Bases derived from some substituted propenylbenzenes with a note on the preparation of pure methylamine / by T.M. Sharp and W. Solomon.

  • Sharp, Thomas Marvel.
Date:
[1931.]
Catalogue details

Licence: Public Domain Mark

Credit: Bases derived from some substituted propenylbenzenes with a note on the preparation of pure methylamine / by T.M. Sharp and W. Solomon. Source: Wellcome Collection.

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    (b) Methyh’soeugenol dibromide (Mannich, loc. cit.) (40 g.) in methyl alcohol (390 c.c.) gave, with the calculated quantity of sodium methoxide in methyl alcohol, the methoxybromide in prac¬ tically quantitative yield as a light brown syrup (Found : Br, 27-4; MeO, 31-2. C12H1703Br requires Br, 27-65; 3MeO, 32-2%). This was treated with methylamine (22 g.) in dry alcohol (80 c.c.) and furnished non-basic material (18-6 g.) as an amber-coloured oil, and crude base (10 g.) as a brown oil. The latter was purified as hydro¬ chloride, separating from acetone in colourless prismatic aggregates (7-65 g.), m. p. 167° (corr.), to a cloudy liquid clear at 190° (Found : C, 56-1; H, 8-0; N, 5-1; Cl, 12-95; MeO, 34-3; NMe, 9-0. Ci3H2i03N,HC1 requires C, 56-6; H, 8-0; N, 5-1; Cl, 12-9; 3MeO, 33-8; NMe, 10-5%). Demethylation was effected in the manner described for the corresponding derivative of isomyristicin (p. 1473). The hydrochloride (8-2 g.) furnished crude base (5-3 g.), from which on addition of acetone crystalline base (3-0 g.) was obtained. The base (IX) crystallises in colourless felted needles from acetone, m. p. 130—131° (corr.) (Found: C, 63-7; H, 8-5. C12H1903N requires C, 63-95; H, 8-5%). The oxalate forms thin colourless prisms from alcohol, m. p. 217—218° (corr., decomp.) [Found : C, 57-9; H, 7-4; N, 5-0; MeO, 22-8; NMe, 10-1. (C12H1903N)2,C2H204 requires C, 57-7; H, 7-5; N, 5-2; 2MeO, 23-0; NMe, 10-7%]. Isomerisation of the methyl ethers of A and B. The finely powdered methyl ether of base A (VIII) (0-7 g.) was added in small portions to a suspension of phosphorus pentachloride (1-4 g.) in cold dry chloroform (5 c.c.). The phosphorus pentachloride slowly dissolved and after standing for 2 hours with occasional shaking the solvent was evaporated in a desiccator. The residue was boiled under reflux for 30 minutes with alcoholic potassium hydroxide (25 c.c. of 12%), water added, and the alcohol removed by distillation. Acid¬ ification of the residue and extraction with ether furnished a brown non-basic oil (0-45 g.), which was not examined; subsequent extrac¬ tion with ether after the addition of alkali gave a colourless oily base which crystallised on standing. After recrystallisation from ether it was obtained in needles, m. p. 130—131° (corr.), which on admixture did not depress the melting point of (3-methylamino- a-hydroxy-a-3 : 4-dimethoxyphenylpropane (IX). The methyl ether of base B (0-5 g.) similarly gave a non-basic oil (0-15 g.) and a base (0-3 g.) which after crystallisation from ether had m. p. 129—130° (corr.), and was also identical with the above p-methylamino-compound. ;p-Acetoxypropenylbenzene.—For the preparation of this substance, which was not isolated, the directions given by Behai and Tiffeneau {Bull. Soc. chim., 1908, 3, 303) for the preparation of p-propenyl-