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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    a separation it is essential to take a mixed melting point before uniting any two crops. The oxalate of A absorbs moisture, forming a hydrate (Found : loss on drying at 120° in a vacuum, 4-6. A2,C2H204,1'5H20 requires loss 5-0%), the oxalate of B is not hygroscopic [Found for oxalate A : C, 55*8; H, 6-9. Found for oxalate B : C, 56-2; H, 6-9. (C11H1703N)2,C2H204 requires C, 56-2; H, 7*1%]. Base A from the pure oxalate forms colourless prisms from alcohol, m. p. 143—146° (corr.); base B is similar, m. p. 166—167° (corr.), mixture m. p. about 140—155° (Found for base A : C, 62-4; H, 8-1; N, 6-4, 6-6; MeO, 14-6, 14-7 ; NMe, 10-2, 10- 0. Found for base B : C, 62-4; H, 8T ; N, 6-6, 6-7; MeO, 14-9, 14-8; NMe, 10-4. CnH1703N requires C, 62*5; H, 8*1; N, 6-6; MeO, 14*7; NMe, 13-75%). Methylation of base A. Base A (7-2 g.) was dissolved in alcohol (120 c.c.) and treated at room temperature with an ethereal solution (150 c.c.) of the diazomethane from nitrosomethylurethane (7 c.c.). After standing over-night, the solution was colourless; the solvents were evaporated, the residue was dissolved in 2% hydrochloric acid and made alkaline with potassium hydroxide, and the base shaken into ether. This gave 6-3 g. of crude base, which was con¬ verted into hydrochloride and crystallised from methyl alcohol. It was thus obtained in rosettes of colourless needles (5-5 g.), m. p. 206—207° (corr.) (Found : Cl, 13-5, 13-55; MeO, 23-7, 23-8; NMe, 9-1, 10-0. Calc, for C12H1903N,HC1 : Cl, 13-55; 2MeO, 23-7 ; NMe, 11- 1%). The base (VIII), prepared from the pure hydrochloride, crystallised from ether in minute colourless prisms, m. p. 60—62° (corr.) (Found : C, 63-9 ; H, 8-15; N, 6-2, 6-1. Calc, for C12H1903N : C, 63-9; H, 8-5; N, 6-2%). Mannich (loc. cit.) records m. p. 63° for the base and 205° for the hydrochloride. The oxalate forms colourless crystals, m. p. 147° (corr., decomp.), from acetone. Methylation of base B. Base B (8-3 g.) in alcohol (125 c.c.) with the diazomethane from nitrosomethylurethane (7-75 c.c.) in ether (100 c.c.) gave 8-3 g. of crude methyl ether of B. This furnished 7-3 g. of pure hydrochloride of the methyl ether of B, crystallising from dry alcohol in rosettes of colourless needles, m. p. 204—205°, which depress the melting point of the hydrochloride of the methyl ether of A to 184—193° (Found : Cl, 13-5; MeO, 23-7, 23-8; NMe, 11-0, 10-6. C12H1903N,HC1 requires Cl, 13-55; 2MeO, 23-7; NMe, 11-1%). The oxalate crystallises from acetone in colourless prisms, m. p. 147° (corr., decomp.), which depress the melting point of the corresponding salt of A to 140°. The base, prepared from the pure hydrochloride, separates from ether in colourless square plates, m. p. 95—97° (corr.) (Found : C, 64-1, 64-2 ; H, 8-0, 8-0 ; N, 6-4, 6-4. C12H1903N requires C, 63-9; H, 8-5; N, 6-2%).