Ethanol → Cyclohexanone, 2-(hydroxymethylene)-

Temperature

0 °C

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.

1. customThe cooling bath was removed
2. temperaturewarmed gradually to room temperature over 6 hours
3. stirringfinally stirred for an additional 16 hours
4. customEther lost by evaporation
5. additionby diluting to 1 liter with fresh ether
6. additionEthanol (12.5 ml.) was added
7. stirringstirring
8. waitcontinued for 1 hour
9. extractionThe mixture was extracted with 125 ml
10. washThe combined aqueous extracts were washed 1×50 ml
11. extraction6N HCl, and extracted 2×150 ml
12. washwashed 1×25 ml
13. dry with materialbrine, dried over Na2SO4
14. customevaporated to an oil
15. distillationdistilled

ORD record

ord-972b7ebf733f46c8be64f8e2ae29b1d2

Source dataset

uspto-grants-1984_02

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US04430337