Triethyl phosphonoacetate, reaction with cyclohexanone

Triethyl phosphonoacetate, reaction of sodium derivative with cyclohexanone to yield ethyl cvclo hexy lideneacetate, 46, 45 1 nfluoroacetic anhydride, 46, 98 p,0 0 Trifluorostyrene, 47, 52 Trusopropvl phosphite as reagent in dechlorination of decachlorobi 2,4 cyclopentadienyl, 46, 93 1,3,5-Tnketones, from aroylationof 1,3-diketones, 46, 59 from 4-pyrones, 46, 59 Tnmethylamine oxide, reaction with x-octyl iodide to yield octanal, 47, 96... 

Triethyl phosphonoacetate, reaction of sodium derivative with cyclohexanone to yield ethyl cyclo-hexylideneacetate, 45, 4S Trifluoroacetic anhydride, 45, 98 a,a,a-Trifluoroacetophenone, reaction with triphenylphosphine and sodium chlorodifluoracetate, 48,116 m-Trifluoromethylaniline, methylation of with trimethylphosphate, 49, 111... 

Triethyl phosphonoacetate (11.2 g, 0.05 mol) is added dropwise at 20 °C to a slurry of 50 per cent sodium hydride (2.4 g, 0.05 mol) in 100 ml of dry 1,2-dimethoxyethane. After the addition, the reaction mixture is stirred for 1 hour at room temperature until gas evolution has ceased. Cyclohexanone (4.9 g, 0.05 mol) is added dropwise at such a rate that the temperature is maintained below 30 °C. After the addition, the solution is stirred for 15 minutes at room temperature during which time a viscous semi-solid appears. The mixture is taken up in a large excess of water, and the aqueous solution extracted with ether. The ether layer, after being dried over magnesium sulphate and evaporated, gives a liquid residue, b.p. 88-90 °C/10mmHg, 5.8 g (70%), 1.4704. 

To a slurry of 50% sodium hydride (2.4 g, 0.05 mol) in 100 mL of dry 1,2-dimethoxyethane at room temperature was added triethyl phosphonoacetate 65 (11.2 g, 0.05 mol) dropwise. Once addition was complete, the reaction was stirred an additional 60 min. until all gas evolution had ceased. Cyclohexanone 157 (4.9 g, 0.05 mol) was added at such a rate as to keep the reaction temperature below 30 °C. The reaction was stirred for 15 min after addition was completed before taking-up the viscous, semi-solid in a large excess of water. The aqueous solution was extracted with ether and the organic phase was dried with MgS04, filtered, and concentrated to give 5.8 g (70%) of 159 as a liquid. 

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