Hydrochloric Acid → HCID 53682263, compound

Participants

Reaction Conditions

Reaction Steps

Sodium hydride (17.32 g, 0.433 mol) was washed with hexane (100 ml×2) then was suspended in dimethylformamide (300 ml). To the mixture was dropwise added thiophenol (44.5 ml, 0.433 mol) in DMF (50 ml) under ice-methanol bath cooling with controlling the inner temperature of 5-10° C. under nitrogen atmosphere. After 1.5 h stirring at -5° C., methyl 4-chloroacetoacetate (50 ml, 0.433 mol) was dropwise added to the reaction mixture under ice-methanol bath cooling with controlling the inner temperature of 5-10° C. under nitrogen atmosphere and the reaction mixture was stirred at room temperature overnight. The mixture was acidified with 1N HCl to pH 2 under ice bath cooling then partitioned between EtOAc (500 ml) and H2O (100 ml). The aqueous phase was extracted with EtOAc (250 ml×2). The combined extracts were concentrated to about 500 ml and then washed with aq. NaHCO3 solution (150 ml) and brine (100 ml×3). The organic solution was dried over MgSO4 and concentrated to afford 100.88 g of methyl 4-phenylthioacetoacetate as an orange color oil. (104% yield).(contained 1/6 eq of DMF) 1H NMR (CDCl3) 7.42-7.18 (m, 5H), 3.80 (s 2H), 3.71 (s, 3H), 3.65 (s, 2H).

Provenance & Evidence