Organic Chemistry. Liquid Ethane and Propane. By A. HAINLEN (Annulen, 1894, 282, 229-245) .-A detailed account of the experiments of which the ’results have already been published by L: Meyer (this vol., i, 1). A. H. Preparation of the Paraffins. By F. KLUGE (A~~nalen, 1894, 282, 214-228) .-A detailed account of the experiments of which the results have already been published by L. Meyer (this vol., i, 2). A. H. Formation of Dicarbon Compounds from Carbon Bisulph- ide at Low Temperatures. By V. MEYER (Bey., 1894, 27,3160- 3161) .-When carbon bisulphide is chlorinated at 20-40°, the carbon tetrachloride formed is found to contain perchlorethylene and perchlorethane. &I. 0. F. New Class of Compounds of the Inactive Hydrocarbons. By J. A. WANKLYN and W. J. COOPER (Chem. News, 1894, 70, 211-212J-The authors find that hydrocarbons from Russian kerosene produce a reduction in temperahwe when mixed with acetic acid, and regard it as indicating combination, and, moreover, the products begin to distil at a lower temperature than would be the case if they were only mixtures of their components.D. A. L. Ferric Thiocyanate. By L. ANDREWS (Chem. News, 1894, 70, 165-166) .-Spectroscopic examination of solutions of ferric thio- cyanatein amylic alcohol distilled from phosphoric acid, and in absolute ethylic alcohol, show that the absorbent power of such solutions diminishes more rapidly than the concentration ; and inasmuch as the molecular conductivity of such solutions is found to diminish, with increasing dilution, in about the same ratio as the reciprocal of the absorption coefficient, the falling off of the colour cannot be due to electrolytic dissociation ; and, as hydrolysis is out of the question in the present case, neither Magnanini’s nor Ostwald’s theory seems capable of fully explaining the behaviour of ferric thiocyanate in solution.Compared with aqueous solutions, a solution containing 0-0625 milligram of ferric thiocyanate per C.C. of amylic alcohol transmitted 48 per cent. of light of wave-length 587, about the same amount as an aqueous solution containing 0.247 milligram per C.C. D. A. L. Linalol and Licareol. By P. BARBIER (Bull. SOC. Chim., 1894, [3], 11, 261).--Referring to Bouchardat’s paper (Abstr., 1893, i, 54$), the author claims priority of discovery (Abstr., 1892, 1236) of the tendency of acetic anhydride to cause the conversion of the alcohola VOL.LXVIII. i. !?78 ABSTRACTS OF CHEMICAL PAPERS. of this class into isomerides. and licareol. L. T. T. He also denies the identity of linalol Constitution of Rhodinol from Oil of Pelargonium. By P. BARBIER and L. BoTJVEAUr,T (Compt. rend., 1894, 119, 334-33'7).- The principal constituent of oil of pelargonium is a somewhat oily liquid with a strong odour of roses ; it boils at 115-116" under a pressure of 10 mm. ; sp. gr. at 0" = 0.8866; rotatory power of a column 20 cm. long -12" 28'. When heated at 150-160" with a large excess of acetic anhydride, it yields (together with a small quantity of a hydrocarbon which boils at 60-80" under a pres- sure of 10 mm.) an acetate which boils at 120" under a pressure of 10 mm., and has a somewhat agreeable odour; sp.gr. at 0" = 0,9158. This acetate combines with one molecular proportion of bromine. When hydrolysed, the liberatled alcohol has its original boiling point, but its odour has become weaker, the sp. gr. has fallen to 0.8825, and the rotatory power of a column 200 mm. long has fallen t o -7" 13'. Phenylic isocyanate acts on the alcohol as a dehydrating agent, and yields only diphenylcarbamide. This rhodinol from pelargonium is a primary alcohol, and when carefully oxidised yields an aldehyde containing the same number of carbon &toms. The yield is, however, somewhat small, a large quantity of condensation products of high boiling point being formed at the same time. The aldehyde has a mixed odour of peppermint and lemon, and boils at 105-108", but cannot be separated from the excess of alcohol that always accompanies it.It yields a liquid oxime boiling at 140-150°, and this is converted by acetic anhydride into a nitrile, Cl0Hj[,,N, which boils at 112-113" under a pressure of 11 mm., and combines with one molecular proportion of bromine. The aldehyde has the composXon CloHI6O. The products of the oxidation of rhodinol contain an acid, C,oH,,02, which boils at 149-150" under a pressure of 10 mm., and combines with one molecular proportion of bromine. More energetic oxidation yields acetone and an acid, C7H120,, which boils without decomposing above 300" under the ordinary pressure and at 250" under a pressure of 10 mm. It is a bibasic acid, and does not combine with bromine; when boiled with aniline, it yields an anilide which crystallises in slender, colourless needles melting at 206-207", somewhat soluble in alcohol, especially on heating, but only slightly soluble in ether.When boiled with acetic anhydride, the acid yields a very viscous anhydride, C7Hlo03, which boils at 180" in a vacuum. This new bibasic acid is a-methyladipic acid; attempts to prepare it syn- thetically were unsuccessful. The rhodinol of oil of pelargoiiium differs from its isomerides, lemonol (geraaiol) aiid licarhodol, with which it has hitherto been confounded, in that it does not readily lose water with formation of a terpeie, &id is not attacked by hydrochloric acid i n the cold. More- over, the hydrochloride, when heated with potassium acetate, yields rhodinol acetate, whereas the hydrochlorides of its isomerides yield a terpene.It is a primary alcohol with a ringconstitution, but with only one ethylenic fuaction. C. H. B.ORGANIO OHEMISTRY. 79 Syntheses in the Sugar Group. By E. FISCHER (Ber., 1894, 27, 3189--3232).--This paper is a compilation of the work accom- plished by the author and his collaborators, together with the more im- portant researches of other chemists in the same domain since the year 1891. It thus forms a continuation of the paper on the same theme (Abstr., 1890, 1223) which the author deiiT-ered as a lecture before the German Chemical Society. The first section deals with experi- mental methods, and in the next section the present aspect of the sugar group is discussed, the known aldoses and ketoses being tabulated together with the mono- and di-basic acids and polyhydric alcohols derived from them.The autlioib then deals with the stereo- chemistry of the sugar group, and from this leads up to the con- figuration of the sugars and allied compounds. He then describes s nomenclature which expresses the configuration of these compounds in a, more concise manner, thus glucose is denoted “ hexose + - + + ” or ‘‘ hexapentoZaZ + - + +.” These formula do not, however, represent, as did those of van% HOE, the influence of a single asymmetrical carbon atom on the optical properties of the molecule, but only the position of one subsfituent to the right or left side of the configuration formulae (compare Abstr., 1891, 1173 and 1444).The last two sections are under the following headings : “ Influence of Configuration on Chemical and Physical Properties ” and “ Im- portance of Stereochemical Results in regard to Physiology.’’ The papers quoted have all appeared in this Journal, principally as abstracts ; their collation has, however, enabled the author t o draw some most important and suggestive deductions. By J. WEISSBERG (Bied. Centr., 1894, 23, 715 ; from Oester.-Uugar. Zeits. Zuclcer.ind. ZL. Landw., 22, 153-155) .-Ignited magnesia is about 300 times less soluble in 10 per cent. sugar solution than lime, and is less soluble in boiling sugar fiolutions than in cold solutions. Inas- much as magnesia is so sparingly soluble i n pure sugar solutions, and much more soluble in sugar-lime solntions, itl was thought possible to prepare a magnesia sucrate, or, at least, a lime-magnesia sucrate; neither compound could, however, be obtained.Beetroot juice (100 c.c.) WAS treated with milk of lime in the usual manner with addition of ignited magnesia (1 gram). After the first saturation, a, few C.C. of milk of lime and some milk of magnesia were added to the juice, which mas then saturated a second time. The filtered solution yielded an ash containing CaO, 0.351 giwn; NgO, 0.021 gram; or about 1 7 times as much lime as magnesia. Limestone containing 2 or 3 per cent. of magnesium carbonate would, therefore, have no appreciably injurious effect on the compo- sition of the products, since magnesia is so slightly soluble in sugar juice. N. H.J. M. A. R. L. Amount of Magnesia and Lime in Sugar Juice. Iodide of Starch Reaction. By C. MEINEKE (Chein. Zeit., 1S94, 18, 157--163).-An aqueous solution of iodine may be added to a solution of starch until the liquid is decidedly yellowish, without developing any blue colour. The smallest amonnt of potassium iodide, 9 2a0 ABSTRAOTS OF CHEMICAL PAPERS. however, is sufficient to give the reaction. This seems a t first a con- firmation of Mylius's statement, that iodide of starch contains potas- sium or hydrogen iodide as .an essential constituent ; but the author's investigat,ion proves that the presence of a soluble iodide is not at all necessary for obtaining the blue compound. The author has tabulated the results of a large number of experiments, showing that the com- pound is also formed, more or less completely, in the presence of other salts such as potassium, sodium, ammonium, calcium, and barium chloride ; potassium, sodium, ammonium, and magnesium sulphate ; Maltol.By H. KmAw and M. BAZLEN (Bey., 1894, 27, 3115- 3120 ; compare J. Brand, Abstr., 1894, i, 270).-Maltol forms charac- teristic metallic salts. The z i m salt separates in colourless needles which retain water ; the copper salt is anhydrous. The calcium salt crystallises in silky needles containing 5Hz0 ; it becomes yellow in contact with air or in a vacuum, owing to loss of water. The lead, barium, cadmium, potassium, and ananzonizm salts are also crystalline. Benzoylmaltol, CsH5O2*OBz, is colourless and neutral ; it melts at Oxidation of maltol with potassium permanganate gives rise solely to acetic acid and carbonic anhydride, the same products being formed on treating the aqueous solution with silver oxide.Maltol is not acted on by hydriodic or sulphuric acids, and no change occurs when the solution in alcohol or acetic acid is saturated with hydrogen chloride. Bromine has no action on maltol dissolved in chloroform, but the aqueous solution yields a syrupy acid which loses bromine very readily. It is clear from these observations that the constitutional formula suggested for maltol (Zoc. cit.) must be considerably modified, and the authors prefer to regard it as a methylpyromeconic acid. Nitrogenous Compound prepared from Fungus-cellulose." By E. WINTERSTEIN (Ber., 1894, 27, 3113-3115 ; compare Abstr., 1894, ii, 425).-The author has already shown that the cellulose ob- tained from various fungi contains a considerable quantity of nitro- genous constituents which are not of a prote'id nature.Further investigation has shown that when the fungus-cellulose is heated with hydrochloric acid, it yields glucosamine hydrochloride, identical with the product obtained in a similar manner from chitine (Abstr., 1885, 53 ; 1886, 329). Whether the constituent which gives rise to the formation of glucosamine is identical with chitine has not yet been ascertained. H. G. C. potassium alum ; potassium and sodium biborate. L. DE I(. 115-116". M. 0. F. Action of Halogen Xydracids on Formaldehyde in presence of Alcohols. By L. HEKRI- (Compt. rend., 1894, 119, 425-426),- The reaction recently described by Fame (this vol., i, 14) was pre- viously observed by the author (Bull. Acad.Sci, Beige, [3], 25, 439), and also by P. Henry (Abstr., 1892, 27) ; the former investigated the action of hydrobromic and hydriodic acids as well as that of hydro- chloric acid. C. H. B.ORGANIC CHEIIISTRY. 81 Chloro-formoxime. By R. ScnoLr, (Ber., 1894,27,2816-2822). -This substance, which has recently been described by Nef (this VO~., i, lo), was obtained by the author in 1892, having been regarded as the dihydrochloride of fulniinic acid. The observations of Nef are fully con firmed. 31. 0. F. Cause of the Transformation of Ethylic a-Bromacetoacetate into Ethylic y-Bromacetoacetate. By A. HANTZSCH ( B e r . , 1894, 27, 3168-3169 ; compare Abstr., 1894, i, 227).-This remarkable intra-molecular change is due to the agency of traces of hydrogen bromide, and is checked by the presence of moisture.M. 0. F. Free Acids from Beeswax. By T. MARIE (Conzpt. rend., 1894, 119, 428--631).-The free acid present in beeswax mas regarded by Brodie as a single substance; but Schalfesew and Nafzger have shown that it is a mixture. The author finds that the separation of the acids cannot readily be effected by Heintz's method of fractional precipitation with metallic acetates, bat is easily attained by means of fractional crystallisation from methylic alcohol, provided all organic substances except the acid's are first removed. The wax is extracted with boiling methylic alcohol, and, after the greater part of the solvent has been distilled off, the cooled and crys- tallised residue is pressed in order to remove the ole'ic compounds and the colouring matters.The cake is melted, mashed several times with boiling water, decolorised with charcoal, and filtered through paper ; it is, then heated with lime and potash-lime until evolution of hydro- gen ceases, in order to destroy myricin. The powdered mass is next suspended in water, heated to boiling, and saturated with dilute hydrochloric acid, the calcium salts which precipitate being col- lected, washed, dried, and treated with boiling alcohol and benzene t@ remove neutral substances. The acids are then liberated, and, after crystallisation from methylic alcohol, melt at 79-80'. The mixture of acids is well triturated with 30 times its weight of msthylic alcohol, heated carefully to boiling, and filtered at 60".The filtrate contains chiefly cerotic acid, which crystallises on cooling. This treatment is repeated with successively diminishing volumes of alcohol until the residue melts at 78". The dissolved product will fhen melt at 76". A single crystallisation from ethylic alcohol raises this melting point to 7'7.5". Crude cerotic acid has beerr described as a single substance, but in reality it contains from 30 to 40 per cent. of analogous acids. The author is investigating the properties of the pure acids and its salts. C. H. 13. Constitution of Ricinoleic and Ricinostearolic acids. BV A. G. GOLDSOHEL ( B e r . , 1894, 27, 313.1-3129; compare J. Ba&ch, Abstr., 1894, i, 170).-Ricinostearolic acid, when treated with concentrated sulphuric acid, yields ketohydroxy- atearic acid, C6H13*CH(OH)*CH,*CH,*CO*[ CH2],*COOH. The latter gives with bydroxylamine, ketoximehydroxystearic acid, CGH13.C H (0 H) CH2.C i C [ C H,] 7.C 0 OH, CGH13*CH (OH) *CH,*CH,*C (MOH) [ CH,] 7*COOH,82 ABSTRACTS OF CHEMICAL PAPERS.and this acid is converted by phosphorus pentachloride into an oil, which, whm heated with fuming hydrochloric acid at 180-200', > 0, amidocaprylic acid, a-hexyl- YHz'CH(C6His) co yields ydecalactme, CH2 - trimethylenimine, C,H,,*CH<CHz>CH,, and azela'ic acid. Ketohydrozystearic acid forms silky crystals, and melts at 8 6 8 5 ' . The barium and s i h e r salts are colourless, and the ethylic salt melts at 54.5" ; the acetyl derivative is a yellow oil.The phenythydrazide is foTmed when the acid is heated with phenylhydrazine at 150'. Ketozimehyd~ozystearic acid is an oil which is decomposed into hydroxylamine and ketoxystearic acid by dilute mineral acids. On heating it with alcoholic ammonia and adding hydrochloric acid, the product exhibits the characteristic reaction of pyrroline derivatives. The hydrochloiide of a-hexyltrimethylenimine is hygroscopic, and yields the yellow platinochloritle, melts at 172", and its hydrochloride at 147'. Turkey-red Oil. By P. JCILLARD (BUZZ. SOC. Cl~im., 1894, [3], 11, 2SO-286) .-This is a continnation of the author's previous work (Abstr., 1892, 819, and 1893, i, 455) on the action of sulphuric acid on castor-oil and on ricinoleic acid. Diricinic acid, 0 (CnH3z*COOH)p, is a bibasic acid.It is a thick, oily liquid, soluble in alcohol in all proportions, whilst its ethylic and methylic saits are but sparingly soluble in alcohol. Ricinoricinic acid, OH~C17H32~C0*O*C17H3z*COOH, best prepared by heating ricinoleic acid at 1 7 0 - B O O , is the first mem- ber of the series of polymerides of ricinoleic acid, and is a monobasic acid. Di h y drox yst e u w w Lpli uric acid, S OaH*C i7H3s ( OH) *C 0 OH, closely resembles ricinosulphuric acid in properties. Diliydrozystearic acid, ClaH3604, is very soluble in alcohol and ether, sparingly in light petroleum, and melts at 66-68". A solid acid, C36H;oO;, was obtained, melting a t 70-73', which appears to be a molecular com- pound of dihydroxystearic acid with ricinoleic acid. Isoricinoleic acid, C118H3t03, is an oily liquid, soluble in alcohol and in light petroleum, and appears to be a ketonic acid.Action of Thionyl Chloride on Organic Acids and Aldox- imes. By C. MOCREU (Compt. T e d . , 1894, 119, 337-340).--See this vol., ii, 43. NH Amidocaprylic acid, NH2* [ C H2] ?*C 0 OH, M. 0. F. L. T. T. Preparation of Thiodiglycollic acid. By J. M. LOV~N (Ber., 1894, 27, 3059-3060) .-An improved method of preparation. 95 grams of crystallised chloracetic acid is placed in a large beaker, and a solution, heated to 35', of 145 grams of crystallised sodium carbonate in 50 C.C. of water is added. 45 grams of sodium hydroxide is dissolved in water, so that th2 solution has a volume of 100 c.c., one half is saturated with hydrogen sulphide, and then the two halves are added simultaneously to the solution in the beaker, which is meanwhile shaken or stirred.The pasty mass is allowed to standORGANIC OHEMISTRY. a3 for three hours ; 110 grams of strong sulphuric acid is then added, carefully, but without cooling, and the hot solution is filtered, and allowed to cool. After six hours, the crystals of crude thiodiglycollic acid are collected and dried; they weigh about 70 grams, aDd con- tain 10-15 per cent. of sodium hydrogen sulphate. The crude crystals are dissolved in hot water (50 C.C. for every 70 grams), and the solution is filtered ; on cooling, 53 grams of very pure thiodigly- collic acid is deposited. The mother liquor horn the crude crystals, evaporated until it weighs 270 grams, is cooled to 40°, and then filtered, The filtrate, on further cooling, yields crystals of thiodiglycollic acid ; these are purified by recrystallisation from the mother liquor of the first crop of pure crystals, and then weigh 10 grams.63 grams of the pure acid are thus obtained from 95 grams of chloracetic acid, a, yield which is 84 per cent. of the theoretical. C. F. B. By H. W. BOLAM (Ber., 1894, 27, 3061-3062) .-When ethylic dicarboxyghita- conate (1 mol.) is boiled with 10 per cent. aqueous barium hydroxide (4 mols.), it is partly hydrolysed, malonic and another acid, 0 H* C H:C (C 0 0 H)z ( ? ) , being formed, The barium salt of the latter acid resembles that prepared by Ruhemann and Norell (Trans., 1891, 749) from etliylic amidoethy lenedicarboxylate. C. F. B. Leucine from Pancreatic Digestion.By R. COHK (Zeit. physiol. Chem., 1894, 20, 203-209) .-The present research brings forward evidence to show that the leucine obtained in a pancreatic digestion of prote'id matter is not a single substance, but a mixture of several isomeric substances. W. D. H. Hydrolysis of Ethylic Dicarboxyglutaconate. Derivatives of Dimethylalloxan. By W. TECHOW (Ber., 1894, 27, 3082-3089) .-DimethyldiaZuvic acid, C 0 < ~ ~ ~ : ~ CH*OH, is best obtained by the action of sodium amalgam on a thick magma of amalic acid (tetramethylalloxantin) and water, the whole being well shaken and cooled. The product is poured into hot dilute hydro- chloric acid, and filtered, the whole series of reactions beicg carried out quickly, as the acid is very soon reddened by the air, especially when moist.The acid forms compact prisms, reddens at loo", melts and decomposes at 170", and reduces silver and copper solutions in the cold. The potassiunt salt, C6H7N,04K, forms voluminous flakes, which soon assume a deep blue colour in the air, and the barizcnz salt, CIzH14N408Ba + 2H20, forms microscopic crystals. Dicldorodimetli ylbarbituvic acid, CO:(NMe*C0)2:CC1,, is readily ob- tained by the action of phosphorus pentachloride on amalic acid at 180" ; it crystallises from alcohol in delicate, white needles or well- developed prisms, melts a t 157" (uncorr.), and on long continued boiling with water loses hydrogen chloride, with formation of dimethylalloxan. When treated with sodium amalgam, it is con-84 ABSTRACTS OF CHEMICAL PAPERS.verted into the dimethylbarbituric acid, already described by Mulder (Abstr., 1879, 618). Dimet1tyl.r;ioluric acid, CO:(NMe*CO),:C:N*OH, is prepared by the action of hydroxylamine hydrochloride on di- methylalloxan, and forms hard, well-developed crysta.ls melting at 124". It is strongly acid, liberating carbonic anhydride from carbon- ates. The potassium salt, C6H6N,04k', forms a deep bluish-violet, flocculent, crystalline mass, the amnzonium salt, C6H6N304NH, + H,O, deep red crystals, which change to pale red on beating, and the barium salt, C12H12N608Ba + H,O, a heavy, red precipitate. When added in small quantities to hot concentrated nitric acid, it is con- verted into dinzethyl.rzitrobarbituric acid, CO:(NMe*CO),:CH*NO,, which separates from acetone as a white, microcrystalline mass, melting at 148"; the sodium salt, CsH6N306Na + 4H20, crystalhes in slender, yellow prisms.The ammonium salt of dimethylthionztric acid, CO:( NMe*C 0) ,:CH*NH*S03NH, + 2H20, is obtained by saturating a concentrated solution of ammonia with sulphurous anhydride and warming with solid ammonium carbonate and dimethylalloxan, and separates, on cooling, i n fascicular aggre- gates of slender, lustrous needles; the water of crystalliRation is evolved at 105", the salt simultaneously assuming a red colour, and, on further heating, it decomposes completely at 180". On adding barium chloride t o its solution, the barium salt, C6H7N306SBa, separates in silky crystals. The free acid is an amorphous mass, which is readily soluble in water, has strongly acid properties, and, on boiling in aqueous solution, is converted into sulphuric acid and dimethyluramil, C0:(NMe*C0),:CH*NH2.The latter compound is also obtained by the reduction of dimethylvioluric acid or of di- methylnitrobarbituric acid, but is besk prepared by boiling ammonium dimethylfhionurate with fuming hydrochloric acid, diluting with water, and neutralising with ammonium carbonate. Dimethyluramil then separates in snow-white, silky flakes, which melt and decompose at about 'LOOo, and, on exposure to the air in the moist condition, quickly become dark red. It reduces silver and copper solutions, is decom- posed by alkalis, even by ammonium carbonate, but unites with acids t o form unstable salts ; the hydrochloride forms small, hard crystals, which lose hydrogen chloride in a vacuum, and the platinochloride, ( C6H9~303),,HzPtC16, crystallises in yellow prisms. Dimeth ylpseudouric acid, C 0: (NMe*CO),:C H*NH*C 0*NH2, is pre- pared by the action of a concentrated solution of potassium cyanate on dimethyluramil.T t forms small, white crystals, reddens at loo", melts and completely decomposes a t 210°, and reduces silver soh- tions. The potussiuin salt, C7H,N40kK + H,O, is crystalline, and the copper salt, (C7H9N404),Cu + 2H20, is a pale green precipitate, which loses its water of crystallisation at 1 0 5 O , the colour changing simul- taneously to yellowish-brown. Action of Iodine and Potassium Hydroxide on Uric Acid. By E. BRYK (Monatsh., 1894, 15, 519--529).-Kreidl has described a method for the estimation of uric acid by treating it with potassium H.G. C.ORGIAKIC CHENISTRY. 85 Iiydroxide and iodine, and subsequently titrating with thiosulphate (Abstr., 1893, ii, 55s). The author finds that the action of iodine on R solution of uric acid, to which potassium hydroxide has been pre- viously added, depends on the proportion in which the substances are present and also on the temperature. If only a small excess of potassium hydroxide is employed, say i n the proportion of 2.25 mols. t o 1.3 atoms of iodine and 1 mol. of uric acid, and the mixture is kept cool, a yellow insoluble substance separates. This on analysis gave the numbers C = 28.37-26.86, H = 4.39-3-71, N = 28.53- 29-19, and on solution in potash or sulphuric acid and subsequent reprecipitation with water gave uric acid.When a similar mixture is warmed, potassium urate, carbonic anhydride, and ammonia are formed. The employment of a hrger proportion of potassium hydrox- ide, say 4 mols. to 2 atoms of iodine and 1 mol. of uric acid, gives rise t o allantoin and carbonic anhydride; the yield of the former is good (40-50 per cent.). G. T. 31. Polymeric E thoxy sulphone t hylene sulp hinic Lac t on e . By G. WALTER (Ber., 1894, 27, 3043-3045).-When an aqueous solu- tion of free ethoxysulphonethylenesulphinic acid is evaporated to dryness, there is formed, in addition to the lactone soluble in water, already described (Abstr., 1893, i, 459), an insoluble poly- meric modification, which has, however, the same melting point and chemical properties as the soluble variety.It can be converted into the latter by hydrolysing it with baryta water, liberating the free acid from the barium salt so obtained, and evaporating the solu- tion of this acid. C. F. B. Some Derivatives of Ethoxymethylsulphone. By G. WALTER (Bey., 1894, 27, 3045-3049; compare Abstr., 1893, i, 459).- Ethoxymethylsulphone, OH*C2Hp*S02*CH1, on treatment with phos- phorus pentachloride, yields chlorethylme thylsulphone, which melts at 8.5-9". When this is tredted with ammonia, there are formed, besides ammonium chloride, the hydrochlorides of primary and secondary metli y lszclphou et hylamine, NH2* C2H& 02*CH3 and NH(C2H4*S0,-CH3)2. The first hydrochloride forms deliquescent prisms, and the corresponding orange platinoclzloride melts and de- composes at 220-221".The second hydrochloyide melts at 202-203", the orange platiwocldoride at 1 59-160°, and the benzoyl-dericative at 131"; the free base forms stable crystals. If ethoxymethylsulphone is allowed to remain with cold, strong, siilphuric acid, and the mixture then added to a magma of water, ice, and barium carbonate, barizcm methylsi~lplphonethyle~ze sulphate, Ba(SOI*C2H4*S02*CH3), + H20, is formed. This is readily hydrolysed, by boiling with water, yielding barium sulphate, sulphiiric acid and ethoxymethylsulphone ; am- monia converts it into the amines described above. C. F. B.86 ABSTRACTS OF CHEMIOAL PAPERS. Action of Sulphuric Acid on Bromothiophen. By A. TORT. and R. SCHULTZ (Ber., 1894, 27, 2834-2839 ; compare Abstr., 1894, i, 117 and 276).-In addition to the results already described (Zoc.cit.), it is found that slightly fuming sulphuric acid converts tri- bromothiophen into tetrabromothiophen, the sulphonic acids of dibromo- and tribromothiophen being also formed in small quantities. If fuming acid is employed, perbromodithienyl and tetrabromothiopheu are formed. M. 0. F. Synthesis of Metachlorotoluene and of Symmetrical Chloro- xylene from Ethylic Acetoacetate. By A. KLAGES and E. KKOEVENAGEL (Ber., 1894, 27, 3019-3025 ; compare this vol., i, 48). -Dih~drometac7~lo~otoZueize [Me : H2 : C1 = 1 : 2 : 3 : 51 is prepared by the action of phosphoric chloride on 3-mebhyl-AZ-keto-tetrahydro- benzene ; the intermediate methyltrihjdrodichlorohenzene could not be isolated, it is a highly refractive liquid with an aromatic odour, boils at 78-80" (25 mm.), at 160-170" under atmospheric pressure, and is volatile with steam, some of the compound being decomposed.The yield is 60 per cent. of the ketone employed. The ketone is re- generated by the action of sulphuric acid (95 per cent.), a tertiary alcohol being first formed which is either identical with the ketone or is converted into it by intramolecular rearrangement. The dibromide is unstable and could not be purified; on warming alone or with quinoline, hydrogen bromide is eliminated and metachloro- toluene is formed. 2 : 3 : 5-Dihydl.ochZol.o-xyZene [Me : Me = 1 : 31 is prepared in a similar manner to the toluene derivative from 3 : 5-dimethyl-A2-keto-tetra- hgdrobenzene, which it closely resembles ; it boils a t 78-80" (15 mm.), and a t 176-178" under ordinary pressures with little decomposition, darkens on exposure to air, and regenerates the ketone on treatment with sulphuric acid.The yield is 70 per cent. of the ketono em- ployed. The dibromide is unstable and is readily converted into symmetricd chloro-xyZene, a highly refractive mobile liquid boiling at 190-191" ; its vapour rapidly attacks the skin. The sulphonic acid crystallises in lustrous plates, is readily soluble in water, and melts at 65-68'. The sodium and barium salts crystallise in plates. The sulphonic chloride and the sulphonamide crystallise in colourless needles melting at 48-49" and 189-190" respectively. The position of the sulphonic p o u p has not been determined. Mercuric Phenoxides and Naphthoxides.By E. DESESQUELLE (Bull. SOC. Chim., 1894, [3], 11, 263-269) .-Mercuric p-naphthoxide chloria'e, ClHg*O*CloH7, obtained by shaking together aqueous solu- tions of mercuric chloride and potassium p-naphthoxide, crystallises in colourless prisms soluble in alcohol, insoluble in water. For medical purposes, the author proposes for this substance the name P-sublimo- naphthol. Nercuyic ,%rtaphthoxide, Hg( 0*C,0H7)2, forms microscopic: crystals, almost insoluble in the usual solvents but slightly soluble in boiling phenol. Acetic acid acts on it with development of heat, yielding mercuric p-naphthoxide acetate as a white, crptalline sub- stance, soluble in alcohol, almost insoluble in water. J. B. T.ORGANIC CHEMISTRY. 87 Jfercuric phenoxide chloride forms colourless crystals melting about 210", soluble in phenol or in a boiling alcoholic or aqueous solution of phenol.Merczwic phenoxide hydyoxide, OH-Hg*OPh, is formed when a large excess of potassium phenoxide is employed, and crystallises in stellar groups of prisms. With acetic acid, this compound yields qizercuric pheiioxide acetate, crystallising in colourless prisms. The author has not been able to obtain the derivative Hg(OPh),. L. T. T. New Colour Reaction of Iridol. By E. NICKEL (Chem. Zeif., 1894, 18, 531).-When a solution of iridol (Abstr., 1894, i, 48) in aqueous alcohol is warmed with a solution of mercuric chloride (2 parts) and sodium nitrite (1 part) in water (40 parts), a beautiful, violet coloration, having a bluish tinge, is developed. This reaction was previously described by the au thor as characteristic of vanillin, and, indeed, there is no essential difference between the colorations produced by the two substances.A. R. L. Thioaniline (m. p. lOS0), and.& new Isomeride. By K. A. HOF- NAX" (Bw., 1894, 27, 2807-2816).-The author has shown that Merz and Weith's thioaniline is orthodiamidophenylic sulphide, S( CsH4.NH2), ; orthodiamidophenylic bisulphide is also formed when aniline is heated with sulphur, and may be converted into ortho- diarnidophenylic sulphide by the addition of lead oxide to its solution in boiling aniline. Pnradiamido~?ieizylic subhide is prepared by heating a mixture of aniline, aniline hydrochloride, and sulphur for 6-7 hours at 175" ; it crystallises from boiling water in colourless, lustrous plates, which melt at 85.5".The hydrochloride yields an emerald-green solution when heated with fuming sulphuric acid for half an hour at .loo". On adding lead peroxide to the solution in alcoholic hydrochloric acid, a green coloration is produced, changing to deep blue. The benzoyl derivative melts a t 234", and the diacetyl derivative at 185"; the corresponding derirstives from orthodiamidophenylic sul phide melt at 255" and 213-215" respectively. Pa~.adiamidophe~aylic bisd@hide, C12Hl,N,S,, is associated with the foregoing compound. It forms colourless needles, and melts a t 80" ; the diacety Z deriva,tive melts a t 205" ; it yields paradiamidophenylic sulphide when sti*ongly heated. The solution of the hydt.ocltloride i n alcohol is coloured deep cherry-red by lead peroxide, and the colour- less solution i n strong sulphiiric acid becomes violet when heated. Sulphur is precipitated when hydrogen sulphide is passed through a solution of the hydrochloride in dilute hydrochloric acid, nmido- phenyl mercaptan remaining dissolved.When paradiamidophenylic bisulphide is diazotised, decomposed in alcoholic solution with copper powder, and saturated with hydrogen sulphide, thiophenol is pro- duced, and parabromothiophenol is formed on displacing the amido- group with bromine. Suggested Non-existence of Isopropyleneparamidophenol, By A. MICHAELIS and K. LUXEMBOURG (Be,.., 1894, 27, 3005-3009). -Haegele's work on this compound has been repeated, and his M. 0. F.88 ABSTRACTS OF CHEMICAL PAPERS. results are confirmed as regards its formation from pure acetone; it melts at 172-174", is slowly hydrolysed by boiling with water, and more readily with dilute acids (compare Hantzsch and Freese, Abstr., 1894, i, 572, and this vol., i, 24).The calcium hypochlorite reaction is a delicate test f o r pararnidophenol; the acetate reacts more readily than the hydrochloride ; the dilute hypochlorite solution should be added gradually, as the violet colour is destroyed by excess of it. Chlorides of Hydroximic Acids and their Products of Change, By A. WERNER (Ber., 1894, 27, 2846-2850).-001.thonitrobenz?~ydr- oximic chloride, NOz*CsH4*CC1:NOH, is formed when dry chlorine is passed into a solution of orthonitrobenzaldoxime in chloroform ; it melts at 92-94'. The ?)zeta-derivative melts at 94-95', and thepara- compound at 115-117".Orthom'trobenzsn ylamidozime, N02*C6H4.C (NH,) :NOH, is obtained by warnling the acid chloride with alcoholic ammonia. It forms bright yellow needles, which contain 1H20 ; the substance loses water at SO", and melts at 141-142". The para-derivative melts at J. B. T. 165-167". when metanitrobenzhydroximic chloride is warmed with concentrated aqueous potash. It melts at 183-183". The para-compound melts a t 197-198'. Orthonitrobenzenylpiperidoxirne, NO2*C6H,*C (C,NH,,) :NOH, is ob- tained by mixing ethereal solutions of piperidine and ortho- nitrobenzhydroximic chloride. It melts at 132-133", and th.e wzeta-derivative melts at 159-160". The para-compound melts a t 166-1 67'. M. 0. El. Action of Amidoacetal on Orthonitrobenzoic Chloride and Paranitrabenzoic Chloride.By W. LOB (Ber., 1894, 27,3093- 3097).- Orthonitrobenzo ylamidoncetal: is obtained in a manner analogous to the benzoyl derivative (Abstr., 1893, i, 300), and ci-ystallises from ether on the addition of light petro- leum in stellate groups of colourless needles melting at 70-71". On treatment with cold fuming hydrochloric acid, it is converted into os-thonitroh~pul'aldeh yde, N02*C6H,*CO*NH*CH,*CH0, an amorphous, pale yellow substance, which softem at 90°, decomposes at a higher temperature, and reduces Fehling's solution. It could not be directly converted into the corresponding orthonitrohippuric acid, but the latter was obtained by the action of orthonitrobenzoic chloride and alkali on glycocine ; it crystallises from hot water in long, narrow plates melt- ing at 188", and gives crystalline precipitates with silver and lead salts.01-thamidobenzoy Zamidoace ta 1, NH2* c6H4* C 0 *NH* CHz* CH (OE t) 2, is prepared by the reduction of the nitro-compound with zinc dust and acetic acid in alcoholic solution, and crystallises from light petroleum coctaiining a little ether, in druses of colourless needles, melting at NOz*C,H,* CO*NH*CH,*CH( OE t ) 2 ,ORGANIC OHEMISTRY. 8 9 80-81". By the action of concentratled hydrochloric acid, not only are both the ethyl groups eliminated, but also the elements of water, with formation of the an12 ydrids of orthcr11tidohippuraldehyde, a white, amorphous compound, which decomposes at 300" withoiit previously melting; it has the empirical formula C,H8N20, but is probably a pol ymeride.Pamnitrobenzoylamidoacetal is prepared in a similar way to, and closely resembles the ortho-derivative ; it melts at 82", and, with hydrochloric acid, yields paraniti-ohippuraldehyde, which forms colour- less, amorphous flakes, softens at loo", and reduces Fehling's solution. Like the ortho-compound, it cannot be converted into the correspond- i n g acid, which was prepared from paranitrobenzoic chloride and glycocine, and forms colourless prisms melting at 129". When paranitrobenzoylamidoacetal is treated with reducing agents, it does not, like the ortho-derivative, yield the amido-compound, but is converted into the azoxy- or azo-derivative according to the strength of the reducing agent employed. Parazoxybenzoylanz.idoacetn1, ON,[ C,H,*CO*NH*CH,*CH(OEt),],, is obtained by the action of zinc dusb and acetic acid in the cold, and crystallises in pale red plates melting at 182".Parazobenzoylamidoacetal, N2* [ CsHd*C O*NH* CH2-CH( OEt),],, is formed if the eolution is boiled with zinc dust and acetic acid; it crystallises in long, narrow, carmine-red plates, melting at 202.5". H. G. C. Derivatives of Amidoaldehyde. By H. HELLER (Be,.., 1894,27, 3097 -3102) .- E. Fischer has already shown that amidoacetal com- bines with aldehydes and acid chlorides, and that the products are resolved by the action of hydrochloric acid into the corresponding derivatives of amidoaldehyde. The author, in the present paper, describes a, number of these derivatives. Yaramethozy bemy lideneantidoacetal, O&fe-C6H4*CH:N-CH2*CH( OE t)2, is obtained by the action of amidoacetal on anisaldehyde, and forms a coloarless oil having a bluish fluorescence, and boiling at 190" (corr.) under 12 mm.pressure. It yields salts, of which the oxalate, melting at 138", is the most stable. On reduction with sodium in alcoholic solution, it yields paramethoxybenzylamidoacetal, OMe*C&t4*CH2*NH*CH2*CH(OEt),, which is a colourless, slightIy fluorescent liquid boiling at 187" (coi-r.} under 12 mm. pressure ; its oxalate crystallises in colourless needles melting at 174". Paramethoxybenzylamidoaldehyde, OMe*C,H,*CH,*NH*CH*CHO, is obtained in the form of the hydl-ochloride by the action of hydro- chloric acid on the foregoing compound at 50" ; it crystallises with iH20, reduces Fehling's solution strongly, and with alkalis yields the free aldehyde, which is amorphous.The phenylhydrazone hydro- chloride crystallises from alcohol in lustrous, colourless plates which become brown a t 150" ; it is converted by alkalis into the oily free pheny lhydrazone. Anisy lamidoacetal, OMw C6H4* CO*NH CH2*C H (OEt ),, is prepared90 ABSTRAOTS OF CITEXIGAL PAPERS. by the action of auisic chloride on a cooled ethereal solution of amidoacetal, the hyd?.ochZoride separating out in lustrous, white plates which are converted into the free base by alkalis ; the latter forms yellowish, prismatic needles melting at 60-61". With hydrochloric acid, it yields paramethoxyhil,puraldehllde, OMe* CsH,*C 0 - C H2*CH0, the hydrochloride of which separates out in colourless cube-shaped crystals melting at 128" with decomposition.The free aldehyde forms amorphous flakes and reduces Fehling's solution strongly. The phenylhydrazone c r p talliscs in colourless needles, which soon become reddish, and on heating turn brown and then melt at 126"; the oxime crystallises in slender, white needles, and melts and de- composes at 1-63". By the action of bromine, the aldehyde is con- verted into metabronzopnramethoxyhippuric acid, C,,,H,,O,NBr, which forms slender, white needles and melts at 161-162" ; its silver salt crystallises from hot water in stellate groups of needles. When strongly heated with concentrated hydrochloric acid, it is converted into metabromanisic acid. Ortli oh ydroxy benz yliden eamidoacetal, OH*C,H,*CH:N*C H2* CH (OE t)2, obtained by the act'ion of salicylaldehyde on amidoacetal, crystal- lises in yellow tablets melting at 32', and boils at 188" (corr.) under 15 mm.pressure. Orthohydroxybenzoylamidoacetal is prepared by heating mothylic salicylate with amidoacetal at 120", and crystallises from light petroleum in yellowish, rhombic plates melting at 54". By the action of strong hydrochloric acid, it is converted into the hydrochloride of orthohydroxyh+puraldeh yde, OH*C,H**CO*NHCH,*CHO,HCI, which forms white tablets, and melts at 150" with decomposition. The free aldehyde has only been obtained as a syrup with strongly reducing properties ; its phenylhydrazone crystallises in pale yellow needles, and melts and decomposes at 134" ; the oxima forms needles melting at 142'.(Be?-., 1894, 27, 3102-3105).-Phthalyldiamidoacetal, H. G. C. Phthalyl Compounds of Amidoacetal. By W. ALEXANDER C,H,[ CO*NH* CH,*CH (OE t)2] 2, is obtained by the action of phthalic chloride on amidoacetal i n ethereal solution, and separates, on the addition of light petroleum, in colourless needles melting at 90', and decomposing rather above 100". The corresponding a!dehyde is formed by the action on it of hydro- chloric acid, the hydrochloride being thus obtained as a syrup which reduces Fehlitig's solution. By the action of alcoholic potash, phthalyl- diamidoacet a I is converted into ortho benzo ytarrdoacetalcar box y 2ic acid, COOH*C,H,.CO*NH*CH,*CH( OEL)~, which separates on the addition of light pet.roleum to its ethereal solution in stellate groups of colonr- less needles containing 1H,O ; it melts and decomposes at about 100°.TerephthalyldiarvLidoacetal is prepared in a manner analogous to the phthalyl-derivative, and cry s t a k e s i n flat needles or plates melt- ing at 165". The corresponding aldehyde, C,H,( CO*NH*CH,*CHO),, is a bulky, white powder which only dissolves in concentrated hydro-ORGANIC UHEMISTRY. 91 chloric acid and alkalis ; its phenylhydrnzone forms yellow flakes. TerephtlzaZ?lldianzidoacetic acid, Cs~l(C!O*N~*CHO.COOH)a, is ob- tained by the action of bromine on the aldehyde, and crystallises from hot water in needles which melt at 240" with evolution of gas; the silver salt is a curdy precipitate which may be recrystallised from hot water, and the copper salt an insoluble, crystalline precipitate, which is blue when moist, but becomes green on drying.The acid may be more conveniently prepared by acting on glycocine with terephthalic chloride according to Baumann's method. Ilsophthalyldiamidoacetal, obtained in the same manner as its isomerides, melts at 75" ; the corresponding aldehyde closely re- sembles the terephthalyl derivative, but cannot readily be converted into isophthalyldiamidoacefic acid, which was therefore obtained from glycocine and isophthalic chloride ; it forms colourless cubes, and melts with decomposition at about 210'. Aromatic Nitro-derivatives. By V. METER (Ber., 1894, 27, :3153--3159).-Triiiitrobenzoic chloride [COCl : (NO2), = 1 : 2 : 4 : 61 is produced on heating trinitrobenzoic acid with a mixture of the oxychloride and pentachloridc of phosphorus. It displays re- markable stability in presence of water, being only slightly decom- posed when boiled with it for an hour (compare Sudborough, Trans., 1894, 1030).The solution of trinitrobenzoic acid in alkali (1 mol.) is colourless, and yields a colourless silver salt with silver nitrate; but if excess of alkali is employed, a deep orange-red liquid is formed. On adding acid to this solution, unchanged trinitrobenzoic acid is thrown down; this behaviour is comparable with the development of a deep red coloration exhibited by trinitrobenzene in presence of alkali. A small quantity of 1 : 3 : 5-dinitrobenzoic acid dissolved i n dilute alkali forms a colourless solution, becoming deep violet when excess of strong alkali is added.After a few minutes, the Iiquid loses colonr, and on remaining for two hours a further change occurs, and a stable, magenta coloration is developed. The author criticises the conclusions drawn by Nef regarding the constitution of salts of the nitro-paraffins (this vol., i, 3). Reduction of Paradimethylamidobenzoic acid and Par- amidobenzoic acid. By A. EINHORN and A. MEYENBERG (Ber., 1894, 27, 2829-28.34 ; compare Abstr., 1894, i, 591).-Yaradimethyla~nido- co - hexah ydrobenzoic acid, CJIlo<NHMe2> 0, is obtained, in associa- tion with hexahydrobenzoic acid, by the reduction with sodium of paradimethylamidobenzoic acid dissolved in amylic alcohol. The acid liquefies at 99-loo", resolidifies at 130°, and finally melts at 218-220" ; i t contains 2+H20.It is a neutral substance, and forms a bright blue coppel- salt ; the platinochloride melts at 232". H. G. C. M. 0. F. #-.A VV- Pnramidohexah ydrabenzoic acid, C6H10<NH,>0, is formed on reducing with sodium paramidobenzoic acid- dissolved in amylic alcohol, hexahydrobenzoic and valeric acids being formed simulta-92 ABSTRACTS OF CHEMIOAL PAPERS. neonsly. acid crystallises in small, white plates which melt at 303-;304". On adding the aqueous solution to absolute alcohol, the If. 0. F. Isomeric Paramethylenedihydrobenzoic acids. By A. EIN- HORN and R. WILLSTATER (Ber., 1894, 27, 2823-2829; compare Abstr., 1894, i, 523) .-In addition to Az> 4-paramethylenedihydro- benzoic acid, and the acid obtained by Einhorn and Friedlander on hg drolysing the methiodides of ethylic r-ecgonine and Z-ecgonine, there exists a third acid, CsH802, which remains liquid a t -20".It is prepared by heating A 2* 4-paramethylenedihydrobenzoic acid with alcoholic potash for 48 hours in a reflux apparatus; it boils at 160" (20 mm.), and the amide melts a t 90". The cr,ptalline acid (m. p. 55-56') described by Einhorn and Friedlander is also formed when A 2s 4-paramethylenedihydrobenzoic acid is boiled with alcoholic potash for 12 hours ; the amide melts at 101-102". This acid and paramethylenedihydrobenzoic acid, on reduction, yield the same 1 : 4-ethylcyclopentanecarboxylic acid. I t is not yet clear whether the liquid acid just described is struc- turally different from the substance obtained by Einhorn and Fried- lander, or whether the isomerism is geometrical in character.M. 0. F. Bismuth Salts. By B. FISCHICR and B. GR~~TZNER (Arch. Pharnz., 1894, 232, 460-466 ; compare Abstr., 1894, i, 416).-The authors prepared basic bismuth salts by heating freshly precipi- tated bismuth hydroxide with the respective acids. Basic bismuth pal-acresotate, C7H70*C00*Bi0, and the metacresotate both form needles similar in all respects to tho salicylate. No definite basic salts could be obtained from anisic, benzoic, or cinnamic acids. Tho tartrate, C4H40,,2Bi(OH)2, forms an amorphous, electrical, white powder. Attempts to prepare the basic nitrate by the action of the calculated quantity of a 5 per cent. alcoholic solution of nitric acid on freshly precipitated bismuth hrdroxide were sometimes suc- cessful and sometimes not.The authors were unable to find out the conditions necessary to ensure a successful result. Hydroxy-derivatives of Phenylbutyric acid. By F. KOPISCH (Bey., 1894, 27, 3109-3113).-In the course of their synthesis of phenylte trose, Fischer and Stewart (Abstr., 1892, 1U7) obtained several hydroxy-derivatives of phenylbutyric acid ; the anthor has subjected these to a further examination in order, if possible, to separate them into optically active compounds. In this he has been unsuccessful ; but a number of interesting derivatives have been obtained which are described in the present paper. Barium phenyltrihydrozybutyrate, (C,,Hl10s)2Ba, is obtained by the action of boiling baryta water on the lactone, and forms slender needles.The strychnine salt, CzlH22N20,,CIoH,z05 + H20, crystallises in microscopic needles or plates, loses its water of cryatallisation at 93", and becomes yellow at 105". Nitrophenyltrihydrozybutyrolactone is obtained by the action of nitric acid of sp. gr. 1.5 on the lactone of the trihydroxy-acid, and crystallises in slender, colourless needles melting at 185" with slight evolution of gas; on boiling with alkalis L. T. T.ORGANIC CHEMISTRY. 93 it first dissolves, after which a crystalline, yellow precipitate sud- denly separates. Phenylamidodihydroxybutyrk anhydride, prepared b y boiling phenylbromhydroxybutyrolactone with ammonia for a short time, forms well-developed, colourless prisms which have a neutral reaction, become brown at 200°, and melt at 215".It is not altered by boiling with alkalis or heating with phenylhydrazine, and it is therefore uncertain whether it is a lactone or a lactam. Phenylbromo- dih ydroxy b ut yranilide, 0 Ha C HP h* C HBr* C H( 0 H)* C 0 NHP h, obtained by heating t'he bromolactone with aniline at loo", crystallises in slender needles melting at 167-168" (uncorr.), and the phenyl- hydrazide, obtained by the action of phenylhydrazine in the cold, forms microscopic, rhombus-shaped plates melting and decomposing a t 168-169". If the bromolactone is warmed with phenylhydrazine, it is converted into phenylhyd?-oa y benzy lh ydrox ypyraiolid&e,- which has , and crystal- probably the constitution CO< CR(OH)*FH*CHPhOH NH-NPh lises in spherical aggregates of colourless needles melting at 208".When the bromolactone is reduced with sodium amalgam, it yields two products having the composition C10H1003 and C10H:1002 respec- tively. The former is probably a phenylhydroxybutyrolactone, and may be a stereoisomeride of the compound described under the same name by Biedermann (Abstr., 1892, 471). It crystallises from ether in colourless needles, melts at 124-126", and gives a white crystal- line precipitate with phenylhydrazine in ethereal solution. The second compound, separated by means of its solubility in light petro- leum, crystallises in large, colourless needles melting a t 87-88", and behaves towards phenylhydrazine in the same manner as the previous compound. Its constitution is unknown. €I. G. C. The Law of Etherification of Aromatic Acids.By V. MEYER and J. J. SUDUOROUCH (Ber., 1894, 27, 3146-3153 ; compare Abstr., 1894, i, 463) .-The nitrophthalic acids behave similarly to substi- tuted benzoic acids as regards the formation of ethereal salts. Dinitrophtbalic acid [NO, : COOH : COOH : NO2 = 1 : 2 : 3 : 41 gives no ethereal salt, whilst the acid [NO2 : COOH : COOH : NO, = 1 : 3 : 4 : 5 ) yields monalkylic salts. 1 : 2 : 6-Dinitrobenzoic acid gives no ethereal salt. Tetrachlorophthalic acid, however, yields small quantities of the normal methylic salt, but as the behaviour of 2 : 4 : 6-trichloro- benzoic acid is normal, the authors conclude that the normal methylic salt is analogous in structure to phthalylic chloride, and cannot, fherefore, be regarded as a true ethereal salt. Both 2 : 4 : 5- and 3 : 4 : 5-trichlorobenzoic acids yield an ethylic salt.2 : 4 : 6-Tri- chlorobenzoic acid was prepared from trichloraniline instead of tri- bromaniline. M. 0. F. Introduction of Acid Radicles into Ethylic Benzoylacetate. By A. B~CRNHARD (Annalen, 1894, 282, 153--191).-When ethylic cuprobenzoylacetate is treated with benzoic chloride, three su bsti tu- tion compounds are produced. Ethy tic dibenzoylncetate, or ethylic a-benzopl-P- hydroxycinnamate, O H C P h: C Bx*C OOE t, has been pre- VOL. LXVIII. i. h94 ABSTRAOTS OF OHEMICAL PAPERS. viously described (Trans., 1891, lOOO), and is converted by bromine into ethylic bromodibeazoylacetate. The copper compound crystal- lises from alcohol in needles melting at 221'. Ethyl ic a - beitzoyl-p)- bemozycimamate, OBz-C P h: CBrC OOE t, con- stitutes about one-hlf of the neutral products formed by the above reaction.It ciytallises from ether in thick prisms, melts a t 9B0, and is readily soluble in hot alcohol, &C. It gives no coloration with ferric chloride, and is only slowly decomposed by warming with aqueous soda. When treated with sodium ethoxide, it yields ethylic benzoate, together with ethylic a-benzoyl-P-hydroxycinnamate. A similar change is produced by phenylhydrazine, benzoylhydrazine being formed. Bromine also acts in a somewhat, similar manner, benzoic bromicle and eth$?ic a-bronzodibenzoylacetate, CBrBz,*COOEt, being produced. The latter crystallises in elongated tablets, and melts at 109-110'. The same bromo-compound is formed directly by the action of bromine on ethylic dibenzoylacetate and ethylic a- benzoyl-/3-acetoxycinnamate. The remainder of the neutral oil referred to above probably consists of etkylic p- Benzoxyisocinnamate, OBz-CPh:CH*COOEt, although this has not yet been isolated from it in the pure state.Benzoic chloride reacts in a precisely similar manner with ethylic sodiobenzoylacetate, the action being in both cases exactly analogous to that of benzoic chloride on ethylic acetoacetate (Nef, Abstr., 1894, i, 628). When ethylic cuprobeuzoylacetate is treated with two-thirds of the calculated amount of acetic chloride, the product consists of ethylic p-acetoxyisocinnamate, and a smell amount of ethylic benzoyl- acetoacetate, together with some regenerated ethylic benzoylacetate. Ethylic ben zoylacetoacet ate (e thylic a-benzoyl-p- hydroxycrotonate), OH*CMe:CBz*COOEt, has been previously described by Bonn6 (this Journal, 1887, ii, 437).Etkylic /I-acetoayisocimzamate, OAc*CPh:CH*COOEt, is a neutral substance, and crystallises in long needles melting a t 27-28'. It reacts with sodium ethoxide in alcoholic solution to form ethylic acetate and ethylic sodiobenzoylacetate, and behaves in a similar manner with phenylhydrazine, acetylphenylhydrazine being produced. Ethylic a-beiazo~l-/3-acetozycl.otolzate, OAc.C'Me:CBz*COOEt, is ob- tained by the action of acetic chloride on the copper compound of ethylic benzoylacetoacetate as a neutral, unstable, brown oil, which is readily decomposed by dilute soda, gives a red coloration with alcoholic ferric chloride when left f o r a few minutes in contact with it, and reacts with sodium ethoxide to form ethjlic acetate and ethylic sodiobenzoylacetoacetate.Ethylic chloroformste reacts with the sodium and copper com- pounds of ethylic benzoylacetate to form ethylic benzoylmalonate and ethylic /3-carbetlioxyisocinnamate, a small amount of ethylic dibenzoylsuccinate (Perkin, jun., Trans., 1883, 263) being also formed in the second case. Etiiylic BemoyhzaZonate, OH*CPh:C(COOEf),, is a yellowish oil,ORQANIC CHEJIISTRY. 95 which boils at 192-193" under a pressure of 13 mm. It has strongly acid properties, dissolves in sodium carbonate, and gires a red coloration wihh alcoholic ferric chloride immediately. When distilled with steam, it decomposes quantitatively into ethylic benzoyl- acetate, carbonic anhydride, and alcohol.Sodium ethoxide, in alcoholic solution, produces the sodium derivatire, which is a fine, white powder, and reacts with copper acetate yielding the coppey dei*ivntive, which crystallises in dark green needles melting at, 180". Ethylic carbethoxy.isoci?znamate, C 0 OE t *O *CPh:C H* COOEt, is a neutral, viscid, yellow oil, which boils at 200-202" under a pressure of 15 mm. It gives no coloration with ferric chloride until the mixture has stood for a considerable time. With sodium ethoxide, it forms ethylic carbonate and ethylic sodiobenzoylacetate, and reacts with phenylhydrazine in an analogous manner, ethylic benzoylacetate, ethylic carbazinate, and 1 : 3-diphenylpyrazolone (m. p. 135") having been isolated from the product.It is noteworthy that almost equal quantities of the neutral and acid products are formed by the action of ethylic chlorolormate on ethylic sodiobenzoylacetate, whilst with the corresponding derivative of ethylic acetoacetate, the neutral compound is the chief product. The action of acid anhydyides 0% ethylic benzoylacetate proceeds in a manner very similar to that of the acid chlorides, as will be seen from the following summary of the products obtained. (1) Acetic anhydride yields ethylic benzoylacetoacetfate (20-30 per cent.), a mix- ture of ethylic P-acetoxy isocinnamate, and ethylic a-benzoyl-p-acetoxF- crotonate (20 per cent.), acetophenone (15 per cent.): acetic acid, ethylic acetate, and ethylic benzoylacetate (18-32 per cent.). (2) Benzoic anhydride yields ethylic dibenzoylacetate (50 per cent.), small amounts of tribenzoylmethane and ethylic dehydrobenzoyl- acetate, ethylic benzoate, benzoic acid, and possilnly ethylic P-benz- oxyisocinnamate.Acetic anhydride also acts on ethylic oxalacetate to1 form ethylic p-acetoxyfitmarate, which is a neutral oil, gives no coloration with ferric chloride, and reacts with phenylhydrazine to form acetylphenyl- hydrazine. The author is of opinion that the difference in behaviour towards alkalis of the two forms of tribenzoylmethane and dibenzoylacetone may be due to physical causes, and is not necessarily to be ascribed to a difference in chemical constitution (compare Claisen, Abstr., 1894, i, 192). Two formulaa are possible for the derivatives of the P-ketonic acids which contain two acid radicles such as ethylic dibenzoylacetoacetate, CAcBz,*COOEt and 0BzGMe:CBvCOOEt.Both formule equally express the neutral character of the compound; if the former of the two formulse were correct, the same substance should be obtained by the action of acetic chloride on ethy lic dibenzoylacetate, and of benzoic chloride on e tbylic benzoylacetoacetate, whereas, according to the second formula, two different compounds should be produced. Experiment shows that the latter is what actually occurs, ethylia h 296 ABSTRACTS OF OEEMIOAL PAPERS. a-benzoyl-P-acetoxycinnamate and ethylic a-beneoyl-P-benzoxycroton- ate respectively being formed. The same view is further confirmed by the fact that sodium ethoxide, phenylhydrazine, and bromine always replace that acid radicle which has been last introduced.I f this formula be accepted, there are still two stereoisomeric con- figurations possible, but at present it is impossible to decide between them with any approach to certainty. A. H. Vinyltriphenylsulphone (Triphenylsulphonethane). By R. OTTO (Ber., 1894, 27, 3055--3058).-When monochlorethylene di- chloride is warmed with sodium benzenesulphinate in alcoholic solu- tion, i t yields, not a trisulphone, but the disulphone, CzH4( S02Ph),, sodium sulphate and benzenesulphonate being simultaneously formed. When warmed with sodium phenyl mercaptide, NaSPh, in alcoholic solution, however, it yields uinyltrithiophenyl (tritTLiophenylethane), SPh*CH,*CH(SPh),. This is an oil having an odour resembling that of lemons ; when oxidised with permnnganate, it yields ethylene- diphenylsulphone and a benzenesulphonate, but, if care is taken to avoid a rise of temperature, uinylts.iphenylsulpho}~e (triphenylsulphon- ethane), S02Ph*CH2*CH( SO2Ph),, is formed.This is insoluble in water; it is readily hydrolysed by aqueous soda, apparently with formation of glycollic aldehyde. C. F. B. Indigo. By C. J. VAN LOOKEREN and P. J. VAN DER VEEN (Landw. Versucks-Stat., 1894, 43, 401-426) .-The authors have prepared indican from the leaves of plants belonging to the species Indigofera, and their results are identical with those obtained by Schunck in his experiments with Isatis tinctoria (woad). The sugar, which the authors obtained as a syrup by hydrolysing their indican, was dextro-rotatory, reduced Fehling’s solution, gave a brown colora- tion with alkalis, and was probably identical with ordinary gluccse (dextrose). The so-called indigo-gluten is probably a mixture of nitrogenous decomposition products of indican, with a certain amount of the enzyme (rendered inactive) which determines the hydrolysis of indican.Schunck’s oxindicanin gives a red precipitate when warmed with Millon’s reagent. Experiments are next de- scribed which point to the existence of an enzyme as the hydrolyst of indican, thus the hydrolysis of indican proceeds under conditions which exclude the presence of micro-organisms. The quality of the indigo-blue is affected by continuing the lixiviation process too long, which is done in practice, and the cause of this may be the action of bacteria.If the so-called fermentation is protracted, the indigo-blue contains a larger proportion of calcium salts and more indigo-gluten. According to the authors, the usual practice is to employ water at a temperature of 27.5” for the fermentation ; better results are obtained by digesting with water at an init#ial temperature of 5 9 , the digestion (fermentation) being continued for about seven hours at a temperature of about 28”. The authors find that in the manu- facture of indigo-blue, equivalent quantities of lime, potash, or soda may be used instead of ammonia. A. R. L.ORGANIC CHEMISTRY. 97 Parahydrazidodiphenyl, By H. MGLLER (Ber., 2894, 27, 3105-3108).--Parah ydrazi'dodiphenyl, C12Hg*NH*NH2, is prepared by diazotising paramidodiphenyl and reducing the diazo-compound with tin and hydrochloric acid, the Jydrochloricle thus formed being decom- posed by alkali and the free base extracted with ether ; after crystal- lisation from hot alcohol, it forms lustrous, colourless plates, melts at 135-136" (uncorr.), and quickly oxidises in the air, especially when moist.The hydrochloride, sulpha.te, and nitrate all wystallise in colourless plates, and are sparingly soluble in cold water. The acetyl derivative, ClzHg*N2H2Ac, crystallises in colourless plates melting at 203", and the thiocarbamide, Cl2Hg*N2H2CS*NHPh, in colourless needles melting at 182" ; the latter dissolves in concentrated sulphuric acid with a deep blue colour. Parahydrazidodiphenyl readily combines with aldehydes and ketones, including the sugars, but the compounds obtained from the latter do not cryst,allise well, and are, therefore, of no use for the recognition or isolation of the sugars.Acetonehydrazolaed~henyl, C12Hg*NH*N:CMe2, is crystalline, melts at 86-87", and yields an indole when heated at 180" with zinc chloride. Acetophenoneh ydrazone- diphenyZ, C12H,*NH*N:CMePh, forms colourless plates melting a t 148", and benzylidir~ehydrazidodipl~enyl, ClzHS*NH*N:CHPh, crystal- lises in yellowish needles meltiiig at 153". Arabinosehydrazonedi- pheny 1, C12H9*NH*N:C5H1004, is obtained with difficulty in nodular aggregates of slender crystals, and melts, when quickly heated, at 138-140", with decomposition. The xylose derivative has similar properties. Glucosehy druzoiied ipheny 1, C12Hg*NH*N: C8HI2O5, forms very slender crystals, melts at 143-1441' with evolution of gas, and, on heating with an excess of the hydrazine, yields the osazone.Galuctosehydrazonediphenyl crystallises in stellate groups of colour- less needles melting and decomposing at 157-158". Stereoisomeric Paraphenylhexahydrobenzoic acids. By B. RASSOW (Annalen, 2894, 282, 139--153).-ParaphenyEhexahydroben- zoic acid, C6Hl,.Ph-COOH, may be prepared by reducing paradiphenyl- carboxylic acid with sodium and boiling amylic alcohol, or by treating the same acid with sodium amalgam in alkaline solution, whereby it is converted into a mixture of tetrahydro-acids, acting on these with hydi-obromic acid, and finally reducing the hydrobromides thus obtained by means of sodium amalgam. The crude hexahydro-acid melts at 190-195"; but on crystallisation yields an acid, which melts at 202", together with a portion of lower melting point, from which an acid, melting a t 113", may be isolated in small quantity by extracting with boiling water, filtering, and adding potassium permanganate to the solution in sodium carbonate until a permanent coloration is produced.Paraphenylhexahydrobanzoic acid (m. p. 202') crystallises from dilute acetic acid or ether in lustrous plates. The silver salt is insoluble in water, the sodium and ammonium aalts sparingly soluble, and the potassium salt readily soluble. A solution of the ammonium salt gives white, insoluble precipitates with barium chloride, calcium chloride, zinc sulphate, and mercuric chloride, whilst the magnesium H.G. C.98 ABSTRACTS OF OBEMICAL PAPERS. salt dissolves in hot water. The mcthylic salt, prepared by treating the chloride with methylic alcohol, forms tabular crystals, and melts at 28-30". On oxidation with potassium permanganate, the hexa- hydro-acid is converted into a hydroxy-acid, which probably has the formula OH*C6H,Ph*COOH. It forms a honey-like mass, with an ill- defined melting point of about 145'. This hydroxy-acid loses a molecule of water when boiled with water, a tetrahyd?-ophen?lZbeiazoic acid being formed, which melts at 158", and, since it is not altered by boiling with aqueous soda, is probably a AlD2-acid. It at once decolorises alkaline potassium permanganate, and com bines with bromine. The silver salt of the hydroxy-acid also loses a molecule of water when boiled with water, yielding the salt of the tetrahydro- acid.More thorough oxidation converts the hexahy dro-acid into benzoic acid, Isoparaphenylheanhydrobenzoic acid (m. p. 113') is best obtained by heating the acid of higher melting point with fuming hydrochloric acid at 170-180". It forms lustrous needles, and dissolves in about 1000 parts of boiling water. The silver salt blackens when heated in contact with the solution from which it has been obtained, and is somewhat soluble in hot water. The sodium, potassium, and ainmonizcm salts are all readily soluble in water, and the calcium salt moderately so. When the iso-acid is heated with fuming hydrochloric acid, it is partially reconverted into the acid of higher melting point, the same state of equilibrium being reached from either acid, that of higher melting point constituting about 90 per cent.of the mixture, The iso-acid is also converted into benzoic acid by oxidation. The paper is prefaced by a note by Baeyer, in which he points out that it has been found impossible to obtain stereoisomeric forms of tetrahydro-a- and [3-naphthoic acids, and that this result, although, as it is negative, it cannot be considered decisive, is in favour of the view that the valencies of the 6 hydrogen atoms of the benzene ring are perfectly symmetrically arranged. The results described in the foregoing paper show that in the closely related hexahydrophenylbenzoic acid the differences between the properties of the two stereoisomerides are quite well marked.A. H. Tetramethyldiamidodiphenylmethane. By J. PINNOW (Bey., 1894, 27, 3161--3167).-The action of nitrous acid on tetramethyl- diamidodiphenylmethane converts it into a mononitro-derivative, which melts a t 87-88'. The further action of nitrous acid gives rise to a &nitro-derivatire, which crystnllises in slender, red needles, and melts at 123-124". An isomeride is produced when a mixture of nitric and sulphuric acids is added to the solution of tetramethyl- diamidodiphenylmethane in concentrated sulphuric acid ; it crysta.llises from glacial acetic acid in red prisms, which melt at 191.5" (uncorr.). This compound yields tetraineth y ltetramidodiphenylmethane when re- duced with tin and hydrochloric acid ; the base crystallises in colour- less needles, which melt at 142" (uncorr.).The action of nitric acid on tetramethyldiamidodiphenylmethane in glacial acetic acid solution 1 eads to the formation of nitibosamines and nitramido-derivatives ;ORGANIC CHEMISTRY. 99 di?nethyldinitrosanaiaoa~p~enyl~nethane is prod uced on adding sodium nitrite to the solution of the base in hydrochloric acid (sp. gr. 1.19). It crystallises in slender, pale yellow needles, which melt a t 101.5". A condensation product of tetramethyldiainicloclipheiiylmethane with formaldehyde appears to be formed when a mixture of dimethylaniline (10 grams), formaldehyde solution (10 grams), and glacial acetic acid (15 grams) is boiled for eight hours; it has the composition With diazobenzenesulphonic acid, tetrametbyldiarnidodiphenyl- methane yields a colouring matter, which, on reduction with tin and hydrochloric acid, is resolved into paramidodimethylaniline and par- Constitution of the Alkali Compounds of Phenolphthalein.By E. HJELT (Chem. Zeit., 1894, 18, 3).--According to Armstrong (Proc., 1893, 58), the coloured salts of the phthale'ins assume a quinono'id structure ; this view presupposes, for example, in the case of phenolphthaleyn, that the phthalide ring (lactone ring) is readily disrupted by alkalis. The author's experiments indicate, however, that the hydrolysis of the phihalide ring, CoH,< :?> 0, proceeds much more slowly in the case of phthalide and of meconine than in the case of the aliphatic lactones (Henry, Abstr., 1892,1S03). According to it in minutes), the following values were the formula Ac = found; for phthalide, Ac = 0.0674 (A = 10.1) ; and for meconine, Ac = 0.0298 (A = 11.2).The hydroxy-acid corresponding with phenolphthalein is unknown, and is probably incapable of existence. (Cl*&N2) 2. amidobenzenesulphonic acid. 31. 0. F. a: (A - x)t A. R. L. Synthesis and Constitution of Vulpic acid. By J. VOLHARD (Armalen, 1894, 282, l-Zl).-According to Spiegeel (Abstr., 1881, 97, 173, 1036; 1882, 1076), vulpic acid is the motiomethylic salt of the bibasic pnlvic acid, which is converted by alkalis into dibenzyl- glycollic acid, OH*C(CH,Ph),*COOH, a diketonic acid, symmetrical diphenylketipic acid, C 0 OH* CHPh-C 0 G O CHPhGOOH, being formed as an intermediate product. I n order to prepare vulpic acid synthetically, the author starts from benzylic cyanide, which is converted by ethylic oxalate and sodium ethoxide in alcoholic solution into the cliuitrile of dipheiyE- ketipic acid, CN*CHPh*CO*CO*CHPh*CN.This substance crystal- Iises from amylic alcohol in olive-green, lustrous scales, and melts and decomposes at 270". When hydrolysed with 60 per cent. sul- phuric acid, the nitrile is converted into pulvic acid dilactone (70 per cent.), and pulvic acid (14-18 per cent.), a small amount of other products of unknown nature being also formed. When the dilactone is treated with a solution of potash in methylic alcohol and the solution acidified, vulpic acid is obtained, identical with that x>reDared from Evernia vulpina. * Piperidifis vullpate f o r i s long, thin, yellow n.eed1es melting at 139-142".100 ABSTRAOTS OF OHEMIOAL PAPERS.The pulvic acid prepared from the dilactone is also identical in every respect with that obtained by Spiegel. It crystallises with lC2H,0 in yellowish-red, rhombic prisms, which have the axial ratio 0.5835 : 1 : 0.4337. Nonohromopuivic acid, C,,H,,BrO, cry stallises in radial groups of yellow tablets, melts at 208-209", and forms a crystalline ba?.ium sult. , is con- CO*$!HPh 0-co tained among the products of hydrolysis of the dinitrile. It forms small needles, and melts at 231-233". It follows from this synthesis that pulvic acid is the anhydride of diphenylketipic acid, but it is at present impossible to decide between the formulae Dibenzylozalylcarboxylic acid lactone, CHPh:C < C P h < ~ ~ ~ > C : C P h * C O O H and O< C:CPh*COOH I C:CPh*COOH A.H. Pulvamio acids and Ethereal Salts of Pulvic acid. By R. SCHENCK (Annalen, 1894, 282, 21-44 ; compare the foregoing abstract) .-Pulvamic acid has previously been described by Spiegel (Abstr., 1881, 1076). The ammonium salt melts at 218", and the potassium salt crystallises in slender needles with 5Hz0, whilst the zirzc and silver salts are insoluble and amorphous. It appears to be impossible to displace a second hydroxyl-group in the molecule by the amido-group. Pulvomethylainic acid, CleH,,04N, is obtained by the action of methyl- amine on the dilsctone. It crystallises in quadratic plates, and melts at 237'. The barium salt is sparingly soluble in water. Pulvanilic acid, C24H,0aN, forms com- pact crystals, and melts at 187-188".The ammonium salt melts a t 1.53" ; the potassium salt forms yellow crystals with 2HE,0. Pulv-a- naphthylamic acid crystallises in iridescenh, reddish-yellow plates, and melts a t 211-212". The ammonium salt melts at 208O, and the barium salt crystallises from alcohol in slender needles. Pulvo-p- naphth ylamic acid forms druses of large, reddish-yellow crystals, and melts at 292". The ammonium salt melts indefinitely a t about 182". Putv- dimethylamic acid crystallises in small prisms, and melts at 211", its dimethylamine salt melting at 210". The acid is quite analogous to pulvamic and pulvrnethy lamic acids. Pulvopiperidinic acid is very unstable, and melts at from 150" to 160". Its piperidine salt melts at 199-220". The metallic salts aro decomposed by boiling with water, piperidine being formed.Pwlvvhy dmxamic acid is obtained by heating the dilactone with hydroxylamine hydrochloride, sodium acetate, and acetic anhydride. It crystallises in quadratic plates, and melts at 194O, with evolution of carbonic anhydride; the acid is bibasic to baryts water. Its monaniline salt forms plates melting a t 163-164". Pzclrop7~enylhydrazinic acid melts at 201-202", and forms The metlzylamine salt melts at 214". The barium salt forms a crystalline powder. Methylaniline and diphenylamine do not yield amic acids.ORGANIC CHEMISTRY. 101 a, phenylhydrazine saZt, which is more readily soluble in alcohol, and melts at the same temperature. The ammonium salt forms pale yellow, slender needles, and melts a t 187-188".The mon-ethereal salts of pulvic acid may be obtained by the action of potash and an alcohol on the dilactone, or by that of an alkylic iodide on the hydrogen silver salt. The normal ethereal salts form compounds with 1 mol. water and 1 mol. piperidine. The following have been prepared. M. p. of piperidine M. p. compound. Methylic vulpate.. ...... 141" 147-148" Ethylic vnlpate ......... 138-139 152-153 Methylic ethylpulvate.. .. 150-151 151 Propylic vulpate ........ 95-96 149 Methylic propylpulvate . . 121-122 126 Propylpulvic acid. ...... 134 - Ammonia reacts with the normal ethereal salts to form an amide and phenylacetic acid. The amide, CIoH8O2N2, crystallises in bronze- coloured plates, and melts at 247.5". When boiled with dilute hydro- chloric acid, it yields cyanophenylpyrnvic acid (compare the following abstract).A. H. Derivatives of Diphenylketipodinitrile. By J. VOLHARD and F. HENKE (Annalen, 1894, 282, 45-84; compare the two preceding abstracts).-The hydrolysis of the dinitrile occur8 in several stages. Dip hen y lke tipamidonitrile, CN*CPh:C (OH) C (OH) :C PhG O*NH2, is obtained by treating the dinitrile in the cold with concentrated sulphuric acid. It forms pale yellow needles containing 1 mol. C2He0, and melts and decomposes at 199-200"; it gives a brownish- red coloration with alcoholic ferric chloride. When boiled with aqueous sodium carbonate, the nitrile is decomposed into benzglic cyanide and hydroxyphenylmaleinimide, CloH7N03, which is described later on. Diphenyl ketiparnidonitrilesuly honk acid, CI8Hl3O3N2*SO3H, is ob- tained by warming a solution of the dinitrile in sulphuric acid on the water bath.It forms microscopic, flat needles, and does not melt below 300". The sodium and barium salts are both crystalline. No diamido-compound was observed among the products of hydrol- ysis of the dinitrile, but a small amount of pulvamic acid (com- pare the preceding abstract) is formed. Thig substance can also be readily obtained by boiling the amidonitrile with hydrochloric acid. The methylic salt forms almost colourless, compact crystals melting at, 216-217". When t h i s salt is hydrolysed, pulvic acid, and not an isomeride of vulpic acid, is formed. The dinitrile readily dissolves in alcoholic potash, forming tt potassium saZt, C18H,202N2K2 + 2C2H60, which crystallises in colour- less plates.The sodium salt may be prepared in a similar manner, The dinitrile also appears to form an unstable compound with 1 mol. HCl. The monacetate, CN*CPh:C(OAc)*C (OH):cPh.CN, is obtained by the action of a mixture of acetic acid and acetic anhydride;102 ABSTRACTS OF CHEMICAL PAPERS. i t crystallises in lustrous needles, and melts at 208-209.5". It is insoluble in water, but dissolves in aqueous alkalis, the sodi?cm salt crystallising with 3H20 in scarlet needles. The nzethylic salt, prepared from the amorphous red silver salt, crystallises in lustrous, yellow needles, and melts at 229-231". When heated with aqueous ammonia at loo", the acetate yields benzylic cyanide and phenylacetamide, together with oxalic and oxamic acids.Acetic and benzoic chlorides act on the sodium and silver salts, but only reproduce the monacetate. The cliacetate is formed when the dinitrile is treated with pure acetic anhydride, and forms gregish- green needles melting at 177-179". It is insoluble in water and alkalis, and combines with 1 mol. of alcohol to form a compoultd, which can be recrystallised from toluene, and melts at 191-191.5". Methylic alcohol forms a similar C O ~ ~ p t n d , which crystallises in colourless granules, and melts and decomposes at 196". The compound with amylic alcohol crys tallises in very slender needles. Acetic chloride reacts with the dinitrile to yield the monacetate together with the anonacetate of the lactone of the semi-hydrolysed dinitrile, C( OAc)*v:CPh*CN co-0 CPh< This crystallises in canary-yellow needles, and melts at 141-142".The corresponding benzoate crystallises in slender, yellowish needles, melting at 168-168.5". The monobenzoate of the dinitrile is also formed in dark, orange-red granules, melting at 220-224", which dissolve in alkalis. Phosphorixs oxyc hloride converts the , corresponding dinitrile into a chloro-derhathe, CPh< in composition with the lactone compounds described above. It crystallises in long, greyish-green needles, and melts at 161-1 62". It is insoluble in water and aqueous alkalis, but dissolves in alcoholic potash, and yields a crystalline bai-iz~rn salt. When heated with sodium acetate and alcohol, it loses chlorine, forming a Izydroxy- compound of the formula CI8Hl1O&, which crystallises in matted, reddish-yellow needles, and melts a t 193-194". When heated with acetic anhydride, this is converted into the acetate of the semi-lactone already described.Dilute alcoholic ammonia at 100" converts the dinitrile into au iso- C C1* f: : C Ph*CN co-0 cyaizop~eny123yrzLz'amide, C(OH)<Cph--&o, C (NH) *NH which crystallises in red needles, and does n o t melt below 280". It dissolves in alkalis, and forms crystalline sodizcm and barium salts. Arnylic nitrite con- verts it into a nitro-derivatiee, C,,H,N,O,*NO,, which melts and decomposes at 246". When heated with dilute hydrochloric acid, it is very readily converted into Fvyd~oxyphenylmalei'nimide, which is best prepared by heating the amidonitrile or its sulphonicORQANlC OHEMISTRY. 103 acid with aqueous sodium carbonate.It crystallises in lustrous, yellow scales, melts at 216-218", gives a green coloration with ferric chloride, and forms salts with one equivalent of metal. The ethylic salt crystallises in long, lustrous needles, resembling the salts of uranium in appearance, and melting at 128-130". This substance is isomeric with the ethylic phenylcynnopyruvnte described by Erlenmeyer, jun. (Annalen, 1892, 271, 172). The latter compound, on hydrolysis, yields a substance which was described by Erlenmeyer as phenyl- cyanopyruvic acid, but which is identical with hydroxyphenglmaleiin- imide. This substance cannot have the constitntion ascribed t o it by Erlenmeyer, as, when its silver salt is treated with ethylic iodide, it yields t,he yellow ethereal salt described above, and not the original colourlem ethylic phenylcyanopyruvate, C N*CPh*CO*COOEt, by the hydrolysis of which it was obtained. It is, moreover, con- verted by ammonia into the phenylamidomaleinimide described below.Acetic anhydride converts hydroxyphenylmale'inimide into the acetate, CloH,N20,Ac, which ci*yst,allises in long, white needles melting a t 134-135". Etl~oxyp7tenyl~taleiia-be?azoyl.imide, C19H,,04N, prepared by treating the yellow ethylic salt with benzoic chloride, crystallises in yellowish needles with a greenish fluorescence, and melts at 105-106"- The isomeric be?zzovt-derivat izie obtained from Erlenmeyer's ethylic phenylcy anopyruvaie crystallises in colourless prisms, and melts at Co--NH is obtained by the CPh*bOy PJLe?aylamidomalei;nimide, NHz*C< 102-103"._ - ~ -~ actioii of alcoholic ammonia on ethoxyphenylmale'inimide, and has also been obtained from the chloro-semilactone described above, and from the neutral ethereal salts of pulvic acid, a proof that it contains no cyanogen group. It crystallises in thin, golden-yello w, lustrous plates, and melts at 248-2419'. The corresponding piperidide, C1,H1,02N2, is formed when ethoxyphenylmale'inimide is heated with piperidine, and crystallises in orange-coloured needles melting at 155-156.5". co-? is formed when CPh* CO' Ethoxypheizylmnteic anhydride, C(0Et) < the imide is warmed with aqueous sodium carbonate. I t crystallises in transparent, prismatic needles, and melts at 97-98". The free acid corresponding with the anhydride cannot Be obtained, but its salts are formed by dissolving the anhydride in boiling alkalis or alcoholic ammonia.The ammonium saZt, C12H1005(NH&, melts at 144-146", and the sodium and barium salts are both crystalline. Fuming hydriodic acid a t 165" converts the anhydride into phenyl- succinic acid, which is a ciytalline powder melting at 160-161" (stated by Spiegel as 167"). The formation of pheiiylarnidomaleinimide from the ethereal salts of pulvic acid can best be explained by adopting Spiegel's view, that this acid is a hydroxy-lactone. A. H. Thio-derivatives of p-Naphthol. By R. HENRIQUES (Ber., 1894, 27, 2993-300S).-By the a.ction of sulphur chloride on p-naphthol in104 ABSTRACTS OF GHEMIOAL PAPERS. chloroform solution, di-P-hydroxydinaphthylic sulpphide, S (CIoH6*OH),, is formed ; it is sparingly soluble in chloroform and in carbon bisul- phide, and separates in long, silky needles, or in colourless, trans- parent, highly lustrous, round crystals, and melts at 211".With con- centrated sulphuric acid, a bl-aish-green coloration is produced ; with diazo-derivatives, sulphur is eliminated, and the ordinary azo-naph- tho1 dyes are produced; the sulphur is not, however, removed by treatment with silver salts. The molecular weight was determined by the boiling point method. The compound is identical with that (m. p. 21pO) prepared by Dahl and Go. by heating P-naphthol, sulphur, and lead oxide at 180-200', and with the compound (m. p. 210') obtained by Lange (Abstr., 1888, 375) by heating naphthol with sulphur in alkaline solution, and to which he errone- ously gives the formula S2(CloH,*OH)2.The Zead salt, C20H12S02Pb, is yellow and amorphous ; the acetyl derivative, S(C10H~*OA~)2, crys- tallises in colourless needles. and melts at 193". S:? *CloH6*OH S:S*CloH6*OH Or Dithiodi- P-It ydroxydinaphthylic biszclphide, 0 H*CloH6*S*S*s*S CloH6* 0 H, is formed, together with the sulphide, from which it is separated by means of its greater solubility in carbon bisulphide, and is deposited in large, sulphur-coloured crystals, melting at 141"; the yield is 15 per cent. of the naphthol employed. The compound is also formed by heating dihydroxydinaph thylic bisulphide (see below) with sulphur in alkaline solution; it is decomposed by silver salts, silver sulphide being precipitated, and dissolves in alkalis with an intense, yellow colour.The Eead salt, C2,H12S402Pb, is orange colonred ; the acetyl derivative, C20H12S,02Ac2, crystallises in pale yellow needles, melting at 164". Di-P-h ydroxydinaphthylic bisdphi'de, S2(CloH6*OH),, is separated by means of its lead salt from the chloroform mother liquors obtained in the preparation of the preceding dithio-compound and sulphide ; it readily dissolves in all organic solvents, in alkali carbonates, and in borax solutions, and crystallises in yellow needles, melting a t 166" ; it is decomposed by silver salts. The lead salt, CZoHl2S2O2Pb, is orange colonred ; the acetyl derivative resembles that of the preceding com- pound, and melts at 194". Dithiodih y droxydinaph thylic bisulphide and dih ydroxydinaphth ylic bisulphide give with potassium ferricyanide pale yellow, sparingly soluble ferricyanides ; dihydroxydinaphthylic sulphide, in the same circumstances, is oxidised to dehy~rodioxydi~aphthylic sulphide, C,H12S02, which is deposited in large, red crystals, melting at 155".The compound contains no hydroxyl, it dissolves in concentrated sulphuric acid with a dark blue colour, and readily reacts with hydroxylamine, although the products could not be isolated. The phercylhydrazide, S (CloH6*N2HPh),, crystallises in brick-red needles, melting at 184'. 2sodihydroxydinaphthylic sulphide is prepared by the reduction of tihe preceding compound with zinc dust and glacial acetic acid; it crystallises in long, pale yellow needles, melts at l52", is readilyORGAN10 OHEMISTRY.105 soluble, and is easily converted into dihydroxydinaphthylic sulphide by heating with alkalis. With potassium ferricyanide, the dehydro- derivative ir;l regenerated ; by the action of diazo-compounds, azo- naphthols are formed and sulphur eliminated. The silver salt is colourless ; the lead salt, C2,H,,S02Pb, resembles that of the isomeric compound ; the acetyl derivatice is crystalline, and melts at Dinaphthy lenethiophen, C2,,HI2S, is prepared by the action of con- centrated sulphuric acid on isodihydroxydinaphthylic sulphide at loo", the sulphrtte dissolving with a blue-green colour, and evolution of sulphurous anhydride ; the compound crystitllises fronr glacial acetic acid in yellow needles, melts at Z47", is neutral, and boils without decomposing ; the coloration produced with sulphuric acid is similar to that of the original sulphide.The yield is 60 per cent. of the sulphide employed. Dihydroxydinaphthylic sulphide gives no thio- phen derivative. The author discusses in detail the oonstitution of dehydrod-ioxydinaphthylic sulphide and of isodihydroxydinaphthylic sulphide ; the former, although generally resembling the quinones, differs from them in its behaviour towards phenylhydrazine and reducing agents ; he considers that the two dihydroxydinaphthylic sulphides are stereoisomeric, 147-148". ylOH6'S*ylOHS 9R ~10H6*s0Cl0H6 OH OH OH Iso- (syn-) sulphide (m. p. 152'). Normal (anti-) sulphide (m. p. 211'). this is in complete accord with their behaviour, and, if correct, is the first example of simple stereoisomeric sulphur compounds.The dehydro-derivative and the thiophen probably have the formulae C,Hs<,>CloHs [s : 0 = 1 : 21 and ~ ~ o ~ ~ - ~ ~ o ~ s respectively. S \/ S J. B. T. Preparation of 1 : 2-Naphthaquinone. By K. LAGODZINSKI and D. HARDINE (Ber., 1894, 27, 3075--3076).-An improvement of the method of Stenhouse and Groves (this Jourual, 1877, ii, 52). Fifty grams of %naphthol is dissolved in a solution of 14 grams of sodium hydroxide in 500 C.C. of water. The whole is tben placed in a 3-litre vessel, diluted with 1 litre of water, and stirred with 25 grams of sodium nitrite ; a large lump of ice (about 500 grams) is then added, and the stirring continued while 700 C.C. of 10 per cent. sulphuric acid is gradually added. After 2-3 hours, the precipitate is col- lected on a calico filter and washed with water until the washings have only a feebly acid reaction.It is then placed in a 14-litre flask, 300 C.C. of 10 per cent. sodium hydroxide added, and the whole diluted with water to 1,200 c.c., and warmed for a time on the water bath. Hydrogen sulphide is passed through the warm solation until white crystals of nmidonaphthol begin to separate. These are col- lected on a porcelain funnel, washed with water, treated with 700 C.C.106 ABSTRACTS OF CHEMICAL PAPERS. of 5 per cent. sulphuric acid previously warmed to 70-80". and filtered through a folded filter ; the residual sulphur is washed with another 700 C.C. of the acid, and the united filtrates are cooled with a large lump of ice and oxidised with potassium dichromate.The 1 : %naphthoquinone, which then separates out in orange-yellow needles, is carefully washed until free from sulphuric acid. The yield is 47.5 grams, 86.6 per cent. of the theoretical. By C. BOTTINGER (Ohem. Zeif,, 1894, 18, 483-484) .-Dz'chloracet-a-na~hthnlide is prepared by moderately warming a mixture of dichloracetic acid and a-naphthyl- amine; it separates from ether in colourless crystals, and melts at 164'. Gl?lceric-a-naphthal~de is obtained by warming a-naphthyl- amine with an alcoholic solutiou of glyceric acid ; it is crystalline, and melts at 137"; a secondary product (m. p . 214') was also isolated in small amount. Pyruvic acid reacts with a-naphthylamine in alcoholic solution, forming p y.l.uvic-a-naphthaZide, which melts at 148-149'.a-Naphthylamine hydrogen tartrate melts and decomposes at 180" ; tartaric-ol-naphthalide crystallises in long, white needles, and melts a t 210", and a-naphthylamine citrate crystallises in four-sided tablets, and melts at 146". The citrate and tartratepf a-naphthylamine have a burning taste. A. R. L. a-Dinaphthalidocitric acid. By C. BOTTINGER (Chem. Zeit., 1894, 18, 672) .-Of the two theoretically possible modifications of a-di- naphthalidocitric acid, one is obtained, together with other products, by heating a pulverised mixture of citric acid and a-naphthylamine at 140"; it crystallises from boiling alcohol in white needles, and melts at 187-188". If dissolved in nitric acid of sp. gr. 1-48, a yellow nitro-compound is formed, which yields intensely reddish- yellow alkali salts.When the acid is treated with acetic anhydride, a ye1lo-r compound is obtained, which is insoluble in soda and is probably an anhy dro-compound. The silver salt of a-dinapbthalido- citric acid is a white precipitate, insoluble in water, and very stable. C. F. B. Derivatives of a-Naphth ylamine. A. R. L. 1 : 2-Amidonaphtholsulphonic acids. By M. B~NIGER (Bey., 1894,27, 3050-3054) .-1 : 2 : 2'-Nitrosodihydroxpaphthalene, when heated with sodium hydrogen sulphite and hydrochloric acid, yields, by a reaction already described (Abstr., 1894, i, 199), 1 : 2 : 2'-amido- dihydro~ynap~~thalene-4-szllp~onic acid ; this can be oxidised with nitrous acid to 2'-hydrozy-l : 2-nap hthapuinone-4-szL~honic acid, and this, with aniline, yields 2 : 2'-dih y d ? .o . r y . 4 - a n i l i d o n a p ~ t ~ ~ ~ ~ i ~ ~ 1 : 2 : 3-Nitrosohydroxynaphthalenesulphonic acid and 1 : 2 : 2'-nitroso- hydroxy naphthalenesulphonic acid undergo an analogous series of reactions. C. I?. B. Nomenclature of Cyclic Derivatives of Naphthalene. By C. GRAEBE (Ber., 1894, 27, 3066--3068).-1t is proposed that when, in compounds of the type of carbazole or ant,hracene, one phenylene group is replaced by naphthylene, the term "Naphtha-" (orORGANIC CHEMISTRY. 107 '' Naphth- ") should be prefixed to the name of the parent substance ; and that when both the phenylene groups are replaced by two naph- thylene groups, the term " Dinaphtho " should be prefixed. Thns the compound C10H6<_0- > C,H, would be termed naphf7zozanfhon~, co the compound c&6<-0_ co >C diiiapht7~oxa?z,thone.C. F. B. 1 : 2-Dihydroxynaphtho-3 : 4-Acridone. By K. LAGODZIXSKI bud D. HARDJNE (Ber., 1894,27, 3066-3075).-When 1 : 2-naphtha- quinone is dissolved in acetic acid and the solution warmed with snthranilic acid, 3-hydroxynnphthaquinone-4-nnilz'do-orthocarbo~~lic x i d , C,oH,0(OH):N*C6H4*COOH [O : OH : N = 1 : 2 : 41, is formed. This crystallises in dark red plates with ft metnllic lustre, and melts at 270-271" ; it yields no anhydride (acridone), but is hydrolysed by dilute mineral acids to 2-hydroxynaphthaquinone and anthranilic: acid. If a solution of anthranilic acid in water and alcohol is warmed with aqueous potassium 1 : %naphthaquinone-4-sulphonate, 1 : 2-nap7i- thapzciizone-4-anthralzilz'c acid, CloH,J12*NH*C6H,-COOH [O, : NH = 1 : 2 : 41, isomeric with the preceding compound, is formed.This crystallises in dark red needles, and melts at 252" ; its methylic sai't forms brilliant, dark red crystals, which melt at 1 8 6 O . When heated with strong sulphuric acid at 200", it yields 1 : Z-izap7~thapzci?zone- co 3 : $-acridone, CloH,O2< HN> C6H4, which crystallises in reddish- yellow needles, and melts above 400". With ortbophcnylenediamine it yields a dark yellow aaine, which melts a t 276", and it can be readily hydrolysed to Eiydroxynaphthaquinone and anthranilic acid. When suspended in acetic acid and reduced with sulphurous an- hydride, it yields brown, crystalline 1 : 2-dihydrozy-3 : 4-naphthac~i- done, C,,H,(OH),< - >C6H,; this is not, like alizarin, a stable sub- stance, nor does it dye with mordants ; it bas rather the properties of a qninol-derivative, being oxidisable with extreme readiness to the. corresponding quinone ; its yellow diacetyl derivative melts at 280".C. I?. B. co IhH Dihydrophenonaphthacridine and Phenonaphthacridine. By M. SCH~PFF (Ber., 1894, 27, 2840-2845 ; compare Abstr., 1894, i, 41) .-Dihyd~opheizoiaaphthacridine, ClOH6<,,"> C6H4, has been already described as phenonaphthacridine (Zoc. cif.) ; the acetyl derivative melts at 181-181.5". Phenonaphtliacridine, cIoH6<& ->CSH,, is obtained by oxidising the dihydro-derivative with silver nitrate ; it melts at 225-226". The hydrochZoride and the nitrate crystallise in dark needles; the platinochloride forms minute, violet needles, and the picrate separates in brown needles.The ethyl derivative crystallises from alcohol in dark needles. CH CH108 ABSTRACTS OF UHEMICAL PAPERS. When phenonaphthacridone is reduced with sodium amalgam, the foregoing substance is formed in association with a red substance, which does not melt below 360". If reduction is effected bv means of zinc dust and acetic acid, the ~ ~ d r o ~ ~ d i h y d r o ~ ~ ~ n o n a ~ ~ c10H6 <NH CH(oH)>C6HA, which melts at 345", is formed. It yield8 brown solutions with sulphuric acid and alcoholic potash, and is not dissolved by aqueous alkali. Reddish-brown fumes are evolved when the substance is heated, and a brown sublimate is formed, exhibiting the violet colour reaction of phenonaphthacridine with sulphuric acid.M. 0. I?. Analyses of Cotton Dyed with Alizarin. By C. LIEBEI~MANN and P. MICHAELIS (Ber., 1894, 27, 3009--3019).-This work was undertaken in order t o ascertain whether the theory of dyes advanced by Liebermann (Abstr., 1893, i, 370) is in accord with the facts so far as regards the relative proportions of base and dye present in the cloth. The theory has so far derived no support from the authors' observations. Technically prepared samples of Turkey red, Bordeaux, and dark madder violet were examined, a detailed description of the analytical methods is given, and the results are tabulated. Specimens of cloth practically identical in appearance may contain totally different compounds ; for example, the relative proportions of alumi- nium and tin in an aluminium-calcium-tin " lake," vary greatly, an d the metals do not replace each other in atomic proportions. These results, and the somewhat contradictory analyses of other observers, are probably due to the presence of uncombined mordant i n the cloth, which should, therefore, always be dyed to the deepest possible shade before being used for analysis.J. B. T. Some Points in Stereochemistry. By A. COMBES (Bull. SOC. Chirn., 1894, [3], 11, 261-263).--8 criticism of Bouveault's recent paper (Abstr., 1894, i, 421). The author disputes (a) the novelty, and ( b ) the correctness of some of Bouveault's theories as to the relation between rotatory activity, and the constitution and stereoisomerism of cyclic compounds. L. T. T. Action of Camphoric Anhydride on Benzene in Presence of Aluminium Chloride. Bey E.BURCKER and C. STABIL (Compt. Tend., 1894,119, 426-428).-The action of camphoric anhydride on benzene in presence of aluminium chloride, yields, as chief product, phenylcamphoric acid (Abstr., 1891, 324), and two others, which the authors have isolated. One of these, pkenylcamphoric anhydride, C,6H1e02, is formed in quantity depending on the temperature, and is separated from the acid by means of i t u greater solubility in benzene. It is a yellowish, syriipy liquid, which does not crystallise even aEter remaining in a vacuum for three months. The other product is formed when the action is violent and the substances remain in contact for a long time. It is a diphenyl com- pound, which has the composition CL2HU02, and crystallises in reddish-yellow masses from benzene, in which it dissolves moreORGANIC CHEMISTRY.109 readily than phenylcamphoric acid. CHPr<CH2-C0 T-T2*cH2> C Ph*C OPh. It may have the constitutioii C. H. B. Natural Resins, By M. BAMBERGER (Hmzatsh., 1894, 15, 505-518 ; compare Abstr., 1832, 204) .-The resin from Pinus Znricio (Poir), which melts at about loo", is resolved, on digestion with ether, into an a-modification (80 per cent.), which is soluble in ether, and a @-modification (20per cent.), which is insoluble i n ether. The a-yesin is a reddish-white, amorphous powder, which is soluble in dilute potash, benzene, and toluene, and dissolves in concentrated sulphurio acid, forming a, reddish solution ; its methoxyl number is 33.The /%resin is a reddish-white powder, also ,soluble in dilute potash, but insoluble i n benzene and toluene; i t has a methoxyl number 62, and gives at first a green, and later a violet, coloration when hydrochloric acid is added to its alcoholic solution. When an excess of potash is added to an alcoholic solution of the a-resin, or of the crude resin, a, colourless, crystalline, potassiuni compound is formed. A cold aqueous solution of the latter, when treated with hydrochloric acid, gives a powdery precipitate of pinoresinob, CleHleOs, which gradually separates from its alcoholic solution in drusy masses, melts at 80-go", contains two methoxyl groups, takes up 2 atoms of iodine, and farnishea the following derivatives. The potassium saEt, CIsH160,K2 + 4H20, is very soluble in water and methylic alcohol, but is insoluble in ethylic alcohol ; the calciwm salt, CIRHl6O6Ca, is a white, insoluble precipitate ; the diucety Z-deriaa- five, Cl,Hl6o6i&, crystallises in slender, white needles, and melts at 164" ; the dibenzoyl-derivative, C19H1606B~2? crystshes in short prisms, and melts at 160".On treatment with methylic iodide, the potassium salt is converted into dimethylpinoresinol, C18H1606Me2, which crystd- lises in scales and melts a t 94". The forniula for pinoresinol must, therefore, be 'C16Hl,02(0H)2(OMe),. The caffeic and ferulic acids found in an earlier investigation (Zoc. cit.) are, in all probability, present in the resin in an uncombined state. Scammony Resin. By H. SPIRGATIS (Arc7~. Pharnt., 1894, 232, 482--486).-A reply to Poleck (Abstr., 1894, i, 471), maintaining the correctness of his former work, and especially c4 tha arialgses and proposed formula of barium scamrnonate.Gaultherin, a New Glucoside from Betula Lenta. By A. SCHNEEGANS and J E. GE~~OCK (Arch. Phnrm., 1894, 232, 437- 444!).-1n 1844, W. Procter, jun., announced (Amer. J. Pharm., N.S., 15, 249) the existence, in the bark of BetuZa Zeizta, of a glucoside, to which he gave the name gaultherin ; he did not, however, obtain i t in the pure state, and the authors have therefore re- examined the Betula Zenta bark. I n extracting the bark, i t was found that even with 94 per cent. alcohol partial hydrolysis of the glucoside took place, the odour of methylic salicylate becoming apparent. By using for extraction a solution of lead acetate (15 per cent.of the weight of the bark) in strong alcohol, this decomposition was pre- G. T. M. L. T. T. YOL. m v m . i. i110 ABSTRACTS OF OHEMICAL PAPERS. vented. Quultlierin, C,,H,,O, + HZO, crystallises in coloui-Iess needles, which are easily soluble in glacial acetic acid and in alcohol, slowly but freely in water, and almost insoluble in ether, chlorofornl, benzene, and acetone. The aqueous solution does not affect iron salts, nor does it affect Fehling's solution in the cold, but at 100" cupyous oxide is at once precipitated. Strong sulphuric acid dissolves the glucoside, forming a pale red solution, which rapidly darkens and de- composes. Wheii the dry glucoside is heated, the odour of methglic salicylate becomes apparent at about loo", and the substance blackens and decomposes at 120".Theaqueous solution has a bitter taste and is lerorotator,y. The glucoside is decomposed bg mineral acids, by alkalis, or by heating the aqueous solution at 130-140", yielding carb0hydrat.e and methylic salicy late. L. T. T, Crystalline Constituents of True Coto Bark. By 0. HESSE (AnnuZen, 1894, 282, 191-207 ; compare Abstr., 1894, i, 380).-The coto bark employed by Jobst and Hesse (Abstr., 1880,325) was derived from Bolivia, whilst riowadays the term has been extended t o include varieties from Venezuela and Brazil. The following results were obtained with the bark from Bolivia. Cotoin extracted from this bark is identical with that obtained from other va-rieties. Bensoylcotoih is formed by the direct action of benzoic anhydride, and crystallises in compact lustrous prisms, melting at 110-112".It gives a brownish-red coloration with ferric chloride. Dibenzoykotoin is best prepared by the action of beuzoic chloride on coto'in, and cryst'allises in concentric groups of small needles, melting at 134-135". Hydrocotoin only yields one benzoyl-derivative, which crystallises in white needles, melts at 113", and gives no coloration with ferric chloride. The substance known as dicoto'in has the formula C?5H2006, and not C44H34O11 as formerly supposed. The cryoscopic determination of the molecular waight, however, gives the number 214, instead of 416, as required by the above formula. This is explained by the fact that dicoto'in is in reality a mixture of coto'in with a, substance which has the composition and moleculnr weight corresponding with the formula C11H602, and may be obtained from dicoto'in by adding ferric chloride to its alcoholic solution and evaporating.The iron compound of coto'in is thus formed, whilst the new substance crystal- lises out in long needles. It separates from light petroleum in colourless, strongly lustrous plates, melts at 60-6 I", and volatilises at a higher temperature. It does not contain the hydroxy-group, and gives no colora.tion with ferric chloride. With phenylbydrazine, it forms a compound of the formula C,,H22N40, which crystallises in colourless needles, melting at 194". In all its properties, i t bears a, very close resemblance to phenylcoumalin ; as, however, the latter melts at 68", the identit,y of the two cannot be considered as proved.Psendodicotoin, C25H2007, is also a mixture of cotoh with a sub- stance of the formula CIIH,Os, which the author terms hydrozy- phenylcoumaZin ; this crystallises from light petroleum in colour- less plates or white needles, and melts at 61". Acetic anhydride con- verts it into acetoxyphenylcoumalin, CIIHTACOS, which crystallises inORGANIC CHEMISTRY. 111 Instrous needles and melts at 65". With phenglhydrazine, it foi*ms a caompound, C23H22N402, crystallising in flat needles arid melting at 193". When treated with aqueous potash, it is converted into ~3-pher;ylcozimalic acid, CllH1003, which crystallises from acetic acid jn prisms or plates and melts at 207". The melting point is, how- ever, uncertain, as the acid passes gradually into its lactone, which melts at 221".The paracoto'in obtained from the specimens in question agreed in properties with that previously described. The author contirms the occurrence of piperonylic acid among the products obtained by fusing paracoto'in with potash (Ciamician and Silber, Abstr., 1894, i, 51). A. H. Properties of the Dihydroquinolines, and the Constitution of Ring Systems containing Nitrogen. By G. CI~nii CIAN (Ber., 1894, 27, 3077--3081).-1t has already been shown by Ferratini (Abstr., 1893, i, 602) that the trimethyldihydroquinolirie obtained by the action of methvlic iodide on 2'-methylindole, which has one of the .I CMe :yH CHMe-EH has NMe*CHMe. Or CsH4<NMe-CMe, following formulse, C6H4< properties which strongly resemble those of the indoles, although it may be readily converted into quinoline derivatives.The author finds further that wheu the hydriodide of dihydrotriniethylquinoline is heated, it loses methylic iodide and is converted into trimethyl- indole, the yield of the latter being very satisfactory. The action is analogous to that which takes place when the hydriodides of tertiary bases are heated, methylic iodide and the corresponding secondary base being obtained. The great similarity in the properties of the two series is readily explained by the above formuloe of the dihydroquinoline derivatives and the usual formula of the indole ring, the former being " nuclear " homologues of the latter. Bamberger's centric formulae with a quinquavalentl nitrogen atom do not, howerer, afford a ready explana- tion of the analogy.Ethereal Salts and Betahes of Quinolinesulphonic acids. By A. CLAUS and J. STEINITZ (Annalen, 1894, 282, 130-138 ; com- pare the ne,xt abstract) .-Meth ylic quinoline-l-sulphonate, H. G. C. is obtained by the action of methylic iodide on the silver salt at 8 5 O , and crystallises in colourless, lustrous prisms melting at 96". It gradu- ally decomposes when kept, with formation, of the free acid and ~1 volatile oil, which bas not yet been analgsed ; this decomposition proceeds much more rapidly at 100". The benzylic salt crystallises in splendid, six-sided tablets and prisms, which have a diamond lustre, and melt a t 84". When heated a t 200", i t decomposes with formation of the free acid and an oil, which has the empirical formula Cl4Hl3.These two salts and the ethylic salt do not appear to form a meth- iodide, and it has therefore been found impossible to prepare the cor- responding be taines.112 ABSTRACTS OF CHEMICAL PAPERS. auinoline-4-su223honic acid methylbetnigte, C9NH,MeS02, is readily formed, and crysttnllises in yellowish prisms, which can be heated to :360" without undergoing any change. It dissolves in alkalis, but cannot be recovered, either free or in the form of a salt, by acidi- fying the solution. The betake, moreover, does not combine with alkylic iodides. Similar results were obtained with gzcinoline-3-sulpholtic acid methyl- betaine, which may be prepared from the silver salt and methylic iodide at 100". The systematic investigation of this action has shown that many of the monobromo-derivatives of the 4- and 3-sulphonic acids only yield ethereal salts when their salts are heated with methylic iodide, whilst others, such as the 3-bromo- and 3-chloro-4-sulphonic acids only yield betaines.A. H. Alkyl Derivatives of Quinaldine-p-carboxylic acid. By A. CLAW and J. STEINITZ (Annalen, 1894, 282, 107-130; compare Abstr., 1893, i, 728). - Ethylic quinaldine-p-carboxylate meth- iodide, C,NH6Me*COOEt,MeI, has been described by Hantzsch (Abst,r., 1886, 369). The methochloride crystallises in long, colourless needles, melting a t 1 5 8 O . The behaviour of these compounds towards alkalis has already been described by Hnntzsch. The authors find that the insoluble amorphons yellow substance finally obtained has the composition ClaNHrd02:CH,, but it is probably a poly meride.Xthylic quiitaldirLecarbozylate ethiodide is formed with considerable difficulty, and cryst,allises in groups of plates which melt and decom- pose at 236". The ethochloride forms well-developed prisms, and melfs at 146" ; its platinochlo?-ide, (C~3H,302N,EtC1)J?tC14, crystallises i n compact, red prisms, and melts and decomposes at 238". Eth ylic ethylidenequi~~aldi~tiurn-~-carBoxylate, Cl~NHI3O2:CHMe, is obtained as an amorphous, yellowish-red mass, which has not been ;malysed, by the action of alkalis on the ethiodide. It is completely soluble in ether, and does not undergo polymerisation to an insoluble compound when kept. On treatment with hydrochloric acid, i t yields the ethochloride melting at 146".The silver suEt of qninaldine- /3-carboxylic acid is a micro-crystalline powder, and when treated with methylic iodide yields the wzethylic salt of the acid. This suh- stance can also be obtained by synthesis from methylic acetoacetate and orthamidobenzaldehyde, and by the action of methylic iodide on quinaldinecarboxylic acid ; in the latter case, the direct product is the hydriodide of the methylic salt. The methylic salt forms colourless needles, melting at 72". The following additive compounds and ethereal salts of quinaldine- /3-carboxylic acid have also been prepared. From the methylic salt, the methiodide, vitreous, yellow prisms, melting at 200" ; the metho- chzoride, colourless, vitreous prisms, melting a t 157" ; the ethiodide, lemon-yellow plates, melting at 210" ; the ethocliloride, colourless, vitreous needles, melting at 150" ; and the ethobromide, granular crystals, melting at 154'. From the ethylic salt, the ethobromide, granular crystals, melting at 21i". The p ~ o p y l i c salt forms colourless,0 R Q A N 1 C C HEN I ST H Y. 113 vitreous prisins, and melts at 51" ; the p o p y l i c methiodide golden- yellow needles, melting at 186" ; the benzylio salt forms colourless prisms, melting at 82O.and the beutylic methiodide flat, golden-yellow needles, melting at 176". The methylic methochloride and iodide, when treated with alkalis, yield a yellow, amorphous substance which behaves in a similar nittnner to the corresponding derivative of the ethylic salt. It is a yellow powder, nielts and decomposes a t 182", and has the formula of methylic ~ ~ i e t h .r J l e r z e ~ z c i i a c c l d ~ ~ z i ~ ~ ~ i a - ~ - c a l . ~ l a t e , C9NH5Me(C0 OMe) :CH2, of which i t is probably a polymeride. Quinaldine-IJ-carboxylic acid cliff ers from the ymrboxglic acids of the quinoline series in two important respects. It forms no direct additive compounds with halogen alkgls without at the same time being converted into an ethereal salt, and the additive compounds of the ethereal salts do not yield the corresponding beta'ine when treated with alkalis. Quinald,ine-p-carboxylic acid rnethochloyide can, however, be readily obtained by heating the methochloride of one of the ethereal salts with fuming hydrochloric acid. I t forms short, vitreous prisms, and melts with decomposition at 230".The corresponding betazne forms thick, monosymmetric prisms containing 2H20, which are lost at loo", the anhydrous compound melting at 144". It has an intensely bitter taste, and is readily decomposed with formation of a violet colouring matter. It unites readily with methylic and ethylic iodides to form compounds which are in every respect identical with the methylic methiodide and ethylic meihiodide already described. This behaviour confirms the view expressed by Claus and Buttner (Abstr., 1893, i, 731) as to the course of the analogous reaction with cc-phenyl- cinchoninic acid. The betajine dissolves i n alkalis, forming a salt which could not be isolated, and does not form an oxinic acid. A. H. 4' - Orthohydroxyphenylquinoline and 4' - Metahydroxy- phenylquinoline.By €3. BESTHORN, E. BANZHAF, and G. J A E Q L ~ (Ber., 1894, 27, 3035-3043) .-Orthoet?coxymeto~henone was prepared from ethylic ethglsalicylate by Tahara's method (Abstr., 1892, 844) ; it melts at 43", and boils at 243-244". It was converted, by the same method as sthat used in the case of the para-compound (Abstr., 1894, i, 344), into orthoethox!ybeuzoylacetmze, 0 Et*C6H4*CO*CH20C Me0 ; this melts at 56", and forms a sodium salt, whicb, when warmed with aniline and acetic acid, yields a yellow nnilide, OEt.C6H**C0.CH,*CMe:NPh. When the latter is heated at 50" with sulphnric acid monohydrate, several reactions take place, and as B result of one of t,hese some 4'- orthoet hozypheny Epuina 1 diizesulphonic a c i d , 0 E t C6H3 (S 0,H) CloNH8, is formed, and crystallises in tiny, white needles.When this is boiled with hydrobromic acid, it is converted into 4'-orthoh yduoxypheizyl- ifl114 ABSTRACTS OF OEEMICAL PAPERS. quinaEdiiLe, OH*C6H4*CI,,H8N, which melts at; about 187-188" ; alld its sodium salt. when heated with benzaldehydc and zinc chloride at, .200", yields a benzylidene compound, OEt*C6H3( S03H)-C,,H6N:CHPh. If the latter is oxidised with permanganste, and the product heated with 11 ydrobi-omi c acid, ye1 low is h-red 4'-orthoh ydmzypli e n ylq uinaldinic acid, OH*CsHl*CgNH5*COOH, is formed ; this melts and decomposes a t 243-245", and, when heated at 950', yields 4'-ol.t?iohyd?.ox~~?lenyi qicinoline, OH*CRH4*CgNHG, identical with the " quinolinephenol " ob- tained by Koenigs from apocinchene (Abstr., 1893, i, 377).Bletanzethoxyacetophenone was prepared like the para-compound (Abstr., 1894, i, 344) ; it boils a t 239-24l". 1Cfetanzethoallbelzzoyl- cicetone was obtained as an oil, its nizilide as yellow needles melting a t 89-85". This anilide yields a sulphonic acid, the barium salt of which forms a benzylidene compound. From the latter 4'-metuhydroxy- p ~ ~ e ~ z y l q u i ~ a a l ~ i ~ z i c acid can be obtained ; this melts and decomposes at about 235", yielding 4'-metahydroxyphen?llquinoZine, identical with the Py-S-/3-phenolquinoline OE Koeniga and Nef (Abstr., 1887, 599). Paramethoxy-a-phenylcinchoninic acid, Parahydroxycin- choninic acid, and Parahydroxy- a-phenylcinchonine. By 3. CLAUS and G.BRANDT (AniznZen, 1894, 282, 85-107).-3-iMethozy-L - yheitylcinchonirric acid methiodide, OMe*CgNHIPh*COOH,MeI, is oh- tnined by heating a-pheriylquininic acid with methylic iodide a t 1:35-136", and forms aggregates of small, reddish-yellow needles, rnelting at 216". The methochloyide is prepared by triturating the methiodide with moist silver chloride, and is a hygroscopic mass, which crystallises from alcohol in small needles, melting at 195". The corresponding betazne is formed when the methiodide is treated with moist silver oxide, aild crystallises with 1H20 in yellow, vitreous prisms, which become anhydrous at 100" and melt a t 218". The betaine is also formed when the aqueous solutions of the metho- (ahloride and iodide are boiled, and when these substances are treated with alkalis.The further action of alkali produces a quaternary ammonium hydroxide of the formula OMe*CgNH4Ph*COOH,MeOH, from which the original betaine, or one of its salts, can readily be regFined 1)s acidi6cation of its solution. This substance, probably owing to the presence of the phenylic group, is much more stable than the corresponding derivative of quininic or cinchcninic acid, and does not form an oxinic acid. It was found impossible to prepare an ethobromide of the acid. ?'he sodium salt of methoxyphenglcinchoni~iic acid forms slender, \-ellow needles, containing 6H20, whilst the copper salt is a light green precipitate. The hydrochloride, Cl,H1&N + 3HC1, crystallises from concentrated hydrochloric acid in lemon-yellow, vitreous needles, and loses 2HCZ at 100".3-H~dro~~~cinchoizilzic acid qnethiodide, OH*CgNR~*COOH,MeI, is formed from its componeuts with considerable difficulty, and c r p - ta,llises from alcohol in splendid, orange-yellow, vitreous prisms, melting at 302". Its solution in water readily decomposes, with formation of resinous compounds. The methochZoride may be pre- pared 1,s the action of silver chloride, but is hest obtained by heating C. F. B.ORQASIC CHEMISTRY. 115 the methochloride oE quininic acid with fuming hydrochloric acid at 2SO", this being a reaction capable of general application to this class of substances. The corresponding betaiite is formed by the action of water, alkalis, or silver oxide on the foregoing compounds, and crystallises with 1H,O in large tablets or prisms, which lose their water at 100" and melt at 304".The product of the action of alkalis on the betaine, methyl- q~Linoliiii~~ml~ydrOxicleca~.boxylic acid, has not been isolated. Its soln- tion is stable in the air, so that the presence of the free hydroxy- group has the same influence on the stability of the compound as has the phenylic group in the case of methoxyphenylcinchoninic acid. 3-Hydrox?l-3'-p7Le?2yZcir~c~oni?z~c acid, OH-C,NH,Ph*COOH, may be prepared, by Dobner's method, from parahydrmyaniline, pyruvic acid, and benzaldehyde, and forms small, vitreous plates and needles, which decompose at 693-300". Its alkaline solutions become dark brown on exposure to the air. The copper and silver salts are amorphous precipitates. The methocldo&le is prepared by the action of hydro- chloric acid at 230-235" on the methochloride of methoxyphenyl- ciiichoninic acid, and forms greenish-yellow, lustrous plates, melting a t 248".The rnethiodide can only be obtained with great difficulty from its components and is very unstable. The betazne forms almost, colourless, grariixlar crystals, and me1 ts at 243". The alkaline sol u- tions of the betaine are somewhat unstable, but no compound of the nature of an oxinic acid is formed, resinous matter being gradually produced. The solubility of the substituted cinchoninic acids is shown in the following table. 100 grams of the boiling saturated solution contains It forms flat, green crystals, and melts at 295". Paramethoxycincho~iinic acid . . . . , . . . . . Paramethoxy-a-phenylcinchoniuic acid .. . 2.22 ,, Paraliydroxycincho~iinic acid. . . . . . . . . . . Parahydroxy-a-phenjlcinchoninic acid . . . 0.44 ,, 1.24 grams. 0.28 gram. A number of ethereal salts have also been prepared by the action of an alkylic iodide on the silver salt of the acid. Methylic salts. Ethylic salt. &I. p. M. p. 2'- Pheny lcinchoninic acid . . . . . . . . . . . . 3-Methoxycinchoninic acid . . , . . . . . . . . 3-Hydroxy-2'-phenylcinchoninic acid , . 148 - 61 " 8.5 - - 3-Methoxy-2'-phenylcinchoninic acid . . 111 105" These salts readily undergo decomposition when heated, the free acid being formed, together with a terpene-like substance, the nat,ure of which has not yet been determined. A. H Pure Dextrorotatory Coniine. By A. LADEXBCRG (Ber., 1894, 27, 3063-3066).--Coniine was prepared synthetically i n the same way as before, but on a larger scale ; YO grams of inactive coiiiine, boiling at 165-169", were obtained.This mas treated with dextro-116 ABSTRACTS OF CHEXICAL PAPERS. rotatory tartaric acid, as before, when tJlie salt of dextrorotatory coniine crystallised out. l'his was. however, now recrystallised three times, after which it yielded a coniine, boiIing a t 167.7" (corr.), and with sp. gr. = 0.8438 and specific rotation [ a ] , = +18*3", both a t 23". The difference between this and the earlier numbers is attributed to the presence of isoconiiiie in the sample then investigated. c. I?. B. Nicotine (Metanicotine). By A. PINNER (Bey.: 1894,27,28tji- 2869 ; compare Abstr., 1894, i, 388).-When the additive compound of benzoic chloride and nicotine is heated with strong hpdrochloric acid at loo", benzoic acid and nicotine are formed, whilst, if boiled with sodium ethoxide, hydrogen chloride is eliminated and benzoyl- metanicotine is produced.dcetylmetanicotine is obtained by heating nicotine with acetic anhydride for 10-12 hours at 170" ; it is hydro- lysed only with difficulty, yielding metanicotine. When metanicotine is heated with a strong solut.ion of barium hydroxide for 10-12 hours at 170°, mehhylamine is formed, together with a base, CgH9N, of which the picrate melts a t 151". The action of bromine on metanicotine gives rise to the compound, CloH,,Br2N2,2HBr,Br2, crystallising in reddish-yellow needles, which melt at 170". On adding dilute caustic soda to the hydrobromide of metanicotine bromide, monobroiriometanicotine, C:10H13BrNZ7 separates in the form of an oil; the picrate melts at 190".Reduction with hydrochloric acid and zinc dust gives rise to the foi*mation of meta- nicotine. The optical activity of cotinine, dibromocotinine, and dibromoti- conine has been determined. The first-named has [a],, = --56", whilst dibromocotinine has [a]= = + 95.5", and dibromoticonine has [a],, = +13*6"; the determinations were made at 20". Derivatives of Caffeine. By L. CRAMER (Ber., 1894, 27, 3089- 3092).-~~~ethyZamidocu~ez~e7 C8H,N402*NHMe, is readily obtained in 8 similar manner to amidocaffe'ine by heating chlorocaffe'ine with methyIaminc and alcohol a t 100"; it crystallises from hot w a t e r in slender, colourless needles, melts a t 310-315", simultaneously be- coming brown.The picrnte crystallises in yellow plates. EthyE- amnidocc@eiize, C8HgNr02*NHEt, is prepared in a similar manner, and also forms slender needles, melting at 226-230" with partial sub- limation. Hydrusidocafleine, CsH,N40,*N,Hs, prepared by boiling chlorocaffelne with an aqueous solution of hydrazine hydrate, crystallises in slender, colourless needles, melting and completely decomposing a t 240". It reduces Fehling's solution on warming, and yields a hyd~ochloridt., which crystallises well and dissolves readily in warm water. With benzaldebyde, the hydrazine compound forms benzylideneh?j~razido- cufezue, CRH,Na02*N2H:C€IPh ; this crystallises in slender needles, melting at 270" to a brown liquid.On treafment with nitrous acid, it is converted into azirnidoccr$eiwe, CRHSN402N3, which forms colour- less needles, sparingly soluble in water, and rapidly becomes red in the air when moist. Anilidocqffeine, C8H9N4O2*NHPh, crystallises from alcohol in colour- M. 0. F.ORGANIC CHEMISTRY. 117 less needles, melting at about 260" and decomposing at a slightly higher temperature ; the hydrochloride, C,,Hl5N,O2,HCl, also crystal- lises in needles, which are dissociated by water. Nitrosonnilido- cafei'ne, C8N,H90,*NPh.N0, decomposes at about 225" and gives Liebermann's reaction. BenzoyZaitilidocu$e~~~e, CBN,Hg02*NPhBz, is obtained by boiling anilidocaflk'ine with beneoic chloride, and, after cryatallisation from alcohol, melts at 225". By the action of alcoholic potash on anilidocaff eine at 120", it is converted into atdidocaffeidine, the sulphate of which crystallises well ; the action of hydrochloric ;wid and potassium ch1orat)e converts it into chloranil and dimethyl- alloxan.Pamtoluidocafeine melts at 270-275", orthotoluidocaffeine a t 230", and metaxylidocafeine at 210-212". Thebaine. By M. FREUND (Ber., 1894, 27, 2961-2963).- Thebenine is not isomeric with thebaine as Hesse thought, but con- tains hgdroxyl in place of methoxyl, its mzethiodide, C,H2,NOsI, is crystalline, melts at 210", and is resolved into trimethylamine and thebenoZ, CIJIlrO, on fusion with alkalis. Thebenol melts at 186", and by distillation with zinc dust, or reduction with hydriodic acid and phosphorue, yields a hydrocarbon which melts at 135O, and is perhaps an ethylphenanthrene.Thebenine ethiodide when fused with alkalis yields thebenol and iiiethyldiet'nylaniine, proving that thebenine is a secondary base. Thebaine is a tertiary base, but its relationship to thebenine pre- cludes the presence in it of the group NMe2. When treated with alkalis, its rnethiodide yields tetramethylethylenediamine, not tri- methylamine, as Roser stated ; it is probable that dimethylhydroxy- ethylamine, which is closely related t o morphine, is formed as intermediate product. The production of the ethylene base resembles that of tetrethylethylenediamine from triethylaminethylene iodide as observed by Ladenburg. The following provisional formuloe are given for thebaine, thebenine, and thebenol respectively H. G.C. > CH,. W J. B. T. Opium Alkaloids. By 0. HESSS (Annulen, 1894, 282, 208- 824).-When crude laudanine (Annalen, Supp1.-Bd., 8, 272) is - con- verted into the hydrochloride and this is recrystallised from water, the mother liquor is found to contain an alkaloid, Zaudanidine, C20&5N04, which is isomeric with laudanine, but differs from it in being optically active ([a],-, = -87.8"). The new alkaloid melts at 177" (laudanine melts at ltiti"), but in other properties closely resembles its isomeride. The hydi*ochZoride is much more readily soluble in water than that of laudanine. The hydriodide is sparingly soluble, and the platinochlo- ride is a brownish-yellow, amorphous mass. The hydrogen oxalate forms small, white needles. Acetic anhydride converts it into acetyl- Zazidanidine, which crystallises with 1H20, melts at about 9 8 O , and dissolves in dilute aqueous potash and soda, but not in ammonia.It118 ABSTRAOTS OF GHEMIOAL PAPERS. seems probable that laudanine consists of two optically opposed con- stituents, of which landanidine is one, but this question is being further investigated . A. H. Benzoylquinine. By A. WUNSCH (Compt. WWZ., 1894, 119, 407-%09).-Schiitzenberger obtained benzoylquinine by the action of benzoic chloride on the alkaloid, and described it as a resinous and uncrystallisable substance. The author prepares i t by adding grad unlly, with frequent agitation, 60 parts of pure, well-dried, and finely-powdered quinine t o 100 parts of benzoic chloride, heated on a water bath. The product, after cooling, is treated with several times its volume of'cold yater, which rapidly dissolves the benzoyl- quinine hydrochloride, but only very slowly attacks the excess of benzoic chloride.The base is purified by precipitation with ammonia and crystallisation from aqueous ether. It forms very distinct, highly refractive, colourless prisms of the composition Benzoylquinine is insoluble in water, and the crystals remain unchanged even in contact with boiling water, but it dissolves readily in alcohol, benzene, chloroform, light petroleum, and carbon bisulphide, atnd also in ether, especially if i t contains water. I t crystallises from all the solvents except alcohol, and the crystals, which are anhydrous, melt at 139", but decompose at a higher tem- perature. Benzoylquinine is distinguished from quinine benzoate by its insolubility in water and its resistance t o the action of potassium hydroxide.Like quinine, it ~7ields a green coloration with chlorine water and ammonia, and the dilute aqueous solutions of its salts are fluorescent. It is neutral to both phenolphthalek and litmus, and even the basic salts are acid to litmus. It forms two series of salts, namely, basic salts, which contain 1 mol. of the base and 1 mol. of a mouobasic acid, and normal su*Zts, which contain twice as much acid. The basic salts are very stable, and are insoluble, or almost insoluble, in water. They are usually hydrated, and effloresce rapidly. The normal salts are partially decomposed by water. The basic hydrochloride crystallises from alcohol in acicular prisms containing + mol.H,O, and is very soluble in alcohol ; the normal hydrochtovide crystallises from absolute alco- hol in small, square prisms, which contain 1 mol. EtOH, absorb moisture rapidly from the air, and dissolve in all proportions in water and alcohol. The basic salicylate cry stallises from dilute alco- hol in anhydrous lamellae ; the basic tartrate forms brilliant needles containing 9H20 ; the basic succinate forms colourless prisms, which contain 8H20, and effloresce very rapidly. 4$1).-This paper is a continuation of the author's previous work (H. Kunz, Abstr., 1887, 980). Methylemetonium hydroxide (loc. cit.) has now been obtained as a golden-yellow, amorphous powder. Its solution is very strongly alkaline, and absorbs carbonic anhydride C.H. B. Emetine. By H. KUNZ-KRAUSE (Arch. P h ~ m . , 1894, 232,466--ORQANlU UHERIISTRP. 119 frum the air. The carbonate is an amorphous powder, softening a t 120", and melting with evolution of carbonic anhydride at 256-160". EthyZemetoniu.nz iodide, C30H4,~N205E tI, cryst allises in white needles ; the hydroxide resembles the methyl base. Both these derivatives are quaternary ammonium bases. In the preparation of emetine, a colozir base, containing both nitro- gen and sulphur, was found among theresidues. The authors believe this to be an acetyl derivative of emetine, and by heating emetine with other acids, and with acetic and benzoic anhydrides, &c., they have obtained derivatives apparently analogous to it. This reaction is being farther studied. When ometine is heated with hydriodic acid, 4 mols. of inethylic iodide are eliminated. Emetine therefore contains four methoxyl groups and almost certainly one hydrosyl group. The constitution of emetine may, therefore, be represented by the formula Cz,H,,N,(OMe)4*OH, aud the nucleus C,,H,,N probably contains one OF more tertiary butyl- toluene groups. The author maintains the correctness of the above formula against Paul and Cownley's contention (Abstr., 1894, i, 155, and Pharnt. J. Truus., 1894, [ 3 ] , 54, l l l ) , that emetine is a mixture of two alkaloids, CI5&NO2 and C,rH20N0,, and calls attention t o the fact that each of these formule contains an uneven number of valencies. Both methylemetiue and the colour base resemble curare in their physiological action, producing paralysis of the motory system and then death. L. T. T. Identity of Cytisine and Ulexine. By A. PARTHEIL (ATc~L, Pharm., 232, 486--488).-The author maintains his claim to priority in proving the identity of these two alkaloids. The Products of Hydrolysis of Convolvulin, and its Com- position. By H. J. TATERNE (Rec. Trav. Chim., 1894,13,187-217).- Convolvulin, extracted by alcohol from jalap-root coming from Vera Crux, was hydrolysed by dissolving it in baryta water, removing the barium with sulphuric acid, and boiling the solution with 8 per cent. of free sulphuric acid. The,re were formed a Folntile acid (methylethylacetic), a crystalline acid (hydroxypentadecylic) not volatile with steam, and a sugar which could not be obtained in the crystalline form, but which the author is nevertheless inclined to regard as glucose. MethyZethyZucetic acid, CHMeEtCOOH, is identical with the sub- stance obtained by Pagenstcoher (Abstr., 1879, 455), except that i t is optically active, having specific rotation [a]= = + 17" 30'. Hydrozy- pentadecylic acid, CHMeEt.CH(OH)*C,H1,*COOH, mei ts at 50.S" when pure; its methylic salt melts at 35", and boils at 606-208" under 15 mm. pressnre. When it is heated with phosphorus pentachloride and the product reduced with hydriodic acid and phosphorus, n peizta- decyEic acid, Cl5HWO2, is obtained ; this melts at 48", and is isomeric, therefore, with the normal acid, which melts at 51"; it boils at 206"120 ABSTRAOTS OF OHEMIOAL PAPERS. under 14 mm. pressure. When the hydroxy-acid is oxidised with nitric acid, i t yields methylethylacetic acid, and au acid, C10HIA04, which melts at 116", and boils at 235" under 13 mm., and at 294" under 100 mm. pressure ; this acid is isomeric with sebacic acid, which melts at 133-133.5" Possibly, convolvulin has the formula C32H62016: and its hydrolysis may then be represented by the equation C32H62016 + H2O = 2c6Hno6 + c5E100, + C,6H&,. C . F. B. Two Cactus Alkaloids. By A. HEFFTER (Ber., 1894, 27, 2975- 2979) .-Anhaline, CloH17N0, is extracted from Anhalonizlnz .fissuratuwz ; it crystallises in colourless, stellate prisms, and melts at 115". The solution in concentrated sulphuric acid is colourless, even when warmed, but becomes green on the addition of a drop of nitric acid. The most characteristic reaction is the production of a yellow colour with nitric acid, changing to orange-red with potash. The sulphate, (C10H17N0)2,H2SO~ + 2H20, crystallises in colourless, lustrous plates, and melts at 197". The hydrochloride, CloHl7NO,HC1, crystallises in slender, hygroscopic plates. The oxalate is anhydrous and resembles the snlphate. The yield of alkaloid was very small, only 0.2 gram from 1 kilo. of the dry plant. Pellotine, C13H21N03, so called from the Mexican name " pellote," of Anhalonium Williamsi, crystallises in colourless, transparent, an- hydrous plates, and melts at 110". The yield is 0.89 per cent. of the fresh plant. It dissolves in sulphuric acid with a slight yellow oolour, changing to deep red with nitric acid. The phospkotungstate and yhosphornolybdate are voluminous, the former white, the latter lemon colonred. The potassiomemuric iodide crystallises in pale yellow prisms ; the potassiocadmizcm iodide in colourless, rectangular plates; thepotassiobisrnzcth iodide is amorphous at first, but changes to needles ; the iodopotassium iodide crystallises in slender needles. The picrate crystallises in stellate prisms. The platinochloride is de- posited in golden-yellow crystals ; the h ydrochZoride, ClaH2,NO3,HC1, in rhombic prisms. The oxalate crystallises in needles. The meth- iodide, ClaH21N03,MeI + H20, is deposited i n colourless prisms melt- ing at 198". The methochloride, CI,H2,,N03,MeCI, crystallises in slender, colourless needles melting at 226". Determinations by Zeisel's method show that pellotine contains two methoxy-groups. By the action of hydrochloric acid at loo", methylic chloride is eliminated and a base formed in small quantity, which yields a PZatinochEoride crystallising in orange-red prisms. J. B. T.