomposes at 171-172' ; the sodium salt is anhydrous, and the ethylic salt crystallises from alcohol and melts at 247'. Diccxotriaxolecarboxylic acid, C,HN,O, + H,O, prepared by diazotis- ing amidotriazolecarboxylic acid, decomposes at 96' ; it does not explode when touched with a hot wire, and detonates with difliculty when struck.Chlorotriazole is produced on heating the substance with hydrochloric acid, and triazole results from boiling an alcoholic solution in a reflux apparatus ; triazole obtained in this manner meltsORGANIC CHEMISTRY. 169 a t 120--120.5', and is identical with the compound described by Bladin and by Andreocci. M. 0. F. Hydrazine Derivatives of Propionic Acid. By JOHANNES THIELE and JAMES BAILEY (Anr~den, 1898, 303, 75-91. Compare Thiele and Heuser, Abstr., 1896, i, 340).-The semicarbaxone of acetaldehyde crystallises from alcohol in white needles, and melts at 1 6 2 '. Cur bonccnhid o h y draxopopionitrile , N H, C 0 CH NH CM e C N , prepared by the action of 60 per cent.hydrocyanic acid on the semicarbazone of acetaldehyde, crystallises from alcohol and melts a t 131' ; i t has a powerful reducing action, and yields hydrogen cyanide when heated. Carbonarnidohyclmxopropionccmide is obtained by the action of cold concentrated hydrochloric acid on the nitrile for 24 hours; it separates from water in lustrous crystals containing 1H,O, and melts at 99-106'. or a t 142' in the anhydrous condition. Y . Dihydroxynaethyldil~ydrotriaxine, OH* C<";rCj-%s>CMe, prepared by treating the foregoing nitrile with fuming hydrochloric acid during 48 hours, diluting the liquid with twice its volume of water, and boiling the product for 3 hours in a reflux apparatus, crystallises from alcohol in lustrous scales and melts at 214". Dihydvoxymethyl- triccxine, OH* C<E' c(oq>CMe, is obtained by oxidising the di- hydro-derivative with bromine water ; it softens at 206' and melts at 209'.The imido-ether of carbonamidohydrazopropionic acid is obtained in the form of the hydrochloride, NH,. CO- NH*NH* CHMe*C(OEt) :NH,2HCl, when an alcoholic solution of the nitrile is saturated with dried hydro- gen chloride ; it is very hygroscopic, deliquescing rapidly on exposure to the air, and melts at 124-128', when it decomposes vigorously. On dissolving the hydrochloride in water, neutralising one-half of the hydrochloric acid with sodium carbonate, evaporating to dryness, and extracting with ethylic acetate, ethylic carbonamidohydvaxopropionate, NH,*CO*NH*NH*CHMe*COOEt, is produced ; it melts at 1 0 8 O .The free acid, obtained by hydrolysis with baryta, melts and decom- posesat 166-1 68'. Hydrazidopropionicacid, NH,*NH* CHMe*COOH, prepared by the action of boiling 80 per cent. sulphuric acid on e thylic car bonamidohydrazopropionate, is identical with the com- pound described by W. Traube and Longinescu (Abstr., 1896, i, 340). The semicarbnzone of pyruvonitrile, NH,* GO *NH*N:GMe.CN, ob- tained by oxidising carbonamidohydrazopropionitrile with potassium permanganate, is a sparingly soluble crystalline powder, which melts and decomposes at 215'; the semicarbazone of pyruvamide and the semicarbazone of ethylic pyruvate melt and decompose at 230' and 206' respectively. Ethylic hydrccxopropionate, N,H,(CHMe*COOEt)2, prepared, under specified conditions, from hydrazine, aldehyde-ammonia, and hydrogen cyanide, by hydrolysing an alcoholic solution of the product with hydrogen chloride, crystallises from benzene, petroleum, or water in thin, elongated prisms; it melts at 78", and boils at 2 4 5 O170 ABSTRACTS OF CHENICAI, PAPERS.under a pressure of 750 mm. The salt can also be obtained from hydrazidopropionic acid, aldehyde-ammonia, and hydrogen cyanide. The methylie salt melts a t 93', m d boils a t 220' under a pressure of 720 mm. The free acid, which crystallises from concentrated aqueous solutions in microscopic needles, begins to darken at 180°, and melts and evolves gas at 198'. If. 0. P. Characteristic Oxidation Reaction of some Cyclic Amines. By EUGEN BAMBERGER and ANTON VON GOLDBERGIER (Ber., 1898, 31, 2636--2640).-The authors have found that the hitherto unknown izimidindazole, C6H4<h (NH2)>NH, may be oxidised in various ways, but in most cases the product is Weddige and Fluger's hydroxy-P- phenotriazine, the so-called benzazimide, C,H,<N $?(OH) 'fi; N A similar change of structure occurs also when the monomethyl, and dimethyl-izimidindazoles are oxidised ; these yield the corresponding monomethyl- and dimethyl-hydroxy-P-phenotriazines. Hydroxy-/3-phenotriazine partakes of the nature of a diazoamido- compound, as its formula indicates.It gives a brilliant red colour with /3-naphthy lamine, and with melted resorcinol it yields a colouring matter, benzamidocceoresorcinol, which crystallises in rosettes of dark- red needles. Its structure is probably NH,*OO*C,H**N,*C,H,(OH)~.When izimidindazole is oxidised in alkaline solution by means of a ferricyanide or even by air, a basic substance is formed, which has colouring properties and forms crystals having an intense green metallic sheen; it gives a sparingly soluble nitrate, and may be diazotised. A. L. Azo- and Hydrazo-compounds of Tetrazole. By JOHAXNES THIELE (Annalen, 1898, 203, 57-75. Compare Abstr., 1894, i, 61), When amidotetrazole is oxidised by potassium permanganate in feebly alkaline solution, it is completely decomposed, but in presence of much alkali, derivatives of azotetrazole are produced. The sodium, potassium, and barium derivatives contain bH,O, and the calcium derivative 8H,O, the ammonium derivative is anhydrous, and crystallises from water in yellow needles, which decrepitate at 2 10' without exploding. The hydroxylamine derivative contains ZH,O, and explodes violently at high temperatures ; the hydraxine derivative also contains 2H,O, and the ccmidoguanidine derivative crystallises in long, yellow needles containing 1H20.The diaxoguanidine derivative, C,H,N,,, is anhydrous. When an aqueous solution of azotetrazole is treated with excess of a mineral acid, tetrazylhydrazine is produced, with elimination of nitrogen and formic acid; oxalic acid gives rise t o diazoimide. On adding dilute acid to a n aqueous solution of sodium azotetrazole covered with ether, the latter takes up a considerable amount of azotetrazole ; the yellow solution rapidly becomes turbid, however, from separation of a brick-red substance of unknown composition, but which probably contains one tetrazole ring.ORGANIC CHEMISTRY.171 Hydrazotetrazole, prepared by boiling an aqueous solution of sodium azotetrazole with magnesium powder, is a white, amorphous compound, insoluble in organic media, and dissolving with great difficulty in boiling water ; the substance is precipitated by ammonia and alkalis from the solution in concentrated hydrochloric acid, and the aqueous solution yields precipitates with many metallic salts. DibromoformaZtetraxylhydraxone, CBr2:N*NH*CN,H, obtained by the action of bromine water on a solution of hydrazotetrazole in con- centrated hydrobromic acid, crystallises from ether in white needles containing $H,O ; it becomes brown when heated, and melts at 177".Concentrated sulphuric acid eliminates hydrogen bromide and carbonic anhydride, forming tetrazylhydrazine. Further treatment of hydrazo- tetrazole with bromineconvertsitinto isocyanogen tetrabromide(Zoc. cit.). MetAyZic uxinocarbonccte, N,[:C(OMe),],, prepared by the action of potash dissolved in methylic alcohol on isocyanogen tetrabromide, separates from etbylic acetate in beautiful crystals, and melts at 111' ; dilute acids resolve the substance into methyliccarbonate and hydrazine. The sodium derivative of the amide of tetrazoleazocarboxylic acid, obtained by oxidising an alkaline solution of tetrazylsemicarbazide (Abstr., 1896, i, 107) with potassium permanganate, crystallises from water in lustrous, orange plates containing 2H,O ; caustic potash eliminates ammonia, and gives rise t o the potassium salt of tetrazole- carboxylic acid, which is decomposed by dilute acids, yielding carbonic anhydride, formic acid, nitrogen, and hydrazine, not tetr- azole.Tetrazoleazodimethylaniline is decomposed by dilute acids in the same way. Derivatives of Amido-orcinol. By FERDINAND HENRICH (Honatsh., 1898, 19, 483-517. Compare Abstr., 1897, i, 446),- Tribennzoykamido-orci~oZ, NH13z*C,H,Me(OBz)2, formed when amido- orcinol-is shaken with an excess of benzoic chloride and soda, crystallises from absolute alcohol in white, prismatic needles, melts a t 165-1 66" (uncorr. ), dissolves readily in benzene, chloroform, and hot alcohol, fairly readily in cold alcohol, and sparingly in ether ; it yields 3-hydr- oxy-2'-phenyl-l-methylbenzoxazole when distilled and hydrolysed.3-Hydroxy-2'-pheny1-1-methylbenzoxazole has a normal molecular weight in boiling acetone, is not altered by boiling with strong hydro- chloric acid, but is hydrolysed when heated with it, under pressure, at 183' for 5 hours. vielding. benzoic acid and amido-orcinol. M. 0. F. , # " >CPh, is made by 3-Ht~droxy-2'-phenylbenxoxaxo Ze, QH:"Hf" OH*C:CH*C*O treating amidoresorcinol with benzoic chloride, heating the product for 15 minutes at its boiling point, and finally hydrolysing with alco- holic potash the benzoyl derivative thus obtained ; it crystallises from benzene in colourless, compact crystals, melts at 2 16-2 1 7", dissolves readily in acetone, acetic acid, hot alcohol, and ether, but sparingly in light petroleum, cold chloroform, and benzene.Its alkaline solution is reddish-yellow and has a lilac fluorescence. When 3-hydroxy-2'-phenyl-l-methylbenzoxazole is treated with strong nitric acid,.the 2 ; 4-dinit.ro-compound, C~,H,O,N(NO,),, is formed. This separates from alcohol and chloroform in yellow, rhombohedra1172 ABSTRACTS OF CHEMICAL PAPERS, crystals and melts a t 188--189O, is sparingly soluble in cold alcohol, ether, acetic acid, and petroleum, but dissolves somewhat more readily in hot benzene and chloroform ; it has very feeble tinctorial properties, decomposes carbonates, liberating carbonic anhydride, and gives n crys- talline sodium salt. 3-Hydroxy-2'-phenyl-l-methylbenzoxazole is not affected by nitrous acid, but reacts in alkaline solution with diazobenzene, yielding benxeneaxo-3-h ydrox y- 2 '-3Jlen yl- 1 -methy Zbenxoxaxole , C,,H,,N,O,, which crystallises from glacial acetic acid in brownish-yellow needles and melts a t 169-170', dissolves readily in benzene and chloroform, but sparingly in cold alcohol and ether ; sulphuric acid dissolves it, form- ing a yellowish-red solution which becomes redder on dilution.The hydrochloride, C,oH,5N,02,HCI (?), separates on passing hydrogen chloride into an ethereal solution of the base ; it decomposes very quickly in presence of moisture. Acetoxybenxeneaxo-3-hydroxy-2'-phen y 2-1-methylbenxoxaxole, (&oH14N30&, made by heating the foregoing base with acetic chloride and anhydrous sodium acetate, crystallises from alcohol in long, orange-coloured, apiculate prisms and melts a t 182-183O; it is only slowly hydrolysed by boiling aqueous or alcoholic alkalis.The corresponding hydraxo- compound, made by heating it with zinc dust and acetic acid, crystal- lises from acetic acid in long leaflets and melts at 184-185'; it dissolves in strong sulphuric acid, giving a faintly coloured solution having a steel-blue fluorescence; on oxidation with nitrous acid, it yields the original hydroxyphenylmethyl benzoxazole. The corres- ponding benxoyl derivative, C,oHl,N,O,Bz, crystallises from absolute alcohol in light, brownish-yellow, prismatic, pointed crystals, sinters a t 160', and melts at 171"; it resembles the corresponding acetyl com- pound in its behaviour towards concentrated sulphuric acid and alkalis. On reduction, it yields a compound which dissolves in alkalis and in sulphuric acid, and the solution in the latter instance has a steel-blue fluorescence ; it gives hydroxyphenylmethylbenzoxazole on treatment with nitrous acid.Paramethoxybenxeneaxo-3-phenyl-I -methyZbenxoxaxole, C,oH,,N,O*OMe, produced when the azo-compound is treated with sodium methoxide and methylic iodide, crystallises from absolute alcohol in small, yellow needles, sinters at about 135O, and melts at 149-150'; it dissolves readily in cold benzene, chloroform, ethylic acetate, ether, and hot alcohol, but only sparingly in light petroleum and cold alcohol. E">CMe, formed when triacetylamido-orcinol is hydrolysed with diluted sulphuric acid or concentrated hydrochloric acid, crystallises from alcohol or benzene in long, colourless needles, melts a t 2 1 O', and dissolves readily in acetic acid, warm ether, and alcohol, but only sparingly in benzene and light petroleum.I t s acetyl derivative, C,,H1,O,N, formed by heating triacetylamido-orcinol at its boiling point for some time, crystal- lises from petroleum in white needles, melts a t 65', and is readily soluble in the ordinary media; it yields the preceding compound on hydro- lysis with alcoholic potash. The benxoyl derivative, C,H,02N* COPh, 3 -Hydroxy- 1 : 2'-dimeth y Zbenxoxaxo Ze, YH ' C( 0H):CH.C 0ORGANIC CHEMISTRY, 173 crystallises from petroleum, melts a t 108-1 lo', and dissolves readily in the usual solvents, with the exception of light petroleum. Benzeneaxo-3-hydroxy-1 : 2'-dimethyZbenxoxaxole, made by the action of diazobenzene' in alkaline solution on hydroxydimethyl benzoxazole, melts a t 116-118", and dissolves readily in the usual media ; it be- haves towards strong sulphuric acid like the corresponding derivative of phenylmethylbenzoxazole, but is much more readily soluble in soda. Formamido-ominol, C7H,(OH),-NH* CHO, obtained when sodium formate and anhydrous formic acid are heated with amido-orcinol hydrochloride at the temperature of a glycerol bath, sinters at 180°, melts and becomes red a t 195-198', and dissolves readily in alcohol and hot water, somewhat sparingly in ether, benzene, and chloroform, and is insoluble in light petroleum.It is quickly dissolved by aqueous soda, and reduces Fehling's solution and ammoniacal silver nitrate. - 3-EFydroxg-1 -methyZbenxoxaxoZe, OH* C7H5<E>CH, produced when the formyl compound is heated at 208', forms long, colourless leaflets and melts a t 162-163" after sintering slightly ; it is readily soluble in acetic acid, alcohol, and ether, somewhat readily in benzene, and sparingly in chloroform and light petroleum, especially in the cold ; it dissolves in strong soda ley, forming a colourless solution, but is not dissolved by a dilute solution of soda; it yields amido-orcinol when hydroly sed by strong hydrochloric acid.3-Benxoxy-l-met?~yZbenxoxccxole, C,H,NO,Bz, is readily soluble in alcohol, ether, benzene, acetic acid, carbon bisulphide, and chloroform, but only sparingly in cold petroleum. It is insoluble in alkalis, melting to an oil when warmed with them. Benxeneazo-3-hydroxy- I-methyZbenxoxaxoZe, C,,H,IN,O,, forms elongated leaflets having a n intense purple colour, and melts a t 186"; it dissolves readily in benz- ene and chloroform, but only sparingly in petroleum and in cold alcohol or acetone; i t ,forms a yellowish solution in strong sulphuric acid, which becomes a deeper red on dilution, and dissolves more readily i n aqueous soda than do the corresponding 2'-phenyl- and- 2'-methyl- derivatives, A. L.New Synthesis of Paraxanthina-Bv EMIL FISCHER and HANS C L E ~ M (Ber., 1898, 31, 2622-262$).-ChZoroparaxanthine, rMe*CO*g*NMe N>CC1, is formed when 1 : 7-dimethyluric acid is CO NH* C-- heated with phosphorus oxychloride at 135-140' for 3 hours, and can be purified by boiling with alcohol and subsequent recrystallisa- tion from a large bulk of hot water; it melts at 284' (295O corr.), dissolves in 170 parts of hot water, and crystallises from it on cooling in colourless, interlacing prisms ; it is more readily soluble in hot alcohol. When heated, it melts and sublimes readily, slight decomposition occurring.The sodium salt is sparingly soluble in cold water, and separates from hot water in slender, shining needles ; the potassium salt is more readily soluble, and crystallises in spherical aggregates of slender, colourless needles. Chloroparaxanthine dis- solves readily in cold dilute ammonia, and the solution gives, with silver nitrate, a white, amorphous precipitate which blackens when174 ABSTRACTS OF CHEMICAL PAPEHY. warmed, and dissolves in warm dilute nitric acid, the solution depositing slender needles on cooling.Chloroparnxanthine is readily reduced to paraxanthine when warmed with hydriodic acid and phosphonium iodide. Xanthine Bases &om Uric Acid. By ERNST E. SUNDVIK (Zeit. physiol. Chem., 1898, 26, 131--132).-1n a previous paper (Abstr., 1897, i, 598), it is stated that, by reduction of uric acid, xanthine and hypoxanthine are probably formed. This view is now shown to be correct, the bases having been isolated and analysed. Some Properties of Caffeine. By E. TASSILLY (BUZZ. SOC. C h h . , 1897, [ iii], 17, 596--599).--Hydrated caffeine, C,H1,N,O, + H,O, does not lose all its water of crystallisation even a t 150°, at whlch bemperature it is partially volatile. At 1 lo", the anhydrous compound does not lose in weight, whereas the hydrate undergoes a loss of 6.93 per cent.Caffeine is not volatile with steam, Calcium hydroxide solution decomposes the alkaloid at looo, ammonia being evolved, whilst with magnesia under similar circumstances no trace of am- monia is given off. The partition of caffeine between different solvents ceases t o be normal when other extractive substances are present. J. J. S. By Emr, FISCHER (Bey., 1898, 31, 2547-2549).-Pinely-powdered trichloropurine, C,HN,Cl,, is added t o 10 times its weight of hydriodic acid (sp. gr. 1-96), excess of powdered phosphonium iodide added, and the mixture kept, first for an hour a t Oo with frequent shaking, and then shaken a t the ordinary temperature for 24 hours by means of a motor ; the product is then warmed to 40°, filtered, evaporated a t 40--50° under diminished pressure, mixed with a little water, and again evaporated ; the crys- talline residue is washed with a little cold water and recrystallised from dilute hydriodic acid, warming gently only. In this way, the hgdriodide of hydurinephosphoric acid, C4H,N,P0,,HI + H20, is obtained ; by treatment with water and freshly preclpitated silver iodide, i t can be converted into the hydrochloride, C,H,N,PO,,HCI.These salts are soluble in water, but the solution soon turns red ; this coloration is hindered by the preseiice of a little halogen acid, but promoted by alkalis, the colour when ammonia is present becoming eventually that of a potassium permanganate solution. When heated with dilute hydrochloric acid on the water-bath, the hydrochloride yields ammonium chloride and phosphoric acid, but no phosphorous acid.The base corresponding with these salts is hydurinephosphoric acid, which is probably C,H7N,*PO(OH),, derived from a hypothetical base hydurine, C4H8N4, in the same way as is the amidophosphoric acid, NH,*PO(OH),, from ammonia, NH,. A. L. W. D. H. Hydurinephosphoric Acid. C. F. B. Purine and its Methyl Derivatives. By EMIL FISCHER (Bey., 1898, 31, 2550-2574).-2-lodo-7-metl~yZpu~*ine, bI C--N>CH, N:CH*g*NMe is obtained by reducing 2 : 6-dichloro-7-methylpurine (Abstr., 1898, i, 97) with hydriodic acid in large excess and phosphonium iodide a t 0" ;ORGANIC CHEMISTRY. 176 it melts at 225' (c0r.r.). verted into 2-oxy-7-methyZpzc~ine, When boiled with normal potash, it is con- >CH + H,O, which T:CH---g *NMe CO*NH* C--N decomposes a t about 323") and with normal potassium hydrosulphide solution in large excess, into an analogous, yellow thio-compound which decomposes at about 295".With half-saturated alcoholic am- monia a t 145-150", i t yields 2-a.mi~o-7-meth~Zpur~~e, melting at 283' (corr,), \which can also be obtained from 2-chloro- 7-methylpurine (see below), a conipound that is more easily prepared than 2-iodo-7-methylpurine. When boiled with zinc dust and water, I & : CH* E*NMe it yields 7-methyZpuvine, CH:N, --N >CH; this melts at 184" (corr.), its ?nercurichZos.ide at 25Z0(corr.), and its methiodide a t 231-232" (corr.). : CH*fi*NMe 2-Cl~Zoro-7-met~~~~ul.ine, CCI:N,C __ >CH, obtained by boiling 2 : 6-dichloro-7-methylpurine or trichloro-7-methylpurine with zinc dust and water, melts a t 200-201" (corr.), the mercurichloride at 206-20'7".When it is boiled wlth normal potash solution, a com- pound, C,H,N,Cl, which melts and decomposes a t about 251", is deposited, whilst 2-oxy-7-methylpurine remains-dissolved in the alkali. 2 : 6-Di-iodopus.ine, CT.N* c-N>CH, obtained by heating tri- chloropurine (Abstr., 1898, i, 47) with hydriodic acid and phosphonium iodide, melts and decomposes at about 224'; when heated with hydrochloric acid (sp. gr. = 1.19) a t 100" in a sealed tube, it yields xanthine, and when boiled with zinc dust and water, the insoluble zinc salt of purine itself is formed, and remains mixed with the excess of r : CI* g*NH iy: CH.@NH zinc dust.Purine, CH:N,C-,N >CH, is a readily soluble, well crystallised substance, which forms salts both with acids and with bases, and as regards its character in general falls naturally in the series uric acid, xanthine, hypoxanthine, purine. It melts at 216 -217" (corr.) ; the nitrate, with IHNO,, melts and decomposes at about 205" ; the yellow picrate, with 1C,H,N,07, melts at about 208' ; the base is very stable towards oxidising agents, and in consequencc does not give the murexide reaction. 2(?)-ChZoro-9-lnzethyZpu~ine, prepared by boiling trichloro-9-methyl- purine (see below) with zinc dust and water, Gelts at 135-136' (corr.). When heated with half-saturated alcoholic ammonia a t 150°, it is converted into 2(l)-amino-9-methylpurine, which melts a t 247" (corr.); with hydriodic acid (sp.gr. =1*96) at the ordinary tem- perature, it yields 2(?)-iodo-9-methylpurine melting at 171-1 72" (corr.). This, when boiled with zinc dust and water, yields 9-methylpurine, >CH, which melts at 162-163° (corr.). CH:N*C*NMe 7: CH* g--N P~eparation of Tricl~loYo-9-)net?L~l~)u~w~~~e.--T his is best prepared with-176 ABSTRACTS OF CHEMICAL PAPERS. out the use of phosphoric chloride ; 2 : 6-dichloro-8-oxy-9-methylpurine (I part) is heated with phosphorus oxychloride (25 parts) for 10 hours at 160-1 65', the product is evaporated under diminished pressure, and the residue washed with cold water and then with cold dilute caustic soda, and recrystallised from alcohol. Identification of Xanthine.-This is best effected by heating the supposed xanthine (1 part) with bromine (5 parts) a t ZOO' in a sealed tube, opening the tube and heating it to 140-145" to expel bromine, washing the residue with sulphurous acid, dissolving i t in warm am- monia and precipitating with hot, dilute sulphuric acid.The bromo- xanthine formed (1 part) is dissolved in normal caustic potash (1 3 parts by vol.), and heated with methylic iodide (24. parts) in a sealed tube a t 80' with constant shaking for 2 hours ; the bromocaffeine which separates is washed with very dilute caustic soda and recrystallised from water; it melts at 206'. This (1 part) is boiled for 5 minutes with 10 per cent, alcoholic potash (7 parts), the mixture is diluted with 3 times its volume of water, and the ethoxycaffeine, which soon separates, is recrystallised from water ; it melts at 140'.By boiling it (1 part) with 10 per cent. hydrochloric acid (10 parts by vol.) it can be converted into hydroxycaffeine, which melts at 345O. All these processes can be carried out with 0.5 gram of xanthine, and in the space of 24 hours. Behaviour of 2-hido-6 : 8-dioxypurine towards Chlorides C. F. B. of Phosphorus, By EMIL FISCHER (Be;., 1898, 31, 2619-2621).- 6-ChZoro-2-amido-8-oxypurine, NH,. ---N-C.NH >COY made by boil- I)' :CCl f*NH - ing 2-amido-6 : 8-dioxypurine wit6 phosphorus pentachloride dissolved in phosphorus oxychloride, can be purified by dissolving it in warm dilute ammonia and treating with animal charcoal ; the filtered liquid, heated t o drive off ammonia, deposits the substance in bundles of slender, microscopic needles.It decomposes at a high temperature without melting, dissolves sparingly in hot water and still more sparingly in alcohol, is readily soluble in warm dilute mineral acids, and fairly readily in dilute ammonia. When heated a t 130' with hydrochloric acid, it yields the hydrochloride of 2-amido- dioxypurine. When 6-iodo-2-amido-8-oxypurine, C,H,N,OI, obtained when chlor- amido-oxypurine is heated,with f uming hydriodic acid and phosphonium iodide at lOO', it is converted into a colourless? granular, indistinctly crystalline powder, which resembles in properties the original chloro- compound, but is more sparingly soluble. Bases Isomeric with Cinchonine. By VICTOR CORDIER VON LOWENHATJPT (Monatsh., 1 S98, 19, 461--482).-When cinchonine hydrobromide is heated with alcoholic potash, a mixture of bases is obtained which may be separated, by means of ether, into two portions.The least soluble portion may be further resolved by crystal- lisation from alcohol, and on treatment with sulphuric acid gives a salt, (C,,H,,N,O),,H,SO, + 2H,O, which has the same crystalline form as Hesse's homocincbonine sulphate (Abstr., 1881, 61 5) and melts a t 199*5', and also the sulphate of a new base, tnutocinchonine, This A. L.ORGANIC CHEMISTRY. 177 base resembles homocinchonine in some respects ; it dissolves in 144 parts of absolute alcohol at 20°, melts at 262*5', and has [a]D= + 209.42' ; its dihydriodide, ClgH,,N,0,2HI, forms beautiful, yellow prisms and melts at 238'. If that portion of the product of hydrolysis of cinchonine hydro- bromide which is readily soluble in ether is treated with hydro- chloric acid and potassium iodide, it yields a-isocinchonime dih ydviodids, which forms beautiful, yellow, prismatic crystals, and melts a t 205-2206', whilst the mother liquor from which it has been deposited contains a mixture of bases, and by successive treatment with hydro- chloric acid and zinc chloride may be made to yield 8-cinchonine hydrochloride and the zincochloride of a new base, E-cinchonine.When cinchonine hydrobromide is hydrolysed with alcoholic silver nitrate, a mixture of bases is obtained which appear to be identical with those produced when alcoholic potash is employed, and only differ in their relative proportions. c-Cinchomine, C,,H,,N,O, melts at 152', dissolves very readily in alcohol, but more sparingly in ether ; it crystallises from the latter in long, slender needles, and its specific rotation in 1 per cent.alcoholic solution a t 20' [.ID = 66.99. Its hydrochloride, C19H22N20,HCI, is anhydrous and crystallises in thick prisms. When water is used to hydrolyse cinchonine hydrobromide, a product is obtained from which ether dissolves s-cinchonine and a-isocinchonine, leaving pseudocinchonine and what is probably apoisocinchonine (allocinchonine 'I). When hydrobromic acid acts on cinchonine, not only is cinchonine hydrobromide formed, but the hydrobromides of a-isocinchonine, pseudocinchonine, and Gcinchonine are also produced. By FERDINAND ROQUES (Ann. Chim. Phys., 1897, [ vii I, 10, 234-288).-The production of crystallised cinchonicine has already been described (Abstr., 1895, i, 688). Full details of the method employed are set forth in the paper ; the specific rotation of the base obtained either from cinchonine or cinchonidine is ROW given as [a]D= 57.60' ; it was formerly stated to be 48.25'.The base from either of the two alkaloids melts at 49-40', differing in this respect from von Miller and Rhode's cinchotoxine,.which melts a t 58-59' ; the two bases are otherwise very similar, and they may be identical (compare Abstr., 1895, i, 434). The basic nitrate crystallises readily in prisms, which melt and decompose at 160'; [a], = 29*5S', the nol.ma2 nitrate in yellow, silky needles, extremely soluble in water ; its alcoholic solution is yellow, the colour disappearing when half the acid is neutralised by potash. The nwmal succinate, C,,H,,N,O,C,H,O, + H,O, crystal- lises in prisms. The double zinc and cadmium chlorides, and the alkylic haloid salts have already been described (Abstr., 1895, i, 688). Chemistry of the Atropine Alkaloids. By ADOLF PINNER (Chem. Centr., 1898, i, 679; from Centr. prakt. Augeralteilk., 20, 1-9). -According to the author, the plants of the order of SoZanacece, and the A. L. Cinchonicine. G. T. M. VOL, LXXVI. i. 92178 ABSTRACTS OF CHEMICAL PAPERS. species Atropa, Byoscyamus, Datwa, Mandragora, 8okanZcm, and Ani- sodua contain at least the two alkaloids, hyoscyamine, C17H23N03, and hyoscine (scopolamine). The former, by the action of alkalis, yields atropine, which may, perhaps, occur in small quantities in the plants, whilst hyoscine, with alkalis, forms inactive scopolamine (atroscine). By the loss of water, hyoscyamine and atropine form apoatropine, which, by an intramolecular change, yields belladonnine. Atropine is always present in commercial hyoscyamine and inactive hyoscine (atroscine), hyoscyamine and atropine are contained in conimercial scopolamine, whilst duboisine contains hyoscyamine, hyoscine, and other alkaloids. All the alkaloids, when hgdrolysed, yield tropic acid ; C9H1003,and tropine, C8H,,N0, is formed from atropine, and oscine (sco- poline), C8H,,N02, from hyoscine-scopolamine ; the alkaloids can be partially regained from these products. Ketones of the Tropine Group, XII. Constitution of Ecgonine. By RICHARD WILLSTATTER and WILHELM MULLER (Ber., 1898, 31, 2655-2669. Compare Abstr., 1898, i, 603).-Hydroecgon- idineamide, C,H,,N* CO *NH2, prepared by the action of ammonia on the ethylic salt of hydroecgonidine, crystallises in long, six-sided tablets melting at 126-127'. When this substance is heated with E. W. W. CH2* $3H-$!H*NH2 I potassium hypobromite, it yelds isotropykamine, J yMeyH2 9 CH2* CH-CH, which is isomeric with the tropylamines formed by the reduction of tropinonoxime; it is a colourless oil, which boils at 206-207' (corr.), and solidifies at 8.5'. The mercurichboride is soluble in hot water, and crystallises in characteristic tablets ; the hydrochlmide crystallises in compact, six-sided tablets, and sublimes when carefully heated ; the picrate melts and decomposes a t 236-237', and the platinochloride decomposes a t 261°, whilst the aurichloride could not be obtained of definite composition. The thiocarbamide, NHPh* CS*NH* C8Rl,N, crystallises in colourless, swallow-tail forms, and melts at 138-139O. Nitrous acid does not convert the base info iqotropine, but into trop- idine. Tsotropylarnine can also be prepared from hydroecgonineamide by Curtius' method. The hydrazide forms a picrate melting at 172O, and, when treated with nitrous acid, yields di-isotropylcarbamide, from which isotropylamine can be prepared by the action of hydrochloric acid. When ecgonine is oxidised by means of chromic acid, it yields tropinone, and this reaction shows that the hydroxyl group of ecgonine is in the same position as that of tropine and $&-opine. Moreover, since the properties of ecgonine are those of a p- and not of a y-hydroxy-acid, it follows that ecgonine has the constitution I. I. 1 rMeyH*OH 11. I YMegH CH2* VH-YH' COOH CH2* 7H-Y"' COOH CH,. C H-CH2 CH2* CH-CH Anhydroecgonine, therefore, has the constitution 11, which is in harmony with the formation from i t of 6-cycloheptatrienecarboxylic acid melting at 32'; this, as shown by its behaviour to alcoholicORGANIC CHEMISTRY. 179 potash (Einhorn and Willstatter, Abstr., 1895, i, 92), does not contain an ethylene linking in the Al-position. Alkaloidal Constituents of Camarilla, Bark. By WILLIAM A. H. NAYLOR (Phurm. J., 1898,5Q, 279).-Two bases are obtained by extracting the powdered bark with chloroform water containing 3 per cent. of oxalic acid. The one allied to choline forms a platinochloride crystallising in yellow, hexagonal plates, and a crystalline hydro- chloride which gives off trimethylamine on heating; analysis of the former salt indicates that the base is in reality, not choline, but betaine. The second base, cascurilline, isolated for the first time, forms a buff-coloured plutinochloride, which is soluble in alcohol and crystallises from water in prismatic plates. By Fa. KUTSCHER (Zeit. physiol. Chem., 1898, 26, 110-122. Compare Abstr., 1898, i, 611).-Antipeptone is not a peptone, neither is it a chemical unit (cnrnic acid) as alleged by Siegfried. It is a mixture of heterogeneous substances which, by means of phosphotungstic acid, can be divided into two parts, basic and acid. Among the bases, histidine, arginine, and another base of unknown nature were found; among the acids, aspartic acid was separated. W. D. H. Guanylic Acid f'rom Pancreas and its Decomposition Pro- ducts. By IVAR BANG (Zeit. phpiol. Chern., 1898, 26,133-159).- The potassium salt of guanylic acid, obtained by heating pancreas or nucleoproteid on the water-bath with 2 per cent. caustic potash, sepa- rates from the filtered extract as a voluminous sediment, which re- dissolves in hot water without decomposition, and is again precipitated as the solution cools. After repeating this treatment several times, the Ealt gives neither the Millon nor the biuret reaction. The free gwnylic acid liberated by the addition of 5 per cent. acetic acid to the warm solution of the potassium salt, is obtained, after washing with alcohol and ether, in the form of a white powder. The other nucleic acids are not liberated from their salts by acetic acid, but in this case the free acid is obtained, and the use of acetic acid is preferable, since guanylic acid is slowly decomposed by hydrochloric acid at ordinary temperatures. Guanylic acid may be prepared directly from nucleo- proteid by extraction with hot water, but the yield is smaller than by the above process. The free acid has a feebly acid reaction; it dissolves readily in alkalis and ammonia, and also in dilute mineral acids ; its aqueous solution gives precipitates with solutions of the heavy metals, but not with albumin dissolved in dilute acetic acid, an acidic solution forms precipitates with phosphotungstic, tannic, and picric acids. Neither iron nor sulphur are present in guanylic acid ; it contains less phosphorus and more nitrogen than the other nucleic acids, the ratio of these elements being P : 3N, whereas in the latter compounds it is P : 5N ; hence the latter ratio can no longer be re- garded as characteristic of these compounds. The analytical results agree most closely with the formula C22H,,Nl,P,0,7, and although it is unlike other nucleic acids in composition and in many of its pro- perties, the products of its decomposition show it to be closely related A. H. G. T. M. Antipeptone.180 ABS'EBACTS OF CHEMICAL PAPERS. to this class of substances. On boiling guanylic acid with dilute mineral acids, it decomposes, yielding a substance belonging t o the pentose group, guanine, phosphoric acid, and ammonia. The exact nature of the pentose derivative has not been determined; i t reduces Fehling's solution, forms an osazone melting a t 151-154', is un- fermentable, and cannot be obtained crystalline ; the quantity pro- duced, calculated in terms of glucose, amounts to about 30 per cent. of the original substance. Nine-tenths of the nitrogen originally present in guanylic acid is obtained, after hydrolysis, in the form of guanine; this is the first example of a nucleic acid giving rise to only one xanthine base, and it is on this account that the name guanylic acid is given to the compound. The only other nitrogenous product of decomposition is ammonia ; no trace of thymine could be obtained, either from guanylic acid or from nucleoproteid. G. T. M. Ovimucoid and a New Glucoproteid from Blood-serum. By CARLO U. ZANETTI (Chem. Centr., 1898, i, 624-625 ; from Ann. Chim. E%rm., 26, 529-534. Compare Henriques, Abstr., 1897, 570).-The author attributes the reducing action of blood to the presence of a substance which is closely related to, or identical with, ovimucoid. Ovimucoid is prepared from egg-albumin by dissolving it in 10 times its volume of a 5 per cent. solution of sodium chloride, adding acetic acid, removing the albumin and globulin by coagulating, filtering, con- centrating, and finally precipitating with alcohol. It can be purified by dissolving in water and precipitating with alcohol, the sodium chloride being removed by dialysing. The white, pulverulent mass cont,ains C = 48*75-48*94, H= 609-6.94, N = 12.46, S = 2.22 per cent., and with hydrochloric acid gives glucosamine, and one third of its sulphur in the form of sulphuric acid. The serum of the blood of oxen yields a similar substance, possibly identical with ovimucoid. E. w. w. Existence of the Proteid Radicle suggested by Bertrand in the Oxydases. By JOSEPH DE REY-PAILHADE (Bull. Xoc. Chim., 1897, [iii], 17, 756-757).-1t has been suggested by Bertrand (Abstr., 1897, ii, 493) that the oxydases contain a radicle of proteid character capable of entering into loose combination with manganese or hydro- gen, and the author points out that philothion, a substance discovered by him in 1889 and subsequently described on many occasions, possesses the 'properties required of such a compound. The existence of philothion and analogous substances in animal tissues in the presence of manganese suggests a series of combinations and decom- positions which offer a clear explanation of the mechanism of respira- tion in the tissues. N. L.