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Metanitrophenylazodimethylamidobenzene (Staedel and Bauer, Abstr., 1886, 944) has already been fully described by the author (Trans., 1884, 120). N. H. M.

Eurhodines and Laurent's Naphthase. By O. N. WITT (Ber.,

19, 2791-2796).-The eurhodol, CuHs

N

CH, OH, is obtained by

fusing sodium diphenylenenaphthaquinoxalinesulphonate (Abstr., 1886, 889) with potash until the yellow colour suddenly changes to a pure cinnabar-red. When the product is diluted with water and treated with hydrochloric acid in excess, the hydrochloride separates as a cinnabar-red, insoluble powder. If acetic acid is used in the place of hydrochloric acid, the free eurhodol separates in orange-yellow crystalline flakes. It is insoluble in all solvents and can only be purified by recrystallising the hydrochloride from boiling phenol. When heated, it sublimes with partial decomposition. Sulphuric acid dissolves it with a pure deep blue colour which changes immediately on addition of very little water to a splendid carmine-red; when the blue solution is heated to a certain point it becomes successively violet, red, and yellow. The dry eurhodol is electric.

N

a-B-Naphthaquinoxaline, C10HC10H6, is prepared by the action of B-naphthaquinone on orthonaphthylenediamine in acetic acid solution; it is purified by crystallisation from naphthalene. It forms yellow needles melting sharply at 275°. It dissolves in sulphuric acid, yielding a pure violet solution which becomes orange-yellow when diluted; when further diluted, the free base is precipitated. It sublimes readily in long, yellow needles, and when quickly heated distils as a yellow oil which soon solidifies. It is identical with Laurent's naphthase (Annalen, 9, 384; compare also Nietzki and Goll, Abstr., 1885, 545). N. H. M.

Indoles from B-Naphthylhydrazine. By A. SCHLIEPER (Annalen, 236, 174-184).-The B-naphthylhydrazine described by E. Fischer (Abstr., 1886, 555) unites with acetone, forming the compound C1H, NH: CMe. This substance crystallises in prisms of a pale-yellow colour. It melts at 65.5°, and is freely soluble in alcohol, ether, benzene, acetone, and in (hot) light petroleum. Ethylidene B-naphthylhydrazine, CH, N2H: CHMe, forms three-cornered plates, soluble in hot alcohol, benzene, and chloroform. It melts at 128-129°. B-Naphthylhydrazinepyruvic acid, C10H7 N2H: CMe COOH, forms yellow needles. This acid melts at 166°, and decomposes with evolution of carbonic anhydride. It dissolves in hot alcohol and acetic acid. The ethyl salt melts at 131°, and is freely soluble in alcohol, ether, benzene, and acetic acid. On fusion with zinc chloride, ß-naphthindole is produced; B-naphthindolecarboxylic acid is formed as an intermediate product. After purification by conversion into the picrate, B-naphthindole, CH<CHCH, boils at 222° under 18 mm. pres

NH

sure, and above 360° under the ordinary atmospheric pressure. It dissolves in alcohol, ether, benzene, and acetic acid with fluorescence. Strong hydrochloric acid forms a crystalline compound with it. NH B-Naphthindolecarboxylic acid, CH<CH>C-COOH, crystallises in colourless plates, soluble in alcohol and acetic acid. It melts at 226° with evolution of carbonic anhydride. The sodium and barium salts are sparingly soluble in cold water. The ammonium and potassium salts are much more soluble.

NH.

Methylnaphthindole, CH<CH>CMe, from acetone-ß-naphthylhydrazine, boils between 314° and 320° under a pressure of 223 mm. It is freely soluble in alcohol, ether, and benzene. The picrate melts at 176°. On reduction with nascent hydrogen, hydromethyl-B-naphthindole is obtained as an oily liquid, boiling between 190 and 200° under 20 mm. pressure. It is a strong base, and with mineral acids, forms salts which are very soluble in water.

W. C. W.

Action of Monamines on Citric Acid. By H. HECHT (Ber., 19, 2614-2618).-Citrotrimethylamide, CH,O,(NÍMe), is prepared by adding a strong solution of methylamine to a concentrated solution of inethyl citrate in absolute alcohol, and keeping the product over sulphuric acid for some time. It separates in prisms melting at 124°; it is very readily soluble in cold water, and is not acted on by alkali or hydrochloric acid.

10

Citrodinaphthylamide, C10H, N: CHO, NH C10H7, is formed when a mixture of citric acid (1 mol.) and B-naphthylamine (3 mols.) is heated at 140-150° for several hours. It crystallises in six-sided plates melting at 233°. It is insoluble in water or hydrochloric acid,

sparingly soluble in alcohol.

The trinaphthylamide, CH,O.(NH CH)3, is obtained by heating the dinaphthylamide with naphthylamine (eq. mols.) at 150-160°; it forms microscopic, prismatic crystals readily soluble in alcohol, insoluble in water; it melts at 215°, and is very stable.

Citrodinaphthylamic acid, OH CH2O、(NH·C1H7)1⁄2, is prepared by heating the dinaphthylamide with an excess of concentrated ammonia for six hours at 170°. It crystallises from alcohol in slender, microscopic needles melting at 172°; it is readily soluble in alkali, insoluble in water. The silver salt was prepared.

Monobasic naphthylamine citrate, C6H5Os, NC10H,, separates as a rosecoloured substance when a hot, concentrated alcoholic, solution of citric acid (1 mol.) is mixed with ẞ-naphthylamine (1 mol.) and cooled. It melts at 89°, dissolves readily in alcohol, ether, nitrobenzene, and

water.

Compounds isomeric with the above were prepared from a-naphthylamine in a similar manner. Citrodinaphthylamide is purified by precipitating the solution in glacial acetic acid with water; it crystallises from benzene in six-sided plates melting at 194°; it is insoluble in hydrochloric acid. Citrotrinaphthylamide, CH,O,(NHC10H)3, crystallises in microscopic, rhombic prisms which melt at 129°. Boiling alkali solution and acids do not act on it. Citrodinaphthylaminic acid

crystallises in small groups of needles melting at 149°; the alcoholic solution reacts slightly acid. The silver salt is sparingly soluble in N. H. M.

water.

Action of Ammonia on Ethyl Acetonedicarboxylate: Synthesis of Pyridine-derivatives. By H. N. STOKES and H. v. PECHMANN (Ber., 19, 2694-2717).-Ethyl B-hydroxamidoglutamate (Abstr., 1885, 1202) is readily soluble in hot water and in alcohol; the aqueous solution decomposes gradually, giving off ammonia. It gives a deep red coloration with ferric chloride.

The compound obtained by the action of alkalis on ethyl p-hydroxamidoglutamate and described as glutazine (loc. cit.), is shown to be a pyridine-derivative, probably having the constitution

[blocks in formation]

It melts at ahout 300° with evolution of ammonia, is moderately soluble in hot water, almost insoluble in hot alcohol, and insoluble in other solvents. The neutral solution acquires a deep-red colour on addition of ferric chloride; on warming, the solution turns darkgreen without becoming turbid. The hydrochloride (with 1 mol. H2O) crystallises in prisms readily soluble in alcohol; water decomposes it. The sulphate was prepared. The sodium, ammonium, and barium salts are very soluble.

Pentabromacetylacetamide (loc. cit.) melts at 148°; at a higher temperature, it gives off bromine and hydrogen bromide. It is insoluble in water, readily soluble in alcohol, ether and glacial acetic acid, moderately in chloroform. When heated with water, it is converted into dibromacetamide, bromoform, and carbonic anhydride. Boiling alcoholic ammonia converts it into dibromomalonamide (melting at 200-5°) and bromoform.

COCH,

Acetylglutazine, NH CO-CH>C: NAc, is obtained by heating glutazine with acetic chloride at 100-120°. It crystallises from water in small lustrous plates, which darken at 230° and melt at 285-290°. When warmed with ferric chloride, it acquires a brilliant violet colour. The ammonium (with 1 mol. H2O), silver, and barium salts were prepared.

2, 4, 6 Trihydroxypyridine is prepared by boiling glutazine for 3-4 minutes with an excess of strong hydrochloric acid and then evaporating the solution in clock glasses as quickly as possible on a water-bath. The dry residue is extracted with cold alcohol and the solution quickly evaporated; the thick syrup so formed is mixed with a little water and a solution of caustic soda (0-3 gram to 1 gram glutazine) in twice its weight of water added, the whole being kept cool. The crystalline product is washed with a little water and dried. It forms yellow, microscopic needles which swell up when heated at 220-230° and give off water. It dissolves readily in hot water, but is insoluble in other solvents. When treated with ferric chloride, it gives a deepred coloration. Bromine-water converts it into pentabromacetylacetamide. It reacts strongly acid and decomposes carbonates. The salts

of the alkalis and alkaline earths are very readily soluble in water. When distilled with zinc-dust, it yields a small quantity of pyridine. Hydroxylamine hydrochloride reacts with trihydoxypyridine, yielding a monoxime, C2NH2O2: N·OH + H2O. The latter is a heavy, sandy powder consisting of hexagonal plates; it melts at 194-196° with evolution of gas. It is rather soluble in hot water, less so in alcohol. When treated with strong soda solution, it becomes blue; with ammonia, it gives a yellowish-red colour which changes to intense purple when warmed. The oxime forms salts with acids. It is also formed by acting on glutazine with hydroxylamine. The phenylhydrazine-compound (obtained from both trihydroxypyridine and glutazine) forms plates readily soluble in hot alcohol; it melts at 230°.

When trihydroxypyridine is heated with ammonium acetate at 120-140°, it is converted quantitatively into glutazine.

Trihydroxypyridine anhydride, CHON2, is formed as the chief product in the decomposition of glutazine by boiling dilute sulphuric acid. It crystallises in flesh-coloured, microscopic prisms; it is very stable, and melts only at a high temperature. It is insoluble in all neutral solvents except water, which dissolves it slowly. readily in an excess of alkali. The hydrogen barium salt,

(C10H7O5N2)2Bа + 4H2O,

It dissolves

forms yellow prisms insoluble in water and alcohol. The normal alkali and alkaline earth salts are readily soluble in water; they are not decomposed by carbonic anhydride. The hydrochloride crystallises in needles readily soluble in alcohol; it is decomposed by water. The sulphate crystallises from water in prisms. The anhydride can be converted into trihydroxypyridine by evaporating its aqueous

solution.

The way in which glutazine is formed shows that the nitrogen of the pyridine-ring has the para-position to the side-chain containing nitrogen, and the ortho-position to both the oxygen-atoms. Hence the three oxygen-atoms in trihydroxypyridine must be symmetrical to one another and to the nitrogen, and trihydroxypyridine is therefore analogous to phloroglucinol. The analogy of the two compounds is seen in their yielding anhydrides and in their behaviour towards ammonia and hydroxylamine (compare Baeyer, Abstr., 1886, 350). It is probable that the pyridine-derivative exists in two forms, as shown in the following formulæ :

CO.CH2.

NH<COCH,

2>CO and N<

C(OH): CH
C(OH): CH

>C.OH.

3, 5 Dichloro-2, 6-dihydroxy-4-amidopyridine (loc. cit.) forms short flat needles melting at 241-5°; it dissolves sparingly in hot water and alcohol, readily in alkali and dilute hydrochloric acid.

2, 4, 6 Trichloro-4-amidopyridine forms long colourless needles melting at 157.5°; it is very readily soluble in alcohol, readily in dilute hydrochloric acid, and insoluble in alkali; it sublimes unchanged.

2, 3, 5 Trichloro-6-hydroxy-4-amidopyridine, melting at 282°, is very readily soluble in hot water, moderately in hot alcohol, sparingly in

ether and benzene. It is a monobasic acid, and decomposes carbonates. The sodium salt is rather soluble in water, sparingly in alcohol.

2, 3, 5, 6 Tetrachloro-4-amidopyridine melts at 212°, and sublimes unchanged. It is insoluble in water, soluble in alcohol and benzene. It can be boiled with strong sulphuric acid without decomposition. When heated with fuming hydriodic acid at 200°, black crystals of an iodine-derivative melting below 80° are formed. This, by solution in dilute sulphuric acid and precipitation with alkali, is converted into what is probably dichloramidopyridine; it melts at 158°. When the tetrachloro-compound is boiled with sodium ethoxide and alcohol, 2, 3, 5 trichloro-6-ethoxy-4-amidopyridine is formed; this crystallises in needles which melt at 83°. It distils with steam, is insoluble in water, alkali, and dilute acids, very readily soluble in alcohol, ether, benzene, &c. Dilute hydrochloric acid converts it (at rather above 100°) into trichlorhydroxyamidopyridine (m.p. 282°) and ethyl chloride. Dichloro-diethoxy-3-amidopyridine, CN2HCl,(OEt), and dichloro-2hydroxyethoxy-4-amidopyridine, C2N2H2Cl2(OH).OEt, are formed by heating tetrachloramidopyridine with excess of sodium ethoxide and alcohol at 190°. The former crystallises in long needles melting at 98°; it is very readily soluble in alcohol and ether, insoluble in water, alkalis, and dilute acids, and distils with steam. The latter crystallises from very dilute alcohol in flat needles which melt at 161.5°. It dissolves readily in alcohol, ether and alkalis, and is insoluble in dilute acids. The two compounds are also formed from trichlorhydroxyamidopyridine and from the diethoxy-compound by the action of sodium ethoxide and alcohol at 190°. N. H. M.

Correction. By A. LADENBURG and C. F. ROTH (Ber., 19, 2586; compare Abstr., 1885, 994).-The authors state that in the mixture of bases of high boiling point from animal oil examined by them, aniline was present and accumulated in the fraction 174-176°, from which they separated the supposed new lutidine. A repetition of the experiments has not yet been possible owing to a difficulty in obtaining the material. W. P. W.

Derivatives of Picolinic and Nicotinic Acids. By E. SEYFFERTH (J. pr. Chem. [2], 34, 241-263).—At the outset, unsuccessful experiments are described, made with a view of obtaining hexahydropicolinic acid from the acid itself by the action of various hydrogenising agents. But in each case either the acid was not acted on or was decomposed with formation of picoline and its hydro-derivatives. Chloropicolinic acid, C,NH,CI-COOH, is obtained by boiling chloropicoline trichloride, C,NH,Cl-CCI, (from picolinic acid and phosphoric chloride), with 80 per cent. sulphuric acid, and pouring the product into water. It crystallises in needles and prisms, often showing twinning. It melts at 180°, is sparingly soluble in cold water, readily soluble in hot water, alcohol and chloroform. It has strongly acid properties and does not form salts with dilute mineral acids. Its calcium salt crystallises with 1H2O in transparent prisms, and its barium salt in nodular aggregates. Both salts are sparingly

VOL. LII.

m

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