Ethanol → Cyclohexanone, 2-(hydroxymethylene)-

Participants

Reaction Conditions

Reaction Steps

A mixture of 50% sodium hydride dispersion in oil (24 g., 0.5 mole) and absolute ethanol (2.5 ml., 43 mmole) in 1 liter ether were stirred under N2 at 0° C. To the cold solution, cyclohexanone (51.5 ml., 0.5 mole) in ethyl formate (60 ml., 0.75 mole) was added dropwise at 0°-5° C. The cooling bath was removed. The temperature rose to the boiling point of ether over 30 minutes. The reaction mixture was recooled, warmed gradually to room temperature over 6 hours and finally stirred for an additional 16 hours. Ether lost by evaporation was replaced by diluting to 1 liter with fresh ether. Ethanol (12.5 ml.) was added and stirring continued for 1 hour. The mixture was extracted with 125 ml. water in two portions. The combined aqueous extracts were washed 1×50 ml. ether, acidified with 82 ml. 6N HCl, and extracted 2×150 ml. with fresh ether. The acid ether extracts were combined, washed 1×25 ml. brine, dried over Na2SO4, evaporated to an oil and distilled to yield title product, 44 g., b.p. 92°-98°/15-20 mm.

Provenance & Evidence