Preparation of Vanillin from Metachloroparanitrobenzaldehyde. By L. LANDSBERG (Dingl. polyt. J., 262. 139). It is proposed to convert metachloroparanitrotoluene into chloronitrobenzyl chloride or bromide, and to treat the latter with lead or copper nitrate, in order to obtain metachloroparanitrobenzaldehyde. On treating this aldehyde with an alkaline methoxide or the hydroxide dissolved in methyl alcohol, the chlorine is displaced by the methoxyl-group with formation of metamethoxy paranitrobenzaldehyde. The same compound is obtained when the chlorine in metachloroparanitrobenzaldehyde is displaced by hydroxyl, and the resultant hydroxynitrobenzaldehyde converted into its methyl ether. Metamethoxyparanitrobenzaldehyde crystallises from boiling water in white needles melting at 62°, and is converted into vanillin according to the known methods. When heated with acetic anhydride or sodium acetate, it is resolved into metamethoxyparanitrocinnanic acid, melting at 218°. D. B.

Action of Potassium Ferricyanide on Acetophenone. By K. BUCHKA and P. H. IRISH (Ber., 20, 386-395).-All attempts to obtain phenylglyoxylic acid by the oxidation of acetophenone have hitherto proved unavailing, the methyl-group always being eliminated and benzoic acid produced. The author finds that by the continued action of an alkaline solution of potassium ferricyanide on acetophenone, phenylglyoxylic acid is produced. The quantity is, however, very small, and appears to be due to a secondary reaction, and not to direct oxidation, a great deal of benzoic acid being formed.

When 3 grams of acetophenone are added to a solution of 50 grams of potassium ferricyanide and 5 grams of potassium hydroxide in half a litre of water, and the whole allowed to stand for about 12 hours, small quantities of a crystalline substance are deposited. This substance, when recrystallised from benzene, is obtained in minute colourless needles having the formula C1HO2N. When heated with caustic potash, ammonia is evolved, and the potassium salt C1H2OK of a new acid is produced; it crystallises in minute needles. The corresponding barium salt yields concentric groups of needles, and contains 3 mols. H2O. The free acid is crystalline, and melts at 99-101° (uncorr.). The compound CHO2N thus seems to be the nitrile of the acid. Both the acid and the nitrile dissolve in concentrated sulphuric acid with a violet-red coloration, but the coloration is destroyed by dilution. The coloration produced by dissolving phenylglyoxylic acid in strong sulphuric acid is, on the other hand, not destroyed by dilution. By continued boiling with concentrated potash, both the nitrile and the acid yield phenylglyoxylic acid and acetophenone.

The author is inclined to think that the formation of these compounds is due to a part of the acetophenone becoming oxidised to benzaldehyde, which then unites with undecomposed acetophenone and hydrocyanic acid to form a cyanhydrin; Ph-COH + Ph.COMe + HCN CPhMe(OH) CPh(OH).CN.

Other mixed aromatic and fatty ketones seem to act in a similar way towards alkaline ferricyanide. These reactions are being further studied.

L. T. T.

Metacyanobenzoic Acid. By W. BRÖMME (Ber., 20, 524-530). -The silver, barium (with 3 mols. H2O), calcium (with 3 mols. H2O), and zinc salts are described; the methyl salt melts at 65°, and is sparingly soluble in alcohol, ether, benzene, and carbon bisulphide, sparingly soluble in water; the ethyl salt melts at 56° (comp. Müller, Abstr., 1886, 802); and the amide melts above 300°, and is soluble in alcohol and ether, insoluble in water. Metacyanobenzoic acid does not yield a nitro-derivative when treated with nitric acid or with a mixture of nitric and fuming sulphuric acids, and is neither reduced by sodium amalgam nor by sodium under various conditions. An alcoholic solution of hydroxylamine hydrochloride and soda converts the acid into the amidoxime (loc. cit.).

When metacyanobenzoic acid is dissolved in strong aqueous ammonia and the solution saturated with carbon bisulphide, a crystalline acid, (COOH-C,H,C: NH),S, is obtained, which melts at 199°, and is soluble in hot water, alcohol, and ether. When reduced with zinc and hydrochloric acid, this compound is converted into an acid of the formula (COOH·C2H, CH2)2NH [13]; it is crystalline, melts above 300°, sublimes without decomposition, and is sparingly soluble in hot water, soluble in alcohol, ether, benzene, and carbon bisulphide. The zinc salt is very hygroscopic, and is readily soluble in all ordinary solvents. An acid of the formula

(COOH CHỌC:NH),0,

is formed when metacyanobenzoic acid and benzene are added to fuming sulphuric acid, allowed to remain for 24 hours, and then poured into cold water; it is crystalline, melts above 300°, shows both acid and feeble basic properties, and is soluble in alcohol and ether, insoluble in water. The silver salt, C16H2ON2Ag1, is insoluble W. P. W.

in water.

Behaviour of Cyanobenzoic Acids on Dry Distillation. By W. BRÖMME (Ber., 20, 521-524).-Why dry calcium metacyanobenzoate is submitted to dry distillation, metadicyanobenzene is obtained in addition to benzonitrile; the melting point of the dicyanobenzene is 157.5°. If, however, calcium paracyanobenzoate is similarly treated, benzonitrile and paradicyanobenzophenone are obtained.

Paradicyanobenzophenone, CO (CH ̧•CN)2 [CN: CO = 1:4], crystallises in nodules, melts at 204-5, sublimes without decomposition, and is sparingly soluble in hot water and light petroleum, soluble in carbon bisulphide, readily soluble in alcohol, ether, and benzene. With phenylhydrazine, it yields a triphenylhydrazide; this crystallises in nodules, melts at 212°, is soluble in alcohol, ether, &c., and when heated is decomposed into the ketone.

Benzophenoneparadicarboxylic acid, CO(CHCOOH)2, formed by hydrolysis of the ketone, sublimes without previous fusion, is very sparingly soluble in ether and benzene, sparingly soluble in alcohol, soluble in hot water to the extent of 1 in 50,000, and is obtained from this solution in microscopic needles. The methyl salt crystallises in large needles, and melts at 138'; the silver salt, C1HO,Ag2 +

Ag2O, prepared by hydrolysis of the pure methyl salt, is insoluble in water. The acid and its methyl salt show a remarkable similarity to terephthalic acid and methyl terephthalate respectively.

Benzonitrile forms a solid compound when treated with phenylhydrazine.

2

W. P. W.

Meta- and Para-hydroxynitrobenzoic Acids. By P. GRIESS (Ber., 20, 403-409). Of the four possible meta-hydroxynitrobenzoic acids [COOH : OH: NO2 = 1 : 3 : 6, 1:3: 4, 1:3: 2, and 135], the author has already described the first three under the names of a-, 6-, and 7-metahydroxynitrobenzoic acids respectively; and also one of the two possible parahydroxynitrobenzoic acids, 1: 4:3 and 14: 2 (the former), under the name -hydroxynitrobenzoic acid (Ber., 5, 856, and Abstr., 1879, 246). Gerland (Annalen, 91, 192) has described the formation of a hydroxynitrobenzoic acid by the dissolution of metahydroxybenzoic acid in nitric acid of sp. gr. 136. The author finds that in this way di- or tri-nitro-compounds are always produced, but by employing only a slight excess of very dilute acid, a mixture of mononitro-compounds may be obtained; this contains three isomerides, his a- and B-acids, and a third g-hydroxynitrobenzoic acid, which is undoubtedly the missing acid, 1:3:5. The separation of the three acids is effected by means of the sparing solubility of the B-acid in water, and the greater solubility of the barium salt of the y-acid than of that of the g-acid.

-Hydroxynitrobenzoic acid,

C&H5(NO2) (OH), COOH [COOH : OH: NO2 = 1:3 : 5], crystallises in white scales or plates. It is easily soluble in alcohol, ether, and boiling water, melts at 167°, and decomposes at a higher temperature with evolution of black fumes. It has an acid and astringent taste; its barium salt crystallises with 6H2O in paleyellow prisms. The acid to which Grube and Hübner ascribe the above formula (Ber., 10, 1704) is, the author considers, undoubtedly identical with V. Meyer and Michler's diazoxybenzoic acid (Ber., 3, 746).

Barth's parahydroxynitrobenzoic acid, obtained by dissolving parahydroxybenzoic acid in nitric acid of sp. gr. 1.46 (Zeit. f. Chem., 1866, 647), is identical with the author's d-acid. L. T. T.

Derivatives of Orthamidophenylvaleric Acid. By L. Diehl and A. EINHORN (Ber., 20, 377-386).-Orthamidocinnamenylpropionic acid, NH2CH,CH: CH·CH2 CH2COOH, is prepared by dissolving orthamidocinnameny lacrylic acid in 50 parts of water in presence of alkali, and adding 5 per cent. sodium amalgam gradually; the solution must be kept almost neutral by addition of sulphuric acid. In 3 or 4 days it is treated with sulphuric acid, filtered, saturated with ammonia, and evaporated to dryness on a water-bath; ammonia is given off, and the free acid is extracted from the residue by absolute alcohol. The alcoholic solution is treated with water, heated to drive off the alcohol, and cooled with ice; the acid separates with 1 mol. H2O. The ethereal solution shows green fluorescence.

Orthamidodibromophenyl-y-d-dibromovaleric acid,

NH, CH,Br,'CHBrCHBrCH,CH, COOH,

is obtained by adding a solution of bromine in glacial acetic acid to a cooled solution of orthamidocinnamenylpropionic acid, also in glacial acetic acid. The product is poured into water containing sulphurous acid, and the precipitated substance dried and recrystallised from chloroform. It forms microscopic needles, which melt at 167°, with decomposition. It is readily soluble in alcohol, ether, and glacial acetic acid, less soluble in chloroform, insoluble in carbon bisulphide, water, and dilute mineral acids. Aqueous alkali solutions dissolve it readily.

Orthamidodibromophenylvaleric acid, NH2 CH2Br2 (CH2), COOH, is formed when a solution of orthamidotetrabromophenylvaleric acid in 5 parts of alcohol and 2 parts of strong hydrochloric acid, is treated with granulated zinc for a quarter of an hour, and then poured into water. It is extracted with ether, and the oil thus obtained dissolved in the smallest possible amount of 10 per cent. aqueous caustic soda and warmed. The acid crystallises from aqueous alcohol in splendid long needles (with 1 mol. H2O). It melts at 96°, and decomposes with evolution of gas at 223°. It dissolves readily in the usual solvents, except cold water, in which it is insoluble. The alkali salts are readily soluble. Ethyl orthamidodibromophenylvalerate hydrochloride, CHINO2Br2Cl, forms slender, white needles, which melt at 135-136°. The acetylderivative, CHINO,Br2, crystallises from 80 per cent. hot alcohol in tufts of slender, white needles, melting at 205-206°. It is readily soluble. The ethyl salt of the acetyl compound crystallises from dilute alcohol in stellate groups of needles. It melts at 139°, dissolves readily in alcohol, ether, &c., more sparingly in benzene, and can be distilled in small quantities without decomposition.

Orthamidophenylvaleric acid, NH2 C2H, CH2 CH2 CH, CH, COOH, is obtained by reducing orthamidodibromophenylvaleric acid dissolved in absolute alcohol with sodium amalgam. The product is made slightly acid with hydrochloric acid, treated with water, and boiled until free from alcohol. It is then made slightly ammoniacal, evaporated repeatedly until no more ammonia comes off, and the free acid thus obtained is crystallised from water containing a little alcohol. It forms white needles, melting at 60-62°. N. H. M.

Substituted Mono- and Di-bromosalicylic Acids. By A. PERATONER (Gazzetta, 16, 405-420).-In this paper are described a series of substituted mono- and di-bromosalicylic acids, obtained by heating the methyl salts of the mono- and di-bromo-acids with the alkyl iodides in presence of potash.

Methyl bromosalicylate, OH CH,BrCOOMe [COOMe: OH: Br= 1:25], obtained by the bromination of methyl salicylate dissolved in carbon bisulphide, crystallises in colourless needles or small prisms of the trimetric system, melting at 61°, and boiling without decomposition at 264-266°, insoluble in water, sparingly soluble in methyl alcohol. On hydrolysis, it yields a bromosalicylic acid melting at 164-165°.

Methyl methoxybromosalicylate, OMe C,H,BrCOOMe, obtained by the methylation of the above, crystallises in colourless needles melting at 39-40°, and distilling without decomposition at 295°, insoluble in water, soluble in other menstrua. The corresponding acid crystallises in long needles melting at 119°, resembling the methyl salt, as regards its solubility. Its alkaline salts are very soluble, the calcium, magnesium, and silver salts crystallise in needles.

Ethoxybromosalicylic acid, OEt·CH,Br·COOH, crystallises in colourless needles melting at 130°; its metallic salts resemble those of the methoxy-acid; the methyl salt crystallises in colourless needles, melting at 49°, and boiling at 300-302°.

Propoxybromosalicylic acid, OPra C,H,BrCOOH, melts at 62°; its methyl salt is a colourless liquid boiling at 321-324°, and solidifying in a freezing mixture; the isopropyl acid, OP.CH,Br·COOH, crysstallises in needles melting at 101°.

Methoxydibromosalicylic acid,

OMe C2H2Br2 COOH [COOH : OMe : Br: Br = 1:2 :3 : 5],

crystallises in long needles melting at 193-194°, and its barium salt, with 2.5H2O, in grouped needles; the methyl salt forms colourless needles melting at 53°. Methyl dibromosalicylate,

OH CH2Br2 COOMe,

obtained as one of the products of the bromination of methyl salicylate, crystallises in long needles, melting at 148-149°.

Ethoxydibromosalicylic acid, OEt·C2H2Br2 COOH, crystallises in colourless needles melting at 155–156°, and its methyl salt in interlaced needles melting at 43°.

None of the above described acids give any coloration with ferric chloride. V. H. V.

Constitution of Dibromosalicylic Acid. By A. PERATONER (Gazzetta, 16, 401-404).-The dibromosalicylic acid, obtained by the direct bromination of salicylic acid, when heated in sealed tubes with dilute sulphuric acid (1 : 3), yields the dibromophenol melting at 36° (40° Körner), the constitution of which is known to be [OH: Br: Br= 2:3:51; the carboxylic acid must then be represented by the formula [COOH OH: Br: Br= 1:2:35]. Tribromo- and 1: 2 bromophenol are also formed as subsidiary products in the above reaction : their formation is due to the ulterior decomposition of the dibromophenol, thus: 2C,H,Br2OH= CH2Br, OH + CH,Br.OH.

:

V. H. V.

Formation of Phenylglyoxylic Acid from Benzoic Cyanide. By K. BUCHKA (Ber., 20, 395-398). The author has repeated his former experiments (this Journal, 1877, ii, 485) on the action of hydrochloric acid on an acetic solution of benzoic cyanide. He finds that his phenoxylic acid is identical with Claisen's phenylglyoxylic acid, the melting point given (loc. cit.) being due to an admixture of