Ammonium Chloride → HCID 21763808, compound

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Reaction Steps

To a solution of lithium dimethyl cuprate in ether (500 ml), prepared from copper iodide (23.81 g, 125 mmol) and methyl lithium (250 mmol, 136 ml of a 1.8 M solution in ether containing lithium bromide), 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 mmol) in benzene (500 ml). The resulting suspension was stirred for 1 hr. in the cold, then poured into saturated NH4Cl solution (600 ml) and the mixture stirred for 15 min. The organic layer was separated, and the aqueous phase adjusted to pH 13-14 by use of 50% NaOH. The aqueous phase was then extracted with two portions of chloroform, the combined organic phases washed with dilute NH4OH and dried. Evaporation gave a foam which crystallized from chloroform with the addition of hexane to give 33.20 g (74%) of 2 as the mono-chloroform 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), H5α; 5.47, d(1), H8, J7,8 =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, J7H,7CH3 =7 Hz; exchangeable, 4--OH at ~6.20.

Provenance & Evidence