Ammonium Chloride → HCID 21763808, compound

Participants

Reaction Steps

To a solution of lithium dimethyl cuprate, prepared from copper iodide (23.81 g, 125 mmole) and methyl lithium (250 mmole, 136 ml of a 1.8 M solution in ether containing lithium bromide), in ether (500 ml) stirred in an ice-salt bath under an argon atmosphere, was added rapidly in a thin stream a solution of thebaine (1, 31.14 g, 100 mmole) in benzene (500 ml). The resulting suspension was stirred for 1 hour in the cold, poured into saturated NH4Cl solution (600 ml) and stirred for 15 minutes. The organic layer was separated and the aqueous phase adjusted to pH 13-14 by use of 50% NaOH solution. The aqueous phase was extracted with two portions of chloroform, the combined organic phases were washed with dilute ammonium hydroxide and dried. Evaporation of the organic phase gave a foam which crystallized from chloroform with the addition of hexane to give 33.20 g (74% theory of (2)) as the monochloroform solvate, mp 97°- 100°. Recrystallization from the same solvent pair gave analytically pure (2.CHCl3), mp 98°-101.5°. IR (CDCl3): 3500 cm-1 (OH). NMR (CDCl3): δ7.30, s (1), CHCl3 ; 6.65, m (2), H1 and H2; 6.13, s (1), H5; 5.47, d (1), H8, J 7,8=3 Hz; 3.86, s (3), 3--OCH3 ; 3.63, s(3), 6---OCH3 ; 2.33, s(3), 17--NCH3 ; 1.17, d(3), 7--CH3, J 7H,7CH3 =7 Hz; exchangeable, 4--OH at ~6.20.

Provenance & Evidence