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once on to ice, left for some time, and the residue collected and extracted with boiling water several times; it is then further purified by means of the barium or sodium salt. It is sparingly soluble in hot water, and crystallises on the addition of hydrochloric acid to the hot dilute solution of the sodium salt in long, lustrous needles (with 1 mol. H2O); when boiled for a long time, it separates as a sandy powder (anhydrous). The barium salt (with 4 mols. H2O) crystallises in groups of slender plates readily soluble in hot water; the magnesium salt forms white needles (with 1 mol. H2O), which show a blue fluorescence. The sodium (with 4 mols. H2O) and potassium salts crystallise respectively in small white needles and groups of needles. The acid is distinguished from the a-acid by the solubility of its sodium salt in alcohol, from the B-acid by the solubility of the free acid in boiling water, and from the 7-acid by the sparing solubility of the barium salt. The acid reacts with tetrazodiphenyl with formation of -purpurin G, and with tetrazoditolyl chloride with formation. of d-purpurin 5B, a splendid red product.

The acid is formed by heating the pure y-acid or a-acid with sulphuric acid at 160° for 1 hour.


B-Naphthol-o-sulphonic acid is obtained by heating to boiling an aqueous solution of the diazo-compound of B-naphthylamine-d-sulphonic acid with sulphuric acid, and neutralising with barium carbonate; it is then collected and extracted with sodium carbonate solution. barium salt is sparingly, the sodium salt readily soluble; the chloride melts at 114° (the chlorides of Bayer's and Schaeffer's acids melt at 61.5° and 135° respectively). The acid is identical with that already prepared by Cassella by heating salts of naphthalene-a-disulphonic acid with alkali. N. H. M.

Purpurogallin. By R. NIETZKI and T. STEINMANN (Ber., 20, 1277 -1280).-Girard and others have described a substance, purpurogallin, obtained by the oxidation of pyrogallol; a somewhat similar substance, pyrogalloquinone, was obtained by the action of quinone on pyrogallol. In this paper, these two substances are examined, and found to be identical and of the formula C20H16O9; the acetyl-derivative has the formula C20H12O9(Ac).. Naphthalene is obtained when purpurogallin is distilled with zinc-dust. V. H. V.

Oxidation of Santonin. By H. WAGNER (Ber., 20, 1662-1665). -Santonin is for the most part unaffected by ordinary oxidising agents; on prolonged treatment with nitric acid, it yields succinic, acetic, and hydrocyanic acids, together with carbonic anhydride; with less complete treatment, oxalic acid is also formed. Other oxidising agents burn only a small proportion of santonin with formation of carbonic anhydride. V. H. V.

Amyrin. By A. VESTERBERG (Ber., 20, 1242-1246).-The crystalline product amyrin, extracted from elemi-resin, has formed the subject of several investigations, but the formulæ assigned to this substance are most discordant. In order to purify the amyrin, it was

converted into the acetyl-derivative; but it was observed that on frequent fractionations of the latter two substances of different crystalline form were obtained, the one, in aggregates of prisms, melting at 235°; the other, in leaflets melting at 220°. The corre sponding alcohols, C30H19 OH, obtained by hydrolysis, are provisionally called a- and B-amyrin; the former crystallises in delicate needles melting at 180-181°; its acetate, mentioned above, melts at 220°, and the benzoate at 192°. When heated with phosphoric chloride, it yields a hydrocarbon, a-amyrilene CH48, crystallising in rhombic prisms, a b c = 0·667: 1:04049, and melts at 134-135°; its specific rotatory power [a]D= 109-84 (C = 4).

B-Amyrin melts at 193-194°, its derivatives are less soluble and fusible than those of the x-compounds; its benzoate crystallises in rectangular leaflets melting at 230°. B-Amyrilene crystallises in rhombic prisms, a:b: c = 0·916 : 1 : 0·540, melts at 175—178°; [a]D= 112:19 (C = 1.515). It is probable that amyrin is allied to cholesterin, and that amyrilene belongs to the class of polymeric terpenes. V. H. V.

Composition of Lac-dye. By R. E. SCHMIDT (Ber., 20, 12851303). Before the introduction of the azo-dyes, the lac-dye obtained from lac was a product of some commercial importance; it is produced on the boughs of various trees of the East Indies and Malay Archipelago as an exudation following the puncture by an insect, Coccus lacca. The statements in the various technological books are, however, very discordant, and the description of the methods used for the extraction of this dye seems incorrect. From the analytical results obtained with the ash, it would appear that the dye is precipitated from the crude material by the addition of lime, and that the product obtained consists of 10 to 13 per cent. of the dye itself, 9 to 11 per cent. of moisture, 15 to 18 per cent. of mineral constituents, and 57 to 68 per cent. of organic matter and water given off above 100°. A full description is given of the method used to extract and purify the colouring matter; the crystalline substance finally obtained is frequently recrystallised from alcohol and ether. The formula deduced. from not very concordant results is C16H12O8, and it is proposed to call the substance laccaic acid; it crystallises in microscopic, rhombic tables of a yellowish-red colour soluble in the alcohols, acetone, and acetic acid. Alkalis produce with it a characteristic red coloration, and the changes of tint caused by the addition of various reagents are described in full.

In many of its chemical properties, as also in its absorption spectrum, laccaic acid resembles carminic acid. The salts can only be obtained as amorphous precipitates. When heated with concentrated nitric acid, it yields picric and oxalic acids together with resinous substances, and with hydrochloric acid in sealed tubes it yields, in addition to a gas burning with a green flame, a substance, CH16O11. Laccaic acid when fused with alkali yields two products, the one of phenolic odour volatile in steam, the other contains a non-volatile, crystalline substance, probably an aromatic hydroxycarboxylic acid giving a red coloration with ferric chloride, an acid, probably para

hydroxymetatoluic acid, which gives no coloration with ferric chloride, and, lastly, a very soluble substance which gives a black precipitate with ferric chloride.

In conclusion, it is noted that laccaic acid and other naturally occurring dyes contain 16 atoms of carbon in the molecule.

V. H. V. B-Methyltetramethylenediamine and ẞ-Methylpyrrolidine. By H. OLDBACH (Ber., 20, 1654-1659).-On hydrogenation of the nitrile of pyrotartaric acid, B-methyltetramethylenediamine, NH2 CH2 CH2 CHMe CH2 NH2, is formed; it is a colourless liquid boiling at 172-173°, fuming in the air and absorbing water and carbonic anhydride; its platinochloride forms small, yellow crystals, the aurochloride, prisms; and the mercurochloride, small prisms. If the hydrochloride is distilled in small quantities, B-methylpyrrolidine, CHIN, is formed with separation of ammonium chloride; it is best purified by distillation with potash, conversion into the nitroso-derivative, and decomposition of the latter with hydrogen chloride. The free base boils at 103-105°, fumes in the air, and resembles in odour its isomeride piperidine; sp. gr. 08654. Its hydrochloride is very deliquescent; the platinochloride crystallises in long prisms, the aurochloride in four-sided tables, the bismutho-iodide, 3C,H,,N, HI,2BII,, in red needles. The B-methylpyrrolidine, above described, is not identical with a base found by Brieger in the culture of the Tetanus bacillus. V. H. V.

Action of Amines on Ethylenedibenzoylorthocarboxylic Acid. By J. BAUMANN (Ber., 20, 1486—1493).—Ethylenedi benzoylcarboxylic acid is prepared by heating 50 grams of succinic acid, 50 grams of phthalic anhydride, and 17 grams of finely-powdered dry sodium acetate for two hours at 210-220°, breaking up the product and extracting with boiling water, and then several times with boiling alcohol (96 per cent.). The crude ethylenediphthalide is boiled for a few minutes in a reflux apparatus with excess of alcoholic potash (25 grams of substance to 17 grams of potash); the product is treated with water and the alcohol evaporated; more water is added, the whole filtered, and the filtrate carefully treated with dilute hydrochloric acid until a precipitate is formed. It is again filtered and an excess of hydrochloric acid added, when ethylene benzoylcarboxylic acid separates; this is purified by crystallisation from alcohol. The yield is about 18 grams.

Phenylpyrrolenedibenzoic acid, NPh<C(CHCOOH): CH>, is ob-C(CHCOOH):CH, tained by heating 5 grams of ethylenedibenzoylcarboxylic acid with 15 grams of aniline in a water-bath for about half an hour; the product is heated with an excess of hydrochloric acid, filtered, washed with water, extracted, and washed with boiling alcohol. It is crystallised from nitrobenzene, from which it separates in slightly yellow crystals melting at 295° (uncorr.); it is very sparingly soluble in boiling alcohol and glacial acetic acid; rather more soluble in boiling alcohol; insoluble in water, benzene, ether, and chloroform. The silver salt forms a white, voluminous precipitate; the ethyl salt crys

tallises in lustrous, yellowish-white needles which melt at 122°; it is readily soluble, except in water.

Ethylpyrrolinedibenzoic acid, C20H17NO, is prepared by heating ethylenedibenzoylcarboxylic acid with 33 per cent. aqueous solution of ethylamine and some alcohol for one hour at 100°, evaporating the alcohol, and treating with an excess of hydrochloric acid. It is crystallised from dilute alcohol, and forms bright yellow plates melting at 220°, sparingly soluble in ether, benzene, and carbon bisulphide, more soluble in alcohol, nitrobenzene, and glacial acetic acid. The silver salt was prepared.

Methylpyrrolinedibenzoic acid, C19H1NO, prepared in manner similar to the ethyl compound, forms splendid, deep yellow plates, melts at 231°, and resembles the ethyl-derivative in solubility.

Paratolylpyrrolinedibenzoic acid, C25H19NO4, is prepared from ethylenedibenzoylcarboxylic acid (5 grams) and paratoluidine (12 grams); it is purified by dissolving the product in ammonia, filtering, and treating with hydrochloric acid. It crystallises from dilute alcohol in yellowish needles melting at 253°; it is readily soluble.


Diphenylpyrroline, NH<CPh: CH>, is obtained by distilling pyrrolinedibenzoic acid mixed with lime (20 parts) in a partial vacuum. It crystallises from alcohol in yellowish-white, microscopic needles melting at 143.5°; it is insoluble in water and alkalis, very sparingly soluble in dilute hydrochloric acid (the solution is rose-coloured), readily soluble with red colour in strong sulphuric acid; it is also readily soluble in ether, benzene, &c.

CPh: CH.

Triphenylpyrroline, NPh<CPh:CH>, is prepared in a manner similar to the diphenyl compound from phenylpyrrolinedibenzoic acid, using barium oxide instead of lime. It may be recrystallised from glacial acetic acid; it melts at 226°, is almost insoluble in alcohol and ether, sparingly in benzene and glacial acetic acid, and very readily soluble in nitrobenzene and chloroform; it dissolves in sulphuric acid without coloration.

Tolyldiphenylpyrroline, C23H9N, is obtained by distilling paratolylpyrrolinedibenzoic acid (2.8 grams) with barium oxide (30 grams). It crystallises from nitrobenzene in groups of bright yellow needles, melts at 201°, dissolves very sparingly in alcohol and glacial acetic acid, is more soluble in benzene and ether, and is readily soluble in nitrobenzene and chloroform.

When 2 grams of ethylenedibenzoylorthocarboxylic acid is heated with 1.3 gram of hydroxylamine hydrochloride, some drops of hydrochloric acid, and 10 c.c. of alcohol for one hour at 100°, long, yellow needles separate which may be crystallised from nitrobenzene. The new compound is the internal anhydride of ethylene benzoylcarboxylic acid dioxime, and has the constitution

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It melts at 270°, and is sparingly soluble except in nitrobenzene.

N. H. M.

The Cinnamene of the Pyridine Series. By A. LADENBUrg (Ber., 20, 1643-1644).-In order to prepare the analogue of cinnamene in the pyridine series, a mixture of ethylene and pyridine was passed through a red-hot tube. Besides subsidiary products not further examined, there was obtained a small quantity of a-vinylpyridine as a colourless liquid of pleasant odour boiling at 160°. When oxidised with potassium permanganate, it is converted into picolinic acid, and on hydrogenation with sodium and alcohol into a-ethylpiperidine. V. H. V.

Constitution of Aldehydecollidine. By E. DÜRKOPF and M. SCHLAUGK (Ber., 20, 1660-1661). It is generally assumed that the collidine obtained from aldehyde is an a-ethyl-ß-methylpyridine (Abstr., 1885, 257); subsequent investigations have shown this view to be incorrect. On oxidation, the collidine yields a methylpyridinecarboxylic acid, convertible on distillation with potash into a-picoline. It thus becomes necessary to determine the constitution of the dicarboxylic acid obtained as the final product of oxidation of the collidine. V. H. V. Reactions of Quinolinic Acid. By A. BERNTHSEN and H. METTEGANG (Bər., 20, 1208—1210).—Quinolinic anhydride,

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is readily obtained by the action of acetic anhydride on free quinolinic acid. It crystallises in prisms melting at 134.5°. When heated with resorcinol, fluorazeïn, C,NH,C(CH,O2). is formed which resembles

ordinary fluoresceïn.

B-Benzoylpicolinic acid, C,NH, Bz-COOH, is obtained by the action. of benzene on quinolinic anhydride in presence of aluminium chloride. It crystallises in prisms which melt at 147°, and is soluble in water. When heated, it is converted, with evolution of carbonic anhydride, into phenylpyridylketone, C,NH,Bz. The latter boils at 307° (uncorr.). The phenylhydrazine-derivative melts at 143.5°. The platinochloride, (C12H,NO)2, H2PtCl, was prepared. The base is converted by oxidaN. H. M.

tion into nicotinic acid.

Quinoline. By. E. LELLMAN and G. LANGE (Ber., 20, 14461451; compare this vol., p. 502).—A mixture of 5 grams of metamidobenzoic acid, 4 to 5 grams of nitrobenzene (better nitrophenol), 20 grams of glycerol, and 25 grams of sulphuric acid, is heated in a reflux apparatus over a free flame until the violent reaction becomes more moderate, when it is kept for six hours at 155-160°. It is cooled to 80°, treated with water, steam distilled, and made alkaline with baryta. It is then filtered, and after the excess of baryta has been removed by means of carbonic anhydride, treated with animal charcoal. The free acid, the yield of which was unsatisfactory, is identical with that obtained by La Coste and Valem by sulphonating quinoline.

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