Researches on the constitution of physostigmine. Pt. III. The formation of substituted indoles from m-4-xylidine, and the reduction of 3-nitro-p-tolylacrylic acid / by Arthur H. Salway.

  • Salway, Arthur Henry.
Date:
1913
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Licence: In copyright

Credit: Researches on the constitution of physostigmine. Pt. III. The formation of substituted indoles from m-4-xylidine, and the reduction of 3-nitro-p-tolylacrylic acid / by Arthur H. Salway. Source: Wellcome Collection.

Provider: This material has been provided by The Royal College of Surgeons of England. The original may be consulted at The Royal College of Surgeons of England.

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    with the formation of 2:4-xylylsuccinamic acid, which is further resolved, oil prolonged heating with the alkali, into xylidine and succinic acid. An attempt was made to convert the above amide into an indole derivative by heating with sodium ethoxide in a manner similar to that described in connexion with 2 :4-xylylsuccinamic acid, but without success, since the only compounds that could be isolated from the reaction mixture were xylidine and 2:4-xylylsuccinamic acid. II. Reduction of 3-N■itro-'p-folylacrylic Acid (VI, p. 1989). The 3-nitro-p-tolylacrylic acid required for these experiments was prepared from p-tolualdehyde in the manner already described by Hanzlik and Bianchi (Ber., 1899, 32, 1288, 2285). In order to ascertain, in the first place, whether reduction could be effected by means of sodium amalgam, 800 grams of the latter (4 jDer cent. Na) were added in small quantities, with continuous mechanical stirring, to a solution of the acid in dilute sodium hydroxide. After the amalgam had been completely decomposed, the alkaline liquid was filtered, then acidified, and the acidic substance, which was precipitated, was collected. The greater part of the latter was found to consist of unchanged material, but a small quantity of an indefinite acid of high melting point was isolated, which appeared to be formed from the original acid by polymerisation under the influence of the alkali. No evidence was obtained of the formation of any /3-3-nitro-p-toiylpropionic acid (VII, p. 1989) in the reaction. 3-Amino-^-tolylacrylic Acid (VIII, p. 1990). This compound was obtained as the first reduction product of 3-nitro-p-tolylacrylic acid when the latter was heated for a short time at 100° with an excess of liydriodic acid (D 1'7) and red phosphorus. As soon as the vigorous initial reaction had subsided, water was added, and the mixture filtered to remove the red phos- phorus. The filtrate, on concentration, yielded well-formed crystals of a liydriodide, which were collected and dissolved in a little water. Aqueous sodium carbonate was then cautiously added to the solution, when the amino-acid was deposited a6 a yellow precipi- tate. It was purified by crystallisation from alcohol, and thus obtained in lemon-yellow, elongated needles, melting at 184°: 0-0984 gave 0'2443 C02 and 0'0548 H20. C = 67‘7; H = 6*2. C10H1xO2N requires C=67'8; 11 = 6-2 per cent. It is evident from the above analysis that the cinnamyl residue
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