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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    extract of the acid liquor (0-6 g.) was not examined. The crude base (7-15 g.) was purified through its hydrochloride, which crystal¬ lised from alcohol in hard, almost colourless prisms (5*9 g.), m. p. 233—235° (corr., decomp.) after previous sintering at 231° (Found : C, 52-3; H, 6-7; N, 5-7; Cl, 12-8; MeO, 10-9; NMe, 9-6. C12H1704N,HC1 requires C, 52-3; H, 6-6; N, 5*1; Cl, 12-9; MeO, 1T3; NMe, 10-5%). The hydrobromide forms colourless prisms from alcohol, m. p. 239° (corr., decomp.) after previous sintering at 219° (Found : C, 45-4; H, 5*5; N, 4-3; Br, 24-6. C12H1704N,HBr requires C, 45-0 ; H, 5*7 ; N, 4-4; Br, 25*0%). The oxalate separates from alcohol in colourless prisms, m. p. 251° (corr., decomp.) [Found: C, 55*2 ; H, 6*2 ; N, 5*5; MeO, 10*9. (C12H1704N)2,C2H204 requires C, 54-9; H, 6-4; N, 4-9; MeO, 10*9%]. The picrate con¬ sists of yellow hemispherical aggregates of needles, m. p. 179—182° (corr.) (Found : N, 12*5. C12H1704N,C6H307N3 requires N, 12-0%). The base (VII), prepared from the pure hydrochloride, is a pale straw-coloured oil. (b) isoMyristicin dibromide (3T6 g.), dry methyl alcohol (30 c.c.J' and sodium methoxide yielded fi-bromo-tx-methoxy-a-S-methoxyA : 5- metliylenedioxyphenylpropane (2-70 g.) as a colourless varnish (Found: Br, 26-2; MeO, 19-3. C12H1504Br requires Br, 26-4; MeO, 20-5%). The methoxybromide (12-3 g.) with methylamine (13 g.) in dry alcohol (50 c.c.) furnished non-basic material (5*25 g.) consisting mainly of 3-methoxy-4 : 5-methylenedioxyphenyl ethyl ketone (Scandola, Atti B. Accad. Lincei, 1912, 21, i, 47), and a pale yellow basic oil (4 g.), which afforded crystalline fi-methylamino-a- methoxy-a.-3-methoxyA : 5-methylenedioxyphenylpropane hydrochloride (3*6 g.). This salt separates from alcohol in small colourless prisms, m. p. 252° (corr., decomp.) (Found : C, 53*6; H, 7*0; N, 5-3; Cl, 12T ; MeO, 210; NMe, 8 0. C13H1904N,HC1 requires C, 53-9; H, 7-0; N, 4*8; Cl, 12-2; 2MeO, 2T4; NMe, 10*0%). Demethylation was effected by allowing the hydrochloride (6-4 g.) to stand in cold hydrochloric acid (d T19, 65 c.c.) during 21 hours. The partially crystalline base (4*97 g.), which was obtained by extracting the alkaline solution with ether, yielded $-methylamino-cx.-methoxy-oL-Z- methoxyA : 5-methylenedioxyphenylpropane (2-3 g.) as colourless fragile prisms from acetone or from benzene-ether, m. p. 122— 124° (corr.) (Found: C, 60-5; H, 7-5; N, 6T ; MeO, 13*0; NMe, 1T2. C12H1704N requires C, 60-2; H, 7*2; N, 5-9; MeO, 13 0; NMe, 12-1%). The hydrochloride forms colourless prismatic aggre¬ gates from alcohol, m. p. 194—198° (corr.) (Found : Cl, 12*8. Ci2Hi704N,HC1 requires Cl, 12-9%). Isomerisation of oL-Methylamino-$-hydroxy-<x-3-methoxy-4:: 5-methyl- enedioxyphenylpropane (VII).—The hydrochloride (see above) (10 g.)