ORGANIC CHEMISTRY. 29 Organic C h e m i s t r y . Isoallylene. By G. GUSTAVSON and N. DEMJANOFF (J. p r . Chem. [Z], 38, 201--207).-1soallylene may be prepared by the action of zinc-dust on an alcoholic solution of dibromopropylene. The latter, best obtained by the action of potassium hydroxide on tribromhydrin, is allowed to drop slowly into the warm mixture of zinc-dust and $0 per cent. alcohol, contained in a flask. The isoallylene evolved is * 100 00 in the original paper.80 ABSTRACTS OF CHEMICAL PAPERS. collected over water, in wliich it is very little soluble. 10 grams of dibromopropylene yield 900 to 1000 C.C. of the gas, IsozLZZyZene is ;I colourless gas, smelling like normal allylene; it burns with a skrongly luminous flame, and gives 110 precipitate with ammoniacal cuprous chloride or silver nitrate.With aqueous solu- tions of mercuric chloride or sulphate it gives a white precipitate. The gas from 10 grams of dibromopropylene was absorbed by 35 grams of bromine, the unaltered bromine dissolved in sodium hydroxide solution, and the colourless oil washed with water. It weighed 17 grams, the calculated yield being 18 grams, and had the formula C3H4Br4. IsoaZZyZene tetrabromide smells of camphor, and has the sp. gr. 2.729 at 0" and 2.658 a t 18" (water a t 0" = 1) ; it solidifies when cooled to -18", and melts below 0" ; a t the ordinary pressure it distils between 215" and 230" with partial decomposition. Normal allylene tetrabromide has the sp. gr. 2.690 a t 0" and 2.652 at It;", and does not solidify in a freezing mixture. That the two are not identical is conclusively proved by the fact that by the action of zioc- dust isoallylene is liberated from the one, and normal allylene from the other.On heating sodium with an ethereal solution of isoallylene in a sealed tube st loo", the sodium is converted into a white powder, which evolves normal allylene when treated with water. Pavorsky has shown that this conversion of iso- into normal hydro-carbons by the action of sodium, is characteristic of the homologues of acetylene. When passed into strong sulphuric acid, isoallylene is absorbed, and on dilution with water and addition of potassium hydroxide, acetone separates ; this is a strong argurnent in favour of isoallylene being dirnethyZenemethane, CH2:C:CH2, thus (1) CH2:C:CH2 + 2H2S04 + 2H2SOa.If this is the case, the dibromopropylene from which isoallylene is obtained must be CH2Br*CBr:CH2, and isoallylene tetrabromide must be CH2Br.CBr2*CH2Br. = CH,*C(HS0,)2*CH3; (2) CH,*C(HSO,)2*CH3 + H2O = CH,.CC)*CH, A. G. B. Cyanurates. By A. CLAUS and 0. PUTENSEN (J. pr. Chem. [2], 38, 20&-229).-The amethyst-coloured crystals, obtained when cyanuric acid is mixed with ammoniacal copper sulphate, have the composition ( C3N303H2),Cu,2NH3. By digesting them with dilute ammonia, violet needles of the composition ( C3N30,H2)2Cu,3NH3 are obtained, and if strong ammonia is used a deep blue compound, (C3N303H2)2C~,4NH3, is formed ; but this last is very unstable, rapidly losing ammonia in the ail.. When the first of these ammoniacal copper cyanurates is digested with water, a basic copper cyanurate, C,N,O,(Cu*OH), + 3H20, is formed.An acid copper cyanurate of the composition ( C3Nd03HL)2C~,C3N303H3,NH3 + H20 is formed when copper carbonate is digested with cpanuric acid and ammonia. The salt, C3N303HCu + 3H20, is precipitated when sodium cyanurate is added to copper sulphate ; and normal copper cyanurate, (C,N,O,),Cu, + H,O, crystallises when acid magnesium cyanurate is mixed with copper sulphate. The following cyanurates are also described : Acid magnesium cyanurate, ammoniacal cadmium cyanurate, ammoniacal zinc cyanurate, ammoniacal nickel cyanurate, cyanurates of nickel,ORGANIC OHEMISTHY. 31 cobalt, and manganese : tetramethylammonium cyanurate, and furhher, cyanurates of quinoline, quinine, cinchonine, strychnine, narc0 tine, and caff ehe.A. G. B. Preparation of a-Dibromhydrin. By 0. ASCHAN (Ber., 21, 2890-2892) .-a-Dibromhydrin is best prepared as follows :-Phos- phorus tribromide (650 grams) is dropped in quantities of from 10 to 20 grams at a bime into pure, warm glycerol (500 grams), the whole being well shaken and cooled after each addition of bromide, The operation is at an end in from three to four hours. After keeping for 24 hours, the mixture is heated on the water-bath for about three hours, cooled, diluted with water (3 to 4 vols.), extracted with ether, and the extract washed with sodium carbonate solution and dried. After evaporating the ether, the residual oil is heated at about 200°, and then fractionated ; the portion boiling at 208-218", which con- stitutes about two-thirds of the whole, is finally distilled under reduced pressure.500 gra'ms of glycerol yield 135 grams of pure a-dibromhydrin. The requisite quantities of yellow phosphorus and bromine can be employed instead of phosphorus tribromide. When a-dibromhydrin is treated with nitric acid of sp. gr. 1.48, the principal product is a liquid boiling at 78-79' (18 mm.), which con- tains bromine and nitrogen. It forms very stable, yellow, readily crystallisable salts. F. S. K, Epichlorhydrin. By C. PAAL (Ber., 21, 2971-2973) .-Chloriodo- hydrin methyl ether, C3H5CII*OMe, is obtained by heating epichlor- hydrin (1 mol.) with methyl iodide (1 mol.) at 190°, fractionating the product, and removing the free iodine wit,h finely divided si!ver.The yield is about 'LO per ceilt. of the theoretical quantity. I t is a colourless oil with a pungent smell, exceedingly sensitive to light, and miscible with the ordinary solrents excepting water, in which it is insoluble. I t boils at about 200" with partial decomposition, and is readily volatile with steam. Chloriodohydrin etlyl ether, C,H,CiI-@Et, is prepared by heating epichlorhydrin with ethyl iodide at 200-220", and purifying the product as described above. The yield is 30-50 per cent. of the theoretical quantity . It boils at 200-210" with slight decomposition and resembles the preceding compound. Chloriodohydrin isopropyl ether, C,H,ClI*OPrF, prepared in like manner, boils at 208-212" with partial decomposition and resembles the ethyl ether. The noymai propyZ ether boils at 200-210" with slight decomposition ; it is relatively stable and less sensitive t o light than the other ethers which, however, it resembles in other respects.F. 8. I(. Propyl-phycite. By A. 'FAUCONNIER (Compt. rend., 107,629-630). -The action of hypochlorous acid on epichlorhydrin results in the rtssimilation of water, most probably because of the acidity of the liquid, and the " propyl-phycite " obtained by Carius by saponifying the product of this reaction, and described by him as a lower homo- logue of erythrol, is in reality ordinary glycerol. C. H. B.32 ABSTRACTS OF CHEMICAL PAPERS. Molecular Weight and Valency of Perseite. By MAQTJENNE (Compt. rend., 107, 583-586) .-When perseite is treated with boil- ing hydriodic acid, it is partly converted into resinous products of indefinite composition, and partly into a volatile liquid which can be separated into two fractions boiling at 100-110" and 133-200" respectively.The first is a heptine, isomeric with oenanthylidene, which boils a t 102-105" after rectification over calcium oxide and over sodium ; sp. gr. at 20" = 0.78. The second fraction is a dense red oil with a slight ethereal odour. It boils at 192-196" under ordinary pressure, and at 02-35" under a pressure of 40-50 mm., but decom- poses to a considerable extent even when distilled in a vacuum. It consists mainly of heptyl iodide with a small quantity of heptine hydriodide. The dibenzok acefal of perseite, C,,H2,O7, is obtained by the action of benzaldehyde on perseite in presence of alcohol saturated with hydrogen chloride.It forms confused, slender, microscopic needles which soften at 215", but have no definite melting point, and are quite insoluble in water and almost insoluble in alcohol. ThePe results show that the formula previously attributed to per- seite (Abstr., 1888, 807) is incorrect, and that perseite is really the next higher homologue of mannitol, and has the formula C,H,,O,. It is the first instance of a heptahydric alcohol and of a sugar containing 7 carbon-atoms. C. H. B. Constitution of the Glucoses. By B. RA~MANN (Bey., 21, 2841- 2842).-The author considers that the aldehyde and ketone formulze explain the chief reactions of the glucoses, and that the reactions which Tollens mentions (KzLrzes Eandb. d. Kohlenhydrate), as incom- patible with the assumption that these compounds are aldehydes do not afford sufficient grounds for changing the formuls.N. H. If. Oxidation of Arabinose with Nitric Acid. By H. KILIANI (Ber., 21, 3006-3009) .--Calcium arabonat'e is obtained in consider- able.quantities when arabinose (1 part) is heated at 35" for about six hours with nitric acid of sp. gr. 1.2 (2 parts), the diluted solution boiled with excess of calcinm carbonate, filtered, enporated, and mixed with alcohol. This method can be suitably employed for the preparation of arabonic acid. Calcium trihydroxyglutarate is obtained from arabinose as follows :- Arabinose (1 part) is digested at 35" with nitric acid of sp. gr. 2.2 (2.5 parts) ; after the evolution of gas has ceased, the solution is evaporated until free from nitric acid, the residual syrup dissolved in water (25 parts), boiled with calcium carbonate, and the hot solu- tion filtered. The sparingly soluble, red calcium salt which separates is spread on porous plates, and by concentrating the mother-liquor, separating the salt, and repeating the process several times, 40-45 per cent.of the weight of the arabinose employed is obtained in the form of calcium trihydroxyglutarate. It is very similar to calcium sacchnrate in appearance and in its behaviour when heated with water. The potassium salt, C5H607K2, crystallises in large, colourless, monoclinic plates or prisms, is readily soloble, and is not convertedORGANIC CHEMISTRY. 33 into the acid salt when the aqueous soIuttion is evaporated with acetic acid.Lead acetate and silver nitrate produce white precipitates in an aqueous solution. TrihydrozyLglutzLric acid, C5H807, obtained by decomposing the calcium salt with oxalic asid, crystallises from alcohol in colourless, microscopic plates, melts a t 127", and does not reduce Fehling's solu- tion. The normal ammonium salt crystallises in slender needles and is very readily soluble. By F. MBYER (Ber., 21, 2883-2t390).-~rLnzeth~Zenetrinitrosamine, C3H6N6O3, is obtained when an ice-cold solution of hexamethyleneamine (1 part) in water (40 parts) is mixed with ice-cold, dilut,e (If per cent.) hydrochloric acid, and a solution of sodium nitrite ( 2 i parts) in a small quantity of water immediately added. After about, 15 minutes, the yellowish, crystalline substance which separates at the surface is tlirown on to a filter, washed with cold water, and dried on porous plates.The yield is 50 to 60 per cent., or more, of the aniine employed. It crystal!ises from boiling alcohol, in which it is moderately soluble, in small, yellowish, silky needles or prisms, melts at 105--106", and is readily soluble in cold acetone, but only moderately so in warm benzene, chloroform, and ether, and insoluble in light petroleum. It dissolves unchanged in cold glacial acetic acid, and the molecular weight determined by Raoult's method was found t o be 196. On exposure to moist air, the crystals lose their silky appearance, and when treated with cold water, a slight evolution of nitrogen occurs. It melts under boiling water to a yellowish oil which gradually dissolves with evolution of nitrogen, and the solution contains formaldehyde.The same decomposition takes place, but much more quickly, when it is warmed with glacial acetic acid or dilute acids, but the decomposition into formaldehyde and nitrogen is not quite quantitative, as traces of ammonia are formed a t the same time. When heated in a capillary tube, or when treated with con- centrated acids, i t is immediately decomposed with evolution of nitrous fumes, and when heated on platinum foil it explodes. It gives Liebermann's reaction. The filtrate obtained in the prepara- tion of this cornpound contains unchanged hexamethyleneamine ; if, however, the mixture is kept for R long time before separating the nitrosoamine, the latter is decomposed into formaldehyde and nitro- gen, and some of the hexamethylenearnine is converted into form- aldehyde and ammonia.Dinitrosopentamethylenetetramine was obtained by gradually add- ing dilute hydrochloric acid to a solution of hexamethyleneamine and sodium nitrite (compare Griess and Harrow, Abstr., 1888, 1268). It melts a t 202--203", arid gives Liebermann's nitroso-reaction. F. S. I(. Action of Nitrous Acid on Hexamethylenearnine. F. S. K. Identity of Putresine and Tetramethylenediamine. By L. V. UURBNSZKY and E. BAUMANN (Bey., 21, 2938-2941).-A direct com- parison of the dibenzoyl-derivatives of putresine (Brieger), tetra- rnetlhylenediamine, and the compound obtained by the authors from YOL. LVt. d34 ABSTHACTS OF GHEMICAL PAPERS. the urine of a patient suffering from cystinuria (compare Abstr., 1888, 1296), proved that these bases are identical. Concentrated solutions of guanidine, creatine, creatinine, and similar compounds give a precipitate with soda and benzoic chloride, whereas no separation occurs in solutions containing less than 0.5 gram of the bases ; it is therefore necessary that when benzoic chloride is used as a reagent for diamines (Zoc. cit.) only very dilute solutions of the latter should be employed.By W. R. ORNDORFF and H. JESSEL (Amer. Chern. J., 10, 363--367).-Liebig stated that acetone could advantageously be substituted for alcohol in the preparation of chloroform ; this statement has been contradicted by Siemerling,.yet chloroform is now largely made from acetone. In a number of trials, the yield was 166 to 173 per cent.of the weight of the acetone used, and the residual liquors contained considerable quan- tities of calcium acetate. The reaction is represented by 2CO(CH,)z + GCaOCl, = SCHCl, + 2Ca(OH), + XaCI, + Ca(CH,*COO),. Liebig states that calcium carbonate is precipitated during the reaction, but the precipitate is calcium hydroxide. Acetophenone similarly treated with blenching powder, yields chloroform, calcium hydrate, and calcium benzoate. H. B. F. S. K. Decomposition of Acetone with Bleaching Powder. Dinitrosoacetone. By H. v. PECHMANN and K. WEHSARG (Ber., 21, 2989-2993) .-When dinitrosoacetone (compare Abstr., 1887, 28) is boiled with water or acids, it is decomposed into carboiiic anhydride, hydrogen cyanide, water, and ammonium hydrogen oxalate ; but when it is heated with glacial acetic acid, oxamic acid, melting at 210°, and hydrogen cyanide are formed.Trinitrosopropnne, NOH:CH*C(NOH)*CH:NOH, prepared by heat- ing a, mixture of dinitrosoacetone (1 mol.), hydroxylamine hydro- chloride (1 mol.), sodium acetate (1 mol.), and water at 50-60' for 1 to 2 hours, separates from hot water in the form of a colourless, crystalline powder melting a t 171" with sudden decomposition. It is only sparingly soluble in ether, but readily solubIe in alcohol, from which it crystallises in needles, and it, dissolves slowly, but in con- siderable quantities, in hot water. It behaves like dinitrosoacetone when heated with dilute acids, but its aqueous solution can be boiled for a short time without decomposition taking place.Ferric chloride gives a brownish-red coloration with a dilute aqueous solution ; ferrous sulphate produces a wine-red colour, and the solution then gives a violet precipitate with soda. Dinitrosoacetone hydrazone, NOH: C H-C (N,HPh) CH :NOH, pre- pared by treating dinitrosoacetone (1 mol.) with phenylhydrazine (1 mol.) in hot, alcoholic solution, crystallises in yellow needles, melts a t 145" with decomposition, and is readily soluble in alcohol and ether, more sparingly in benzene and light petroleum, and insoluble in water. It dissolves in alkalis with a yellow, and in concentrated sulphuric acid with an orange-yellow coloration. The metyZ-deriv% tive, C9H9N4O2Ac, a light yellow, crystalline compound, melts a t 133", and is soluble i n dilute alcohol.It dissolves in alkalis with aORGIAKIC CHEMISTRY. 35 yellowish coloration, but the soliltion becomes colourless on boiling, md on adding acids, a compound, C,H8N*0, is precipitated in shining, colourless needles. This substance is also formed when the acetyl- derivative is boiled with water. A compound, C,,H,,N,, is obtained when dinitrosoacetone is beaked with excess of phenylhydrazine acetate. It crystallises from hot alcohol or benzene in shining, yellow plates melting at 122". It is not acted on when boiled with ferric chloride, and its solution in concentrated sulphuric acid does not give a coloration with this reagent. Sulphoisovaleric Acid. By G. DE VARDA (Chew,. Ceiztr., 1888, 587-888, from Rend. Acad. dei Lincei [4], 4, 1).-100 parts of isovaleric acid are mixed with 100 parts of chlorosulphonic acid, and, after the spontaneous reaction has ended, the mass is heated to 230" ; it is then diluted with several volumes of water, and distilled from the oil-bath until the distillate no longer has an acid reaction.The distil- late is then heated with plumbic carbonate for some time, filtered while hot, and the lead precipitated from the solution by hydrogen sul- pbide, the solution of the free acid being concentrated in a vacuum. The aqueous solution partly decomposes when heated on the water-bath. The lead salt, C6H,S0,Pb.'LHz0, crystallises from water in colourless, odourless, small plates, which taste sweet ; they are slightly soluble in water, and insoluble in alcohol, ether, and chloroform.The barium salt, containing 1 mol. HzO, forms small, tabular crjstals, without smell o r colour, and taste bitter. It is soluble in water, insoluble in alcohol, ether, and chloroform. F. S. K. Su7phoisowaZeric acid so obtained forms deliquescent crystals. J. W. L. Constituents of Cocoa Fat. By P. GRAF ( A d . Pharm. [3], 26, 830-846 ; comp. Kingzett, Trans., 1878, 38).-l1he melting point of various samples of commercial cocoa butter from widely different sources was determined both in open and closed glass tubes. In the open tube, the results varied from 29" to 33-44', whilst in the closed tube 11 samples gave 34.3" and one 33.5". The whole of the samples were mixed together for the further investigation. The €at was found to contain hardly any free acid. Two determinations of glycerol averaged 9-59 per cent.A little cholesterin and small quantities of formic, acetic, and butyric acids were detected. After the separation of oleic acid, the solid fatty acids were isolated by fractional crystallisation, followed by Heintz's method of fractional precipitation by means of magnesium and barium acetates. No acid with a higher molecular weight than arachidic acid was found ; this confirms Traub's statement that he was unable to find theohromic acid asserted to be present by Kingzett. The presence of oleic, stearic, and palmitic acids was confirmed ; and either lauric acid o r one of its isomerides was isolated : there was not sufficient material at hand to settle this point. J. T. Action of Hydrogen Phosphide on Aldehydes and Ketone Acids.By J. MEESINGER and C. ENGELS (Ber., 21,2919-2928).- The compound obtained by passing hydrogen phosphide and hy- d 236 ABSTRACTS OF CHEXICAL PAPERS. drogen chloride into an ethereal solution of pyruvic acid has the constitution P(CMe<C0>)3, and is named by the authors phos- iUhorus-trianhyd~o~yru~ic acid (compare Abstr., 1888, 441). It is in- soluble in cold acids, and on heating, decomposition takes place. It dissolves in warm, glacial acetic acid, and separates unchanged on cooling. It is not acted on by bromine even a t 150", but when boiled with water it is decomposed into pyruvic acid and hydrogen phosphide. 0 Phospho1.zks-trihydroplll.uvic acid hydrazide, P[ CMe(OH)*C(OH):N,HPh],, is formed when the preceding compound is warmed with phenyl- hjdrazine in alcoholic solution ; it is a colourless, crystalline com- pound, melts a t 132", and is moderately soluble in alcoholic ether, but only sparingly in cold alcohol, and almost insoluble in ether.Hy drazonepyruvic acid hydyazide, Cl5'EIZI6N40, is formed , together with hydrogen phosphide, when phosphorustrianhydropyruvic acid is heated with excess of phenylhydrazine, in which i t is readily soluble. It crys tallises from hot alcohol in colourless, shining plates, melts at 162", and is only sparingly soluble in cold alcohol and ether. Phosphorus-t,.ihyclro~yruvic acid dianilide, is obtained when aniline is gradually added to an alcoholic solution of phosphorus-trianhydropyruvic acid. It separates from warm alcohol in colourless crystals, melts a t 158", is very sparingly soluble in cold alcohol and insoluble in water or ether.It is completely decom- posed, with separation of phosphorus, when treated with hydrogen chloride in alcoholic or ethereal solution. Dihy dyazonepy rzsv ic acid hy drazide, NP h (C 0-CMe: X2H Ph), , is formed when the preceding compound is treated with phenylhydrazide. It crystallises from alcohol in small needles melting at 169". Phosphorus-trianhydropyruvio acid and toluylenediamine yield a crystalline compound, CQHgOGP 3- 2C6H3Me(NH2),, which melts at 178" with decomposition. Hydrogen phosphide, in presence of hydrogen chloride, has no action on ethyl acetoacetate or benzoylcarboxylic acid, but tribromo- pyruvic acid absorbs the gas in considerable quantities with evolution of hydrogen bromide and the ultimate formation of phosphorus-fri- anhydropyruvic acid.3'. S. K. Action of Heat on Tartaric Acid in Aqueous Solution. B.7 E. M. WEDARD (Chenz. Centr., 1888, 889, from Atti. R. Acad. Scz. Torino, 6, 65-67).-The author noticed that when tartaric acid had been heated for several days in sealed tubes with ferrous sulphate, several of the tubes exploded violently, and in the others a consider- able quantity OE carbonic anhydride was found. As the ferrous salt had not become oxidised a t all, the reaction had not been a simple reduction of the tartaric acid. Tartaric acid heated with water alone at 150" in sealed tubes also suffered a considerable loss of carbonicORQANIC CHEMISTRT. 37 anhydride. In one experiment, the author opened the tube after heating, allowed the carbonic anhydride to escape, then sealed it again, and submitted the contents to a further heating, and repeated the operation until no further evolution of carbonic anhydride took place, after which the resulting liquid was found to contain pyro- tartaric acid along with undecomposed tartaric acid. Freezing Points of Solutions of' Aluminium Alkyls.By E. LOUISE and L. Roux (Cowpt. rend., 107, 600--603).-Pure ethylene bromide was used as a solvent, the molecular reduction, T, with this liquid being 118. The number obtained with mercury propyl was 124.8 ; mercury isobutyl, 122.7 ; mercury isoamyl, 123.6 ; mercury phenyl, 120.4. Aluminium ethyl gave a molecular reduction of 115.6, which agrees with the formula A1,Et6.Alunzinium proyy2, obtained by the action of aluminium on mercury propyl, is a colourless, mobile liquid, which boils a t 250" and takes fire in contact with the air. Aluminium isoam!jl, obtained in a similar way, is a somewhat viscous, colourless liquid, with an odour of amyl compounds ; it boils at 250" under a pressure of 80-100 mm., and does not readily take fire in contact with the air. The molecular reduction with aluminium propyl is 92.8, and with aluminium iso- amyl 84.5. These values agree more closely with the formula A]&, than with AIRs, and hence confirm the conclusions deduced from J. W. L. vapour-density determinations (Abstracts, l8S8, 583). C. H. B. Substituted Pyromucic Acids. By H. B. HILL and A. W. PALMEK. (Amer. Chen?. J., 10, 375--391).-With the exception of a sulphopyromucic acid briefly described b r Schwanert, no furf uran- derivatives containing the sulplionic group are described ; yet the general behaviour of pyromucic acid is similar to that of benzoic acic1.6- Sulphopyromucic acid is readily formed bay treating pyromucic acid with fuming sulphuric acid. The acid itself is extremely soluble in water, but may be obtained in large, deliquescent crystals. The follow- ing salts are described : RnC,H2S06 + 4H20 ; Ba( C5&SO,)a + 4H20, and also with 6H,O; CaC,H,SO, + 3H20; PbC,H,SO, + 2H20, all readily soluble in hot water; Ag,C5H2S06 is sparingly soluble in water; K,C5H,S0, + 4x20 ; KC,H,so, ; Na,C5H,S06 4- 5H20, and NaC&SO, + H20, all very soluble, All these salts crjstallise readily. By treating the dry sodium salt with phosphorns penta- chloride. and the resulting viscous oil with ammonia, the crystalline 6-suZphopyromucal.riide, C,H,SO,(NH,),, is obtained ; it is readily soluble in hot water, and melts a t 213'.The dry acid is only decom- posed by bromine at loo", dibromosuccinic acid and other products being formed ; in aqueous solution the acid is mainly converted into fumaric acid. Dilute nitric acid oxidises i t slowly, and also produces fumaric acid and some oxalic acid ; concentrated nitric acid at 100" readily converts it into Klinkhardt's 8-nitropyrom ucic acid, and at t h e same time a neutral substance, in all probability aa-dinitro- furfuran, is formed. Although bro,nine-derivatives of 8-sulphopyromucic acid camot be38 ABSTRACTS OF CHEMICAL PAPERS.obtained by the action of bromine, they may be obtained by sul- phonating the corresponding bromopyromucic acids : P-Hromo- 6-sulyhopyromucic acid is extremely soluble in cold water, and forms deliquescent crystals. The salts- BaC5HBrSo6 + 4H20; CaC5HBrS06 + 6H,O ; PbC5HBrS06 + 4H,O ; K,C5HBrS0, + 1+H20 (2) are described ; they are all crystalline and soluble in water. That the acid is really a derivative of 6-sulphopyromucic acid is proved by obtaining this acid by treatment of the bromo-acid with zinc and ammonia. Bromive in aqueous solution readily converts the bromo- acid into monobromofumaric acid. Concentrated nitric acid readily yields P-bro.uno-~-nitropyronzucic acid, soluble in water, alcohol, &c., and melting at 159-160". 8-r-Dibromo-6-su~h(~~~omucic acid is prepared by dissolving /3-y-di- bromopyromucic acid in fuming sulphuric acid, b u t it is more advan- tageous to use the mixture of P-61- and /3-6-dibromopyromucic acids resulting from the decomposition of the tetrabromo-acid, as the p-8-dibromo-acid is but little acted on by the sulphuric acid.Tbe acid in question is very soluble in water, and is crystalline; the following salts are described: BaC,Br2S06 + 5H20 and also with 3&O; PbC,Br2S06 + 4H20 ; AgzC,Br,So6 4- HzO ; K2C5Br2SO6 + H,O. That the sulphoriic acid occupies the 8-position, the only pos- sible one, is proved by treatment of the above barium salt with zinc-dust and ammonia, when the a-sulphopyromucic acid first described is obtained. Bromine in aqueous solution readily oxidises the barium salt, giving barium sulphate and dibromonialeic acid.Dilute nitric acid oxidises it to dibroruosuccinic acid. Concentrated nitric acid yields a mixture of P-ri-dibromo-8-nitropyrornucic acid, crystallising from water in sparingly soluble, slender, yellow needles, that melt a t 204- 205", and /3/3-dibromo-aa-dinitrofurfuran, a substance melting at 150-151" and crystallising from benzene, as the compound C',Br2(NO,),O,C6H6, which readily gives off this benzene of cqstal- lisation. H. B. Metadiethylbenzene. By A. VOSWINKEL (Ber., 21,2829- 2831). i7.letudiethyZbeiizene, C6H4Et2, is obtained, together with the para- compound, by the action of ethyl bromide and aluminium chloride on benzene ; the two compounds are separated from each other by means of the barium sulphonates.It boils a t 181--182", and does not solidify a t -20", but bccomes thicker. Sp. gr.. = 0.8602 at 20" com- pared with water a t 4". When boiled with dilute nitric acid, ethyl- benzoic and isophthalic acids are formed. The barium sulphonate (with 3 mols. H,O) crystallises in hemispherical groups of prisms, rather sparingly soluble in cold water. The coppr saZt (with 4 mols. H,O) forms bright-blue plates of a satiny lustre ; the potussium salt (with 1 mol. H20) crystsllises in quadratic plates. The sulphor~arnide separates from the dilute alcoholic solution in long, flat needles, melting a t 101-102". The bromir~e-derivatii.e, C6H3Et2Br, boils at about 238". The teirnbromo-compciund, C6Et2Br4, crybtrcllises from alcohol in small, colourless prisms melting a t 74".Nat,ometuJ!iefhyZ- btlzneiie, C,B,Et,*NO2, is a pale yellow liquid, which boils atORGANIC CHEMISTRY. 39 280-285", with decomposition. The trirdro-compound, CsHEt,(NO,)-, crystallises from light petroleum in prisms melting at 62". A;mido- metadiethylbenzene, C6H3Et2.NHa, prepared by reducing the nitro- derivative, is a colourless liquid which distils readily with steam ; the hydrochloi-ide crystallises in groups of very long needles ; the acetyl- derivative forms stellate groups of needles melting at 104". Metadi- ethyZphenoZ, C6H3Et2*OH, is obtained by fusing the sulphonic acid with potash ; it boils at 225", and dissolves spariugly in water ; the solution gives a blue-violet colour (which changes to green on adding alcohol) with ferric chloride. Zeta-ethylbenzoic acid, C6H4Et.COOH, crystallises in long needles, melts a t 47", and is almost insoluhle in water.The calcium salt (with 4 mols. H,O) forms lustrous needles, readily soluble in water and alcohol. Synthesis of Consecutive Tetramethylbenzene. By 0. JACOBSEN (Ber., 2 1, 282 1-28 28) .-Dinitro bromopseudocumene, N. H. M. [(N02)2 : Br : Me3 = 5 : 6 : 2 : 1 : 3 : 41, obtained by the action of nitric and sulphuric acids on bromopseudo- cumene [Br : Mes = 2 : 1 : 3 : 41, crystdlises from hot alcohol in small, yellowish-white, lustrous prisms, melts a t 182", and dissolves readily in hot benzene, sparingly in hot alcohol. Bromopseudocumene, [Br : Me, = 2 : 1 : 3 : 41, has the same boiling point as the 5, 1, 3, 41 compound: 237-238" (not 226-229").The sulphonamide nielts at 185" (not 137-188"; compare Kelbe and Pathe, Her., 19, 1546). 1, 2, 3, 4-'l'ctramet,hylbenzene is prepared by heatiiig pure bromo- pseudocumene (25 grams), methyl iodide (40 grams), and sodium (14 grams), in presence of sufficient absolute ether to cover the latter. After two or three days, it is distilled. The yield of tetramethyl- benzene is 38 per cent. of the weight of the bromopseudocumene. Dibromonietnzylene, [Me, : Br2 = 1 : 3 : 2 : 41, is obtained in the preparation of spinietrical dibromometaxylene by brominating the hydrocarbon ; it is an oily liquid which, when cooled, solidifies to a hard crystalline mass melting a t -So, and boils a t 269" under 760 mm. pressure. The di~itro-deri~atiwe forms a1 rriost colourless, microscopic crystals, melts a t 191", and dissolves readily in toluene, very sparingly in alcohol.When exposed to light it becomes yellow. The sodium sulphowie, C6HNe,Br,*S03Na + H,O [= 1 : 3 : 2 : 4 : 61, crystallises in groups of needles; the potassium salt with 1 mol. H20 forms lustrous plates, sparingly soluble in cold water; the barium salt crystallises in small prisms. The amide separates from alcohol in small prisms, which melt with decomposition above 300". When the sodium salt is treated with zinc-dust and ammonia, the salt of ordinary unsymmetrical metaxylenesulphonic acid is formed. OrthoiZicLmidometaayZene, [Me, : (NH,), = 1 : 3 : 5 : 61, is obtained by very prolonged action of tin and hydrochloric acid on the dinitro- dibromo-compound, and is liberated from its hydrochloride by dry distillation with sodium carbonate in a stream of hydrogen.It crys- tallises from water in rhombic plates, melts a t 78.5", and dissolves readily in alcohol, ether, and hot water. When exposed to moist air,40 ABSTRACTS OF CHEMICAL PAPERS. it beeomes grey-violet. The constitution of this compound as given is proved by the synthesis of 1, 2, 3, 4-tetramethylbenzene from the liquid dibromometdxylene by the action of methyl iodide and sodium, using ether as a diluent. When symmetrical dibromometaxylene is heated with sulphuric acid (3 parts) at 240", it is converted into the liquid isomeride. Tetrethylbenzene. By 0. JACOBSEN (Ber., 21, 2819-2821). -Symnretrscal tetrethylbmzene, C,H.,Et, [Eta = 1 : 'L : 4 : 51, is obtained, together with a smaller amount of the isomeride [Et, = 1 : 2 : 3 : 41, by the action of ethyl bromide on benzene in presence of aluminium chloride, at a temperature not above the boiling point of the bromide ; the product is sulphonated in the cold and the sodium sulphonnte heated a t 170" with hydrochloric acid.It melts a t 13", and boils a t 250". When boiled with dilute nitric acid, and the product further oxidised with permanganste, pyromellitic acid is formed. Dibromotetrethylbenzene, C,Br,Et, [Et, = 1 : 2 : 4 : 51, crystallisea from hot alcohol in long, thin prisms melting a t 112.5". S o d i u m tetreth y1benzenesubphonate, C,H E t,*SO,Na + 4H20, crystal- lises from water in very large, lustrous plates, sparingly soluble in cold water, much more readily in alcohol, almost insoluble in cold dilute aqueous soda.The barium salt (with 9 mols. H20) is sparingly soluble in hot water. The sulphona?~~ide, C14H21.S02*NH2, crystallises from hot dilute alcohol in rhombic plates, melting at 122". Pentethylbenzene and its Decomposition by Sulphuric Acid. By 0. JACOBSEN (Ber., 21, 2814-2819 ; compare Abstr., 1887, 660 ; 1888, 137).-PentsthyZbenzene, C,HEt,, is prepared by the action of ethyl bromide on benzene in presence of aluminium chloride, and purified in a manner similar to the pentamethyl-compound (loc. cit.). I t forms a thick oil, which boils at 277", and does not solidify at -20". Brornopentethylbe?inene, C,BrEt,, obtained by brominating the hydro- carbon dissolved in glacial acetic acid, crystallises from alcohol in long needles, melts at 47*5", and boils a t about 315". It is readily soluble in hot alcohol.The suZphone, SO,( C6Ets),, crystallises from light petroleum con- taining some alcohol in large, transparent, hexagonal prisms of a glassy lnstre, melts a t 76", and is very readily soluble in alcohol, much less in light petroleum, and insoluble in water. Sodium perdeth y Zb enseisesulphonate, C,,H,,-S 0,Na + 4H,O, crystal - lises from water in thin, lustrous plates, moderately soluble in hot water, much more soluble in alcohol. The anhydrous salt crystallises froin 90 per cent. alcohol in groups of hair-like needles. The potccssium salt (with 2 mola. H,O) crystallises in thin plates, rather readily soluble in hot water, much more soluble in alcohol. The aniinonium (with 1 mol.H,O) and barium (with 9 mols. H20) saZfs crystallise respectively in large, thin plates and small scales. When pentethylbenzene is treated with an equal volume of sulpburic acid sy much fumiug sulphuric acid added to the cooled mixture that N. H. M. N. H. M. Sp. gr. = 0.8985 a t 19".ORGANIC CHEMISTRY. 41 a clear, brownish-yellow solution is obtained, and the whole kept for 4-5 days a t the ordinary temperature, hexethylbenzene and tetrethyl- benzene [Et, = 1 : 2 : 3 : 41 are formed. Hexethylbenzene melts at 229" and boils a t 298". Tetrethylbenzene [Et, = 1 : 2 : 3 : 41 boils a t 254", and does not solidify a t -20". It is probably identical with Galle's compound (Abstr., 1883, 109 1). The dibronzo-derivative, CsBi.,Et4, crystallises in prisms of a glassy lustre, melts at 77", and is sparingly soluble i l l boiling alcohol.Barium tetrethylbenxenesdphonate, (C,,EI,,*SO,),Ba + 6H20, crystal- lises from water in flat prisms OF a glassy lustre; the sodium saZt (with 5 mols. H,O) forms readily soluble rhombic plates. The amide sepa- rates from its solution in water and alcohol in well-formed crystals of a glassy lustre, and melts at 107". N. H. M. Synthesis of Aromatic Selenium Compounds. By C. CHABRIF: (Bull. SOC. Chlm., 50, 133-137) .-Phenyl selewide, SePh,, is obtained by adding aluminium chloride to selenium tetrachloride (I part) and benzene (3 parts), contained in a reflux apparatus, until no more hydrogen chloride is evolved. The temperature in the flask varies from 22' to 27", and the operation is finished in about 60 hours.It boils a t 227" under a few cm. pressure. Phenyl chloride and an oil boiling at 250" under a pressure of A few cm. are also formed. Selenium oxychloride in presence of aluminium chloride and selenious anhydride, also react with benzene. Consecutive Metaxylenol. By 0. JACOBSEN (Ber., 21, 2828- 2829) .-The author previously (Abstr., 1878, 412) ascribed t o con- secutive metaxylenol the melting point 74.5". Nolting isolated the compound from commercial xylidine, and found the melting pointl 49". This melting point is now confirmed by preparing metaxylenol by heating pure parahydroxymesitylic acid ; the product melted a t 47-48'. The xylenol previously obtained (Zoc. cit.) was paraxylenol. Nitronitrosoresorcinol. By C:. DE LA HARPE and F.REVERDIN N. H. M. N. H. M. (Bull. SOC. Chim., 49, 760-763).-Nitronitrosoresorcil/ol, [OH: NO,: 0 : NOH = I : 2 : 3 : 41, is obtained when a cooled mixture of nitroresorcinol (1 mol.), melting a t 85", with a solution of soda (1 mol.) in 10 parts of water and an aqueous solution of sodium nitrite (1 or 2 mols.) is gradually added t o excess of dilute and well-cooled sulphuric acid. The yellow, flocculent precipitate is washed with water, dried over sulphuric acid, and extracted with ether to ~emove traces of nitrosoresorcinol. It cvystallises from alcohol in brownish needles, and is readily soluble in water, acids, and alkalis, but only moderately soluble in alcohol, and insoluble in ether, benzene, and chloroform. It is not changed when heated to about 200", but at higher temperatures it deflagrates violently.It yields diamidoresorcinol (compare Bite, Ber., 8, 631) when reduced with tin and hydrochloric acid. The aqueous solutioii gives an intense green coloration with ferrous sulphate o r with iron filings, and a slightlly acid solution of the colouring matter, which can42 ABSTRACTS OF CHEXICAL PAPEkS. be precipitated from the aqueous solution by adding sodium chloride, dyes wool green (compare F h r e , Abstr., 1883, 733). Concentrated snlphuric acid added to a mixture of resorcinol and nitronitroso- resorcinol? produces a green colour, which changes to blue and t,hen to a dirty violet; from this solution water precipitates brown flocks, which dissolve in alkalis with a greenish-brown coloration. Nitroresorcinol, [(OH), : NO2 = 1 : 3 : 41, melting at 115", does not form a nitroso-derivative when treated as described above.Condensation-product of Quinone and Ethyl Acetoacetate. By H. V. PECHMANN (Ber., 21, 3OO5-WO6) .-A Condensation-product, C16H1606, is formed when quinone (1 gram) is heated a t 100" with ethyl acetoacetate (2.5 grams) and a 50 per cent. solution of zinc chloride (6 grams) in absolute alcohol. It melts a t 184", and is solu- ble i n boiling alcohol or glacial acetic acid, but insoluble in water. The solution in Concentrated sulphuric acid turns deep blue when heated. It yields crystalline derivatives when treated with bromine, but it is not acted on by phenylhydrazine, benzoic chloride, sodium ethoxide and alkyl iodides, or by boiling hydriodic acid.A crystalline bibasic acid, C14K1,06, is precipitated when the preceding compound is hydrolysed with alcoholic potash and the solution acidified with acetic acid. It sublimes without melting, and is insoluble in all ordinary solvents. The potassium salt, C,4HloK206 + 2H,O, is a colourless, crystalline, spariugly soluble compound, and loses its water at 125". F. S. I(. Derivatives of Paramidoisobutylbenzene. By C. GE LZER (Ber., 21, 2941-2949, and 2Y49-2961).-l?aracetarnidobromisobutyl- benzene, C4HS*C,H,Br.NHAc, prepared by brominating acetamidoiso- butylbenzene: crybtallises from hot dilute alcohol or benzene in large, shining scales or plates, and melts a t 1.53". It is readily soluble in alcohol, hot benzeoe, ether, carbon bisulphide, and chloroform, but only very sparingly soluble in boiling water.B~Iiir7obrumi.sobzctylbenzene, C4H,*C6H,Br*NH2, is a heavy,. yellowish, aromatic-smelling oil, boiling a t 264-265" (710 mm.) with decom- position, and volatile with steam ; i t is readily soluble in alcohol, ether, and benzene, b u t insoluble in water. The hydrochloride, CloHI4NBr,HCl, crystallises from benzene in moss-like needles, and is readily soluble in water, alcohol, and warm benzene, but almost insoluble in ether. The platinochloride, (CloH14NBr)2,B ZPtCI6, obtained by precipitating a cold alcoholic solution of the base with a hydrochloric acid solution of platinic chloride, crystallises in slender,. yellow needles, and is readily soluble in alcohol, but only sparingly in cold water, and insoluble in ether; it is decomposed when boiled with water.A light yellow, crystalline substance, ( CloH14NBr),PtCl,, is obtained when a cold alcoholic solution of the base is precipitated with a neutral solution of platinic chloride ; it; is sparingly soluble in cold alcohol, and is decomposed when the solution is heated. The picrate, CloH14NBr,CsH,N,07, separates from a mixture of warm benzene and light petroleum in slender, yellow, spear-shaped crystals, and is readily soluble in cold alcohol, ether, or liot water, but only sparingly in cold water or cold benzene, and moderately soluble in hot benzene. F. S. IC.ORQANIC CHEMISTRY. 43 Bi-onzisobutylbenzene, C4H,.C6H4Br, obtained by treating the amido- derivative with nitrous acid and distilling the product, is a heavy, slightly yellow, aromatic-smelling oil, boiling a t 231-232" (710 mm.), and only slightly volatile with steam.It is readily soluble in alcohol, ether, and benzene, but irisoluble in water. It yields metanitrobenzoic acid when heated a t 235-240" with nitric acid of sp. gr. 1.15. 17letanitroi-cobzLtylbenxene, C4HS*CqH4-NO2, obtained by treating the amido-derivative with nitrous acid, and fractionating the product in a partial vacuum, is a bright yellowish-red, aromatic-smelling oil, boil- ing a t 250-252" (740 mm.). It yields metanitrobenzoic acid when heated at 200" with nitric acid of sp. gr. 1.12. I~iti-oisobut2/l~henoZ, [C4Hg : NO, : OH = I : 3 : 41, prepared by boiling amidonitroisobntylbenzene with dilute potash and distilling the product, separates from alcohol in yellowish-red, deliquescent crystals, melts at 95", and boils at 289-290" (711 mm.) with only slight decomposition.It is readily soluble in alcohol, ether, benzene, light petroleum, alkalis, and hot water. Metainidoisobuty lbenzene, C4H9*Cj6H1*NH,, prepared by reducing the nitro-derivative with stannous chloride and hydrochloric acid, is a yellowish oil, boiling a t 229' (708 mm.), and moderately volatile with steam. It is readily soluble in alcohol, ether, and benzene, b u t only sparingly in water. It dissolves in a solution of bleaching powder with a bright riolet colour, and with potassium dichromate and sulphuric acid yields a reddish-violet coloration, which quickly changes to brown. The hydrochloride, ClOH,,N,HCl, crystallises from hot benzene in colouiless plates, and is readily soluble in aater and hot alcohol, but only sparingly soluble in benzene.The platino- chloride, ( C,oH,,N)2,H,PtCl,, crystnllises in bright yellow plates, and is readily soluble in boiling water and hot alcohol, but only sparm.gly in benzene and ether. The ozalate, CloH&,C2H204, crysthllises from hot water or dilute alcohol, in which it is readily soluble, in large white plates. The acetyl-derivative, C4Hg*C6H4*NHAc, crys- tallises from boiling water in colonrless, shining plates, melts at 101", and is readily soluble in alcohol, ether, and benzene. n~etacetamidonit,.oisobzctylbenzene, [C4Hg : NO, : NHAc = 1 : 2 : 31, obtained by nitrating the acetamido-derivative, crystallises from hot dilute alcohol in small, yellow needles, melts a t 105*5", and is readily soluble in alcohol, benzene, and ether, but very sparingly in boiling water.Ainidonitroisobut?lZbenzene, C4H9.C,H,(X0,)*NH2, separates from dilute alcohol in bright yellow crystals, melts at 1 2 4 , and is readily soluble in alcohol, ether, benzene, and boiling water, but sparingly soluble in cold water. It is only a feeble base, and the salts are readily soluble. Dia.r.lzidoisoEutyZbenzene, [CIHg : (NH,), = 1 : 2 : 31, prepared by reducing the preceding compound with stannous chloride and hydro- chloric acid, crystallises from alcohol in colourless plates, melts at log", is readily soluble in water, alcohol, ether, and benzene, and blackens on exposure to the air. The oaalate, (CloH16N,),,C2H204, crystallises in flat needles, and is readily soluble in boiling water, but only sparingly in cold, ahsolute alcohol, and almost insoluble in ether.44 ABSTRACTS OF CHEMlCAL PAPERS.an alcoholic solution of the dinmine is mixed with a glacial acetic acid solution of phenanthraquinone. It separates from hot dilute alcohol in yellow nodular crystals, melts a t 144" with previous soften- ing, and is readily soluble in warm alcohol, ether, and benzene, but only sparingly in boiling water. It dissolves in concentrated nitric acid with a brownish-red. in concentrated sulphuric acid with a scarlet coloration, and is precipitated unchanged from both solutions on adding water. U NCPh \N*CPhH Benzilisobuty@hennzitze, C,Hg*C6H,/ I \, prepared in like man- ner from the dinmine and benxil, crystallises in small, light-yellow prisms, melts a t 96", and is only sparingly soluble in cold alcohol, but readily in ether, benzene, and hot alcohol.It dissolves in concen- trated nitric acid or concentrated sulphuric acid, but is precipitated unchanged on adding water. AcefLt?nidobromonifroisobuf!llbenzene, C4Hg~C,H,Br(N0,)~NHAc, pre- pared by nitrating acetamidobromisobutylbenzene, crystallises from a mixture of ether and light petroleum in small, rhombic plates, melts at 144O, and is readily soluble in hot alcohol, ether, or benzene, but only very sparingly soluble i n boiling water. Amidobromonitroisobuty Zbenxene, C,Hg*c6H2Br( NO,) .NH2, crystallises in long needles, melts a t 69*5", boils a t 278-280" with partial decom- position, and is volatile with steam. It is very sparingly soluble in boiling water, but readily in alcohol, ether, and benzene.Diamidobromisobutylbenzene, c4Hg*C6~,Br(N&),, obtained by re- ducing the preceding compound with stannous chloride and hydro- chloric acid, crystallises from ether in slender, colourless needles, melts a t 85*5", and turns brown on exposure to the air. It sublimes with considerable decomposition, forming colourless needles which are stable in the air. It is readily soluble in alcohol, ether, and benzene, but only very sparingly in hot water. Ferric chloride produces a brownish-red coloration ; bleaching powder precipitates oily drops, and platinic chloride gives a brownish-black coloration in a hydrochloric acid solution of t.he base. The oxulate, C1oH15BrNzl CJLO4, crystallises in small needles, and is moderately soluble in boiling alcohol, but only sparingly in ether, benzene, and warm water.The picrate, CloHlbBrN2*2, C6H3N307, crystallises from hot water in yellow needles. and is readilv soluble in alcohol and ether. lises from boiling alcohol in slender? yellow needles, melts- at 153-5", and is readily soluble in benzene, ether, and boiling alcohol, b u t only sparingly in cold alcohol. It dissolves in concentrated mineral acids, forming red solutions, from which it is precipitated unchanged on adding water.ORGANIC CHEJIISTET. 45 X*C*Ph \N*C-Ph Beiizilbromisobuty ~ h e n a z i ~ e , C4Hg*C,H2BJ I II 3 crystallises from hot alcohol in colourless needles, melts at 172", and behares towards solvents similarly to the preceding compound ; it dissolves in (son- cen trated acids with a yellowish-red coloration.Dibi-oniisobutylbenzene, [C4Hg : BrP = 1 : 3 : 51, obtained by heating metabromisobutylbenzene with bromine in presence of iodine, and distilling the product with steam, is a light yellow oil, boils a t 376-277" (718 mm.), and is readily soluble in all ordinary solvents except water. When heated a t aboxt 250" with nitric acid, sp. gr. 1.20, i t is converted into symmetrical dibromobenzoic acid. F. S. K. Decomposition of some Diazo-compounds by Formic and Acetic Acids. By W. R. ORNDORFF (Amer. Che1.12. J., 10, 368-372). -The decomposition of diazo-compounds by formic acid might be expected to furnish an easier means of displacing the amido-group by hydrogen than the decomposition with alcohol.But the reaction proceeds otherwise and could not be followed out, a9 the phenyl formate that was probably formed could not be isolated. Substitut- ing acetic acid for formic acid, it is shown that phenyl acetate is pro- duced ; the yield is, however, small, as milch tar is also formed ; the reaction is analogous to the production of phenetnil by the action of alcohol. The boiling point of phenyl acetate has been variously stated; it has been redetermined as 195" at 733 mm. pressure. Similarly, paradiazotoluene sulphate, when boiled with acetic acid, yields paracresyl acetate, boiling a t 213", and identical with that pre- pared from paracresol. Paradiazobenzenesulphonic acid appears to undergo a similar change, and the reaction therefore seems to be general.H. B. Chryso'idincarbamide. Amidophenylenecarbamide. By A. JENTZSCH (J. pr. Chem. [ 2 ] , 38, 121-139). -When carbonyl chloride is passed into a moderately strong solution of chrysoidin in dry chloroform, it is rapidly absorbed with development of heat, and red-brown flocks separate which become of a darker brown as the action proceeds. The brown matter is collected, dried, powdered, heated with dilute hydrochloric acid, and filtered hot ; brilliant golden-yellow laminae crystallise out on cooling, together wit8h octo- hedral crystals of diamidoazobenzene hydrochloride. By dissolving the mixed crystals in alcohol and adding ammonia, golden-yellow needles of the correspoiiding bases are obtained, which may be separs ted by digestion with chloroform, the diamidoazobenzene being dlssolved.The residue, consisting of the new base, is purified by dis- solving in alcohol and passing hydrogen chloride through the solution to obtain the hydrochloride which is then decomposed by ammonia. Chrysozdincarbarnide, NPh:NC,H,:(NH)Z:CO, thus obtained, crys- tallises in brilliant, golden-yellow laminae, sparingly soluble in alcohol, nearly insoluble in water, ether, and chloroform. It does not meit at 300". I f the chloroform solution of diamidoazobenzene be satur;rted with carbonyl chloride and allowed to stand for some days, only46 ABSTRACTS OF OHEMMIGAL PAPERS. carbamide hydrochloride and unaltered chrysoi'din hydrochloride will be found on evaporating the chloroform. The hydrochloride crystallises in golden-yellow laniinse, sparingly soluble in water, more so in alcohol, insoluble in ether.The pZatiizochZoride, ( C13H11NaUC1)2PtC14, forms red-brown laminse. The nitrate crystal- lises in brilliant, golden-yellow scales, very sparingly soluble in water, sparingly soluble in alcohol, and insoluble in ether ; they decompose with slight explosion at above 200". The suZphate forms a yellowish- red powder ; it is very sparingly soluble in water, more so in alcohol. When heated with moderately strong hydrochloric acid in a sealed tuhe at 200" for eight hours, chrysoidincarbamide is decomposed, with the formation of carbonic anhydride and a dark-brown mass. The same dark-brown substance is obtained when chrysoidin is treated in the same way. It yields phenol when distilled with steam, and a reddish-brown residue which has not been identified.Inasmuch as chrysoidin splits up into aniline and triamidobenzene when reduced by hydrochloric acid and tin, it seemed probable that its carbamide would yield aniline and a new substance, by the same treatment, thus showing that both NH-groups are attached to the same benzene nucleus. 100 grams of the carbarnide were heated with 50 grams of tin aud 250 grams of hydrochloric acid (sp. gr. 1.2) in a flask. The solution became colourless at first, and subsequently brown, through oxidation ; after the action had ceased, the hydrochloric acid was evaporated, the residue dissolved in hot water, and hydrogen sulphide passed through the solution ; the filtrate from the tin sulphide was evaporated in a current of hydrogen sulphide, the crystalline residue dissolved in water, and made alkaline with barium hydroxide.This precipitated aniline, which was dis- tilled off; the excess of barium hydroxide was precipitated from the liquid remainisg in the retort by sulphuric acid, and the excess of the latter by barium chloride. From the filtrate, the hydrochloride of the new base did not crystallise well, so the solution was digested with ammonium oxala te and filtered hot. On cooling, amidophenyZene- arbamide oxalate crystallised out in nearly white minute needles, collected in spheres, freely soluble in hot, sparingly in cold water, nearly insoluble in alcohol. Amido~he?zyZerzecai.bnmide, NHz*C6H3: (NH),:CO, obtained from the oxalate by adding sodium carbonate to a hot solution of it in hydro- chloric acid, forms brilliant and nearly colourless, pointed laminm, sparingly soluble in cold, easily in hot water, freely soluble in hot alcohol, and decomposing at 220".The hydrochloride crystallises in minute needles, freely soluble in water, very sparingly so in alcohol. The sulphate also forms minute needles, having the same solubility. The triacetyZ-derivutzve, NHAc.C6H3:(NAc)z:C0, forms fine, white, silky needles, insoluble in water, fairly soluble in alcohol, and melting at 248'. NH,* CsH,: (NH),:CO, /NH*CO\ c 6 H 3 \ ~ ~ - ~ ~ / N 7 Dicarboity ltriainidobenzene, was obtained beating amidophenylene carbamide with liquid carbonyl chloride in aORGANIC CHEMISTRY. 47 sealed tube for eight hours at 130". The excess of carbonyl chloride was evaporated and the residue heated with water, which extracted the hydrochloride of the carbamide fo~med during the reaction, and left the carbonyl compound as a crystalline residue, insoluble in alcohol, ether, benzene, toluene, aniline, and acids, but very soluble in alkaline solutions, from which it is precipitated by acids.By passing nitrous acid through a cooled, acidified aqueous solution of the sulphate of amidophenylenecarbamide, yello wish-green crystals, giving the reactions of a diazo-compound of the carbamide, were obtained, but they were not pure. By dissolving them in hydro- bromic acid and adding a few drops of bromine, yellowish-red needles of the perbromide of the diazo-compound crystallised out- ; these lost bromine as they dried, and by digesting them with warm alcohol they weye converted into yellow crystalline laminm of the diazo- hroinide of amidophenylenecarbamide.By H. v. PECHMANN and I(. WEHSARG (Rer., 21, 2994 - 3004).-Nitrosoa~etonehydrazone (methylglyoxal-aw- hydrciz- oain2 e ) N,H Ph: CMe.CH:NO H, prepared by mixing nit rosoacetone (1 mol.) with phenylhydrazine (1 mol.) in alcoholic or ethereal solu- tion, crystallises from alcohol in yellowish prisms or needles, melts at 134", and is soluble in ether and benzene, but insoluble in hot water. It dissolves in concentrated sulphuric acid with a reddish-yellow colour which becomes deep blue on adding ferric chloride. Met hylglyoxalosnzone hydrochloride is obtained when the preceding compound is warmed with concentrated hydrochloric acid in alcoholic solution. It crystallises from boiling methyl alcohol, melts a t 197", and yields the free base (compare Abstr., 1888, 1287) when treated with ammonia.A. G. B. Hydrazoxirnes. Diacety Eli ydrazoxime (methylnitrosoacetone h ydraxone) , CMe(N,BPh)*CMe:NOR, prepared in like manner from nitrosometbylacetone, crystallises from dilate alcohol in large, colourless needles, melts at 158", and resembles nitrosoacetonehydrazone in its behaviour towards solvents. It dig- solves in concentrated sulphuric acid with a yellow coloration which changes to a bluish-violet on adding ferric chloride, and when heated with concentrated hydrochloric acid in alcoholic solution, yields a mixture of diacetylosazone melting at 241--242", and diacetyl- hydrazone melting at 13.3". Gl~/ox~Zcya?zide-a-hydrazone, CRO*C(N,HPh).CN, is formed, together with hydroxylamine, when dinitrosoacetonehytlrazone (com- pare this vol., p.34) is warmed with alcohol and hydrochloric acid. It crystallises from boiling alcohol in pale-yellow needles, melts at 161" with decomposition, and is dissolved on warming in most sol- vents except water. It is soluble in dilute alkalis, and dissolves in concentrated sulphuric acid with a yellow colour which is not changed by ferric chloride. When boiled with hydriodic acid, it yields the theoretical quantity of aniline. Glyoxy Zr y anideosazone, NZHP h:CH*C (N2HPh) *CN, prepared by mixing a hot, alcoholic solution of the preceding compound with48 ABSTRACTS OF CHEMICAL PAPERS phenyl hydrazine, cry stallises from alcohol in orange-red needles, melts at 161" with decomposition, and is soluble in alcohol and glacial acetic acid, but, only sparingly in most other solvents.The concentrated siilphnric acid solution is yellowish-red, and its colour is not changed bv ferric chloride. .I GlyoxylcyarLideosotetrazone, < ~ ~ ~ ~ ~ $ is formed when the preceding compound is m-armed with ferric chloride or with a solution of potassium dichromate and dilute acetic acid. It crystallises from acetone or alcohol in brownish-red, moss-like needles melting at 137" with decomposition. When heated with hydrochloric acid, a colour- less, crystalline product, probably an osotriazone (loc. cit.) volatilises. This compound, CgH6N@:N2Ph, is formed by the combination of glyoxylcyanidehydrazone with diazobenzene chloride ; it crystallises from alcohol in brownish plates, melts a t 162-163", and is insoluble in alkalis. Gll/ox?/lcZlanide-aw-hydrazox~~ne, NOH:CH.C(N,HPh).CN, prepared by boilicg an alcoholic solution of the hydrazone (1 mol.) with hydroxylamine hydrochloride (1 mol.) and a few drops of hydro.cliloric acid, crystallises from alcohol in citron-yellow, sparingly soluble needles melting a t 240" with decomposition. It dissolves in alkalis with a yellow coloration, but the yellow, concentrated sul- phuric acid solution is not changed on adding ferric chloride. A compound, C,H,N 4, is obtained when glyoxylcyanidehydrax- oxime is dissolved in phosphorus oxycbloride, heated with phosphoric chloride, the solution poured on to ice, the precipitated product ex- tracted with ether, dissolved in dilute alkali, and fractionally pre- cipitated with hydrochloric acid.It crystallises from a mixture of ether and light petroleum in yellowish needles, melts a t 135" with decomposition, and is soluble in hot water, alkalis, and most of the ordinary solvents. It dissolves in Concentrated sulphuric acid with a blood-red coloration which is not changed on adding ferric chloride. When warmed with concentrated hydrochloric acid or when boiled with alcoholic potash, it is converted into a ccmpouiid, C9H9N40, which crystallises in small, yellow needles melting a t 244-245". - A compound, C,,H,,N,, is formed i n the preparation of glyoxyl- cyanidehydrazone, and can also be obtained by heating the hydraz- oxime with alcohol ( 3 patbts) and cmcentrated hydrochloric acid (10 parts). I t crystallises from benzene in shining, orange-yellow plates melting a t 165", and does not give the osazone reaction (loc.cit.). MethylgZyoxal-ocw-met?~Zl~hen~~l~iy~~raz~~~~e, N,MePh:CMe*CH:NOH, prepared by mixing an aqueous solution of nitrosoacetone with a solution of methylpbenylhydrazine sulphate and sodium acetate, -crystallises from dilute alcohol in orange-yellow prisms melting at 118". Alkaline solutions are dark yellow, and the yellow, concen- trated sulphuric acid solution changes to violet on adding ferric chloride. Mesoxala7deh yde- a w w-n7 eth y lphen y lh ydrazonedioxim e (dinitrosoaceton e methylphenylhydruzolze), N OH:CH.C(N,MePh)*CH:NOH, prepared in like manner, crystallises from dilute alcohol in orange-yellow ueedlesORGANIC CHEMTSTRY.49 or plates, melts a t 137", and is soluble in alkalis and most of the ordinary solvents. It dissolves in concentrated sulphuric acid, forming a brownish-red solution in which ferric chloride produces a light violet coloration. When heated with hydrochloric acid, it yields decomposition products the nature of which varies according to the conditions of the experiment. Glyoxylcyanide-a-msfhyZphenylhydrnzone, CHO*C(N,MePh).CN, is obtained by dissolving the preceding compound in acetone ( 7 parts), adding concentrated hydrochloric acid (7 parts) and, after the first energetic reaction is a t an end, heating the mixture for about a minute and adding water to the cold solution. It crystallises from benzene, alcohol, or light petroleum in yellow, feathery needles, or thick, spear-shaped crystals, melts a t 113*5", and is insoluble in alkalis.When mixed with phenylhydrazine, it yields a compound, probably N,HPh:CH.C (N,MePh) CN, which crystalliseq from abso- lute alcohol in golden-yellow plates melting a t 181". The and, NPh:CH*C (X,MePh).CN, prepared by mixing the hpdrazone with aniline i n acetic acid solution, crystallises from alcohol in slender, yellow needles, melts a t 150-151°, and is reconverted into the hy$hzone when warmed with dilute hydrochloric acid. The hydrar- oxz112e, NOH:C H*C (N,MePh).CN, obtained by treating the hydrazone with hydroxylamine, crystallises in small, yellow needles melting at 178'. The acetyl-derivative, NOAc:CH*C(N,MePh).CN, of the hydrazoxime crystallises from alcohol in yellow needles, melts a t 122*5", and is reconverted into the hydrazoxime when boiled with soda.F. S. K. Ethyl Phenylhydraxineacetylacrylate. By H. D ECICER (Ber., 21, 2937-2938).-Tbe compound obtained by Bender (Abstr., 1888, 1188) by hydrolysing ethyl phenylhydrazineacetylacrylate, has already been fully described by L. Wolff (Abstr., 1887, 464). F. S . K. Theory of Dyeing. By E. KNECHT (Ber., 21, 2804-2805 ; com- pare Abstr., 1888, 832).-When wool is boiled with a mixture of sulphuric acid (2 parts) and water (3 parts) for two hours, it dissolves almost entirely ; when filtered, a clear, light-brown solution is ob- tained. If this is mixed with aqueous solutions of acid coal-tar dyes, intensely coloured precipitates are formed, which dissolve readily in alkalis, but not in water or dilute acids.A solution of silk in moderately dilute sulphuric acid behaves in like manner. Animal fibres, therefore, yield a substance which forms insoluble bases with acid coal-tar dyes; it has not yet been deter- mined whether this substance already exists in the fibres, or whether it is gradually formed by the action of the acid bath. N. H. M. Product of the Action of Nitric Acid on Acetophenone. By A. F. HOLLEMAR" (Bei-., 21, 2835-2840 ; compare Abstr , 1888, 275). -The molecular weight of the compound C,,H,,N,04. obtained by the actioii of nitric acid on acetophenone (Zoc cit.), was confirmed by a determination by Raoult's method (BPT., 21, 861). When the alco- holic solution is reduced with stannous chloride, benzoic and hydro- VOL.LVI. e50 ABSTRACTS OF CHEMICAL PAPERS. cyanic acids are formed. By qrolonged boiling with strong hydro- chloric acid, it is decomposed into benzoic and oxalic acids; am- monia and hydroxylamine are also formed. These reactions make it probable that the compound has the constitution <CBaiN.O>, CBz'N-0 which is further supported by the fact that the substance, which is named diphenyldi.nitrosacyl, can be prepared by oxidising nitroso- acetophenone. Diphenjldinitrosacyl reacts with aniline with formation of benz- anilide and a compound crystallising in lustrous, brown needles. When this is heated a t 100" €or some time, it gives an odour somewhat like that of carbylamine : when crystallised from dilute alcohol, it is nearly white, and melts a t 205".When diphenyldinitrosacyl is heated with acetic anhydride at 110-120" for six hours, the compound C,6H10N204 + OAc, is formed. This crystallises in stellate groups of needles melting at 149". The sparingly soluble compound melting at 177-179", which is also obtained by the action of nitric acid on acetophenone (loc. cif.), has the same empirical composition as diphenpldinitrosacyl ; it is, how- ever, much more stable than the latter. Boiling aqueous potash and hot sulphuric acid decompose it, yielding benzoic acid ; with potash, ammonia is evolved. N. H. M. Consecutive Duryl Methyl Ketone. By A. CLAUS and E. FOHLISCH ( J . pr. Chew. [a], 38, 230-235; compare Abstr., 1888, 275) .-The boiling point of consecutive dureno is 199-200" (uncorr.) and its melting point is -4".Consecutive duryl methyl ketone, C6HMe4*COMe [Me4 : COMe = 2 : 3 : 4 : 5 : 11, is prepared in the manner previously described, by which 80-90 per cent. of the durene used is couverted into the ketone ; it is a brown, strongly refractive oil, of agreeable aromatic odour, boiling a t 258-260" (uncorr.), and easily soluble in the nsual solvents, except water. The pkenylhydrazine compound forms,, colourless laminae melting a t 129" (uncorr.). 2 : 3 : 4 : 5 - 1 ' e t r a m e t h y ~ ~ ~ e n y ~ g l y o a y ~ i c acid, C6Hh!fe4*CO*COOH, is formed when the above ketone is oxidised with potassium perman- ganate in the cold. It is a bright yellow syrupy oil, very little soluble in cold, more so in hot water, very soluble in alcohol, ether, carbon bisulpliide, and chloroform ; it solidifies on prolonged cooling and decomposes when heated. The barium and calcium sa2ts (with 4 mols.H,O), the copper (with 3 mols. H,O), azd the silver salts are described. 2 : 3 : 4 : El-Tetramethylmandelic acid, C6H%~e4.CH(OH)*COOH, is obtained by reducing the foregoing acid with sodium amalgam. 'It crystallises from alcohol in colourless hexahedra, sparingly soluble in cold, readily in hot water and in alcohol, ether, and chloroform, and meits at 160" (uncorr.). The potassium (with 4 mols. H,O), barii~m (with 3 mols. H,O), calcium (with 24, mols. H,O), and silver salts are described. 2 : 3 : 4 : 5-Tetrainethy123herz2llacstic acid, C6HMep-CHz.COOH, is formed when either of the above described acids is reduced withORGANIC CHEMISTRY.51 hydriodic acid. It crystallises from hot water in slender, colourless needles, me1 ting a t 125" (uncorr.), and easily soluble in alcohol, ether, and chloroform. The calcium salt forms colourless, silky needles con- taining 3 mols. H,O. By oxidising consecutive duryl methyl ketone or the foregoing de- rivatives, with the calculated quantity of potassium permanganate, at a gentle heat, 2 : 3 : 4 : 5- tetramethylbenzoic acid is obtained as a thick, colourless oil, sparingly soluble in water, freely so in other sol- vents. When heated, it decomposes a t 270°, and an oil distils over, which solidifies and melts at 150" ; this contains 73.8 per cent. of carbon and 7.9 per cent. of hydrogen. The sodium (with 3 mols. H,O), calcium (with 3 mols.H,O), bariunc (with 6 mols. H,O), silver and coypel- salts are described. A. G. B. Stilbene. By I;. ARONSTEIN and A. F. HOLLEMANN (Ber., 21, 2831-%334) .-The experiments described were made with a vicw to obtain a geometrical isomeride of stilbene which should exist according to Wislicenus' theory. No definite results were obtained, but the investigation is being continued. Action of Heat on Benzildihydrazone. By I(. AUWERS and V. CPh'N M E ~ R (Ber., 2 1,2806 -2 80 7). --Tripheny losotriazone, < CPhiN >NPh, formed when benzilhydrazone is heated with alcohol at 200-210", crystallises in white, lustrous plates, melts a t 122O, and boils without decomposition. N. 13. M. Thio-derivatives of p-Dinaphthylamine. By 0. KYN (Ber., 21, 2807-28 13) .-When sulphur chloride dissolved in benzene is added to /3-dinaphthylamine, also dissolved in benzene, hydrogen chloride is evolved and two isomeric dithiudinaphth ylainines, C20H13NS2, are ob- tained.The one forms lustrous, brass-coloured plates melting a t 205O, whilst the other crystallises in reddish-yellow prisms melting a t 220". Both compounds are sparingly soluble. When the dithio-compounds are boiled with cumene or with aniline, they are both converted with evolution of carbon bisulphide into Ris's thio-P-dinaphthylamine (Abstr., 1886, 1036). A small quantity of the latter compound is formed in the reaction between dinaphthylamine and sulphur chloride. Acetylthio-p-dinnphthylainiwe, Cz2Hl5NOS, is obtained by the action of acetic anhydride on the dithio-compound (ni.p. 605") or on the monothio-compound. It crystallises in slender, lustrous, almost white needles, melts a t 211", and is readily soluble in hot alcohol or benzene. When the dithio-compound (m. p. 205O) is treated with an ammoniacal alcoholic silver solution, a compound free from sulphur is obtained, which melts a t 240°, and sublimes in slender, lemon- yellow needles. Sulphur dichloride acts on p-dinaphthylamine, yielding as chief product thio-p-dinaphthylamine, and a sparingly soluble isomeride which melts a t 303". Sometimes a small amount of a compound, probably thiotetranayhthylanline, S ( C,oH6*NH.CloH7)2, is obtained. This forms dark-yellow crystals melting at 307". N. H. M. N. H. M. e 252 ABSTRACTS OF CHEMICAL PAPERS. Naphthoic Acids. By A. G. EKSTRAND (J.pr.Chem. [2], 38, 139--285).-This paper is a summary of the author's work on the subject; much of it has already appeared. The following new corn- pounds are described :- Chloro-a-naphthoic arnide is obtained by heating chlopo-a-naphtho- nitrile (Abstr., 1884, 1361) with an alcoholic solution of potassium hydroxide ; it forms crystalline laminae, soluble in alcohol and melting a t 239". The chloro-a-naphthoic acid which melts a t %5" (Abstr., 1884, 1361) has the constitution [COOH : C1 = 1 : 4'1, as it is obtained by treating 1 : 4' amido-a-naphthoic acid by Sandmeyer's method (Abstr., 1884, 1312). Chloro-a-nayhthoic a,cid (1 : 1') is obtained when 1 : 1' amido-a- naphthoic acid (Abstr., 1885, 549) is dissolved in the calculated quantity of sodium hydroxide and potassium nitrite (1 mol.to 1 mol. of the amido-acid) added ; the mixture is cooled to 0" and treated with excess of hydrochloric acid. The hydrochloride of the diazonaphthoic acid thus obtained is added to a boiling solution of cuprous chloride in hydrochloric acid ; colourless crystals of the chloro-acid are formed ; they melt a t 167" and sublime as plates. The calcium salt crystallises with 2 mols. €LO in long tabular needles, soluble in 42 parts of water at the ordinary temperature. The ethyZ salt forms long needles melting at 50". Dichlor-a-naplithoic acid is obtained when the foregoing acid is dissolved in glacial acetic acid, some iodine added, and chlorine passed t o saturation ; crystalline scales separate, melting at 186-187". The calcium salt crystallises with 2 mols.H,O in long, colourless needles ; the ethyl salt forms fine needles melting at 61". It is possible to obtain this acid from chlornitro-a-naphthoic acid [COOH : NO, : C1 = 1 : 1' : 4'1 (Abstr., 1886, 156), consequently its constitution is [COOH : C1 : C1 = 1 : 1' : 4'1. Trichloro-a-nap hthoic acid, the mother-liquor from the preparation of chloro-a-naphthoic acid (1 : 4') by the action of chlorine on a-naph- thoic acid in acetic acid solution, is saturatedwith chlorine at the boiling point : dilution with water then throws down a crystalline precipitate, which is heated with calcium carbonate, filtered, and the filtrate pre- cipitated with acid ; when crystallised from alcohol and water, this precipitate forms small, colourless needles, melting at 163-164' and subliming in fine needles.The ethyl salt of monobromo-a-naphthoic acid, 1 : 4' (Abstr., 1886, 715), forms colourless tables melting a t 48-49'. Mononitro-a-naphthoic acid of meltiug point 215" (Abstr., 1885, 54$) is soluble in 21.5 parts of commercial alcohol, and in 2590 parts of water a t the ordinary temperature. During its formation a small quantity of a-mononitronaph.t//alene (melting point 60') is obtained. The calcium salt of amido-a-naphthoic acid (Absbr., 1885, 549) crystallises with 9.5 mols. H20 in fine needles, soluble in water. The hydroch Zoride, COOH.C,oH6*NH,,HC1, is precipitated in fine needles O n adding hydrochloric acid to a solution of the sodium salt. Nsphthostyril, C,,H,<ZE> (Abstr., 1886, 715), crystallises fromORGANIC CHEMISTRY.53 an alcoholic solution of the amido-a-naphthoic acid ; it is also formed when the acid is heated with water ; it melts a t 180-181". The benxoyl-derivative forms slender needles melting a t 170" ; the hydrochloride melts a t 178". a-Naphtlzoybz aph thostyri1.-When a-naphthoyl chloride and naph - thostyril are heated together, a gi-een product is formed, which is dissolved in alcohol and decolorised hy animal charcoal. A mixture of granular crystals (melting a t 110") and needles (melt- ing at 132") is obtained ; by recrystallking these, partly from alcohol and partly from glacial acetic acid, a mixture of the same crystals is obtained, melting a t 150". /3-Naphthoylnaphthostyril, is obtained in the same way tw tlie above, only a t a lower temperature, in slender colourless needles, melting at The calcium salt of chlornitro-a-naphlhoic acid, of melting point 225" (Abstr., 1886, 156), forms slender colourless needles, crystallising with 3 mols.H,O, and the ethyl salt tabular crystals melting at 121", and very soluble in alcohol. The question whether this acid has the constitution [COOH : NO, : C1 = 1 : 1' : 4' or 1 : 4 : 4') is settled in favour of the former, as chZoronaphthostyJriB (with C1 in position 4') is obtained in yellow needles melting at 670", by reducing the acid with ferrous sulphate in an ammoniacal solution. Nitronaphthostyril (1 : 4') is formed when nitric acid (sp. gr. 1.42) is added to a solution of naphthostyril in glacial acetic acid, and the mixture heated on the water-bath ; the crystalline mass thus obtained is partially soluble in alcohol, from which yellow needles, melting about 235", are obtained ; the greater part recrystallises from glacial acetic acid in orange-yellow needles melting a t 300".Both are nitro- nap hthostyrils. Arraidonuplzthostllril is formed when nitronaphthostyril is reduced with tin and hydrochloric acid. and the hydrochloride thus produced decomposed with ammonia ; it crystallises in red needles melting a t 239-240", and freely solable in alcohol and hot water: The hydro- chloride crystallises in yellow needles melting above 290". Dinitronaphthostyrd is obtained when the nitronaphthostyril is heated with nitric acid (1.43 sp. gr.) ; it forms yellow needles, or, when pre- pared by the action of nitric acid on naphthostyril, rhombic tables, melting above 290".Naphthostyrilpuinone, C,,H,O,<EE>, is obtained when a Bolution of naphthostyril in glacial acetic acid is mixed with chromic acid and then with water; fine red needles are precipitated, which, after re- crystallisation from glacial acetic acid, melt near 278". When it is dissolved in warm glacial acetic acid and an acetic acid solution of toluylenediamine added, a yellow, crystalline powder, consisting of nuphthostyriZtoZ~p~inoaali.ne, CllH5N30,C6H3CH3, is obtained ; it melts above 290". Nitronaphthosty1.ilquinone forms orange-red needles or tables, melt- ing near 685", soluble in alcohol and sparingly so in glacial acetic acid. A. G. B. 19 7-198". The acetyl-derivative melts above 290".54 ABSTRACTS OF C'HERIICAL PAPERR p-Chloronaphthalenesulphonic Acid.By S. FoRsrmG (Be?.., 21, 2802--2804).--When ,!3-amidonaphthalenesulphonic acid (Abstr., 1887, 962) is converted into the diazo-compound, and this is boiled with strong hydrochloric acid and neutralised with potassium carbonate, potassi um p-chloronapht h alenesulph onate separates. p- Chloronaph thalenesulphonic chloride, CloH6C1*SO2C1 (Arnell, Ahstr., 1886, Fj55), is prepared by mixing the well-dried potassium salt with phosphorus pentachloride and heating ; it crystallises from chloroform in broad needles melting a t 129". The brornide, CloH6C1*S 02Br, prepared by the action of phosphorus bromide on the potassium salt, crystallises from chloroform in small needles melting at 139". The amide, CIoH6C1.S02*NH,, is obtained by boiling the chloride with a mixture of equal parts of ammonia and alcohol, and crys- tallising the product from dilute alcohol, in which it is sparingly soluble; it melts at 235". p-Chloronaphthalenesulphonic acid has the constitution [Cl : SOsH = 2 : 4 o r 2 : 1 ] .N. H. M. Filicic Acid. By G. DACCOMO (Bey., 21, 2962-2970) .-Filicic acid, prepared by the method already described (Daccomo, Abstr., 1888,521) , has the composition Cl4H1,O6. It is a yellowish, odonrless, crystalline powder, melts at 179-180" (uncorr.), and. is insoluble in water, almost insoluble in absolute alcoho1,'moderately soluble in glacial acetic acid, ether, amyl alcohol, and toluene, and readily in chloroform, cwbon bisulphide, and benzene. The benzoyl-deriva tive, C2,H,,0,, separates from dilute alcohol in colourless crystals, melts a t 123", and is very readily soluble in ether, but insoluble in water.The ethyt salt, C,H,,O,, prepared by treating the acid with alcoholic potash and ethyl iodide, separates from dilute alcohol in reddish crystals, melts at 142", and is very readily soluble in ether and benzene, but insoluble i n water, The propyl salt melting at 158", and the ethylene salt melting at 165", resemble the ethyl salt in appearance and solu- bility. Bronzo$Zicic acid, Cl4HI5BrO6, prepwed by treating the acid with bromine in glacial acetic acid solution, crystnllises from alcohol in red prisms, meits a t 122", and is very readily soluble in absolute alcohol and ether, but insoluble in water. AniZidoJiZicic acid, C14HZ50,*NHPh, obtained by boiling a glacial acetic acid solution of the acid with aniline, separates from alcohol in reddish-violet crystals, melts a t 140°, and is soluble in alcohol and benzene, but insoluble in water.The hydraaide, C,Hl,O.( NZHPh),, prepared by boiling an ethereal solution of the acid with phenylhydrazine, crystallises from ether ill red needles, melts at 198", and is readily soluble in alcohol, but insoluble in waker. When the acid (100 parts) is heated above its melting point (compare Luck, AnnaZen, 54, 119), or heated with water at 170-190", it is decomposed into isobutyric acid (32.5 parts) and a compound, the composition of which is C?OH,AOI. Hydrochloric acid produces the same decomposition at 150-160". Filicic acid is completely oxidised when treated with chromic acidORGANIC CEIEMISTRT.55 in glacial acetic acid solution, but when a solution of the potassium salt is oxidised in the cold with a 2 per cent. solution of potassium permnnganate, isobutyric acid and oxalic acid are obtained. Tbe same products are formed when nitric acid of sp. gr. 1.48 is employed. When the acid is treated with zinc-dust in alkaline solution, i t is con- verted into an acid, the composition of which is probably Cl4Hz2011, and at the same time a small quantity of isobutyric acid is formed. When treated with sodium in amyl alcohol solution, it, yields butyric acid and resinous products. The compound CZOH,80,, referred to above, separates from ether or amyl alcohol as an amorphous, red powder, and has no well-detined melting point.It is soluble in most ordinary solvents, has an acid reaction, decomposes carbonates, and dissolves in alkalis, forming red solutions from which it is precipitated in red flocks on adding acids. It yjelds phthalic acid and small quantities of ovalic acid when oxidised with nitric acid of sp. gr. 1.40 in the cold. When reduced with zinc-dust in alkaline solution, it gives a colourless substance which rapidly oxidises, and is probably reconverted into the original compound. From the above results, it follows that filicic acid is probably an isobutyric acid derivative of hydroxynaplithaquinone. F. S. K. Quillajic Acid. By R. KOBERT (CYhesn. Centr., 1888, 927-928, from Arch. ex$. Path. Pharm., 23, 233).--The saponin of commerce, as all other specimens of saponin, is an almost inactive, non-poisonous modification of quillajic acid.The author precipitated the acid from the aqueous extract of the bark of Quillaja sapomaria with neutral lead acetate ; the precipitate was fresd from lead, the solution of the acid evaporated almost to dryness, and then taken up with hot absolute alcohol. The colouring matter was precipitated with chloroform ; the quillajic acid eventually crystallised out in pure white flakes. It is insoluble in ether, soluble in water and alcohol. On treatment with concentrated sulphuric acid, it becomes dark red. By boiling with dilui e mineral acids, it is split up into an unfermentable glucose and sapo- ginin ; this solution reduces Fehling's solution. Quillajic acid has the formula Cl,H,oOlo.The sodium salt acts as a very severe caustic on the tongue and throat, and the smallest particles coming in contact with the nose or throat cause violent sneezing and coughing. Brought on to the eye, it causes severe pain, flow of tears, and swelling of the lids. Injected into the blood, the sodium salt proves fatal, causing cramp arid paralysis of the respiratory organs and brain. On the other hand, it may be imbibed into the stomach without injury to the extent of 500 times the quantity which proves fatal when injected into the blood. J. W. L. Brazilin. By C. SCHALL and G. DRALLE (Bey., 21, 3009-3017, compare Abstr., 1888, 295) .-Tetramethylbrazilin is best prepared as follows:-A solution of brazilin (100 grams) in warm 98 per cent. alcohol is mixed with sodium ethoxide (30.26 grams sodium) and methyl iodide (206 grams), the mixture kept a t 60-70" for 40 to 50 hours, cooled and poured into cold water.The precipitate is collected,56 ABSTRACTS OF CHEMICAL PAPERS. washed with water, dissolved in ether, the solution shaken with soda ( 1 7 2 per cent.), washed with water, the ether evaporated, and the residue crystnllised from alcohol with addition of animal charcoal. The yield is 58.5 per cent. of the theoretical quantity. Trirnethylbrazilin, C16H1105Me3 + iH,O, is obtained by neutralising the alkaline washings from the tetramethyl-derivative, extracting with ether, washing the extract first with sodium hydrgen carbonate, then with sodium carbonate, and evaporating the ether a t the ordinary temperature. The residue is mixed with concentrated soda, the pre- cipitated sodium-derivative collected, washed with alcoholic ether, dissolved in water, and precipitated from the filtered solution by treat- ment with carbonic anhydride.If the product is pure, it is obtained in the crystalline condition containing about 1 mol. H,O, but the impure compound does not crystallise well even after keeping for months. It dissolves in dilute alcohol, and the solution gives a brown precipitate with ferric chloride ; the solution in soda is colourless, and does not alter on keeping. The acetyl-derivative, C16H,,05Me,Ac, is crystalline, and melts a t 95-97" with previous softening. Rrornotetrainethylbrazilin, C16H9BrMe40,, obtained by treating the tetramethyl-derivative (1 mol.) with bromine (1 mol.) in glacial acetic acid solution, crystallises from dil-cite alcohol in long, colourless prisms melting a t 180-181".A crystalline tetrabromo-derivative, C,,H,Br,Me,O,, is formed when a larger quantity of bromine (2-3 mols.) is employed ; this snbstance loses bromine (about 26 per cent.) when treated with dilute ammonia, or soda, and appears to be dibromotetramethylbrazilin dibromide. It is probable that other bromo-derivatives exist, and a crystalline iodo- additive product was also obtained. Tribrornobrazilin dibyomide, C16HllBr305,Br2 + 2H20, is obtained in reddish-brown needles when bromine (4-6 mols.) is added gradually to a boiling glacial acetic acid solution of brazilin. A compound, C20Hld09, is obtained when brazilin (2.7 grams) is dissolved in water (150 c.c.) and soda of sp. gr.1.37 (10 c.c.), and a stream of air passed through the solution for about 36 hours. It crystallises from alcohol in light brown, flat, microscopic needles, melts at &71", and is readily soluble in dilute soda, sparingly soluble in ether or sodium carbonate, and insoluble in sodium bicarbonate. The aqueous alcoholic solution gives a slight violet coloration with ferric chloride, and a citron-yellow coloration with concentrated nitric acid. When heated above its melting point, shining scales sublime, but considerable' decomposition takes place. F. S. K. Nomenclature of Compounds containing Nitmgenous Nuclei. By 0. WIDMAN ( J . pr. Chem. [a], 38, 185-20l).-A new system of nomenclature for the quinoxalines and compounds of allied structure.(Compare Mason, Proc., 1888, 109.) Metapyrazolones. By E. GRINAUX (BUZZ. SOC. C'him., 49, 739- 740) .-The compounds described by Pinner and Lifschutz, and named by them metapyrazolone-derivatives, are derivatives of glycolylcarb-ORGANIC CHE3IIISTRY. 57 amide or hydantojin, and the isomeric substances which Pinner and Lifschutz name metapyrazole-derivatives are simple ureides. P. S. K. Action of Phenylhydrazine and Hydroxylamine on Acetyl. acetone. By A. COMBES (Bull. SOC. China., 50, 145-146 ; compare ibid., 48, 471) .-Dimethy~hei.ly~yrazole, CMe<Nph,N>CMe, is formed by the action of phenylhydrazine on acetylacetone : it boils at 270.5". Derivatives of Methylpyrroline. By G. DE VARDA (Ber., 21, 28 7 1-28 74) .-MethyZtetrabromo~yrrol~ne, C4NBr4Me, obtained by digesting tetrabromopyrroline with caustic alkali and methyl iodide dissolved in methyl alcohol, crystallises from light petroleum in long, colourless needles, which melt at 154-155" to an intensely blue liquid.Dibromomaleinmethy limide, C4Br,0zNMe, is prepared by slowly adding tbe above t,etrabromide to fuming nitric acid (3 parts), cooled to 0", and pouring the product into water (10 parts). It crystallises from boiling water in long, light-yellow needles melting a t 121". It distils readily with steam ; the vapour has an irritating odour. N e t h y k y r r y lg Zy ozy Zic acid, CaNH,Me-CO*COOH, is obtained by treating a boiling solution of methylacetylpyrroline (5 grams) in alkaline water (500 c.c.) with a solution of potassium permanganate (15.5 grams) in water (500 c.c.).The whole is boiled, steam-distilled, and filtered ; it is then evaporated down, acidified, and extracted with ether. The acid is crystallised from benzene, from which it separates in light-yellow needles which melt a t 141-142.5' with decomposi- tion; it is sparingly soluble. The silver salt was prepared, The dibromo-derivatice, C4NHIMeBr2*CO*COOH, prepared by brominating the acid dissolved in acetic acid, crystallises from benzene in small, sulphur-coloured prisms melting a t 160". When the dibromo-acid is slowly added to fuming nitric acid (10 parts), dibromomalei'n- methvlimide is formed. The bromine-atoms and the --CO*COOH CH-- (Compare Claisen, Abstr., 1888, 692 ; and Zedel, 1051.) N. H. M. grou; have, therefore, the positions 3, 4, and 5 respectively.N. H. M. Derivatives of Unsymmetrical Dimethylpyrroline. By G. MAGNANINI (Ber., 21,2864-2868, 2874-2879) .-Ethy I diwethylasetyl- pyrrolinecnrboxylate, C4NHMe2Ac*COOEt [ 2 : 4 : 5 : 31, prepared by heating ethyl hydrogen dimethylpyrrolinedicarboxylate (Know, A n d e n , 236, 318) with acetic anhydride at 'LOO", crystallises in needles, melts at 142-143", dissolves very readily in alcohol, etlier, acetic acid, and benzene, &c., sparingly in light petroleum. The f r e e acid obtained by boiling the ethyl salt with aqueous potash, melts at about 152-158Owith formation of dimethylacet~I-pyrroZine and evolution of carbonic anhydride, is almost insoluble in boiling water, very sparirigiy soluble in ether, chloroform, and benzene, and readily soluble in hot acetic acid, from which it separates in long, lustrous needles.It gives a green coloration when heated with isatin and sulpbnric acid. DimethyZacety~yl.roZine, C4NH,MezAc [ = 2 : 4 : 51, is prepared by distilling dimethy lacetylcarbopyrrolic acid in a retort heated in a58 ABSTRACTS OF CHEMICAL PAPERS. metal-bath a t ZOO". It is first crystalliscd from water containing a little sodium carbonate, then from dilute alcohol, and lastly from light petroleum. It melts a t 122-123", sublimes a t loo", and is readily soluble in the usual organic solvents. Dimethylpyi-rolinedica.l.boxylic acid irnineanhydride, c O / y M e \c . c 0 OH, 'N*C Me/ is obtained by boiling Knorr's unsymmetrical dicarboxylic acid (Abstr., 1887, 275) with acetic anhydride (10 parts) in a reflux apparatus for three to four hours.The acetic anhydride is distilled off under diminished pressure, the residue washed with alcohol, dis- solved in aqueous sodium carbonate, filtered, and precipitated with acetic acid. It is almost insoluble in the usual solvents, becomes slightly brown a t 300", and decomposes a t a higher temperature into dimethylpyrroline and dimethylpyrocoll. It resists the action of mineral acids, but seems to be pastially decomposed by aqueous ammonia. The silver salt is a yellowish, amorphous substance ; the m a p e s i u m saZt forms lustrous needles. The ethyl salt crystallises in thread-like needles, melts a t 270", and is sparingly soluble. 2, 4-DiiizethylpyrocoZZ, C7H7N0, obtained by distilling the copper or silver salt of the above acid in a stream of carbonic anhydride, is light, yellow, melts a t 272--272*5", dissolves very readily in chloroform, readily in acetic acid, but only sparingly in ether, light petroleum, and cold alcohol ; it is insoluble in water.The crystals are rhombic ; cc : b : c = 0.788:-(4 : 1 : 0.94606. The compound is hardly attacked by aqueous potash. N. H. M. Derivatives of Pyrrolinephthalide. By F. ANDERLINI (Bey., 21, 2869-2870) .-Dibromopyrrolinephthalide, C,,H5Br,NO2, .prepared by treating a warm solution of pyrroliuephthalide (2 grams) in glacial acetic acid (15 grams) with bromine (8 grams), crystallises in small, yellow, lustrous needles, melts at 199", is insoluble in water, sparingly soluble in boiling alcohol and ether. Nitropyrroli.,iep7itAalide, C,,H6N2O4, is formed when the phthalide is dissolved in strong nitric acid ; it crystallises from alcohol in needles.When pyrrolinephthalide is treated with bromine in alkaline solution, tetrabromopyrroline and phthalic acid are formed. On similarly treating the dibromo- and nitro-derivatives, both compounds yield phthalic acid; the substituted radicles are therefore in the pyrroline nucleus. When potassium pyrrolinephenylcarbinolorthocarboxylate, CINH3:C (0 H) *c6H4.co~K, is distilled with potassium carbonate, it is decomposed into pyrroline and benzene. N. H. M. Action of Methyl Iodide on some Pyrroline-derivatives. By G. CIAMiCraN and F. ANDERLlNr (Bey., 21, 2855--2864).-Dihydro- tetl.ainethyl~,llridine, C9kI15N, is obtained, together with other bases,ORGAN I0 CHEMISTRY.59 when sodium carbopyrrolate (5 grams), methyl iodide (10 grams), and methyl alcohol (7 grams) are heated a t 120" for 12 hours. It boils a t about 160". The aurochloride, CgH15N,HAuC14, crystallises from very dilute solutions in long, flat, monoclinic needles ; a : b : c = 54: 10 : 5 i ; j? = 85%. When the base is reduced with sodium and alcohol, the compound C&HI9N is formed. This boils a t 150-152°. The azirochloride separates from its solution as an oil, which crystal- lises after some days in yellow needles melting a t 117-119". When the base C,HlgN is boiled with methyl iodide in a, reflux apparatus, and the product, freed from tlhe excess of methyl iodide, is dissolved in alcohol and precipitated with ether, the compound CI9Hl8NMeZI is obtained in colourless prisms which melt at 262".It is very readily soluble in water, insoluble in ether. The mother-liquor from the di- methyl compound contains a small amount of a buse, C9HI8NMe, which forms an oil. MetliyZL~il~yd70~2/0^roZine, CloHl7N, is prepared by heating methyl- pyrroline (3 grams), methyl iodide (7 grams), potassium carbonate (3 grams), and methyl alcohol ( 5 grams), for 10 hours ah 140". The oily product is heated with strong hydrochloric acid at, 125-130", and distilled with potash. The aurochloride, Cl7HI7N,HAuCI4, crystal- lises from dilute hydrochloric acid in flat, yellow needles, which melt at 100". N. H. M. Dipiperidyl and Dipicolyl. By F. B. AHRENS (Eey., 21, 2929- 2932).-Dipiperidyl is obtained when pi-dipyridyl is reduced with sodium and alcohol and the product purified by means of the nitroso- derivative.It crystallises in colourless needles, melts at 120-122" with previous softening, and is readily soluble in alcohol and ether, but insoluble in water. It absorbs carbonic anhydride when exposed to the air, and is only slighhly volatile with steam. The pkr,tiv,o- chloride, CloH,,M,,H,PtC16, forms microscopic crystals, is only sparingly soluble in water, and blackens when heated a t 195". The aurochloride, CloH,N2,HAuC14, crystallises in small, yellow needles, is readily soluble in hot, dilute hydrochloric acid, and is gradually decomposed when heated a t about 160". The p i c r a t e crystallises from hot water in needles ; it blackens when heated, and is completely decomposed at about 257".Mercuric chloride,. phosphomolybdic acid, and potas- sium ferroqanide produce precipitates in a solution of the hydro- chloride. DipicoZyZ, CI2Hl2N2, is obtained when picoline, boiling a t 128-1 34", is treated with sodium at 80-90". After washing the product with water, it is dissolved in ether, the solution filtered, and the base ex- tracted wit8h dilute hydrochloric acid. The extract is mixed with excess of soda, the treatment with ether and hydrocliloric acid repeated several times, and finally the ethereal solution is dried over potash and evaporated. The residual yellow oil is then distilled, and the portion passing at 270-300" collected ; this dist,illate solidi- fies to a mass of yellowish, very deliquescent needles. The platino- chloride, C12Hl,N2,H2PtC16, crystallises in small plates, and is very sparingly soluble in water, but readily in hydrochloric acid ; it, is only partially decomposed when heated at 2 75".The aurochloride,60 ABSTRACTS OF CHEMICAL PAPERS. C1,H,,N2,HAnC14, separates from warm, concentrated hydrochloric acid, in which it is readily soluble, in nodular crystals mixed with metallic gold ; it is completely decomposed when heated a t 200-201". The picrate forms yellow, moss-like crystals, and is readily soluble in hot water. An aqueous solution of the hydrochloride gives precipi- tates with mercuric chloride, phosphomolybdic acid, potassium iodide, and potassium ferrocyanide. Action of Chlorine on Hydroxyquinoline. By H. HERhRRAND (Ber., 21, 2977 - 2989).- Chlcrrhyd,.uxyqztinoline, CgNH,OCl, is formed in small quantities when chlorine is passed into a well-cooled solution of 1-hydroxyquinoline ( 5 grams) in glacial acetic acid. Dichlorhydroxyquinohne (see below) separates a t hst, and is further converted into the hydrochloride whilst a further portion of the hydr- oxyquinoline is oxidised t o the rnonochloro-derivative. As soon as the whole of the hydroxyquirioline 1s changed, the solution is filtered and the residue treated with absolute alcohol to dissolve the dichlorhydroxy- salt. The residue is dissolved in hot, dilute hydrochloric acid, the solution mixed with excess of sodium carbonate, and the precipitated monochlorh ydroxy-compound recrystallised fram methyl alcohol and light petroleum. It is thus obtained in colourless needles melting a t 129-130'.The hydrochloride crystallises in small, yellow needles, melts a t 253", and is moderately soluble in alcohol and hot, dilute hydrochloric acid ; it is very stable and sublimes in compact crystals. The platinochbride, (C9NH60C1)2,H2Pt C1, + 2H20, crystallises in yellow needles, and is readily soluble in hot but only sparingly in cold, dilute hydrochloric acid. DichZorhydroxyqzLinoZine, CgMH4C12*OH [OH : CI, = 1 : 2 : 41, is prepared by passing chlorine into a 10 per cent. glacial acetic acid solution of hydroxyquinoline until the colour changes to yellow, pouring the solution into water, and recrystallising the precipitated product from alcohol. It is also obtained when t~ichloroketoqu~noline (see below) is treated with hydrogen sodium snlphite or boiled w i t h alcohol or dilute acids.It crystallises in long, slender needles, melts at 179-180", and is readily soluble in warm alcohoi or glacial acetic acid, but only moderately in hot benzene and light petroleum. It dissolves readily in alkalis and acids, forming yellow solutions, but the salts are unstable and cannot be recrystallised, and acid solutions are precipitated by water. When treated with chlorine in chloroform solution, it is converted into trichloroketoquinoline, The h y d ~ o - chloride crgstallises in long, yellow needles, and in aqueaus solution gives a black precipitate with ferric chloride. The platircochloride, ( C9NH,0C1,),,H2PtC16 + 2H20, crystallises in long, orange needles, and loses its water a t 120"- The acety l-derivative, CgMH40C1,Ac, separates from light petroleum in small, colourless ci-ystals melting at 97-98"; it is very unstable, and is decomposed by water or when boiled for a long time with glacial acetic acid.Tricl~lorl2ydroxyyuinoZ~ne, [OH : C1, = 1 : 2 : 3 : 41, is formed when the mother-liquor from trichloroketoquinolitie is boiled or when the hydrochloric acid solution of pentachloroketoquinoline is treated witli hydrogen sodium sulphite or with water. It crystallises from glacial F. S . I(.ORGANIC CHEMISTRY. 61 acetic acid i n long, colourless, moss-like needles, melts a t 213-214", and is readily soluble in hot alcohol or glacial acetic acid, but only sparingly in the cold solvents and in dilute acids ; it is readily soluble in concentrated acids, but is reprecipitated on adding water.When treated with chlorine in chloroform solution, it yields a yellow powder, probably tetrachloroketoquinoline, which melts a t 175" with decomposition, and is recoiiverted into trichlorhydroxyquinoline when boiled with alcohol. When heated with sodium carbonate, it yields a sodium-derivative melting a t 270". The potassium-derimtive is c r p talline. The hydrochzoride crystallises in small, yellow needles. The p latinochzoride, ( C,NH4C130) %, H2Pt C1, + 2 H,O, crys t allises from dilute hydrochloric acid in long, orange needles and loses its water at 140-150". The acety2-derivative separates from a mixture of glacial acetic acid and acetic anhydride in thin, transparent, forked, efflore- scent crystals, melts a t 172-173", and is readily decomposed.Tricli Zoroketoquinoline hydrochloride, C,NH40C13,HC1 + 2H20, pre- pared by saturating a well-cooled glacial acetic acid solution of hydr- oxyquinoline with chlorine and washing the product with glacial acetic acid, is very unstable, hygroscopic, and sensitive t o light. When simply dried between blotting paper, it melts at 93-95" to a yellow liquid which decomposes a t 100-120" with evolution of gas and then solidifies, melting again at 170-1 80" with decomposition. When dried over sulpburic acid under reduced pressure, it does not begin to decompose until heated a t 160" and melts at 180". It is readily soluble in moderately dilute hydrochloric acid, but when the solution is evapo- rated under reduced pressure dichlorhydroxyquinoline separates.14, is decomposed when warmed with solvents, generally with forma- tion of the dichlorhydroxy-derivative, and this substance is formed very readily when the keto-derivative is reduced with hydrogen sodium sulphite. The platinochloride is very readily soluble, and when the solution is boiled or evaporated under reduced pressure, a mixture CO*CCl, of platinochlorides is obtained. The free base, C,NH,< CCl:CH >, obtained by decomposing the hydrochloride with water and extracting the precipitated oil with ether, crystallises in long, thin, yellow prisms or needles, melts a t 9So, turns brown a t 130", and is completely decomposed a t 170". It is readily soluble in benzene, alcohol, and glacial acetic acid, and does not decompose when kept.EthoxydichZor7~ydroxyqzlinoZine, OEt*C,NH,Cl,*OH [OH : C1, : OEt = 1 : 2 : 4: 1'3, is formed, together with dichlorhydroxyquinoline and a small quantity of the trichloro-derivative, when an alcoholic solution of freshly prepared trichloroketoqninoline is boiled for 1-2 hours. It crystallises from alcohol or benzene in long, thin, colourless needles, melts at 150-151", and dissolves sparingly in most ordinary solvents in the cold but readily on warming. It is soluble in acids, forming colourless solutions, from which i t is reprecipitated by water, and when warmed with alcoholic soda, it yields a solution from which a spongy sodium-derivative separates on cooling. Dihydroxydzchloroquiizoline, [(OH), : C1, = 1 : 1' : 2 : 41, is ob- tained, together with ethyl chloride, when the preceding compound is heated a t 110-120" with concentrated hydrochloric acid; it is also62 ABSTRACTS OF CHEMICAL PAPERS.formed when trichloroketoquinoline is boiled with methyl alcohol. It crystallises from alcohol in needles, melts atv 278", and is more sparingly soluble than the chloro-derivatives of hydroxyy uinoline. It crystallises from methyl alcohol in efflorescent needles containing alcohol. Anilidoquinolinequinoneani lide, C,NH,< C'O*C(NPh)- d (NH ,:cEI>, is ob- tained by treating an alcoholic solution of the ketochloro-derivative with excess of aniline. It crystallises in small, golden plates or long needles, melts a t 222", and shows all the properties of a feeble base. It is moderately soluble in glacial acetic acid, sparingly in alcohol, insoluble in water, and dissolves in dilute acids with a bluish-violet coloration.It is not changed by boiling with alcohol or concentrated potash, but is readily decomposed when heated with acids, yielding. a, yellow, crystalline substance which was not, obtained in the pure state. The hydrochZoride crystallises from acidified alcohol in small, dark- golden needles and is unstable. The yicrate crystallises from alcohol in dark, copper-red needles. The acetate crystallises in needles, melts a t 19Y", and is decomposed by water. Pentach loroketopuinoline platinochloride, (CJ H,Cl,O) 2, H,Pt Cl,, is formed when trichloroketoquinoline hydrochloride (5 grams) is heated at 140-150" for six hours with manganese dioxide (35grams) and concentrated hydrochloric acid (18 grams), the resulting solution filtered and mixed with platinic chloride.It is a yellow, crystalline compound, and when recrystallised or dried, it seems to lose hydro- gen chloride and be convei-ted into the salt of tetrachloroketoquinoliae. A solution of pentachloroketoquinoline hydrochloride yields trich lor- bydroxyquinoline when mixed with water or hydrogen sodium sulphite. F. S. I(. Alkaloids from Papaveraceae. By E. SCHMIDT (Arch. Pharm. [ 3 ] , 26, 622-623).-The following abstract is the first of a series on these alkaloids, giving the results of investigations undertaken a t the instance of the author. Schiel's conclusion that chelerythrine and sanguinarine are identical is not confirmed. The former appears to have the formula CI9Hl7N04, as deduced from the analysis of the small quantities obtained, whilst the latter, from the analysis of various compounds, has the formula, CI7Hl5NO4, thus confirming Naschold's result.Three more bases have recently been separated from Chelidonlum majus which are now the subject of research. Chelidonine. By A. HENSCHKE (Arch. Pharm. [3], 26,624-644 ; compare Abstr., 1887, 854) .--The alkaloi'd was obtained partly by recrystallisation of the commercial base, and partly by direct extrac- tion from the root of CheZidoriiunz rnajus. Probst's method of ex- traction was employed, the stamped root being boiled in water acidified with sulphuric acid, ammonia in excess added, and the filtrate dried. This was purified by treatment with acidified alcohol, and again with ether, and finally was repeatedly crystallised from boiling alcohol.Chel idonine, CzoH19N05 + HzO, forms vitreous, tabular, colour- less, monocliuic crystals of about 3 mm. diameter. The reactions of J. T.PHYSIOLOGICAL CHEMISTRT. ti3 the base are given in detail. Solutions of the salts of this base have an acid reaction, and tlie hydrochloride has the formula C,,H,,NO,-HCl ; the nitrate, C,,HlgN05,HN03; the sulphate, C20H19N05,H2SO~ + 2H20 ; the platinochloride, (C20H,9N05)2,H2PtC16 + 2H20 ; this was not, ob- tainable in a crystalline form ; the aurochloride, C2,,H,,N05,HAuC14, is easily obtained in crystals. Ethyl iodide combines with the base, and the compound is not acted on by potassium hydroxide ; these and less positive results lead to the conclusion that chelidonine is a tertiary base.By oxidation with potassium permanganate in alkaline solution, chelidonine yields oxalic acid, methylamine and ammonia, the latter resulting from the decomposition of methylamine. In acid solution, the oxidation goes further, carbonic anhydride and methyl- amine resulting. J. T. Alkaloids from Cod-liver Oil. By A. GAUTIER and L. MOURGUES (Compt. rmd., 107, 626-629 ; compare Abstr., 1888,1325) .-Aselline, C25H32N4, is an amorphous, colourless solid which becomes green on exposure to light. It melts to a viscom, yellowish liquid with an aromatic odour recalling that of the ptomaines, is very slightly soluble in water, to which it imparts a bitter taste and an alkaline reaction, but dissolves in ether and still more readily in alcohol ; sp.gr. about 1-0,5. The salts of aselline crystallise readily, but are partially de- composed by water. The mercurochloride crystallises from warm water ; the aurochloride is very easily reduced ; the platinochloride is orange-yellow, and dissolves in warm water, but is decomposed by boiling water. Aselline is feebly toxic, and produces fatigue and stupor; 3 mgrms. of the hydrochloride killed a greenfinch in 14 minutes. Morrhuivae, C19H2,N3, is separated from aselline by taking advantage of tlie greater solubility of its platinochloride. It is a thick, oily, amber-coloured liquid with an odour which recalls that of aselline, and is only slightly soluble in water, but more soluble in alcohol and ether. It is caustic and strongly alkaline, and absorbs carbonic anhydride from the air.The hydrochloride is very deliquescent ; the aurocbloride is yellow, and dissolves in warm water; the platino- chloride is somewhat soluble and crystallises in needles. Morrhuine constitutes one-third of the total bases in the oil, and an ordinary dose of one fluid ounce contains 2 milligrams. It excites the appetite and has remarkable diaphoretic and diuretic properties. In large doses it produces fatigue and stupor. C. H. B.ORGANIC CHEMISTRY. 29Organic C h e m i s t r y .Isoallylene. By G. GUSTAVSON and N. DEMJANOFF (J. p r . Chem.[Z], 38, 201--207).-1soallylene may be prepared by the action ofzinc-dust on an alcoholic solution of dibromopropylene. The latter,best obtained by the action of potassium hydroxide on tribromhydrin,is allowed to drop slowly into the warm mixture of zinc-dust and$0 per cent.alcohol, contained in a flask. The isoallylene evolved is* 100 00 in the original paper80 ABSTRACTS OF CHEMICAL PAPERS.collected over water, in wliich it is very little soluble. 10 grams ofdibromopropylene yield 900 to 1000 C.C. of the gas,IsozLZZyZene is ;I colourless gas, smelling like normal allylene; itburns with a skrongly luminous flame, and gives 110 precipitate withammoniacal cuprous chloride or silver nitrate. With aqueous solu-tions of mercuric chloride or sulphate it gives a white precipitate.The gas from 10 grams of dibromopropylene was absorbed by35 grams of bromine, the unaltered bromine dissolved in sodiumhydroxide solution, and the colourless oil washed with water.Itweighed 17 grams, the calculated yield being 18 grams, and had theformula C3H4Br4. IsoaZZyZene tetrabromide smells of camphor, and hasthe sp. gr. 2.729 at 0" and 2.658 a t 18" (water a t 0" = 1) ; it solidifieswhen cooled to -18", and melts below 0" ; a t the ordinary pressureit distils between 215" and 230" with partial decomposition. Normalallylene tetrabromide has the sp. gr. 2.690 a t 0" and 2.652 at It;",and does not solidify in a freezing mixture. That the two are notidentical is conclusively proved by the fact that by the action of zioc-dust isoallylene is liberated from the one, and normal allylene fromthe other.On heating sodium with an ethereal solution of isoallylene in a sealedtube st loo", the sodium is converted into a white powder, whichevolves normal allylene when treated with water. Pavorsky hasshown that this conversion of iso- into normal hydro-carbons by theaction of sodium, is characteristic of the homologues of acetylene.When passed into strong sulphuric acid, isoallylene is absorbed,and on dilution with water and addition of potassium hydroxide,acetone separates ; this is a strong argurnent in favour of isoallylenebeing dirnethyZenemethane, CH2:C:CH2, thus (1) CH2:C:CH2 + 2H2S04+ 2H2SOa.If this is the case, the dibromopropylene from whichisoallylene is obtained must be CH2Br*CBr:CH2, and isoallylenetetrabromide must be CH2Br.CBr2*CH2Br.= CH,*C(HS0,)2*CH3; (2) CH,*C(HSO,)2*CH3 + H2O = CH,.CC)*CH,A. G. B.Cyanurates.By A. CLAUS and 0. PUTENSEN (J. pr. Chem. [2],38, 20&-229).-The amethyst-coloured crystals, obtained whencyanuric acid is mixed with ammoniacal copper sulphate, have thecomposition ( C3N303H2),Cu,2NH3. By digesting them with diluteammonia, violet needles of the composition ( C3N30,H2)2Cu,3NH3 areobtained, and if strong ammonia is used a deep blue compound,(C3N303H2)2C~,4NH3, is formed ; but this last is very unstable,rapidly losing ammonia in the ail.. When the first of these ammoniacalcopper cyanurates is digested with water, a basic copper cyanurate,C,N,O,(Cu*OH), + 3H20, is formed. An acid copper cyanurate of thecomposition ( C3Nd03HL)2C~,C3N303H3,NH3 + H20 is formed whencopper carbonate is digested with cpanuric acid and ammonia. Thesalt, C3N303HCu + 3H20, is precipitated when sodium cyanurate isadded to copper sulphate ; and normal copper cyanurate, (C,N,O,),Cu, + H,O, crystallises when acid magnesium cyanurate is mixed withcopper sulphate.The following cyanurates are also described : Acidmagnesium cyanurate, ammoniacal cadmium cyanurate, ammoniacalzinc cyanurate, ammoniacal nickel cyanurate, cyanurates of nickelORGANIC OHEMISTHY. 31cobalt, and manganese : tetramethylammonium cyanurate, and furhher,cyanurates of quinoline, quinine, cinchonine, strychnine, narc0 tine, andcaff ehe. A. G. B.Preparation of a-Dibromhydrin. By 0. ASCHAN (Ber., 21,2890-2892) .-a-Dibromhydrin is best prepared as follows :-Phos-phorus tribromide (650 grams) is dropped in quantities of from 10 to20 grams at a bime into pure, warm glycerol (500 grams), the wholebeing well shaken and cooled after each addition of bromide, Theoperation is at an end in from three to four hours.After keepingfor 24 hours, the mixture is heated on the water-bath for about threehours, cooled, diluted with water (3 to 4 vols.), extracted with ether,and the extract washed with sodium carbonate solution and dried.After evaporating the ether, the residual oil is heated at about 200°,and then fractionated ; the portion boiling at 208-218", which con-stitutes about two-thirds of the whole, is finally distilled underreduced pressure. 500 gra'ms of glycerol yield 135 grams of purea-dibromhydrin. The requisite quantities of yellow phosphorus andbromine can be employed instead of phosphorus tribromide.When a-dibromhydrin is treated with nitric acid of sp.gr. 1.48, theprincipal product is a liquid boiling at 78-79' (18 mm.), which con-tains bromine and nitrogen. It forms very stable, yellow, readilycrystallisable salts. F. S. K,Epichlorhydrin. By C. PAAL (Ber., 21, 2971-2973) .-Chloriodo-hydrin methyl ether, C3H5CII*OMe, is obtained by heating epichlor-hydrin (1 mol.) with methyl iodide (1 mol.) at 190°, fractionatingthe product, and removing the free iodine wit,h finely divided si!ver.The yield is about 'LO per ceilt. of the theoretical quantity. I t is acolourless oil with a pungent smell, exceedingly sensitive to light,and miscible with the ordinary solrents excepting water, in which itis insoluble.I t boils at about 200" with partial decomposition, andis readily volatile with steam.Chloriodohydrin etlyl ether, C,H,CiI-@Et, is prepared by heatingepichlorhydrin with ethyl iodide at 200-220", and purifying theproduct as described above. The yield is 30-50 per cent. of thetheoretical quantity . It boils at 200-210" with slight decompositionand resembles the preceding compound.Chloriodohydrin isopropyl ether, C,H,ClI*OPrF, prepared in likemanner, boils at 208-212" with partial decomposition and resemblesthe ethyl ether. The noymai propyZ ether boils at 200-210" withslight decomposition ; it is relatively stable and less sensitive t o lightthan the other ethers which, however, it resembles in other respects.F. 8. I(.Propyl-phycite.By A. 'FAUCONNIER (Compt. rend., 107,629-630).-The action of hypochlorous acid on epichlorhydrin results in thertssimilation of water, most probably because of the acidity of theliquid, and the " propyl-phycite " obtained by Carius by saponifyingthe product of this reaction, and described by him as a lower homo-logue of erythrol, is in reality ordinary glycerol. C. H. B32 ABSTRACTS OF CHEMICAL PAPERS.Molecular Weight and Valency of Perseite. By MAQTJENNE(Compt. rend., 107, 583-586) .-When perseite is treated with boil-ing hydriodic acid, it is partly converted into resinous products ofindefinite composition, and partly into a volatile liquid which can beseparated into two fractions boiling at 100-110" and 133-200"respectively. The first is a heptine, isomeric with oenanthylidene,which boils a t 102-105" after rectification over calcium oxide andover sodium ; sp.gr. at 20" = 0.78. The second fraction is a dense redoil with a slight ethereal odour. It boils at 192-196" under ordinarypressure, and at 02-35" under a pressure of 40-50 mm., but decom-poses to a considerable extent even when distilled in a vacuum. Itconsists mainly of heptyl iodide with a small quantity of heptinehydriodide.The dibenzok acefal of perseite, C,,H2,O7, is obtained by the actionof benzaldehyde on perseite in presence of alcohol saturated withhydrogen chloride. It forms confused, slender, microscopic needleswhich soften at 215", but have no definite melting point, and arequite insoluble in water and almost insoluble in alcohol.ThePe results show that the formula previously attributed to per-seite (Abstr., 1888, 807) is incorrect, and that perseite is really thenext higher homologue of mannitol, and has the formula C,H,,O,. Itis the first instance of a heptahydric alcohol and of a sugar containing7 carbon-atoms.C. H. B.Constitution of the Glucoses. By B. RA~MANN (Bey., 21, 2841-2842).-The author considers that the aldehyde and ketone formulzeexplain the chief reactions of the glucoses, and that the reactionswhich Tollens mentions (KzLrzes Eandb. d. Kohlenhydrate), as incom-patible with the assumption that these compounds are aldehydes donot afford sufficient grounds for changing the formuls.N. H. If.Oxidation of Arabinose with Nitric Acid.By H. KILIANI(Ber., 21, 3006-3009) .--Calcium arabonat'e is obtained in consider-able.quantities when arabinose (1 part) is heated at 35" for aboutsix hours with nitric acid of sp. gr. 1.2 (2 parts), the diluted solutionboiled with excess of calcinm carbonate, filtered, enporated, andmixed with alcohol. This method can be suitably employed for thepreparation of arabonic acid.Calcium trihydroxyglutarate is obtained from arabinose as follows :-Arabinose (1 part) is digested at 35" with nitric acid of sp. gr. 2.2(2.5 parts) ; after the evolution of gas has ceased, the solutionis evaporated until free from nitric acid, the residual syrup dissolvedin water (25 parts), boiled with calcium carbonate, and the hot solu-tion filtered. The sparingly soluble, red calcium salt which separatesis spread on porous plates, and by concentrating the mother-liquor,separating the salt, and repeating the process several times, 40-45per cent.of the weight of the arabinose employed is obtained in theform of calcium trihydroxyglutarate. It is very similar to calciumsacchnrate in appearance and in its behaviour when heated withwater. The potassium salt, C5H607K2, crystallises in large, colourless,monoclinic plates or prisms, is readily soloble, and is not converteORGANIC CHEMISTRY. 33into the acid salt when the aqueous soIuttion is evaporated with aceticacid. Lead acetate and silver nitrate produce white precipitates inan aqueous solution.TrihydrozyLglutzLric acid, C5H807, obtained by decomposing thecalcium salt with oxalic asid, crystallises from alcohol in colourless,microscopic plates, melts a t 127", and does not reduce Fehling's solu-tion.The normal ammonium salt crystallises in slender needles andis very readily soluble.By F.MBYER (Ber., 21, 2883-2t390).-~rLnzeth~Zenetrinitrosamine, C3H6N6O3,is obtained when an ice-cold solution of hexamethyleneamine (1 part)in water (40 parts) is mixed with ice-cold, dilut,e (If per cent.)hydrochloric acid, and a solution of sodium nitrite ( 2 i parts) in asmall quantity of water immediately added. After about, 15 minutes,the yellowish, crystalline substance which separates at the surface istlirown on to a filter, washed with cold water, and dried on porousplates. The yield is 50 to 60 per cent., or more, of the aniineemployed.It crystal!ises from boiling alcohol, in which it ismoderately soluble, in small, yellowish, silky needles or prisms, meltsat 105--106", and is readily soluble in cold acetone, but onlymoderately so in warm benzene, chloroform, and ether, and insolublein light petroleum. It dissolves unchanged in cold glacial acetic acid,and the molecular weight determined by Raoult's method was foundt o be 196. On exposure to moist air, the crystals lose their silkyappearance, and when treated with cold water, a slight evolution ofnitrogen occurs. It melts under boiling water to a yellowish oilwhich gradually dissolves with evolution of nitrogen, and the solutioncontains formaldehyde. The same decomposition takes place, butmuch more quickly, when it is warmed with glacial acetic acid ordilute acids, but the decomposition into formaldehyde and nitrogen isnot quite quantitative, as traces of ammonia are formed a t the sametime.When heated in a capillary tube, or when treated with con-centrated acids, i t is immediately decomposed with evolution ofnitrous fumes, and when heated on platinum foil it explodes. Itgives Liebermann's reaction. The filtrate obtained in the prepara-tion of this cornpound contains unchanged hexamethyleneamine ; if,however, the mixture is kept for R long time before separating thenitrosoamine, the latter is decomposed into formaldehyde and nitro-gen, and some of the hexamethylenearnine is converted into form-aldehyde and ammonia.Dinitrosopentamethylenetetramine was obtained by gradually add-ing dilute hydrochloric acid to a solution of hexamethyleneamine andsodium nitrite (compare Griess and Harrow, Abstr., 1888, 1268).Itmelts a t 202--203", arid gives Liebermann's nitroso-reaction.F. S. I(.Action of Nitrous Acid on Hexamethylenearnine.F. S. K.Identity of Putresine and Tetramethylenediamine. By L. V.UURBNSZKY and E. BAUMANN (Bey., 21, 2938-2941).-A direct com-parison of the dibenzoyl-derivatives of putresine (Brieger), tetra-rnetlhylenediamine, and the compound obtained by the authors fromYOL. LVt. 34 ABSTHACTS OF GHEMICAL PAPERS.the urine of a patient suffering from cystinuria (compare Abstr.,1888, 1296), proved that these bases are identical.Concentrated solutions of guanidine, creatine, creatinine, and similarcompounds give a precipitate with soda and benzoic chloride, whereasno separation occurs in solutions containing less than 0.5 gram of thebases ; it is therefore necessary that when benzoic chloride is used asa reagent for diamines (Zoc.cit.) only very dilute solutions of thelatter should be employed.By W.R. ORNDORFF and H. JESSEL (Amer. Chern. J., 10, 363--367).-Liebigstated that acetone could advantageously be substituted for alcohol inthe preparation of chloroform ; this statement has been contradictedby Siemerling,.yet chloroform is now largely made from acetone. Ina number of trials, the yield was 166 to 173 per cent. of the weight ofthe acetone used, and the residual liquors contained considerable quan-tities of calcium acetate.The reaction is represented by 2CO(CH,)z + GCaOCl, = SCHCl, + 2Ca(OH), + XaCI, + Ca(CH,*COO),.Liebig states that calcium carbonate is precipitated during the reaction,but the precipitate is calcium hydroxide. Acetophenone similarlytreated with blenching powder, yields chloroform, calcium hydrate, andcalcium benzoate. H. B.F. S. K.Decomposition of Acetone with Bleaching Powder.Dinitrosoacetone. By H. v. PECHMANN and K. WEHSARG (Ber.,21, 2989-2993) .-When dinitrosoacetone (compare Abstr., 1887, 28)is boiled with water or acids, it is decomposed into carboiiic anhydride,hydrogen cyanide, water, and ammonium hydrogen oxalate ; but whenit is heated with glacial acetic acid, oxamic acid, melting at 210°, andhydrogen cyanide are formed.Trinitrosopropnne, NOH:CH*C(NOH)*CH:NOH, prepared by heat-ing a, mixture of dinitrosoacetone (1 mol.), hydroxylamine hydro-chloride (1 mol.), sodium acetate (1 mol.), and water at 50-60' for1 to 2 hours, separates from hot water in the form of a colourless,crystalline powder melting a t 171" with sudden decomposition.Itis only sparingly soluble in ether, but readily solubIe in alcohol, fromwhich it crystallises in needles, and it, dissolves slowly, but in con-siderable quantities, in hot water. It behaves like dinitrosoacetonewhen heated with dilute acids, but its aqueous solution can be boiledfor a short time without decomposition taking place. Ferric chloridegives a brownish-red coloration with a dilute aqueous solution ;ferrous sulphate produces a wine-red colour, and the solution thengives a violet precipitate with soda.Dinitrosoacetone hydrazone, NOH: C H-C (N,HPh) CH :NOH, pre-pared by treating dinitrosoacetone (1 mol.) with phenylhydrazine(1 mol.) in hot, alcoholic solution, crystallises in yellow needles, meltsa t 145" with decomposition, and is readily soluble in alcohol andether, more sparingly in benzene and light petroleum, and insolublein water.It dissolves in alkalis with a yellow, and in concentratedsulphuric acid with an orange-yellow coloration. The metyZ-deriv%tive, C9H9N4O2Ac, a light yellow, crystalline compound, melts a t133", and is soluble i n dilute alcohol. It dissolves in alkalis with ORGIAKIC CHEMISTRY.35yellowish coloration, but the soliltion becomes colourless on boiling,md on adding acids, a compound, C,H8N*0, is precipitated in shining,colourless needles. This substance is also formed when the acetyl-derivative is boiled with water. A compound, C,,H,,N,, is obtainedwhen dinitrosoacetone is beaked with excess of phenylhydrazineacetate. It crystallises from hot alcohol or benzene in shining, yellowplates melting at 122". It is not acted on when boiled with ferricchloride, and its solution in concentrated sulphuric acid does not givea coloration with this reagent.Sulphoisovaleric Acid. By G. DE VARDA (Chew,. Ceiztr., 1888,587-888, from Rend. Acad. dei Lincei [4], 4, 1).-100 parts ofisovaleric acid are mixed with 100 parts of chlorosulphonic acid, and,after the spontaneous reaction has ended, the mass is heated to 230" ;it is then diluted with several volumes of water, and distilled from theoil-bath until the distillate no longer has an acid reaction. The distil-late is then heated with plumbic carbonate for some time, filtered whilehot, and the lead precipitated from the solution by hydrogen sul-pbide, the solution of the free acid being concentrated in a vacuum.Theaqueous solution partly decomposes when heated on the water-bath.The lead salt, C6H,S0,Pb.'LHz0, crystallises from water in colourless,odourless, small plates, which taste sweet ; they are slightly soluble inwater, and insoluble in alcohol, ether, and chloroform.The bariumsalt, containing 1 mol. HzO, forms small, tabular crjstals, withoutsmell o r colour, and taste bitter.It is soluble in water, insoluble inalcohol, ether, and chloroform.F. S. K.Su7phoisowaZeric acid so obtained forms deliquescent crystals.J. W. L.Constituents of Cocoa Fat. By P. GRAF ( A d . Pharm. [3], 26,830-846 ; comp. Kingzett, Trans., 1878, 38).-l1he melting point ofvarious samples of commercial cocoa butter from widely differentsources was determined both in open and closed glass tubes. In theopen tube, the results varied from 29" to 33-44', whilst in the closedtube 11 samples gave 34.3" and one 33.5". The whole of the sampleswere mixed together for the further investigation. The €at wasfound to contain hardly any free acid. Two determinations ofglycerol averaged 9-59 per cent.A little cholesterin and smallquantities of formic, acetic, and butyric acids were detected. Afterthe separation of oleic acid, the solid fatty acids were isolated byfractional crystallisation, followed by Heintz's method of fractionalprecipitation by means of magnesium and barium acetates. Noacid with a higher molecular weight than arachidic acid was found ;this confirms Traub's statement that he was unable to find theohromicacid asserted to be present by Kingzett. The presence of oleic,stearic, and palmitic acids was confirmed ; and either lauric acid o rone of its isomerides was isolated : there was not sufficient materialat hand to settle this point. J. T.Action of Hydrogen Phosphide on Aldehydes and KetoneAcids.By J. MEESINGER and C. ENGELS (Ber., 21,2919-2928).-The compound obtained by passing hydrogen phosphide and hy-d 36 ABSTRACTS OF CHEXICAL PAPERS.drogen chloride into an ethereal solution of pyruvic acid has theconstitution P(CMe<C0>)3, and is named by the authors phos-iUhorus-trianhyd~o~yru~ic acid (compare Abstr., 1888, 441). It is in-soluble in cold acids, and on heating, decomposition takes place.It dissolves in warm, glacial acetic acid, and separates unchanged oncooling. It is not acted on by bromine even a t 150", but whenboiled with water it is decomposed into pyruvic acid and hydrogenphosphide.0Phospho1.zks-trihydroplll.uvic acid hydrazide,P[ CMe(OH)*C(OH):N,HPh],,is formed when the preceding compound is warmed with phenyl-hjdrazine in alcoholic solution ; it is a colourless, crystalline com-pound, melts a t 132", and is moderately soluble in alcoholic ether, butonly sparingly in cold alcohol, and almost insoluble in ether.Hy drazonepyruvic acid hydyazide, Cl5'EIZI6N40, is formed , togetherwith hydrogen phosphide, when phosphorustrianhydropyruvic acidis heated with excess of phenylhydrazine, in which i t is readilysoluble. It crys tallises from hot alcohol in colourless, shining plates,melts at 162", and is only sparingly soluble in cold alcohol and ether.Phosphorus-t,.ihyclro~yruvic acid dianilide,is obtained when aniline is gradually added to an alcoholic solution ofphosphorus-trianhydropyruvic acid.It separates from warm alcoholin colourless crystals, melts a t 158", is very sparingly soluble in coldalcohol and insoluble in water or ether.It is completely decom-posed, with separation of phosphorus, when treated with hydrogenchloride in alcoholic or ethereal solution.Dihy dyazonepy rzsv ic acid hy drazide, NP h (C 0-CMe: X2H Ph), , is formedwhen the preceding compound is treated with phenylhydrazide. Itcrystallises from alcohol in small needles melting at 169".Phosphorus-trianhydropyruvio acid and toluylenediamine yield acrystalline compound, CQHgOGP 3- 2C6H3Me(NH2),, which melts at178" with decomposition.Hydrogen phosphide, in presence of hydrogen chloride, has noaction on ethyl acetoacetate or benzoylcarboxylic acid, but tribromo-pyruvic acid absorbs the gas in considerable quantities with evolutionof hydrogen bromide and the ultimate formation of phosphorus-fri-anhydropyruvic acid.3'. S. K.Action of Heat on Tartaric Acid in Aqueous Solution. B.7 E. M. WEDARD (Chenz. Centr., 1888, 889, from Atti. R. Acad. Scz.Torino, 6, 65-67).-The author noticed that when tartaric acid hadbeen heated for several days in sealed tubes with ferrous sulphate,several of the tubes exploded violently, and in the others a consider-able quantity OE carbonic anhydride was found. As the ferrous salthad not become oxidised a t all, the reaction had not been a simplereduction of the tartaric acid. Tartaric acid heated with water aloneat 150" in sealed tubes also suffered a considerable loss of carboniORQANIC CHEMISTRT. 37anhydride. In one experiment, the author opened the tube afterheating, allowed the carbonic anhydride to escape, then sealed itagain, and submitted the contents to a further heating, and repeatedthe operation until no further evolution of carbonic anhydride tookplace, after which the resulting liquid was found to contain pyro-tartaric acid along with undecomposed tartaric acid.Freezing Points of Solutions of' Aluminium Alkyls.By E.LOUISE and L. Roux (Cowpt. rend., 107, 600--603).-Pure ethylenebromide was used as a solvent, the molecular reduction, T, with thisliquid being 118. The number obtained with mercury propyl was124.8 ; mercury isobutyl, 122.7 ; mercury isoamyl, 123.6 ; mercuryphenyl, 120.4.Aluminium ethyl gave a molecular reduction of 115.6, which agreeswith the formula A1,Et6.Alunzinium proyy2, obtained by the action of aluminium onmercury propyl, is a colourless, mobile liquid, which boils a t 250" andtakes fire in contact with the air.Aluminium isoam!jl, obtained in asimilar way, is a somewhat viscous, colourless liquid, with an odourof amyl compounds ; it boils at 250" under a pressure of 80-100 mm.,and does not readily take fire in contact with the air. The molecularreduction with aluminium propyl is 92.8, and with aluminium iso-amyl 84.5. These values agree more closely with the formula A]&,than with AIRs, and hence confirm the conclusions deduced fromJ. W. L.vapour-density determinations (Abstracts, l8S8, 583).C. H. B.Substituted Pyromucic Acids. By H. B. HILL and A.W.PALMEK. (Amer. Chen?. J., 10, 375--391).-With the exception of asulphopyromucic acid briefly described b r Schwanert, no furf uran-derivatives containing the sulplionic group are described ; yet thegeneral behaviour of pyromucic acid is similar to that of benzoic acic1.6- Sulphopyromucic acid is readily formed bay treating pyromucic acidwith fuming sulphuric acid. The acid itself is extremely soluble inwater, but may be obtained in large, deliquescent crystals. The follow-ing salts are described : RnC,H2S06 + 4H20 ; Ba( C5&SO,)a + 4H20,and also with 6H,O; CaC,H,SO, + 3H20; PbC,H,SO, + 2H20, allreadily soluble in hot water; Ag,C5H2S06 is sparingly soluble inwater; K,C5H,S0, + 4x20 ; KC,H,so, ; Na,C5H,S06 4- 5H20, andNaC&SO, + H20, all very soluble, All these salts crjstallisereadily.By treating the dry sodium salt with phosphorns penta-chloride. and the resulting viscous oil with ammonia, the crystalline6-suZphopyromucal.riide, C,H,SO,(NH,),, is obtained ; it is readilysoluble in hot water, and melts a t 213'. The dry acid is only decom-posed by bromine at loo", dibromosuccinic acid and other productsbeing formed ; in aqueous solution the acid is mainly converted intofumaric acid. Dilute nitric acid oxidises i t slowly, and also producesfumaric acid and some oxalic acid ; concentrated nitric acid at 100"readily converts it into Klinkhardt's 8-nitropyrom ucic acid, and att h e same time a neutral substance, in all probability aa-dinitro-furfuran, is formed.Although bro,nine-derivatives of 8-sulphopyromucic acid camot b38 ABSTRACTS OF CHEMICAL PAPERS.obtained by the action of bromine, they may be obtained by sul-phonating the corresponding bromopyromucic acids : P-Hromo-6-sulyhopyromucic acid is extremely soluble in cold water, and formsdeliquescent crystals. The salts-BaC5HBrSo6 + 4H20; CaC5HBrS06 + 6H,O ; PbC5HBrS06 + 4H,O ;K,C5HBrS0, + 1+H20 (2)are described ; they are all crystalline and soluble in water. That theacid is really a derivative of 6-sulphopyromucic acid is proved byobtaining this acid by treatment of the bromo-acid with zinc andammonia. Bromive in aqueous solution readily converts the bromo-acid into monobromofumaric acid.Concentrated nitric acid readilyyields P-bro.uno-~-nitropyronzucic acid, soluble in water, alcohol, &c.,and melting at 159-160".8-r-Dibromo-6-su~h(~~~omucic acid is prepared by dissolving /3-y-di-bromopyromucic acid in fuming sulphuric acid, b u t it is more advan-tageous to use the mixture of P-61- and /3-6-dibromopyromucic acidsresulting from the decomposition of the tetrabromo-acid, as thep-8-dibromo-acid is but little acted on by the sulphuric acid.Tbeacid in question is very soluble in water, and is crystalline; thefollowing salts are described: BaC,Br2S06 + 5H20 and also with3&O; PbC,Br2S06 + 4H20 ; AgzC,Br,So6 4- HzO ; K2C5Br2SO6 + H,O.That the sulphoriic acid occupies the 8-position, the only pos-sible one, is proved by treatment of the above barium salt withzinc-dust and ammonia, when the a-sulphopyromucic acid firstdescribed is obtained.Bromine in aqueous solution readily oxidisesthe barium salt, giving barium sulphate and dibromonialeic acid.Dilute nitric acid oxidises it to dibroruosuccinic acid. Concentratednitric acid yields a mixture of P-ri-dibromo-8-nitropyrornucic acid,crystallising from water in sparingly soluble, slender, yellow needles,that melt a t 204- 205", and /3/3-dibromo-aa-dinitrofurfuran, a substancemelting at 150-151" and crystallising from benzene, as the compoundC',Br2(NO,),O,C6H6, which readily gives off this benzene of cqstal-lisation. H. B.Metadiethylbenzene. By A. VOSWINKEL (Ber., 21,2829- 2831).i7.letudiethyZbeiizene, C6H4Et2, is obtained, together with the para-compound, by the action of ethyl bromide and aluminium chloride onbenzene ; the two compounds are separated from each other by meansof the barium sulphonates.It boils a t 181--182", and does notsolidify a t -20", but bccomes thicker. Sp. gr.. = 0.8602 at 20" com-pared with water a t 4". When boiled with dilute nitric acid, ethyl-benzoic and isophthalic acids are formed. The barium sulphonate(with 3 mols. H,O) crystallises in hemispherical groups of prisms,rather sparingly soluble in cold water. The coppr saZt (with 4 mols.H,O) forms bright-blue plates of a satiny lustre ; the potussium salt(with 1 mol. H20) crystsllises in quadratic plates. The sulphor~arnideseparates from the dilute alcoholic solution in long, flat needles,melting a t 101-102". The bromir~e-derivatii.e, C6H3Et2Br, boils atabout 238".The teirnbromo-compciund, C6Et2Br4, crybtrcllises fromalcohol in small, colourless prisms melting a t 74". Nat,ometuJ!iefhyZ-btlzneiie, C,B,Et,*NO2, is a pale yellow liquid, which boils aORGANIC CHEMISTRY. 39280-285", with decomposition. The trirdro-compound, CsHEt,(NO,)-,crystallises from light petroleum in prisms melting at 62". A;mido-metadiethylbenzene, C6H3Et2.NHa, prepared by reducing the nitro-derivative, is a colourless liquid which distils readily with steam ; thehydrochloi-ide crystallises in groups of very long needles ; the acetyl-derivative forms stellate groups of needles melting at 104". Metadi-ethyZphenoZ, C6H3Et2*OH, is obtained by fusing the sulphonic acidwith potash ; it boils at 225", and dissolves spariugly in water ; thesolution gives a blue-violet colour (which changes to green on addingalcohol) with ferric chloride.Zeta-ethylbenzoic acid, C6H4Et.COOH,crystallises in long needles, melts a t 47", and is almost insoluhle inwater. The calcium salt (with 4 mols. H,O) forms lustrous needles,readily soluble in water and alcohol.Synthesis of Consecutive Tetramethylbenzene. By 0.JACOBSEN (Ber., 2 1, 282 1-28 28) .-Dinitro bromopseudocumene,N. H. M.[(N02)2 : Br : Me3 = 5 : 6 : 2 : 1 : 3 : 41,obtained by the action of nitric and sulphuric acids on bromopseudo-cumene [Br : Mes = 2 : 1 : 3 : 41, crystdlises from hot alcohol insmall, yellowish-white, lustrous prisms, melts a t 182", and dissolvesreadily in hot benzene, sparingly in hot alcohol.Bromopseudocumene, [Br : Me, = 2 : 1 : 3 : 41, has the same boilingpoint as the 5, 1, 3, 41 compound: 237-238" (not 226-229").Thesulphonamide nielts at 185" (not 137-188"; compare Kelbe andPathe, Her., 19, 1546).1, 2, 3, 4-'l'ctramet,hylbenzene is prepared by heatiiig pure bromo-pseudocumene (25 grams), methyl iodide (40 grams), and sodium(14 grams), in presence of sufficient absolute ether to cover the latter.After two or three days, it is distilled. The yield of tetramethyl-benzene is 38 per cent. of the weight of the bromopseudocumene.Dibromonietnzylene, [Me, : Br2 = 1 : 3 : 2 : 41, is obtained in thepreparation of spinietrical dibromometaxylene by brominating thehydrocarbon ; it is an oily liquid which, when cooled, solidifies to a hardcrystalline mass melting a t -So, and boils a t 269" under 760 mm.pressure.The di~itro-deri~atiwe forms a1 rriost colourless, microscopiccrystals, melts a t 191", and dissolves readily in toluene, very sparinglyin alcohol. When exposed to light it becomes yellow. The sodiumsulphowie, C6HNe,Br,*S03Na + H,O [= 1 : 3 : 2 : 4 : 61, crystallisesin groups of needles; the potassium salt with 1 mol. H20 formslustrous plates, sparingly soluble in cold water; the barium saltcrystallises in small prisms. The amide separates from alcohol insmall prisms, which melt with decomposition above 300". When thesodium salt is treated with zinc-dust and ammonia, the salt of ordinaryunsymmetrical metaxylenesulphonic acid is formed.OrthoiZicLmidometaayZene, [Me, : (NH,), = 1 : 3 : 5 : 61, is obtainedby very prolonged action of tin and hydrochloric acid on the dinitro-dibromo-compound, and is liberated from its hydrochloride by drydistillation with sodium carbonate in a stream of hydrogen.It crys-tallises from water in rhombic plates, melts a t 78.5", and dissolvesreadily in alcohol, ether, and hot water. When exposed to moist air40 ABSTRACTS OF CHEMICAL PAPERS.it beeomes grey-violet. The constitution of this compound as given isproved by the synthesis of 1, 2, 3, 4-tetramethylbenzene from theliquid dibromometdxylene by the action of methyl iodide and sodium,using ether as a diluent.When symmetrical dibromometaxylene is heated with sulphuricacid (3 parts) at 240", it is converted into the liquid isomeride.Tetrethylbenzene.By 0. JACOBSEN (Ber., 21, 2819-2821).-Symnretrscal tetrethylbmzene, C,H.,Et, [Eta = 1 : 'L : 4 : 51, isobtained, together with a smaller amount of the isomeride [Et, =1 : 2 : 3 : 41, by the action of ethyl bromide on benzene in presence ofaluminium chloride, at a temperature not above the boiling point ofthe bromide ; the product is sulphonated in the cold and the sodiumsulphonnte heated a t 170" with hydrochloric acid. It melts a t 13",and boils a t 250". When boiled with dilute nitric acid, and theproduct further oxidised with permanganste, pyromellitic acid isformed.Dibromotetrethylbenzene, C,Br,Et, [Et, = 1 : 2 : 4 : 51, crystalliseafrom hot alcohol in long, thin prisms melting a t 112.5".S o d i u m tetreth y1benzenesubphonate, C,H E t,*SO,Na + 4H20, crystal-lises from water in very large, lustrous plates, sparingly soluble incold water, much more readily in alcohol, almost insoluble in cold diluteaqueous soda.The barium salt (with 9 mols. H20) is sparinglysoluble in hot water. The sulphona?~~ide, C14H21.S02*NH2, crystallisesfrom hot dilute alcohol in rhombic plates, melting at 122".Pentethylbenzene and its Decomposition by Sulphuric Acid.By 0. JACOBSEN (Ber., 21, 2814-2819 ; compare Abstr., 1887, 660 ;1888, 137).-PentsthyZbenzene, C,HEt,, is prepared by the actionof ethyl bromide on benzene in presence of aluminium chloride,and purified in a manner similar to the pentamethyl-compound (loc.cit.). I t forms a thick oil, which boils at 277", and does not solidifyat -20".Brornopentethylbe?inene, C,BrEt,, obtained by brominating the hydro-carbon dissolved in glacial acetic acid, crystallises from alcohol inlong needles, melts at 47*5", and boils a t about 315".It is readilysoluble in hot alcohol.The suZphone, SO,( C6Ets),, crystallises from light petroleum con-taining some alcohol in large, transparent, hexagonal prisms of aglassy lnstre, melts a t 76", and is very readily soluble in alcohol, muchless in light petroleum, and insoluble in water.Sodium perdeth y Zb enseisesulphonate, C,,H,,-S 0,Na + 4H,O, crystal -lises from water in thin, lustrous plates, moderately soluble in hotwater, much more soluble in alcohol. The anhydrous salt crystallisesfroin 90 per cent.alcohol in groups of hair-like needles. Thepotccssium salt (with 2 mola. H,O) crystallises in thin plates, ratherreadily soluble in hot water, much more soluble in alcohol. Theaniinonium (with 1 mol. H,O) and barium (with 9 mols. H20) saZfscrystallise respectively in large, thin plates and small scales. Whenpentethylbenzene is treated with an equal volume of sulpburic acidsy much fumiug sulphuric acid added to the cooled mixture thatN. H. M.N. H. M.Sp. gr. = 0.8985 a t 19"ORGANIC CHEMISTRY. 41a clear, brownish-yellow solution is obtained, and the whole kept for4-5 days a t the ordinary temperature, hexethylbenzene and tetrethyl-benzene [Et, = 1 : 2 : 3 : 41 are formed.Hexethylbenzene melts at 229" and boils a t 298".Tetrethylbenzene [Et, = 1 : 2 : 3 : 41 boils a t 254", and does notsolidify a t -20".It is probably identical with Galle's compound(Abstr., 1883, 109 1). The dibronzo-derivative, CsBi.,Et4, crystallisesin prisms of a glassy lustre, melts at 77", and is sparingly soluble i l lboiling alcohol.Barium tetrethylbenxenesdphonate, (C,,EI,,*SO,),Ba + 6H20, crystal-lises from water in flat prisms OF a glassy lustre; the sodium saZt (with5 mols. H,O) forms readily soluble rhombic plates. The amide sepa-rates from its solution in water and alcohol in well-formed crystals ofa glassy lustre, and melts at 107". N. H. M.Synthesis of Aromatic Selenium Compounds. By C. CHABRIF:(Bull. SOC. Chlm., 50, 133-137) .-Phenyl selewide, SePh,, is obtainedby adding aluminium chloride to selenium tetrachloride (I part) andbenzene (3 parts), contained in a reflux apparatus, until no morehydrogen chloride is evolved.The temperature in the flask variesfrom 22' to 27", and the operation is finished in about 60 hours. Itboils a t 227" under a few cm. pressure. Phenyl chloride and an oilboiling at 250" under a pressure of A few cm. are also formed.Selenium oxychloride in presence of aluminium chloride andselenious anhydride, also react with benzene.Consecutive Metaxylenol. By 0. JACOBSEN (Ber., 21, 2828-2829) .-The author previously (Abstr., 1878, 412) ascribed t o con-secutive metaxylenol the melting point 74.5". Nolting isolated thecompound from commercial xylidine, and found the melting pointl49". This melting point is now confirmed by preparing metaxylenolby heating pure parahydroxymesitylic acid ; the product melted a t47-48'.The xylenol previously obtained (Zoc. cit.) was paraxylenol.Nitronitrosoresorcinol. By C:. DE LA HARPE and F. REVERDINN. H. M.N. H. M.(Bull. SOC. Chim., 49, 760-763).-Nitronitrosoresorcil/ol,[OH: NO,: 0 : NOH = I : 2 : 3 : 41,is obtained when a cooled mixture of nitroresorcinol (1 mol.), meltinga t 85", with a solution of soda (1 mol.) in 10 parts of water and anaqueous solution of sodium nitrite (1 or 2 mols.) is gradually addedt o excess of dilute and well-cooled sulphuric acid. The yellow,flocculent precipitate is washed with water, dried over sulphuric acid,and extracted with ether to ~emove traces of nitrosoresorcinol.Itcvystallises from alcohol in brownish needles, and is readily solublein water, acids, and alkalis, but only moderately soluble in alcohol,and insoluble in ether, benzene, and chloroform. It is not changedwhen heated to about 200", but at higher temperatures it deflagratesviolently. It yields diamidoresorcinol (compare Bite, Ber., 8, 631)when reduced with tin and hydrochloric acid. The aqueous solutioiigives an intense green coloration with ferrous sulphate o r with ironfilings, and a slightlly acid solution of the colouring matter, which ca42 ABSTRACTS OF CHEXICAL PAPEkS.be precipitated from the aqueous solution by adding sodium chloride,dyes wool green (compare F h r e , Abstr., 1883, 733). Concentratedsnlphuric acid added to a mixture of resorcinol and nitronitroso-resorcinol? produces a green colour, which changes to blue and t,hen toa dirty violet; from this solution water precipitates brown flocks,which dissolve in alkalis with a greenish-brown coloration.Nitroresorcinol, [(OH), : NO2 = 1 : 3 : 41, melting at 115", doesnot form a nitroso-derivative when treated as described above.Condensation-product of Quinone and Ethyl Acetoacetate.By H.V. PECHMANN (Ber., 21, 3OO5-WO6) .-A Condensation-product,C16H1606, is formed when quinone (1 gram) is heated a t 100" withethyl acetoacetate (2.5 grams) and a 50 per cent. solution of zincchloride (6 grams) in absolute alcohol. It melts a t 184", and is solu-ble i n boiling alcohol or glacial acetic acid, but insoluble in water.The solution in Concentrated sulphuric acid turns deep blue whenheated.It yields crystalline derivatives when treated with bromine,but it is not acted on by phenylhydrazine, benzoic chloride, sodiumethoxide and alkyl iodides, or by boiling hydriodic acid. A crystallinebibasic acid, C14K1,06, is precipitated when the preceding compound ishydrolysed with alcoholic potash and the solution acidified with aceticacid. It sublimes without melting, and is insoluble in all ordinarysolvents. The potassium salt, C,4HloK206 + 2H,O, is a colourless,crystalline, spariugly soluble compound, and loses its water at 125".F. S. I(.Derivatives of Paramidoisobutylbenzene. By C. GE LZER(Ber., 21, 2941-2949, and 2Y49-2961).-l?aracetarnidobromisobutyl-benzene, C4HS*C,H,Br.NHAc, prepared by brominating acetamidoiso-butylbenzene: crybtallises from hot dilute alcohol or benzene in large,shining scales or plates, and melts a t 1.53".It is readily soluble inalcohol, hot benzeoe, ether, carbon bisulphide, and chloroform, butonly very sparingly soluble in boiling water.B~Iiir7obrumi.sobzctylbenzene, C4H,*C6H,Br*NH2, is a heavy,. yellowish,aromatic-smelling oil, boiling a t 264-265" (710 mm.) with decom-position, and volatile with steam ; i t is readily soluble in alcohol, ether,and benzene, b u t insoluble in water. The hydrochloride, CloHI4NBr,HCl,crystallises from benzene in moss-like needles, and is readily soluble inwater, alcohol, and warm benzene, but almost insoluble in ether. Theplatinochloride, (CloH14NBr)2,B ZPtCI6, obtained by precipitating a coldalcoholic solution of the base with a hydrochloric acid solution of platinicchloride, crystallises in slender,.yellow needles, and is readily solublein alcohol, but only sparingly in cold water, and insoluble in ether;it is decomposed when boiled with water. A light yellow, crystallinesubstance, ( CloH14NBr),PtCl,, is obtained when a cold alcoholic solutionof the base is precipitated with a neutral solution of platinic chloride ;it; is sparingly soluble in cold alcohol, and is decomposed when thesolution is heated. The picrate, CloH14NBr,CsH,N,07, separates froma mixture of warm benzene and light petroleum in slender, yellow,spear-shaped crystals, and is readily soluble in cold alcohol, ether, orliot water, but only sparingly in cold water or cold benzene, andmoderately soluble in hot benzene.F.S. ICORQANIC CHEMISTRY. 43Bi-onzisobutylbenzene, C4H,.C6H4Br, obtained by treating the amido-derivative with nitrous acid and distilling the product, is a heavy,slightly yellow, aromatic-smelling oil, boiling a t 231-232" (710 mm.),and only slightly volatile with steam. It is readily soluble in alcohol,ether, and benzene, but irisoluble in water. It yields metanitrobenzoicacid when heated a t 235-240" with nitric acid of sp. gr. 1.15.17letanitroi-cobzLtylbenxene, C4HS*CqH4-NO2, obtained by treating theamido-derivative with nitrous acid, and fractionating the product in apartial vacuum, is a bright yellowish-red, aromatic-smelling oil, boil-ing a t 250-252" (740 mm.).It yields metanitrobenzoic acid whenheated at 200" with nitric acid of sp. gr. 1.12.I~iti-oisobut2/l~henoZ, [C4Hg : NO, : OH = I : 3 : 41, prepared byboiling amidonitroisobntylbenzene with dilute potash and distillingthe product, separates from alcohol in yellowish-red, deliquescentcrystals, melts at 95", and boils at 289-290" (711 mm.) with onlyslight decomposition. It is readily soluble in alcohol, ether, benzene,light petroleum, alkalis, and hot water.Metainidoisobuty lbenzene, C4H9*Cj6H1*NH,, prepared by reducing thenitro-derivative with stannous chloride and hydrochloric acid, is ayellowish oil, boiling a t 229' (708 mm.), and moderately volatilewith steam. It is readily soluble in alcohol, ether, and benzene, b u tonly sparingly in water.It dissolves in a solution of bleachingpowder with a bright riolet colour, and with potassium dichromateand sulphuric acid yields a reddish-violet coloration, which quicklychanges to brown. The hydrochloride, ClOH,,N,HCl, crystallisesfrom hot benzene in colouiless plates, and is readily soluble in aaterand hot alcohol, but only sparingly soluble in benzene. The platino-chloride, ( C,oH,,N)2,H,PtCl,, crystnllises in bright yellow plates, andis readily soluble in boiling water and hot alcohol, but only sparm.glyin benzene and ether. The ozalate, CloH&,C2H204, crysthllisesfrom hot water or dilute alcohol, in which it is readily soluble,in large white plates. The acetyl-derivative, C4Hg*C6H4*NHAc, crys-tallises from boiling water in colonrless, shining plates, melts at 101",and is readily soluble in alcohol, ether, and benzene.n~etacetamidonit,.oisobzctylbenzene, [C4Hg : NO, : NHAc = 1 : 2 : 31,obtained by nitrating the acetamido-derivative, crystallises from hotdilute alcohol in small, yellow needles, melts a t 105*5", and is readilysoluble in alcohol, benzene, and ether, but very sparingly in boilingwater.Ainidonitroisobut?lZbenzene, C4H9.C,H,(X0,)*NH2, separates fromdilute alcohol in bright yellow crystals, melts at 1 2 4 , and is readilysoluble in alcohol, ether, benzene, and boiling water, but sparinglysoluble in cold water.It is only a feeble base, and the salts arereadily soluble.Dia.r.lzidoisoEutyZbenzene, [CIHg : (NH,), = 1 : 2 : 31, prepared byreducing the preceding compound with stannous chloride and hydro-chloric acid, crystallises from alcohol in colourless plates, melts atlog", is readily soluble in water, alcohol, ether, and benzene, andblackens on exposure to the air.The oaalate, (CloH16N,),,C2H204,crystallises in flat needles, and is readily soluble in boiling water, butonly sparingly in cold, ahsolute alcohol, and almost insoluble in ether44 ABSTRACTS OF CHEMlCAL PAPERS.an alcoholic solution of the dinmine is mixed with a glacial aceticacid solution of phenanthraquinone. It separates from hot dilutealcohol in yellow nodular crystals, melts a t 144" with previous soften-ing, and is readily soluble in warm alcohol, ether, and benzene, butonly sparingly in boiling water.It dissolves in concentrated nitric acidwith a brownish-red. in concentrated sulphuric acid with a scarletcoloration, and is precipitated unchanged from both solutions onadding water. U NCPh\N*CPhHBenzilisobuty@hennzitze, C,Hg*C6H,/ I \, prepared in like man-ner from the dinmine and benxil, crystallises in small, light-yellowprisms, melts a t 96", and is only sparingly soluble in cold alcohol, butreadily in ether, benzene, and hot alcohol. It dissolves in concen-trated nitric acid or concentrated sulphuric acid, but is precipitatedunchanged on adding water.AcefLt?nidobromonifroisobuf!llbenzene, C4Hg~C,H,Br(N0,)~NHAc, pre-pared by nitrating acetamidobromisobutylbenzene, crystallises froma mixture of ether and light petroleum in small, rhombic plates,melts at 144O, and is readily soluble in hot alcohol, ether, or benzene,but only very sparingly soluble i n boiling water.Amidobromonitroisobuty Zbenxene, C,Hg*c6H2Br( NO,) .NH2, crystallisesin long needles, melts a t 69*5", boils a t 278-280" with partial decom-position, and is volatile with steam.It is very sparingly soluble inboiling water, but readily in alcohol, ether, and benzene.Diamidobromisobutylbenzene, c4Hg*C6~,Br(N&),, obtained by re-ducing the preceding compound with stannous chloride and hydro-chloric acid, crystallises from ether in slender, colourless needles,melts a t 85*5", and turns brown on exposure to the air. It sublimeswith considerable decomposition, forming colourless needles whichare stable in the air. It is readily soluble in alcohol, ether, andbenzene, but only very sparingly in hot water.Ferric chlorideproduces a brownish-red coloration ; bleaching powder precipitatesoily drops, and platinic chloride gives a brownish-black coloration in ahydrochloric acid solution of t.he base. The oxulate,C1oH15BrNzl CJLO4,crystallises in small needles, and is moderately soluble in boilingalcohol, but only sparingly in ether, benzene, and warm water. Thepicrate, CloHlbBrN2*2, C6H3N307, crystallises from hot water in yellowneedles. and is readilv soluble in alcohol and ether.lises from boiling alcohol in slender? yellow needles, melts- at 153-5",and is readily soluble in benzene, ether, and boiling alcohol, b u tonly sparingly in cold alcohol.It dissolves in concentrated mineralacids, forming red solutions, from which it is precipitated unchangedon adding waterORGANIC CHEJIISTET. 45X*C*Ph\N*C-PhBeiizilbromisobuty ~ h e n a z i ~ e , C4Hg*C,H2BJ I II 3 crystallises fromhot alcohol in colourless needles, melts at 172", and behares towardssolvents similarly to the preceding compound ; it dissolves in (son-cen trated acids with a yellowish-red coloration.Dibi-oniisobutylbenzene, [C4Hg : BrP = 1 : 3 : 51, obtained by heatingmetabromisobutylbenzene with bromine in presence of iodine, anddistilling the product with steam, is a light yellow oil, boils a t376-277" (718 mm.), and is readily soluble in all ordinary solventsexcept water. When heated a t aboxt 250" with nitric acid, sp.gr.1.20, i t is converted into symmetrical dibromobenzoic acid.F. S. K.Decomposition of some Diazo-compounds by Formic andAcetic Acids. By W. R. ORNDORFF (Amer. Che1.12. J., 10, 368-372).-The decomposition of diazo-compounds by formic acid might beexpected to furnish an easier means of displacing the amido-group byhydrogen than the decomposition with alcohol. But the reactionproceeds otherwise and could not be followed out, a9 the phenylformate that was probably formed could not be isolated. Substitut-ing acetic acid for formic acid, it is shown that phenyl acetate is pro-duced ; the yield is, however, small, as milch tar is also formed ; thereaction is analogous to the production of phenetnil by the action ofalcohol.The boiling point of phenyl acetate has been variouslystated; it has been redetermined as 195" at 733 mm. pressure.Similarly, paradiazotoluene sulphate, when boiled with acetic acid,yields paracresyl acetate, boiling a t 213", and identical with that pre-pared from paracresol. Paradiazobenzenesulphonic acid appears toundergo a similar change, and the reaction therefore seems to begeneral. H. B.Chryso'idincarbamide. Amidophenylenecarbamide. By A.JENTZSCH (J. pr. Chem. [ 2 ] , 38, 121-139). -When carbonylchloride is passed into a moderately strong solution of chrysoidinin dry chloroform, it is rapidly absorbed with development of heat,and red-brown flocks separate which become of a darker brown as theaction proceeds. The brown matter is collected, dried, powdered,heated with dilute hydrochloric acid, and filtered hot ; brilliantgolden-yellow laminae crystallise out on cooling, together wit8h octo-hedral crystals of diamidoazobenzene hydrochloride. By dissolvingthe mixed crystals in alcohol and adding ammonia, golden-yellowneedles of the correspoiiding bases are obtained, which may besepars ted by digestion with chloroform, the diamidoazobenzene beingdlssolved. The residue, consisting of the new base, is purified by dis-solving in alcohol and passing hydrogen chloride through the solutionto obtain the hydrochloride which is then decomposed by ammonia.Chrysozdincarbarnide, NPh:NC,H,:(NH)Z:CO, thus obtained, crys-tallises in brilliant, golden-yellow laminae, sparingly soluble in alcohol,nearly insoluble in water, ether, and chloroform. It does not meit at300".I f the chloroform solution of diamidoazobenzene be satur;rtedwith carbonyl chloride and allowed to stand for some days, onl46 ABSTRACTS OF OHEMMIGAL PAPERS.carbamide hydrochloride and unaltered chrysoi'din hydrochloridewill be found on evaporating the chloroform. The hydrochloridecrystallises in golden-yellow laniinse, sparingly soluble in water,more so in alcohol, insoluble in ether. The pZatiizochZoride,( C13H11NaUC1)2PtC14, forms red-brown laminse. The nitrate crystal-lises in brilliant, golden-yellow scales, very sparingly soluble in water,sparingly soluble in alcohol, and insoluble in ether ; they decomposewith slight explosion at above 200". The suZphate forms a yellowish-red powder ; it is very sparingly soluble in water, more so in alcohol.When heated with moderately strong hydrochloric acid in a sealedtuhe at 200" for eight hours, chrysoidincarbamide is decomposed,with the formation of carbonic anhydride and a dark-brown mass.The same dark-brown substance is obtained when chrysoidin istreated in the same way. It yields phenol when distilled with steam,and a reddish-brown residue which has not been identified.Inasmuch as chrysoidin splits up into aniline and triamidobenzenewhen reduced by hydrochloric acid and tin, it seemed probable thatits carbamide would yield aniline and a new substance,by the same treatment, thus showing that both NH-groups areattached to the same benzene nucleus.100 grams of the carbarnidewere heated with 50 grams of tin aud 250 grams of hydrochloricacid (sp. gr. 1.2) in a flask. The solution became colourless at first,and subsequently brown, through oxidation ; after the action hadceased, the hydrochloric acid was evaporated, the residue dissolved inhot water, and hydrogen sulphide passed through the solution ; thefiltrate from the tin sulphide was evaporated in a current of hydrogensulphide, the crystalline residue dissolved in water, and made alkalinewith barium hydroxide. This precipitated aniline, which was dis-tilled off; the excess of barium hydroxide was precipitated from theliquid remainisg in the retort by sulphuric acid, and the excess ofthe latter by barium chloride. From the filtrate, the hydrochloride ofthe new base did not crystallise well, so the solution was digested withammonium oxala te and filtered hot.On cooling, amidophenyZene-arbamide oxalate crystallised out in nearly white minute needles,collected in spheres, freely soluble in hot, sparingly in cold water,nearly insoluble in alcohol.Amido~he?zyZerzecai.bnmide, NHz*C6H3: (NH),:CO, obtained from theoxalate by adding sodium carbonate to a hot solution of it in hydro-chloric acid, forms brilliant and nearly colourless, pointed laminm,sparingly soluble in cold, easily in hot water, freely soluble in hotalcohol, and decomposing at 220". The hydrochloride crystallises inminute needles, freely soluble in water, very sparingly so in alcohol.The sulphate also forms minute needles, having the same solubility.The triacetyZ-derivutzve, NHAc.C6H3:(NAc)z:C0, forms fine, white,silky needles, insoluble in water, fairly soluble in alcohol, and meltingat 248'.NH,* CsH,: (NH),:CO,/NH*CO\c 6 H 3 \ ~ ~ - ~ ~ / N 7Dicarboity ltriainidobenzene, was obtainedbeating amidophenylene carbamide with liquid carbonyl chloride in ORGANIC CHEMISTRY.47sealed tube for eight hours at 130". The excess of carbonyl chloridewas evaporated and the residue heated with water, which extractedthe hydrochloride of the carbamide fo~med during the reaction, andleft the carbonyl compound as a crystalline residue, insoluble inalcohol, ether, benzene, toluene, aniline, and acids, but very solublein alkaline solutions, from which it is precipitated by acids.By passing nitrous acid through a cooled, acidified aqueous solutionof the sulphate of amidophenylenecarbamide, yello wish-green crystals,giving the reactions of a diazo-compound of the carbamide, wereobtained, but they were not pure.By dissolving them in hydro-bromic acid and adding a few drops of bromine, yellowish-red needlesof the perbromide of the diazo-compound crystallised out- ; these lostbromine as they dried, and by digesting them with warm alcoholthey weye converted into yellow crystalline laminm of the diazo-hroinide of amidophenylenecarbamide.By H. v. PECHMANN and I(. WEHSARG (Rer., 21,2994 - 3004).-Nitrosoa~etonehydrazone (methylglyoxal-aw- hydrciz-oain2 e ) N,H Ph: CMe.CH:NO H, prepared by mixing nit rosoacetone(1 mol.) with phenylhydrazine (1 mol.) in alcoholic or ethereal solu-tion, crystallises from alcohol in yellowish prisms or needles, melts at134", and is soluble in ether and benzene, but insoluble in hot water.It dissolves in concentrated sulphuric acid with a reddish-yellowcolour which becomes deep blue on adding ferric chloride.Met hylglyoxalosnzone hydrochloride is obtained when the precedingcompound is warmed with concentrated hydrochloric acid in alcoholicsolution. It crystallises from boiling methyl alcohol, melts a t 197",and yields the free base (compare Abstr., 1888, 1287) when treatedwith ammonia.A. G.B.Hydrazoxirnes.Diacety Eli ydrazoxime (methylnitrosoacetone h ydraxone) ,CMe(N,BPh)*CMe:NOR,prepared in like manner from nitrosometbylacetone, crystallises fromdilate alcohol in large, colourless needles, melts at 158", and resemblesnitrosoacetonehydrazone in its behaviour towards solvents. It dig-solves in concentrated sulphuric acid with a yellow coloration whichchanges to a bluish-violet on adding ferric chloride, and when heatedwith concentrated hydrochloric acid in alcoholic solution, yields amixture of diacetylosazone melting at 241--242", and diacetyl-hydrazone melting at 13.3".Gl~/ox~Zcya?zide-a-hydrazone, CRO*C(N,HPh).CN, is formed,together with hydroxylamine, when dinitrosoacetonehytlrazone (com-pare this vol., p.34) is warmed with alcohol and hydrochloric acid.It crystallises from boiling alcohol in pale-yellow needles, melts at161" with decomposition, and is dissolved on warming in most sol-vents except water.It is soluble in dilute alkalis, and dissolves inconcentrated sulphuric acid with a yellow colour which is not changedby ferric chloride. When boiled with hydriodic acid, it yields thetheoretical quantity of aniline.Glyoxy Zr y anideosazone, NZHP h:CH*C (N2HPh) *CN, prepared bymixing a hot, alcoholic solution of the preceding compound wit48 ABSTRACTS OF CHEMICAL PAPERSphenyl hydrazine, cry stallises from alcohol in orange-red needles, meltsat 161" with decomposition, and is soluble in alcohol and glacial aceticacid, but, only sparingly in most other solvents. The concentratedsiilphnric acid solution is yellowish-red, and its colour is not changedbv ferric chloride..IGlyoxylcyarLideosotetrazone, < ~ ~ ~ ~ ~ $ is formed when thepreceding compound is m-armed with ferric chloride or with a solutionof potassium dichromate and dilute acetic acid. It crystallises fromacetone or alcohol in brownish-red, moss-like needles melting at 137"with decomposition. When heated with hydrochloric acid, a colour-less, crystalline product, probably an osotriazone (loc. cit.) volatilises.This compound, CgH6N@:N2Ph, is formed by the combination ofglyoxylcyanidehydrazone with diazobenzene chloride ; it crystallisesfrom alcohol in brownish plates, melts a t 162-163", and is insolublein alkalis.Gll/ox?/lcZlanide-aw-hydrazox~~ne, NOH:CH.C(N,HPh).CN, preparedby boilicg an alcoholic solution of the hydrazone (1 mol.) withhydroxylamine hydrochloride (1 mol.) and a few drops of hydro.cliloric acid, crystallises from alcohol in citron-yellow, sparinglysoluble needles melting a t 240" with decomposition.It dissolves inalkalis with a yellow coloration, but the yellow, concentrated sul-phuric acid solution is not changed on adding ferric chloride.A compound, C,H,N 4, is obtained when glyoxylcyanidehydrax-oxime is dissolved in phosphorus oxycbloride, heated with phosphoricchloride, the solution poured on to ice, the precipitated product ex-tracted with ether, dissolved in dilute alkali, and fractionally pre-cipitated with hydrochloric acid. It crystallises from a mixture ofether and light petroleum in yellowish needles, melts a t 135" withdecomposition, and is soluble in hot water, alkalis, and most of theordinary solvents. It dissolves in Concentrated sulphuric acid with ablood-red coloration which is not changed on adding ferric chloride.When warmed with concentrated hydrochloric acid or when boiledwith alcoholic potash, it is converted into a ccmpouiid, C9H9N40,which crystallises in small, yellow needles melting a t 244-245".- A compound, C,,H,,N,, is formed i n the preparation of glyoxyl-cyanidehydrazone, and can also be obtained by heating the hydraz-oxime with alcohol ( 3 patbts) and cmcentrated hydrochloric acid(10 parts).I t crystallises from benzene in shining, orange-yellowplates melting a t 165", and does not give the osazone reaction(loc. cit.).MethylgZyoxal-ocw-met?~Zl~hen~~l~iy~~raz~~~~e, N,MePh:CMe*CH:NOH,prepared by mixing an aqueous solution of nitrosoacetone with asolution of methylpbenylhydrazine sulphate and sodium acetate,-crystallises from dilute alcohol in orange-yellow prisms melting at118".Alkaline solutions are dark yellow, and the yellow, concen-trated sulphuric acid solution changes to violet on adding ferricchloride.Mesoxala7deh yde- a w w-n7 eth y lphen y lh ydrazonedioxim e (dinitrosoaceton emethylphenylhydruzolze), N OH:CH.C(N,MePh)*CH:NOH, prepared inlike manner, crystallises from dilute alcohol in orange-yellow ueedleORGANIC CHEMTSTRY. 49or plates, melts a t 137", and is soluble in alkalis and most of theordinary solvents. It dissolves in concentrated sulphuric acid,forming a brownish-red solution in which ferric chloride produces alight violet coloration.When heated with hydrochloric acid, it yieldsdecomposition products the nature of which varies according to theconditions of the experiment.Glyoxylcyanide-a-msfhyZphenylhydrnzone, CHO*C(N,MePh).CN, isobtained by dissolving the preceding compound in acetone ( 7 parts),adding concentrated hydrochloric acid (7 parts) and, after the firstenergetic reaction is a t an end, heating the mixture for about aminute and adding water to the cold solution. It crystallises frombenzene, alcohol, or light petroleum in yellow, feathery needles, orthick, spear-shaped crystals, melts a t 113*5", and is insoluble inalkalis. When mixed with phenylhydrazine, it yields a compound,probably N,HPh:CH.C (N,MePh) CN, which crystalliseq from abso-lute alcohol in golden-yellow plates melting a t 181".The and,NPh:CH*C (X,MePh).CN, prepared by mixing the hpdrazone withaniline i n acetic acid solution, crystallises from alcohol in slender,yellow needles, melts a t 150-151°, and is reconverted into thehy$hzone when warmed with dilute hydrochloric acid. The hydrar-oxz112e, NOH:C H*C (N,MePh).CN, obtained by treating the hydrazonewith hydroxylamine, crystallises in small, yellow needles melting at178'. The acetyl-derivative, NOAc:CH*C(N,MePh).CN, of thehydrazoxime crystallises from alcohol in yellow needles, melts a t122*5", and is reconverted into the hydrazoxime when boiled withsoda. F. S. K.Ethyl Phenylhydraxineacetylacrylate. By H. D ECICER (Ber.,21, 2937-2938).-Tbe compound obtained by Bender (Abstr., 1888,1188) by hydrolysing ethyl phenylhydrazineacetylacrylate, has alreadybeen fully described by L.Wolff (Abstr., 1887, 464). F. S . K.Theory of Dyeing. By E. KNECHT (Ber., 21, 2804-2805 ; com-pare Abstr., 1888, 832).-When wool is boiled with a mixture ofsulphuric acid (2 parts) and water (3 parts) for two hours, it dissolvesalmost entirely ; when filtered, a clear, light-brown solution is ob-tained. If this is mixed with aqueous solutions of acid coal-tar dyes,intensely coloured precipitates are formed, which dissolve readily inalkalis, but not in water or dilute acids.A solution of silk in moderately dilute sulphuric acid behaves inlike manner. Animal fibres, therefore, yield a substance which formsinsoluble bases with acid coal-tar dyes; it has not yet been deter-mined whether this substance already exists in the fibres, or whetherit is gradually formed by the action of the acid bath.N. H. M.Product of the Action of Nitric Acid on Acetophenone. ByA. F. HOLLEMAR" (Bei-., 21, 2835-2840 ; compare Abstr , 1888, 275).-The molecular weight of the compound C,,H,,N,04. obtained by theactioii of nitric acid on acetophenone (Zoc cit.), was confirmed by adetermination by Raoult's method (BPT., 21, 861). When the alco-holic solution is reduced with stannous chloride, benzoic and hydro-VOL. LVI. 50 ABSTRACTS OF CHEMICAL PAPERS.cyanic acids are formed. By qrolonged boiling with strong hydro-chloric acid, it is decomposed into benzoic and oxalic acids; am-monia and hydroxylamine are also formed.These reactions makeit probable that the compound has the constitution <CBaiN.O>, CBz'N-0which is further supported by the fact that the substance, which isnamed diphenyldi.nitrosacyl, can be prepared by oxidising nitroso-acetophenone.Diphenjldinitrosacyl reacts with aniline with formation of benz-anilide and a compound crystallising in lustrous, brown needles.When this is heated a t 100" €or some time, it gives an odour somewhatlike that of carbylamine : when crystallised from dilute alcohol, it isnearly white, and melts a t 205".When diphenyldinitrosacyl is heated with acetic anhydride at110-120" for six hours, the compound C,6H10N204 + OAc, is formed.This crystallises in stellate groups of needles melting at 149".The sparingly soluble compound melting at 177-179", which is alsoobtained by the action of nitric acid on acetophenone (loc.cif.), hasthe same empirical composition as diphenpldinitrosacyl ; it is, how-ever, much more stable than the latter. Boiling aqueous potash andhot sulphuric acid decompose it, yielding benzoic acid ; with potash,ammonia is evolved. N. H. M.Consecutive Duryl Methyl Ketone. By A. CLAUS and E.FOHLISCH ( J . pr. Chew. [a], 38, 230-235; compare Abstr., 1888,275) .-The boiling point of consecutive dureno is 199-200" (uncorr.)and its melting point is -4".Consecutive duryl methyl ketone, C6HMe4*COMe [Me4 : COMe =2 : 3 : 4 : 5 : 11, is prepared in the manner previously described, bywhich 80-90 per cent.of the durene used is couverted into theketone ; it is a brown, strongly refractive oil, of agreeable aromaticodour, boiling a t 258-260" (uncorr.), and easily soluble in the nsualsolvents, except water. The pkenylhydrazine compound forms,,colourless laminae melting a t 129" (uncorr.).2 : 3 : 4 : 5 - 1 ' e t r a m e t h y ~ ~ ~ e n y ~ g l y o a y ~ i c acid, C6Hh!fe4*CO*COOH,is formed when the above ketone is oxidised with potassium perman-ganate in the cold. It is a bright yellow syrupy oil, very little solublein cold, more so in hot water, very soluble in alcohol, ether, carbonbisulpliide, and chloroform ; it solidifies on prolonged cooling anddecomposes when heated. The barium and calcium sa2ts (with 4mols.H,O), the copper (with 3 mols. H,O), azd the silver salts aredescribed.2 : 3 : 4 : El-Tetramethylmandelic acid, C6H%~e4.CH(OH)*COOH, isobtained by reducing the foregoing acid with sodium amalgam. 'Itcrystallises from alcohol in colourless hexahedra, sparingly soluble incold, readily in hot water and in alcohol, ether, and chloroform, andmeits at 160" (uncorr.). The potassium (with 4 mols. H,O), barii~m(with 3 mols. H,O), calcium (with 24, mols. H,O), and silver salts aredescribed.2 : 3 : 4 : 5-Tetrainethy123herz2llacstic acid, C6HMep-CHz.COOH, isformed when either of the above described acids is reduced witORGANIC CHEMISTRY. 51hydriodic acid. It crystallises from hot water in slender, colourlessneedles, me1 ting a t 125" (uncorr.), and easily soluble in alcohol, ether,and chloroform.The calcium salt forms colourless, silky needles con-taining 3 mols. H,O.By oxidising consecutive duryl methyl ketone or the foregoing de-rivatives, with the calculated quantity of potassium permanganate, ata gentle heat, 2 : 3 : 4 : 5- tetramethylbenzoic acid is obtained as athick, colourless oil, sparingly soluble in water, freely so in other sol-vents. When heated, it decomposes a t 270°, and an oil distils over, whichsolidifies and melts at 150" ; this contains 73.8 per cent. of carbon and7.9 per cent. of hydrogen. The sodium (with 3 mols. H,O), calcium(with 3 mols. H,O), bariunc (with 6 mols. H,O), silver and coypel- saltsare described. A. G. B.Stilbene. By I;. ARONSTEIN and A.F. HOLLEMANN (Ber., 21,2831-%334) .-The experiments described were made with a vicwto obtain a geometrical isomeride of stilbene which should existaccording to Wislicenus' theory. No definite results were obtained,but the investigation is being continued.Action of Heat on Benzildihydrazone. By I(. AUWERS and V.CPh'N M E ~ R (Ber., 2 1,2806 -2 80 7). --Tripheny losotriazone, < CPhiN >NPh,formed when benzilhydrazone is heated with alcohol at 200-210",crystallises in white, lustrous plates, melts a t 122O, and boils withoutdecomposition. N. 13. M.Thio-derivatives of p-Dinaphthylamine. By 0. KYN (Ber., 21,2807-28 13) .-When sulphur chloride dissolved in benzene is addedto /3-dinaphthylamine, also dissolved in benzene, hydrogen chloride isevolved and two isomeric dithiudinaphth ylainines, C20H13NS2, are ob-tained.The one forms lustrous, brass-coloured plates melting a t 205O,whilst the other crystallises in reddish-yellow prisms melting a t 220".Both compounds are sparingly soluble. When the dithio-compoundsare boiled with cumene or with aniline, they are both converted withevolution of carbon bisulphide into Ris's thio-P-dinaphthylamine(Abstr., 1886, 1036). A small quantity of the latter compound isformed in the reaction between dinaphthylamine and sulphur chloride.Acetylthio-p-dinnphthylainiwe, Cz2Hl5NOS, is obtained by the actionof acetic anhydride on the dithio-compound (ni. p. 605") or on themonothio-compound. It crystallises in slender, lustrous, almostwhite needles, melts a t 211", and is readily soluble in hot alcohol orbenzene. When the dithio-compound (m.p. 205O) is treated with anammoniacal alcoholic silver solution, a compound free from sulphuris obtained, which melts a t 240°, and sublimes in slender, lemon-yellow needles.Sulphur dichloride acts on p-dinaphthylamine, yielding as chiefproduct thio-p-dinaphthylamine, and a sparingly soluble isomeridewhich melts a t 303". Sometimes a small amount of a compound,probably thiotetranayhthylanline, S ( C,oH6*NH.CloH7)2, is obtained.This forms dark-yellow crystals melting at 307".N. H. M.N. H. M.e 52 ABSTRACTS OF CHEMICAL PAPERS.Naphthoic Acids. By A. G. EKSTRAND (J.pr. Chem. [2], 38,139--285).-This paper is a summary of the author's work on thesubject; much of it has already appeared.The following new corn-pounds are described :-Chloro-a-naphthoic arnide is obtained by heating chlopo-a-naphtho-nitrile (Abstr., 1884, 1361) with an alcoholic solution of potassiumhydroxide ; it forms crystalline laminae, soluble in alcohol andmelting a t 239".The chloro-a-naphthoic acid which melts a t %5" (Abstr., 1884,1361) has the constitution [COOH : C1 = 1 : 4'1, as it is obtained bytreating 1 : 4' amido-a-naphthoic acid by Sandmeyer's method (Abstr.,1884, 1312).Chloro-a-nayhthoic a,cid (1 : 1') is obtained when 1 : 1' amido-a-naphthoic acid (Abstr., 1885, 549) is dissolved in the calculatedquantity of sodium hydroxide and potassium nitrite (1 mol. to 1 mol.of the amido-acid) added ; the mixture is cooled to 0" and treated withexcess of hydrochloric acid.The hydrochloride of the diazonaphthoicacid thus obtained is added to a boiling solution of cuprous chloridein hydrochloric acid ; colourless crystals of the chloro-acid areformed ; they melt a t 167" and sublime as plates. The calcium saltcrystallises with 2 mols. €LO in long tabular needles, soluble in 42parts of water at the ordinary temperature. The ethyZ salt formslong needles melting at 50".Dichlor-a-naplithoic acid is obtained when the foregoing acid isdissolved in glacial acetic acid, some iodine added, and chlorine passedt o saturation ; crystalline scales separate, melting at 186-187".The calcium salt crystallises with 2 mols. H,O in long, colourlessneedles ; the ethyl salt forms fine needles melting at 61".It is possible to obtain this acid from chlornitro-a-naphthoic acid[COOH : NO, : C1 = 1 : 1' : 4'1 (Abstr., 1886, 156), consequently itsconstitution is [COOH : C1 : C1 = 1 : 1' : 4'1.Trichloro-a-nap hthoic acid, the mother-liquor from the preparationof chloro-a-naphthoic acid (1 : 4') by the action of chlorine on a-naph-thoic acid in acetic acid solution, is saturatedwith chlorine at the boilingpoint : dilution with water then throws down a crystalline precipitate,which is heated with calcium carbonate, filtered, and the filtrate pre-cipitated with acid ; when crystallised from alcohol and water, thisprecipitate forms small, colourless needles, melting at 163-164' andsubliming in fine needles.The ethyl salt of monobromo-a-naphthoic acid, 1 : 4' (Abstr., 1886,715), forms colourless tables melting a t 48-49'.Mononitro-a-naphthoic acid of meltiug point 215" (Abstr., 1885,54$) is soluble in 21.5 parts of commercial alcohol, and in 2590 partsof water a t the ordinary temperature.During its formation a smallquantity of a-mononitronaph.t//alene (melting point 60') is obtained.The calcium salt of amido-a-naphthoic acid (Absbr., 1885, 549)crystallises with 9.5 mols. H20 in fine needles, soluble in water. Thehydroch Zoride, COOH.C,oH6*NH,,HC1, is precipitated in fine needlesO n adding hydrochloric acid to a solution of the sodium salt.Nsphthostyril, C,,H,<ZE> (Abstr., 1886, 715), crystallises froORGANIC CHEMISTRY. 53an alcoholic solution of the amido-a-naphthoic acid ; it is also formedwhen the acid is heated with water ; it melts a t 180-181".The benxoyl-derivative forms slender needles melting a t 170" ; thehydrochloride melts a t 178".a-Naphtlzoybz aph thostyri1.-When a-naphthoyl chloride and naph -thostyril are heated together, a gi-een product is formed, whichis dissolved in alcohol and decolorised hy animal charcoal. Amixture of granular crystals (melting a t 110") and needles (melt-ing at 132") is obtained ; by recrystallking these, partly from alcoholand partly from glacial acetic acid, a mixture of the same crystals isobtained, melting a t 150"./3-Naphthoylnaphthostyril, is obtained in the same way tw tlie above,only a t a lower temperature, in slender colourless needles, melting atThe calcium salt of chlornitro-a-naphlhoic acid, of melting point225" (Abstr., 1886, 156), forms slender colourless needles, crystallisingwith 3 mols. H,O, and the ethyl salt tabular crystals melting at 121",and very soluble in alcohol.The question whether this acid has theconstitution [COOH : NO, : C1 = 1 : 1' : 4' or 1 : 4 : 4') is settled infavour of the former, as chZoronaphthostyJriB (with C1 in position 4') isobtained in yellow needles melting at 670", by reducing the acid withferrous sulphate in an ammoniacal solution.Nitronaphthostyril (1 : 4') is formed when nitric acid (sp. gr. 1.42)is added to a solution of naphthostyril in glacial acetic acid, and themixture heated on the water-bath ; the crystalline mass thus obtainedis partially soluble in alcohol, from which yellow needles, meltingabout 235", are obtained ; the greater part recrystallises from glacialacetic acid in orange-yellow needles melting a t 300".Both are nitro-nap hthostyrils.Arraidonuplzthostllril is formed when nitronaphthostyril is reducedwith tin and hydrochloric acid. and the hydrochloride thus produceddecomposed with ammonia ; it crystallises in red needles meltinga t 239-240", and freely solable in alcohol and hot water: The hydro-chloride crystallises in yellow needles melting above 290".Dinitronaphthostyrd is obtained when the nitronaphthostyril is heatedwith nitric acid (1.43 sp. gr.) ; it forms yellow needles, or, when pre-pared by the action of nitric acid on naphthostyril, rhombic tables,melting above 290".Naphthostyrilpuinone, C,,H,O,<EE>, is obtained when a Bolutionof naphthostyril in glacial acetic acid is mixed with chromic acid andthen with water; fine red needles are precipitated, which, after re-crystallisation from glacial acetic acid, melt near 278".When it isdissolved in warm glacial acetic acid and an acetic acid solution oftoluylenediamine added, a yellow, crystalline powder, consisting ofnuphthostyriZtoZ~p~inoaali.ne, CllH5N30,C6H3CH3, is obtained ; it meltsabove 290".Nitronaphthosty1.ilquinone forms orange-red needles or tables, melt-ing near 685", soluble in alcohol and sparingly so in glacial aceticacid. A. G. B.19 7-198".The acetyl-derivative melts above 290"54 ABSTRACTS OF C'HERIICAL PAPERRp-Chloronaphthalenesulphonic Acid.By S. FoRsrmG (Be?.., 21,2802--2804).--When ,!3-amidonaphthalenesulphonic acid (Abstr., 1887,962) is converted into the diazo-compound, and this is boiled withstrong hydrochloric acid and neutralised with potassium carbonate,potassi um p-chloronapht h alenesulph onate separates.p- Chloronaph thalenesulphonic chloride, CloH6C1*SO2C1 (Arnell,Ahstr., 1886, Fj55), is prepared by mixing the well-dried potassiumsalt with phosphorus pentachloride and heating ; it crystallises fromchloroform in broad needles melting a t 129".The brornide, CloH6C1*S 02Br, prepared by the action of phosphorusbromide on the potassium salt, crystallises from chloroform in smallneedles melting at 139".The amide, CIoH6C1.S02*NH,, is obtained by boiling the chloridewith a mixture of equal parts of ammonia and alcohol, and crys-tallising the product from dilute alcohol, in which it is sparinglysoluble; it melts at 235".p-Chloronaphthalenesulphonic acid has the constitution [Cl : SOsH= 2 : 4 o r 2 : 1 ] .N. H. M.Filicic Acid. By G. DACCOMO (Bey., 21, 2962-2970) .-Filicicacid, prepared by the method already described (Daccomo, Abstr.,1888,521) , has the composition Cl4H1,O6. It is a yellowish, odonrless,crystalline powder, melts at 179-180" (uncorr.), and. is insoluble inwater, almost insoluble in absolute alcoho1,'moderately soluble in glacialacetic acid, ether, amyl alcohol, and toluene, and readily in chloroform,cwbon bisulphide, and benzene.The benzoyl-deriva tive, C2,H,,0,,separates from dilute alcohol in colourless crystals, melts a t 123", andis very readily soluble in ether, but insoluble in water. The ethytsalt, C,H,,O,, prepared by treating the acid with alcoholic potash andethyl iodide, separates from dilute alcohol in reddish crystals, meltsat 142", and is very readily soluble in ether and benzene, but insolublei n water, The propyl salt melting at 158", and the ethylene saltmelting at 165", resemble the ethyl salt in appearance and solu-bility.Bronzo$Zicic acid, Cl4HI5BrO6, prepwed by treating the acid withbromine in glacial acetic acid solution, crystnllises from alcohol in redprisms, meits a t 122", and is very readily soluble in absolute alcoholand ether, but insoluble in water.AniZidoJiZicic acid, C14HZ50,*NHPh, obtained by boiling a glacialacetic acid solution of the acid with aniline, separates from alcohol inreddish-violet crystals, melts a t 140°, and is soluble in alcohol andbenzene, but insoluble in water.The hydraaide, C,Hl,O.( NZHPh),, prepared by boiling an etherealsolution of the acid with phenylhydrazine, crystallises from ether illred needles, melts at 198", and is readily soluble in alcohol, butinsoluble in waker.When the acid (100 parts) is heated above itsmelting point (compare Luck, AnnaZen, 54, 119), or heated withwater at 170-190", it is decomposed into isobutyric acid (32.5 parts)and a compound, the composition of which is C?OH,AOI. Hydrochloricacid produces the same decomposition at 150-160".Filicic acid is completely oxidised when treated with chromic aciORGANIC CEIEMISTRT.55in glacial acetic acid solution, but when a solution of the potassiumsalt is oxidised in the cold with a 2 per cent. solution of potassiumpermnnganate, isobutyric acid and oxalic acid are obtained. Tbe sameproducts are formed when nitric acid of sp. gr. 1.48 is employed.When the acid is treated with zinc-dust in alkaline solution, i t is con-verted into an acid, the composition of which is probably Cl4Hz2011,and at the same time a small quantity of isobutyric acid is formed.When treated with sodium in amyl alcohol solution, it, yields butyricacid and resinous products.The compound CZOH,80,, referred to above, separates from ether oramyl alcohol as an amorphous, red powder, and has no well-detinedmelting point.It is soluble in most ordinary solvents, has an acidreaction, decomposes carbonates, and dissolves in alkalis, forming redsolutions from which it is precipitated in red flocks on adding acids.It yjelds phthalic acid and small quantities of ovalic acid whenoxidised with nitric acid of sp. gr. 1.40 in the cold. When reducedwith zinc-dust in alkaline solution, it gives a colourless substancewhich rapidly oxidises, and is probably reconverted into the originalcompound.From the above results, it follows that filicic acid is probably anisobutyric acid derivative of hydroxynaplithaquinone. F. S. K.Quillajic Acid. By R. KOBERT (CYhesn. Centr., 1888, 927-928,from Arch.ex$. Path. Pharm., 23, 233).--The saponin of commerce,as all other specimens of saponin, is an almost inactive, non-poisonousmodification of quillajic acid. The author precipitated the acid from theaqueous extract of the bark of Quillaja sapomaria with neutral leadacetate ; the precipitate was fresd from lead, the solution of the acidevaporated almost to dryness, and then taken up with hot absolutealcohol. The colouring matter was precipitated with chloroform ;the quillajic acid eventually crystallised out in pure white flakes. Itis insoluble in ether, soluble in water and alcohol. On treatment withconcentrated sulphuric acid, it becomes dark red. By boiling with dilui emineral acids, it is split up into an unfermentable glucose and sapo-ginin ; this solution reduces Fehling's solution.Quillajic acid hasthe formula Cl,H,oOlo. The sodium salt acts as a very severe causticon the tongue and throat, and the smallest particles coming in contactwith the nose or throat cause violent sneezing and coughing. Broughton to the eye, it causes severe pain, flow of tears, and swelling of thelids. Injected into the blood, the sodium salt proves fatal, causingcramp arid paralysis of the respiratory organs and brain. On theother hand, it may be imbibed into the stomach without injury to theextent of 500 times the quantity which proves fatal when injectedinto the blood. J. W. L.Brazilin. By C. SCHALL and G. DRALLE (Bey., 21, 3009-3017,compare Abstr., 1888, 295) .-Tetramethylbrazilin is best prepared asfollows:-A solution of brazilin (100 grams) in warm 98 per cent.alcohol is mixed with sodium ethoxide (30.26 grams sodium) andmethyl iodide (206 grams), the mixture kept a t 60-70" for 40 to 50hours, cooled and poured into cold water.The precipitate is collected56 ABSTRACTS OF CHEMICAL PAPERS.washed with water, dissolved in ether, the solution shaken with soda( 1 7 2 per cent.), washed with water, the ether evaporated, and theresidue crystnllised from alcohol with addition of animal charcoal.The yield is 58.5 per cent. of the theoretical quantity.Trirnethylbrazilin, C16H1105Me3 + iH,O, is obtained by neutralisingthe alkaline washings from the tetramethyl-derivative, extractingwith ether, washing the extract first with sodium hydrgen carbonate,then with sodium carbonate, and evaporating the ether a t the ordinarytemperature.The residue is mixed with concentrated soda, the pre-cipitated sodium-derivative collected, washed with alcoholic ether,dissolved in water, and precipitated from the filtered solution by treat-ment with carbonic anhydride. If the product is pure, it is obtained inthe crystalline condition containing about 1 mol. H,O, but the impurecompound does not crystallise well even after keeping for months. Itdissolves in dilute alcohol, and the solution gives a brown precipitatewith ferric chloride ; the solution in soda is colourless, and does notalter on keeping. The acetyl-derivative, C16H,,05Me,Ac, is crystalline,and melts a t 95-97" with previous softening.Rrornotetrainethylbrazilin, C16H9BrMe40,, obtained by treating thetetramethyl-derivative (1 mol.) with bromine (1 mol.) in glacialacetic acid solution, crystallises from dil-cite alcohol in long, colourlessprisms melting a t 180-181".A crystalline tetrabromo-derivative, C,,H,Br,Me,O,, is formed whena larger quantity of bromine (2-3 mols.) is employed ; this snbstanceloses bromine (about 26 per cent.) when treated with dilute ammonia,or soda, and appears to be dibromotetramethylbrazilin dibromide. Itis probable that other bromo-derivatives exist, and a crystalline iodo-additive product was also obtained.Tribrornobrazilin dibyomide, C16HllBr305,Br2 + 2H20, is obtained inreddish-brown needles when bromine (4-6 mols.) is added graduallyto a boiling glacial acetic acid solution of brazilin.A compound, C20Hld09, is obtained when brazilin (2.7 grams) isdissolved in water (150 c.c.) and soda of sp.gr. 1.37 (10 c.c.), and astream of air passed through the solution for about 36 hours. Itcrystallises from alcohol in light brown, flat, microscopic needles,melts at &71", and is readily soluble in dilute soda, sparingly solublein ether or sodium carbonate, and insoluble in sodium bicarbonate.The aqueous alcoholic solution gives a slight violet coloration withferric chloride, and a citron-yellow coloration with concentratednitric acid. When heated above its melting point, shining scalessublime, but considerable' decomposition takes place. F. S. K.Nomenclature of Compounds containing NitmgenousNuclei.By 0. WIDMAN ( J . pr. Chem. [a], 38, 185-20l).-A newsystem of nomenclature for the quinoxalines and compounds of alliedstructure. (Compare Mason, Proc., 1888, 109.)Metapyrazolones. By E. GRINAUX (BUZZ. SOC. C'him., 49, 739-740) .-The compounds described by Pinner and Lifschutz, and namedby them metapyrazolone-derivatives, are derivatives of glycolylcarbORGANIC CHE3IIISTRY. 57amide or hydantojin, and the isomeric substances which Pinner andLifschutz name metapyrazole-derivatives are simple ureides.P. S. K.Action of Phenylhydrazine and Hydroxylamine on Acetyl.acetone. By A. COMBES (Bull. SOC. China., 50, 145-146 ; compareibid., 48, 471) .-Dimethy~hei.ly~yrazole, CMe<Nph,N>CMe, isformed by the action of phenylhydrazine on acetylacetone : it boilsat 270.5".Derivatives of Methylpyrroline. By G.DE VARDA (Ber., 21,28 7 1-28 74) .-MethyZtetrabromo~yrrol~ne, C4NBr4Me, obtained bydigesting tetrabromopyrroline with caustic alkali and methyl iodidedissolved in methyl alcohol, crystallises from light petroleum in long,colourless needles, which melt at 154-155" to an intensely blueliquid.Dibromomaleinmethy limide, C4Br,0zNMe, is prepared by slowlyadding tbe above t,etrabromide to fuming nitric acid (3 parts), cooledto 0", and pouring the product into water (10 parts). It crystallisesfrom boiling water in long, light-yellow needles melting a t 121". Itdistils readily with steam ; the vapour has an irritating odour.N e t h y k y r r y lg Zy ozy Zic acid, CaNH,Me-CO*COOH, is obtained bytreating a boiling solution of methylacetylpyrroline (5 grams) inalkaline water (500 c.c.) with a solution of potassium permanganate(15.5 grams) in water (500 c.c.).The whole is boiled, steam-distilled,and filtered ; it is then evaporated down, acidified, and extracted withether. The acid is crystallised from benzene, from which it separatesin light-yellow needles which melt a t 141-142.5' with decomposi-tion; it is sparingly soluble. The silver salt was prepared, Thedibromo-derivatice, C4NHIMeBr2*CO*COOH, prepared by brominatingthe acid dissolved in acetic acid, crystallises from benzene in small,sulphur-coloured prisms melting a t 160". When the dibromo-acidis slowly added to fuming nitric acid (10 parts), dibromomalei'n-methvlimide is formed.The bromine-atoms and the --CO*COOHCH--(Compare Claisen, Abstr., 1888, 692 ; and Zedel, 1051.)N. H. M.grou; have, therefore, the positions 3, 4, and 5 respectively.N. H. M.Derivatives of Unsymmetrical Dimethylpyrroline. By G.MAGNANINI (Ber., 21,2864-2868, 2874-2879) .-Ethy I diwethylasetyl-pyrrolinecnrboxylate, C4NHMe2Ac*COOEt [ 2 : 4 : 5 : 31, prepared byheating ethyl hydrogen dimethylpyrrolinedicarboxylate (Know,A n d e n , 236, 318) with acetic anhydride at 'LOO", crystallises inneedles, melts at 142-143", dissolves very readily in alcohol, etlier,acetic acid, and benzene, &c., sparingly in light petroleum. The f r e eacid obtained by boiling the ethyl salt with aqueous potash, melts atabout 152-158Owith formation of dimethylacet~I-pyrroZine and evolutionof carbonic anhydride, is almost insoluble in boiling water, verysparirigiy soluble in ether, chloroform, and benzene, and readily solublein hot acetic acid, from which it separates in long, lustrous needles.It gives a green coloration when heated with isatin and sulpbnric acid.DimethyZacety~yl.roZine, C4NH,MezAc [ = 2 : 4 : 51, is prepared bydistilling dimethy lacetylcarbopyrrolic acid in a retort heated in 58 ABSTRACTS OF CHEMICAL PAPERS.metal-bath a t ZOO".It is first crystalliscd from water containing alittle sodium carbonate, then from dilute alcohol, and lastly from lightpetroleum. It melts a t 122-123", sublimes a t loo", and is readilysoluble in the usual organic solvents.Dimethylpyi-rolinedica.l.boxylic acid irnineanhydride,c O / y M e \c .c 0 OH,'N*C Me/is obtained by boiling Knorr's unsymmetrical dicarboxylic acid(Abstr., 1887, 275) with acetic anhydride (10 parts) in a refluxapparatus for three to four hours. The acetic anhydride is distilledoff under diminished pressure, the residue washed with alcohol, dis-solved in aqueous sodium carbonate, filtered, and precipitated withacetic acid. It is almost insoluble in the usual solvents, becomesslightly brown a t 300", and decomposes a t a higher temperature intodimethylpyrroline and dimethylpyrocoll. It resists the action ofmineral acids, but seems to be pastially decomposed by aqueousammonia. The silver salt is a yellowish, amorphous substance ; them a p e s i u m saZt forms lustrous needles.The ethyl salt crystallises inthread-like needles, melts a t 270", and is sparingly soluble.2, 4-DiiizethylpyrocoZZ, C7H7N0, obtained by distilling the copper orsilver salt of the above acid in a stream of carbonic anhydride, is light,yellow, melts a t 272--272*5", dissolves very readily in chloroform,readily in acetic acid, but only sparingly in ether, light petroleum,and cold alcohol ; it is insoluble in water. The crystals are rhombic ;cc : b : c = 0.788:-(4 : 1 : 0.94606. The compound is hardly attackedby aqueous potash. N. H. M.Derivatives of Pyrrolinephthalide. By F. ANDERLINI (Bey.,21, 2869-2870) .-Dibromopyrrolinephthalide, C,,H5Br,NO2, .preparedby treating a warm solution of pyrroliuephthalide (2 grams) in glacialacetic acid (15 grams) with bromine (8 grams), crystallises in small,yellow, lustrous needles, melts at 199", is insoluble in water, sparinglysoluble in boiling alcohol and ether.Nitropyrroli.,iep7itAalide, C,,H6N2O4, is formed when the phthalide isdissolved in strong nitric acid ; it crystallises from alcohol in needles.When pyrrolinephthalide is treated with bromine in alkaline solution,tetrabromopyrroline and phthalic acid are formed.On similarlytreating the dibromo- and nitro-derivatives, both compounds yieldphthalic acid; the substituted radicles are therefore in the pyrrolinenucleus.When potassium pyrrolinephenylcarbinolorthocarboxylate,CINH3:C (0 H) *c6H4.co~K,is distilled with potassium carbonate, it is decomposed into pyrrolineand benzene. N.H. M.Action of Methyl Iodide on some Pyrroline-derivatives.By G. CIAMiCraN and F. ANDERLlNr (Bey., 21, 2855--2864).-Dihydro-tetl.ainethyl~,llridine, C9kI15N, is obtained, together with other basesORGAN I0 CHEMISTRY. 59when sodium carbopyrrolate (5 grams), methyl iodide (10 grams),and methyl alcohol (7 grams) are heated a t 120" for 12 hours.It boils a t about 160". The aurochloride, CgH15N,HAuC14, crystallisesfrom very dilute solutions in long, flat, monoclinic needles ; a : b : c =54: 10 : 5 i ; j? = 85%. When the base is reduced with sodium andalcohol, the compound C&HI9N is formed. This boils a t 150-152°.The azirochloride separates from its solution as an oil, which crystal-lises after some days in yellow needles melting a t 117-119". Whenthe base C,HlgN is boiled with methyl iodide in a, reflux apparatus,and the product, freed from tlhe excess of methyl iodide, is dissolvedin alcohol and precipitated with ether, the compound CI9Hl8NMeZI isobtained in colourless prisms which melt at 262".It is very readilysoluble in water, insoluble in ether. The mother-liquor from the di-methyl compound contains a small amount of a buse, C9HI8NMe, whichforms an oil.MetliyZL~il~yd70~2/0^roZine, CloHl7N, is prepared by heating methyl-pyrroline (3 grams), methyl iodide (7 grams), potassium carbonate(3 grams), and methyl alcohol ( 5 grams), for 10 hours ah 140". Theoily product is heated with strong hydrochloric acid at, 125-130",and distilled with potash.The aurochloride, Cl7HI7N,HAuCI4, crystal-lises from dilute hydrochloric acid in flat, yellow needles, which meltat 100". N. H. M.Dipiperidyl and Dipicolyl. By F. B. AHRENS (Eey., 21, 2929-2932).-Dipiperidyl is obtained when pi-dipyridyl is reduced withsodium and alcohol and the product purified by means of the nitroso-derivative. It crystallises in colourless needles, melts at 120-122"with previous softening, and is readily soluble in alcohol and ether,but insoluble in water. It absorbs carbonic anhydride when exposedto the air, and is only slighhly volatile with steam. The pkr,tiv,o-chloride, CloH,,M,,H,PtC16, forms microscopic crystals, is only sparinglysoluble in water, and blackens when heated a t 195". The aurochloride,CloH,N2,HAuC14, crystallises in small, yellow needles, is readilysoluble in hot, dilute hydrochloric acid, and is gradually decomposedwhen heated a t about 160".The p i c r a t e crystallises from hot waterin needles ; it blackens when heated, and is completely decomposedat about 257". Mercuric chloride,. phosphomolybdic acid, and potas-sium ferroqanide produce precipitates in a solution of the hydro-chloride.DipicoZyZ, CI2Hl2N2, is obtained when picoline, boiling a t 128-1 34",is treated with sodium at 80-90". After washing the product withwater, it is dissolved in ether, the solution filtered, and the base ex-tracted wit8h dilute hydrochloric acid. The extract is mixed withexcess of soda, the treatment with ether and hydrocliloric acidrepeated several times, and finally the ethereal solution is dried overpotash and evaporated.The residual yellow oil is then distilled,and the portion passing at 270-300" collected ; this dist,illate solidi-fies to a mass of yellowish, very deliquescent needles. The platino-chloride, C12Hl,N2,H2PtC16, crystallises in small plates, and is verysparingly soluble in water, but readily in hydrochloric acid ; it, is onlypartially decomposed when heated at 2 75". The aurochloride60 ABSTRACTS OF CHEMICAL PAPERS.C1,H,,N2,HAnC14, separates from warm, concentrated hydrochloricacid, in which it is readily soluble, in nodular crystals mixed withmetallic gold ; it is completely decomposed when heated a t 200-201".The picrate forms yellow, moss-like crystals, and is readily soluble inhot water.An aqueous solution of the hydrochloride gives precipi-tates with mercuric chloride, phosphomolybdic acid, potassium iodide,and potassium ferrocyanide.Action of Chlorine on Hydroxyquinoline. By H. HERhRRAND(Ber., 21, 2977 - 2989). - Chlcrrhyd,.uxyqztinoline, CgNH,OCl, isformed in small quantities when chlorine is passed into a well-cooledsolution of 1-hydroxyquinoline ( 5 grams) in glacial acetic acid.Dichlorhydroxyquinohne (see below) separates a t hst, and is furtherconverted into the hydrochloride whilst a further portion of the hydr-oxyquinoline is oxidised t o the rnonochloro-derivative. As soon as thewhole of the hydroxyquirioline 1s changed, the solution is filtered andthe residue treated with absolute alcohol to dissolve the dichlorhydroxy-salt.The residue is dissolved in hot, dilute hydrochloric acid, thesolution mixed with excess of sodium carbonate, and the precipitatedmonochlorh ydroxy-compound recrystallised fram methyl alcohol andlight petroleum. It is thus obtained in colourless needles melting a t129-130'. The hydrochloride crystallises in small, yellow needles,melts a t 253", and is moderately soluble in alcohol and hot, dilutehydrochloric acid ; it is very stable and sublimes in compact crystals.The platinochbride, (C9NH60C1)2,H2Pt C1, + 2H20, crystallises inyellow needles, and is readily soluble in hot but only sparingly in cold,dilute hydrochloric acid.DichZorhydroxyqzLinoZine, CgMH4C12*OH [OH : CI, = 1 : 2 : 41, isprepared by passing chlorine into a 10 per cent.glacial acetic acidsolution of hydroxyquinoline until the colour changes to yellow,pouring the solution into water, and recrystallising the precipitatedproduct from alcohol. It is also obtained when t~ichloroketoqu~noline(see below) is treated with hydrogen sodium snlphite or boiled w i t halcohol or dilute acids. It crystallises in long, slender needles, meltsat 179-180", and is readily soluble in warm alcohoi or glacial aceticacid, but only moderately in hot benzene and light petroleum. Itdissolves readily in alkalis and acids, forming yellow solutions, butthe salts are unstable and cannot be recrystallised, and acid solutionsare precipitated by water. When treated with chlorine in chloroformsolution, it is converted into trichloroketoquinoline, The h y d ~ o -chloride crgstallises in long, yellow needles, and in aqueaus solutiongives a black precipitate with ferric chloride.The platircochloride,( C9NH,0C1,),,H2PtC16 + 2H20, crystallises in long, orange needles,and loses its water a t 120"- The acety l-derivative, CgMH40C1,Ac,separates from light petroleum in small, colourless ci-ystals melting at97-98"; it is very unstable, and is decomposed by water or whenboiled for a long time with glacial acetic acid.Tricl~lorl2ydroxyyuinoZ~ne, [OH : C1, = 1 : 2 : 3 : 41, is formed whenthe mother-liquor from trichloroketoquinolitie is boiled or when thehydrochloric acid solution of pentachloroketoquinoline is treated witlihydrogen sodium sulphite or with water.It crystallises from glacialF. S . I(ORGANIC CHEMISTRY. 61acetic acid i n long, colourless, moss-like needles, melts a t 213-214",and is readily soluble in hot alcohol or glacial acetic acid, but onlysparingly in the cold solvents and in dilute acids ; it is readily solublein concentrated acids, but is reprecipitated on adding water. Whentreated with chlorine in chloroform solution, it yields a yellowpowder, probably tetrachloroketoquinoline, which melts a t 175" withdecomposition, and is recoiiverted into trichlorhydroxyquinoline whenboiled with alcohol. When heated with sodium carbonate, it yields asodium-derivative melting a t 270". The potassium-derimtive is c r ptalline. The hydrochzoride crystallises in small, yellow needles.Thep latinochzoride, ( C,NH4C130) %, H2Pt C1, + 2 H,O, crys t allises from dilutehydrochloric acid in long, orange needles and loses its water at140-150". The acety2-derivative separates from a mixture of glacialacetic acid and acetic anhydride in thin, transparent, forked, efflore-scent crystals, melts a t 172-173", and is readily decomposed.Tricli Zoroketoquinoline hydrochloride, C,NH40C13,HC1 + 2H20, pre-pared by saturating a well-cooled glacial acetic acid solution of hydr-oxyquinoline with chlorine and washing the product with glacial aceticacid, is very unstable, hygroscopic, and sensitive t o light. When simplydried between blotting paper, it melts at 93-95" to a yellow liquidwhich decomposes a t 100-120" with evolution of gas and thensolidifies, melting again at 170-1 80" with decomposition. Whendried over sulpburic acid under reduced pressure, it does not begin todecompose until heated a t 160" and melts at 180". It is readily solublein moderately dilute hydrochloric acid, but when the solution is evapo-rated under reduced pressure dichlorhydroxyquinoline separates.14, is decomposed when warmed with solvents, generally with forma-tion of the dichlorhydroxy-derivative, and this substance is formedvery readily when the keto-derivative is reduced with hydrogensodium sulphite. The platinochloride is very readily soluble, and whenthe solution is boiled or evaporated under reduced pressure, a mixtureCO*CCl, of platinochlorides is obtained. The free base, C,NH,< CCl:CH >,obtained by decomposing the hydrochloride with water and extractingthe precipitated oil with ether, crystallises in long, thin, yellowprisms or needles, melts a t 9So, turns brown a t 130", and is completelydecomposed a t 170". It is readily soluble in benzene, alcohol, andglacial acetic acid, and does not decompose when kept.EthoxydichZor7~ydroxyqzlinoZine, OEt*C,NH,Cl,*OH [OH : C1, : OEt =1 : 2 : 4: 1'3, is formed, together with dichlorhydroxyquinoline and asmall quantity of the trichloro-derivative, when an alcoholic solutionof freshly prepared trichloroketoqninoline is boiled for 1-2 hours.It crystallises from alcohol or benzene in long, thin, colourlessneedles, melts at 150-151", and dissolves sparingly in most ordinarysolvents in the cold but readily on warming. It is soluble in acids,forming colourless solutions, from which i t is reprecipitated by water,and when warmed with alcoholic soda, it yields a solution from whicha spongy sodium-derivative separates on cooling.Dihydroxydzchloroquiizoline, [(OH), : C1, = 1 : 1' : 2 : 41, is ob-tained, together with ethyl chloride, when the preceding compound isheated a t 110-120" with concentrated hydrochloric acid; it is als62 ABSTRACTS OF CHEMICAL PAPERS.formed when trichloroketoquinoline is boiled with methyl alcohol.It crystallises from alcohol in needles, melts atv 278", and is moresparingly soluble than the chloro-derivatives of hydroxyy uinoline.It crystallises from methyl alcohol in efflorescent needles containingalcohol.Anilidoquinolinequinoneani lide, C,NH,< C'O*C(NPh)- d (NH ,:cEI>, is ob-tained by treating an alcoholic solution of the ketochloro-derivativewith excess of aniline. It crystallises in small, golden plates or longneedles, melts a t 222", and shows all the properties of a feeble base.It is moderately soluble in glacial acetic acid, sparingly in alcohol,insoluble in water, and dissolves in dilute acids with a bluish-violetcoloration. It is not changed by boiling with alcohol or concentratedpotash, but is readily decomposed when heated with acids, yielding. a,yellow, crystalline substance which was not, obtained in the pure state.The hydrochZoride crystallises from acidified alcohol in small, dark-golden needles and is unstable. The yicrate crystallises from alcoholin dark, copper-red needles. The acetate crystallises in needles,melts a t 19Y", and is decomposed by water.Pentach loroketopuinoline platinochloride, (CJ H,Cl,O) 2, H,Pt Cl,, isformed when trichloroketoquinoline hydrochloride (5 grams) isheated at 140-150" for six hours with manganese dioxide (35grams)and concentrated hydrochloric acid (18 grams), the resulting solutionfiltered and mixed with platinic chloride. It is a yellow, crystallinecompound, and when recrystallised or dried, it seems to lose hydro-gen chloride and be convei-ted into the salt of tetrachloroketoquinoliae.A solution of pentachloroketoquinoline hydrochloride yields trich lor-bydroxyquinoline when mixed with water or hydrogen sodiumsulphite. F. S. I(.Alkaloids from Papaveraceae. By E. SCHMIDT (Arch. Pharm.[ 3 ] , 26, 622-623).-The following abstract is the first of a series onthese alkaloids, giving the results of investigations undertaken a t theinstance of the author. Schiel's conclusion that chelerythrine andsanguinarine are identical is not confirmed. The former appears tohave the formula CI9Hl7N04, as deduced from the analysis of thesmall quantities obtained, whilst the latter, from the analysis ofvarious compounds, has the formula, CI7Hl5NO4, thus confirmingNaschold's result. Three more bases have recently been separatedfrom Chelidonlum majus which are now the subject of research.Chelidonine. By A. HENSCHKE (Arch. Pharm. [3], 26,624-644 ;compare Abstr., 1887, 854) .--The alkaloi'd was obtained partly byrecrystallisation of the commercial base, and partly by direct extrac-tion from the root of CheZidoriiunz rnajus. Probst's method of ex-traction was employed, the stamped root being boiled in wateracidified with sulphuric acid, ammonia in excess added, and the filtratedried. This was purified by treatment with acidified alcohol, andagain with ether, and finally was repeatedly crystallised from boilingalcohol. Chel idonine, CzoH19N05 + HzO, forms vitreous, tabular, colour-less, monocliuic crystals of about 3 mm. diameter. The reactions ofJ. TPHYSIOLOGICAL CHEMISTRT. ti3the base are given in detail. Solutions of the salts of this base have anacid reaction, and tlie hydrochloride has the formula C,,H,,NO,-HCl ;the nitrate, C,,HlgN05,HN03; the sulphate, C20H19N05,H2SO~ + 2H20 ;the platinochloride, (C20H,9N05)2,H2PtC16 + 2H20 ; this was not, ob-tainable in a crystalline form ; the aurochloride, C2,,H,,N05,HAuC14,is easily obtained in crystals. Ethyl iodide combines with the base, andthe compound is not acted on by potassium hydroxide ; these and lesspositive results lead to the conclusion that chelidonine is a tertiarybase. By oxidation with potassium permanganate in alkalinesolution, chelidonine yields oxalic acid, methylamine and ammonia,the latter resulting from the decomposition of methylamine. In acidsolution, the oxidation goes further, carbonic anhydride and methyl-amine resulting. J. T.Alkaloids from Cod-liver Oil. By A. GAUTIER and L. MOURGUES(Compt. rmd., 107, 626-629 ; compare Abstr., 1888,1325) .-Aselline,C25H32N4, is an amorphous, colourless solid which becomes green onexposure to light. It melts to a viscom, yellowish liquid with anaromatic odour recalling that of the ptomaines, is very slightly solublein water, to which it imparts a bitter taste and an alkaline reaction,but dissolves in ether and still more readily in alcohol ; sp. gr. about1-0,5. The salts of aselline crystallise readily, but are partially de-composed by water. The mercurochloride crystallises from warmwater ; the aurochloride is very easily reduced ; the platinochlorideis orange-yellow, and dissolves in warm water, but is decomposed byboiling water. Aselline is feebly toxic, and produces fatigue andstupor; 3 mgrms. of the hydrochloride killed a greenfinch in14 minutes.Morrhuivae, C19H2,N3, is separated from aselline by taking advantageof tlie greater solubility of its platinochloride. It is a thick, oily,amber-coloured liquid with an odour which recalls that of aselline,and is only slightly soluble in water, but more soluble in alcohol andether. It is caustic and strongly alkaline, and absorbs carbonicanhydride from the air. The hydrochloride is very deliquescent ; theaurocbloride is yellow, and dissolves in warm water; the platino-chloride is somewhat soluble and crystallises in needles.Morrhuine constitutes one-third of the total bases in the oil, andan ordinary dose of one fluid ounce contains 2 milligrams. It excitesthe appetite and has remarkable diaphoretic and diuretic properties.In large doses it produces fatigue and stupor. C. H. B