Methyl acetoacetate → Decanoic acid, 3-oxo-, methyl ester

Participants

Reaction Conditions

Reaction Steps

A dry tetrahydrofuran suspension (4 l) containing 440 g (11 mol) of 60% sodium hydride was cooled to 0° C., and 1.8 l of a tetrahydrofuran solution of 1.161 kg (10 mol) of methyl acetoacetate was added thereto dropwise, followed by stirring at room temperature for 1 hour. To the reaction mixture was added dropwise 1.789 kg (11 mol) of octanoyl chloride at 0 to 5° C., followed by stirring at room temperature overnight. After confirming disappearance of the octanoyl chloride by thin layer chromatography (TLC), tetrahydrofuran was evaporated, and the residue was poured into ice-water and extracted with 8 l of ethyl acetate. Ethyl acetate was evaporated, and the residue was poured into a mixture of 400 g of a 28% methanol solution of sodium methoxide and 1.2 e of methanol and heated at 60 to 65° C. for 6 hours while stirring to conduct deacylation. The product was cooled with ice, adjusted to pH 5 with a 10% sulfuric acid aqueous solution, and extracted with ethyl acetate. The ethyl acetate layer was washed successively with a 5% sodium carbonate aqueous solution and a saturated sodium chloride aqueous solution. The ethyl acetate was evaporated, and the concentrated residue was distilled under reduced pressure to give 1.10 kg (5.5 mol; yield: 50%) of methyl 3-oxodecanoate (boiling point: 121° C./5 mmHg).

Provenance & Evidence