Condensation-derivatives of Ethylenediamine.

By A. T. MASON (Ber., 20, 267—277).—In a previous communication (Abstr., 1886, 329), the author described a condensation product of ethylenediamine and phenanthraquinone, to which he now assigns the name C&H C•N•CH2

xenylenedihydropyrazine, | || | |- Its basic powers are very CH, C-N-CH2

feeble, the hydrochloride even decomposing in dry air; the platinochloride, (C16H12N2)2,H,PtCle, crystallises in small, slender, pale-yellow needles. It is not decomposed when heated with concentrated hydrochloric acid, even at 230°.

Diphenyldihydropyrazine, C,N,H,Ph2, is prepared by heating equimolecular proportions of benzil and ethylenediamine in alcoholic solution in a reflux apparatus for hour. It crystallises in pale-yellow prisms, melts at 160-161°, is sparingly soluble in cold, readily in hot alcohol, in ether and benzene, and is insoluble in water. It is insoluble in cold mineral acids, but is decomposed by them into its components on warming. When hydrogen chloride is passed into its solution in benzene or ether, ethylenediamine hydrochloride separates whilst benzil remains in solution. This ready decomposibility points to its constitution being dissimilar to that of the stable xenylenedi.CPh:NCH, hydropyrazine; it is probably represented by CPh: N-CH,>·

Ethylenediamine reacts readily with aldehydes with formation of condensation products which, like that last described, are but little stable towards acids.

Dibenzylidenethylenediamine, C2H,(N: CHPh), is prepared by mixing ethylenediamine (1 mol.) and benzaldehyde (2 mols.), when considerable evolution of heat occurs; the reaction is completed by heating for half an hour at 120°. It crystallises in large, colourless tables, melts at 53-54°, is insoluble in water, and readily soluble in alcohol and benzene. Dilute acids reconvert it into its components. It is quickly decomposed by boiling with water, or even by exposure to moist air. Diisopropylbenzylidenemethylenediamine, CH(N:CH·CH ̧Pr)2, is obtained by heating cuminaldehyde and ethylenediamine for about a quarter of an hour at 120°. It crystallises in long, pale-yellow needles, melts at 63-64°, is readily soluble in ether, alcohol, benzene, chloroform, and light petroleum, and resembles the preceding compound in its behaviour with water and acids.

Diphenylallidenethylenediamine, C2H1(N: CH·CH: CHPh), is obtained by mixing cinnamaldehyde with ethylenediamine, external heating being unnecessary; it forms large, colourless tables, melts at 109-110°, is but moderately soluble in ether, readily in alcohol and benzene. When treated with acids, cinnamaldehyde separates.

Diorthohydroxybenzylidenethylenediamine, C,H.(N: CH·C2H, OH), prepared by boiling salicylaldehyde and ethylenediamine in alcoholic solution, crystallises in large, yellow tables, melts at 125-126°, is sparingly soluble in cold alcohol or ether, readily in hot, or in benzene. Cold dilute acids do not seem to act on it, but on heating it is resolved into its components.

Diorthomethoxybenzylidenethylenediamine, C.H(N: CH-CH, OMe),

prepared from methylsalicylaldehyde, crystallises in colourless rhombohedrons, melts at about 113°, and is sparingly soluble in ether, readily in alcohol and benzene. The corresponding para-compound, prepared from anisaldehyde and ethylenediamine, forms large pale-yellow tables, melts at 110-111°, and is sparingly soluble in cold benzene, readily in ether or alcohol. Both compounds are readily decomposed by acids.

Dimethylbenzylidenethylenediamine, C2H.(N: CMe Ph)2, is prepared by mixing phenyl methyl ketone with ethylenediamine and completing the reaction by heating for a short time at 120°. It crystallises in white needles, softens at 95°, melts at 103-105°, is sparingly soluble in ether, readily in alcohol and benzene; it is very readily reconverted into the ketone and amine.

Ethyl ethylenedi-B-amido-a-crotonate, C2H,(NH.CMe: CH.COOEt)2, is obtained by mixing ethylenediamine and ethyl acetoacetate together with a little water or, better, by employing alcoholic solutions of the two substances. It crystallises in large, well-formed prisms, melts at 126-127°; is decomposed on distillation with formation of a basic substance, and is insoluble in water, very sparingly soluble in light petroleum, sparingly in cold but readily in hot alcohol, ether, and benzene. The free acid is obtained by heating the ethyl salt with water, or the formation and hydrolysis of the ethyl salt may be combined by heating ethylenediamine and ethyl acetoacetate in sealed tubes at 120-140°. It forms white scales of silky lustre, melts at 167-168, is readily soluble in water, sparingly in ether, benzene, and cold alcohol, does not show any reaction to litmus-paper, and in aqueous solution gives an intense violet coloration with ferric chloride. Much ethylenediamidopropylene is formed at the same time as the acid. A. J. G.

Condensation of Aldehydes with Phenols and Aromatic Amines. By L. CLAISEN (Annalen, 237, 261-274).-The action of benzaldehyde on B-naphthol has been described by Trzcinski (Abstr., 1884, 1185) and also by the author (this vol., p. 270). The product, benzal dinaphthal oxide, cannot be directly prepared by the action of B-dinaphthyl oxide on benzaldehyde.

Ethylidene dinaphthyl acetal and ethylidene B-dinaphthyl oxide have been previously described by the author (loc. cit.).

Benzaldehyde unites with B-naphthylamine, forming benzal-ßnaphthylamine, Ph CH: NC1oH, a crystalline compound soluble in chloroform. It melts at 102-103°. At a higher temperature, and under suitable conditions, the aldehyde and amine condense, forming phenylhydronaphthacridine. This substance is insoluble in alcohol. On oxidation, it yields phenyl-6-naphthacridine (m. p. 294), which has been described by Claus and Richter (Abstr., 1884, 1358).

W. C. W. Action of Chlorine on Aceto-a-naphthalide. By P. T. CLEVE (Ber., 20, 448-451).-When chlorine is passed into a solution of acet-a-naphthalide in acetic acid, crystals of a dichloro-derivative, CH,Cl2 NHAC, separate out; this compound melts at 214°, is readily soluble in acetic acid, alcohol, and chloroform. When boiled with

concentrated potash, it yields dichloronaphthylamine, C1HCl, NH2, melting at 82°, soluble in alcohol, volatile in steam; it yields phthalic acid when heated with nitric acid. By the diazo-reaction, the amine is converted into dichloronaphthalene, crystallising in needles which melt at 60°; on oxidation, it yields phthalic acid. It has been shown by Ciaus that B-3-dichloronaphthalene melts at 60°, whereas the author has obtained a dichloronaphthalene of the same melting point from two isomeric nitronaphthalene-p-sulphonic acids; hence there are either two isomeric dichloronaphthalenes of the same melting point or an isomeric transformation occurs. If the above dichloroacetnaphthalide is treated with tin and hydrochloric acid, a tin salt, CHCI-NH2,HSnCl3, separates, from which monochloronaphthylamine may be obtained; this crystallises in white needles, melting at 56°, and is sparingly soluble in boiling water, soluble in alcohol. Its hydrochloride and sulphate crystallise with 1 mol. H2O in delicate white needles. It is not identical with the monochloronaphthylamine prepared by Atterberg. V. H. V.

Naphthoxyacetic Acids. By M. SPICA (Gazzetta, 16, 437-445). -The x- and B-naphthoxyacetic acids are readily obtained by heating monochloracetic acid with the corresponding naphthol in equimolecular proportions, and gradually adding potash solution; the product is most conveniently purified by acidifying the crude product and separating the unaltered naphthol by solution in ammonium carbonate. a-Naphthoxyacetic acid crystallises in small prisms of pale-rose tint, soluble in ether and alcohol, sparingly soluble in water. It melts at 190°, and is slightly altered by light, especially when moist. The ammonium salt crystallises in stellate groups of needles or scales, soluble in water, more so in alcohol; it melts at 119-120°; the potassium salt with 1H2O forms long silky needles: the magnesium with 65H2O crystallises in rose-coloured lamine; the lead salt and the barium salt with 4.5H2O in sparingly soluble lamina. The ethyl salt crystallises in small colourless crystals, soluble in alcohol and ether, melting at 173-174°, and the amide in colourless needles, sparingly soluble, and melting at 155°.

The corresponding ß-acid crystallises in the trimetric system, and is coloured an azure-green tint on exposure to light; it melts at 151 -152°. Its ammonium and potassium salts crystallise in white micaceous scales, the barium salt with 3.5H2O in lamina; whilst the lead salt is a white, sparingly soluble crystalline powder. The ethyl salt crystallises in large, transparent scales, melting at 48-49°, and the amide in long tablets, melting at 147°, very soluble in alcohol and ether. The above acids are isomeric with the naphthylglycollic acid, of V. H. V.

which the a-modification has been described.

Constitution of Acenaphthene and of Naphthalic Acid. By E. BAMBERGER and M. PHILIP (Ber., 20, 237-244).-Naphthalic acid, obtained from acenaphthene by oxidation, has been generally regarded as a 1 : 2 derivative of naphthalene, inasmuch as it yields an anhydride and an imide-properties characteristic of the ortho-position in the benzene molecule. Starting, however, from 1: 1' nitro

naphthoic acid (melting at 215°), the authors have effected the synthesis of naphthalic acid, and hence have proved that both it and acenaphthene are 1 : 1' derivatives of naphthalene; this fact, taken in conjunction with Ekstrand's observation (Abstr., 1886, 155) that 1: 1' nitronaphthoic acid when reduced yields an amido-acid which undergoes spontaneous conversion into naphthostyril (an "internal" anhydride), and the fact that 1: 1' diamidonaphthalene reacts with benzaldehyde as though it were an orthodiamine, proves that in naphthalene the position 1: 1' functions as an ortho-position, and renders inevitable an extension of our conception of the latter in hydrocarbons built up of two or more benzene nuclei. The authors propose to distinguish the 1: 1' position in naphthalene by the prefix peri," and term naphthalic acid, for example, perinaphthalenedicarboxylic acid.

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To obtain naphthalic acid, the hydrochloride of the amido-acid prepared from naphthostyril by boiling it with aqueous soda and adding hydrochloric acid to the cold solution was converted into cyanonaphthoic acid by diazotising, and from it, by hydrolysis with aqueous potash, an acid was obtained which agreed with naphthalic acid in all its properties.

a-Naphthamide, CH, CONH2, crystallises in large, white, monoclinic tables, showing a satiny lustre, and melting at 202°.

W. P. W.

Pyrene. By E. BAMBERGER and M. PHILIP (Ber., 20, 365-371; compare Abstr., 1886, 718, 948, this vol., p. 271).-The formation of naphthalenetetracarboxylic acid by the oxidation of pyrenic acid shows that the latter has the constitution C1H (C2H2CO) (COOH)2. The positions of the four carboxyl-groups in naphthalenetetracarboxylic acid, which are shown to be [1:4: 1': 4'], point to the further CH.

developed constitutional formula COCH.(COOH), [C2H,CO

CH'

= 1:1' and (COOH), = 4: 4'] for pyrenic acid.

The constitution of pyrene is represented by a combination of a naphthalene nucleus with two benzene-rings thus:

The constitutional formulæ of pyrene quinone and pyrene ketone are

CH.

CH.

respectively CO CHICO [CH: CH = 1: 1' and 4: 4']

Derivatives of Camphoroxime. By H. GOLDSCHMIDT (Ber., 20, 483-485).-A reply to Leuckart (this vol., p. 376) in which the author maintains the correctness of his formula for camphoroximederivatives. Calcium campholenate by dry distillation yields a hydro

carbon boiling chiefly between 130° and 140°; an imperfect analysis points to the formula C,H1, and the compound is possibly identical with campholene. W. P. W.

Naringin. By W. WILL (Ber., 20, 294-304).-Methylnaringenic acid (Abstr., 1885, 906), when oxidised, yields anisaldehyde and anisic acid the conclusion that this leads to, that methylnaringenic acid is paramethylcoumaric acid, and that naringenic acid is paracoumaric acid was at once confirmed by a comparison of these various acids and their derivatives. As previously shown (loc. cit.), naringenin yields phloroglucinol and "naringenic acid" when heated with aqueous potash, it must therefore be phloroglucinolparacoumarate,

OH CHCH CH·COO·C2H2(OH)2,

naringin being a compound of this substance with isodulcitol. Naringin in aqueous solution has a rotatory power [a]D=84.5, in alcoholic solution the rotation is stronger, [a]D 87.6.

= —

A. J. G. Substances Extracted from the Illicium Religiosum. By J. T. EIJKMAN (Rec. Trav. Chem., 5, 299-304; compare Abstr., 1886, 95). From various portions and especially from the fruit of the species of the illicium genus, the author has extracted an acid, C-H10O, soluble in alcohol and ether, insoluble in chloroform and benzene. It is proposed to designate this substance shikimic acid. On distillation, it is for the most part decomposed into phenol and carbonic anhydride, but small quantities of protocatechuic acid are obtained; this acid is also present in the above-mentioned plants.

Shikimic acid is thus probably an additive product of protocatechuic acid, C.H(OH), COOH, and is thus analogous to quinic acid, with whose anhydride it is isomeric. The specific rotatory power of the acid in aqueous solution is [a]D=-1793; it shows some slight aptitude for etherification. The ammonium salt crystallises well, and on dry distillation yields a basic substance which gives precipitates with the reagents for the alkaloïds. V. H. V.

Andromedotoxim. By H. G. DE ZAAIJER (Rec. Trav. Chim., 5, 313-322).—Andromedotoxim, a toxical substance, present in various species of the Andromeda, was first isolated by Plugge; it can also be extracted from the Rhododendron ponticum by infusion with water, concentration of the extract, precipitation of the albuminous substances with basic acetate of lead, and evaporation of the filtrate. It is best purified from accompanying impurities by frequent recrystallisations from chloroform and ether. Thus obtained, it crystallises in long needles, melts at 228°, is more soluble in cold water than in hot, soluble in alcohol. Its specific rotatory power in aqueous solution is 9.7, in alcohol = -14, but in chloroform is +10 to +12. Its composition is CHO; thus it appears not to be identical with asbetoxime. In its chemical properties it is neither acidic nor basic, and is not of the nature of a glucoside; it does not reduce silver salts, and gives no precipitate with the salts of the heavy metals and the reagents for the alkaloids. Heated with dilute sulphuric acid, it gives

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