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to those detailed for the methyl-derivative, yields a-ethylhomo-orthophthalonitrile, CN.CH, CHEt CN, which crystallises in short, compact prisms, melts at 39-40°, and distils at 293-295°. On treatment with sulphuric acid, the ethyl nitrile is converted into a-ethylhomoorthophthalimide, C1HNO2; this crystallises in colourless needles, melts at 97-99°, dissolves in alkalis, and when heated with phosphorus oxychloride yields ethyldichlorisoquinoline,

CEt CCI
CH-CCI: N-
N->

Orthocyanobenzyl cyanide, when heated at 80° with concentrated sulphuric acid, or at 100° with fuming hydrochloric acid, is converted into homo-orthophthalimide. W. P. W.

Transformation of Homologues of Indole into those of Quinoline. By G. MAGNANINI (Gazzetta, 17, 246-254).-Though indole and pyrroline are regarded as possessing an analogous constitution, yet this view has not as yet been confirmed by experimental evidence. Ciamician and Dennstedt have shown that derivatives of pyrroline are readily converted by chloroform or bromoform into those of pyridine; by the same reaction, derivatives of indole shoul be converted into those of quinoline. In this paper, it is shown that methylketole and skatole yield substances which are in all probability halogen-derivatives of quinoline. For example, methylketole when heated with chloroform in presence of alcoholic soda is converted by a violent reaction into a chloroquinaldine thus: C,H,N+ 2NaOH + CHCI, CH,CIN+ 2NaCl + 2H2O; the product is best purified by means of the picrate, and subsequent decomposition of the salt formed by potash.

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Chloroquinaldine, C,H,NMeCl, crystallises in delicate, white needles, melting at 71-72°, insoluble in water, very soluble in alcohol and ether; the picrate forms sparingly soluble, yellow needles melting at 223° with decomposition.

Bromoquinaldine, C,H,NMeBr, obtained from bromoform under identical conditions, crystallises in white needles melting at 78° : system, monoclinic; a b c = 0·91 : 1 : 0·624; ß = 64° 31′ 33′′. The picrate melts at 224-225°.

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In like manner, skatole yields a chloro- and bromo-lepidine; the former crystallises in delicate needles melting at 54-55°, and the picrate melts at 208°; the latter melts at 58.5-59.5°, and its picrate at 214-215° with decomposition.

The above derivatives are not identical with the methyl halogenderivatives previously described; the author considers that the chloroquinaldine from methylketole has the constitution Me : Cl = 2'3', while the chlorolepidine from skatole has the constitution Cl: Me 3': 4'.

V. H. V.

Chlorobromonaphthalene. By J. GUARESCHI and P. BIGINELLI (Chem. Centr., 1887, 518-519).-By the action of bromine (1 mol.) on a-monochloronaphthalene (1 mol.), and by the action of chlorine on a-monobromonaphthalene, the same dihalogen-naphthalenes are 4 f

VOL. LII.

obtained; in both cases two chlorobromonaphthalenes, CH,CIBг, melting at 66-67° and at 119-119.5° are formed. Parachlorobromonaphthalene melts at 66-67°, boils at 303° (uncorr.), dissolves in ether and acetic acid, and sublimes in needles; when oxidised with chromic acid (two parts) in acetic acid solution, chlorobromonaphthaquinone and parachlorobromophthalide are formed. The quinone (probably parachlorobromo-a-naphthaquinone) crystallises from alcohol in yellow needles of a silky lustre melting at 166-5-167°. Parachlorobromophthalide crystallises in tabular, rhombohedral crystals melting at 179.5-180°.

The derivative melting at 119-119.5° forms thin, lustrous plates, more sparingly soluble in alcohol and glacial acetic acid than its isomeride; when oxidised with chromic acid, a-chlorophthalic acid, melting at 183-184°, is formed (Guareschi, Abstr., 1886, 353). In the compound melting at 119°, the halogen is therefore contained in both benzene nuclei.

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N. H. M.

Nitrosamines. By O. FISCHER and E. HEPP (Ber., 20, 2471— 2478). When an alcoholic solution of B-naphthylethylnitrosamine, cooled in ice, is treated with alcoholic hydrogen chloride, a-nitroso-3ethylnaphthylamine, [NO: NHEt 1: 2], is obtained; this crystal1:2], lises from benzene in well-formed, flat tables, melts at 120-121°, and yields salts readily soluble in water. On the addition of potassium nitrite to the solution of the base in dilute sulphuric acid, a nitrosamine is formed, and crystallises in long, hair-like needles, whilst on reduction with tin and hydrochloric acid, or allowing a solution of the base in alcoholic hydrogen chloride to remain at 10-15° for some time, or on treating B-naphthylethylnitrosamine with alcoholic hydrogen chloride at the ordinary temperature, ethenyl-a-8-naphthylenediamine, C12H16N2 (this vol., p. 729), is obtained. The hydrochloride of the anhydro-base, C12H10N2,HCl + 2H2O, crystallises in slender, colourless needles, and is sparingly soluble in water, and the base itself is identical with that prepared by Liebermann and Jacobson (Abstr., 1882, 521).

The base obtained from B-phenylnaphthylnitrosamine by treating its alcoholic solution in the cold with alcoholic hydrogen chloride, is identical with naphthaphenazine (this vol., p. 591); the yield amounts to 10 per cent.

Nitrosoaniline, CH,N2O, is formed when nitrosophenol (1 part) is heated with ammonium chloride (5 parts) and ammonium acetate (10 parts) at 100° for half an hour; the product is then poured into water, and the dark-green, crystalline precipitate is purified by crystallisation from benzene. It forms steel-blue, curved needles, and melts at 173-174°. Like nitrosodimethylaniline, it yields sodium nitrosophenol and ammonia, when boiled with aqueous soda. Although nitrosoaniline could not be obtained by the action of ammonia on nitrosophenol, it is possible to prepare a-nitroso-ß-ethylnaphthylamine by heating a-nitrosonaphthol with ethylamine at 100°, and the authors suggest that Ilinski's orthonaphthalene-a-oximeB-imide (Abstr., 1886, 474) should be regarded as a-nitroso-pnaphthylamine.

When nitrosophenylglycocine (Abstr., 1878, 795) is dissolved in 2 parts of alcohol, treated with 3 parts of alcoholic hydrogen chloride, and allowed to remain for 12 hours, a crystalline mass is obtained which is precipitated from cold alcoholic solution by ether in yellow scales of the composition C&H,N2OCI. The compound explodes when heated, is decomposed by water with the evolution of two-thirds. of its nitrogen, and dissolves in concentrated hydrochloric acid without decomposition. Its platinochloride, (C&H&NŎCI), PtCl,. crystallises in yellow scales, and decomposes on boiling with water with a separation of platinum. The compound is regarded as the diazo-salt of phenylhydroxylamine, since the aqueous solution after boiling reduces silver and cupric salts, and the compound when added to boiling absolute alcohol decomposes with evolution of nitrogen and an odour of aldehyde, and after distilling off the alcohol it yields a residue from which a pale-yellow oil can be separated by steam distillation. The oil, C12H12Ñ2O2, has all the properties of a feeble base, and forms a hydrochloride crystallising in white prisms. This compound also reduces an ammoniacal silver solution, slowly reduces Fehling's solution, and is wholly converted into benzidine on treatment with tin and hydrochloric acid. It is regarded as diphenyldihydroxylamine, OH•NH CHẠCH,NH•OH[NHOH : CH =1:4].

W. P. W.

Derivatives of Camphor. By L. BALBIANO (Gazzetta, 17, 240245).—It has recently been shown by the author (this vol., p. 1049) that the reaction of phenylhydrazine on camphor is essentially different from that of the same reagent on substances formed on the ethylenic oxide type, such as epichlorhydrin. In continuation of experiments on the derivatives of camphor, it is shown that chloroand bromo-camphor, on oxidation with alkaline permanganate, yield camphoric acid, thus confirming the results of Armstrong (Ber., 12, 1358) and Schiff (Gazzetta, 9, 324) in opposition to those of Cazeneuve. The inertness of derivatives of camphor towards hydroxylamine affords no evidence as to the absence of the carbonyl-group in these compounds, inasmuch as the reaction will not proceed in the presence of solvents, and even phenylhydrazine under these conditions will not always react, and, secondly, some compounds containing two carbonylgroups, such as benzoylacetone and phenanthraquinone, react only with partial substitution of the isonitroso-residue.

V. H. V.

Strophanthin. By T. R. FRASER (Pharm. J. Trans. [3], 18, 69). -It has been found that the substance obtained by the former process for the preparation of strophanthin, is resolved by lead acetate into at least two others—one an extremely active glucoside, and the other an acid for which the name kombic acid is suggested. To obtain pure strophanthin, the following is the process ultimately adopted. The product obtained in the earlier process is dissolved in water, tannic acid is added, and the tannate digested with recently precipitated lead oxide. The alcoholic extract from this is precipitated with ether, the precipitate dissolved in weak alcohol, and carbonic anhydride is passed through the liquid for several hours to remove lead. The solution is then evaporated at a low temperature and dried in a

vacuum. Strophanthin thus obtained is imperfectly crystalline. neutral, intensely bitter, freely soluble in water, less so in rectified spirit, and nearly insoluble in ether and chloroform. It burns without residue, and the results of analysis agree fairly with the formula C20H3O10. Nearly all acid reagents cause its solutions to become turbid, and the liquid is then found to contain glucose. This decomposition is also produced by hydrogen sulphide, especially when heated. Many organic acids, and all mineral acids, except carbonic, resolve strophanthin, even in the cold, into glucose and a substance which the author names strophanthidin. Therefore, neither hydrogen sulphide nor acids (especially mineral acids) should be used in the preparation of strophanthin. The crystalline product obtained by Hardy and Gallois in 1877, by extracting the seeds with rectified spirit acidified with hydrochloric acid, was supposed by them to be strophanthin; and as it failed to yield glucose when heated with dilute sulphuric acid, they inferred that strophanthin is not a glucoside. But there can be little doubt, both from the mode of its preparation and also from its reactions, that their product was strophanthidin.

R. R.

Strophanthus and Strophanthin. By E. MERK (Pharm. J. Truns. [3], 18, 72).—When the fatty oil in the seeds of Strophanthus is extracted by ether previously to treating them with alcohol, the ethereal solution will also contain a certain amount of strophanthin, and to this circumstance the small activity of the alcoholic tincture of strophanthus of commerce is in part due. The author obtains strophanthin as a white, crystalline powder which melts at 185° and volatilises without residue.

R. R.

Strophanthus and Strophanthin. By W. ELBORNE (Pharm. J. Trans. [3], 18, 219).-The following process for preparing strophanthin obviates certain objections to which Gerrard's process is open. The seed in fine powder is mixed into a thin paste with water to which 10 per cent. of alcohol has been added; this is set aside for 12 hours, then agitated with six times its volume of absolute alcohol, and, after six hours, is filtered. The residue is washed with rectified spirit, and the washings added to the filtrate, and from the whole four-fifths of the alcohol is removed by distillation. To the remainder, solution of lead subacetate is added, and the mixture is heated to 100°, filtered, and allowed to cool. The lead is then removed from the cold filtrate by precipitation with hydrogen sulphide; the filtrate is agitated with amyl alcohol, which dissolves out the strophanthin and yields it on evaporation as a colourless film that crumbles on removal into a nondeliquescent, white powder.

R. R.

Chlorophyll. By A. TSCHIRCH (Chem. Centr., 1887, 669).-Phyl locyanic acid is obtained by dissolving crude chlorophyllan in concentrated hydrochloric acid, and precipitating with excess of water. This substance can also be obtained in minute crystals from solutions in alcohol and ether. Its spectrum agrees with that of chlorophyllan ; it also gives a zinc compound containing 11:07 per cent. of the metal: with alkalis it forms very soluble combinations. The formula

47

C28HN2O is provisionally assigned to this compound. The proportion of phyllocyanic acid present, which appears in leaves in the form of chlorophyll, can be estimated by the chemical or spectroscopical methods. In the dark-brown leaves of the Fuchsia ovata, the proportion of the absorbing chlorophyll matter varied from 2.5 to 5 per cent. of the dried substance, apart from the ash of the leaves; the presence of copper diminishes the fluorescence. V. H. V.

Preparation of Picrocarmine. By L. GEDÖLST (Chem. Centr., 1887, 599). In order to prepare picrocarmin for microscopical purposes the following method is proposed. About half a gram of

carmine is dissolved in 100 c.c. of water containing 5 c.c. of a 1 per cent. solution of soda; the solution is then boiled, filtered, and made up again to 100 c.c. To neutralise the liquid, it is mixed with an equal volume of water; a 1 per cent. solution of picric acid is then added, which causes at first a turbidity which subsequently disappears; the non-disappearance of the turbidity serves as an indication that the point of neutralisation has been passed..

V. H. V.

Diastase. By L. SCHÄRTLER (Chem.. Centr., 1887, 534).-Pure diastase is prepared as follows:-10 kilos. of light, ground malt, 50 grams of sodium hydrogen carbonate, and 12 to 14 litres of water are heated at 40°, digested for two hours, the liquid drawn off, and 6 to 8 litres more water added. After some time, the second supply of water is drawn off, added to the first liquor, heated at 65°, and passed through a sieve; twice the volume of alcohol is added and the clear solution drawn off; the residue containing the diastase is treated with a little warm distilled water, the solution separated from the undissolved albuminoïds, and precipitated with alcohol. It is dried at 50° and then powdered. The yield is 1 to 1 per cent. N. H. M.

Pyridinepolycarboxylic Acids. By J. WEBER (Annalen, 241, 1-32).-Carbodinicotinic acid, or 2:3:5-pyridinetricarboxylic acid, cannot be obtained directly from pyridinetetracarboxylic acid, but it can be prepared by starting from symmetrical lutidinedicarboxylic acid. On oxidation with the theoretical quantity of potassium permanganate, a-methylcarbodinicotinic acid (2:3: 5 a-picolinetricarboxylic acid), C,NHMe (COOH)3, is formed. It is isolated by acidifying the crude product with acetic acid and adding barium chloride. The precipitate is washed and decomposed by a slight excess of dilute sulphuric acid. On evaporating the filtrate, a-methylcarbodinicotinic acid is deposited in crystalline masses. The acid crystallises with 1 mol. H2O. It turns yellow at 170°, and melts with decomposition at 226°, forming a crystalline sublimate; if kept at a temperature of 150° for some time, it is converted into a-methyldinicotinic acid. The free acid forms precipitates in solutions of silver, lead, mercurous, cadmium, and zinc salts, also with barium and calcium salts in the presence of ammonia. The copper and silver salts, and the acid potassium salt, CNH Me(COOH), + C,NHMe(COOH),COOK + 6H2O, are crystalline.

a-Methyldinicotinic acid, C,NH,Me(COOH)2 + H2O [Me: (COOH),

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