Bromide ion → HCID 14751115, compound

Participants

Reaction Steps

Ethylcyanoacetate (6.30 g, 55.7 mmoles) was added to a solution of sodium ethoxide (50 mmoles) in ethanol (25 mL) and refluxed 15 minutes. After cooling, the mixture was treated with bromide, 1A, (7.68 g, 25.3 mmoles) as a solution in ethanol (25 mL) and refluxed for 6 hours. The mixture was filtered, and the filtrate was treated with acetic acid to pH 7.0 and was evaporated to a viscous residue. The residue was partitioned between water (50 mL) and ether (50 mL), and the ether phase collected. The aqueous phase was washed with 4 volumes (50 mL) of ether, and the combined ether fractions were dried (CaSO4) and filtered. The filtrate was evaporated in vacuo, and the residue chromatographed (400 g silica, 3:1 hexane/ethyl acetate) to yield 6.06 g (70%) of the title compound, 1B, as a pale yellow oil. NMR (DMSO-d6) δ1.17 (t, 3H, CH3 of benzoate ether), 1.7 (m, 2H, CH2CH2 --CH2), 1.95 (m, 2H, CH2 --CH2CH2 --S), 1.28 (t, 3H, CH3 of acetate ester), 3.1 (m, 2H, CH2 --S), 4.15 (m, 1H, CH), 4.15 (q, 2H, CH2 of benzoate ester), 4.28 (q, 2H, CH2 of acetate ester), 7.4 (d, 2H, benzoate H's ortho to S), 7.85 (d, 2H, benzoate H's ortho to carbonyl). Compound 1B was used in the next reaction without further purification.

Provenance & Evidence