반응 #2206424

반응 방정식

sodium hydride

3-carboxypropyl triphenylphosphonium bromide

diisopropylethylamine

methyliodide

cyclohexanone

→

title compound

수율 68.0%

4-Cyclohexylidene butanoic acid, methyl ester

수율 68.0%

용매

ethyl acetate

dimethyl sulfoxide

tetrahydrofuran

반응 조건

후처리

1. 1
   세척A twice hexane washed
2. 2
   온도cooled to 15° C.
3. 3
   workup.STIRRINGstirred 1 hour at room temperature, 2 hours at 40°-45° C.
4. 4
   온도cooled to 0° C.
5. 5
   기타quenched with 10 ml of water
6. 6
   workup.ADDITIONdiluted with 600 ml of ice water containing 50 ml of concentrated sulfuric acid and 250 ml of brine
7. 7
   추출extracted with ethyl acetate
8. 8
   세척The combined organic layers were washed with brine
9. 9
   건조dried over anhydrous sodium sulfate
10. 10
    여과filtered
11. 11
    농축concentrated in vacuo
12. 12
    workup.DISSOLUTIONThe resulting yellow oil was dissolved in 500 ml of acetonitrile
13. 13
    기타degassed
14. 14
    workup.STIRRINGstirred for 18 hours under nitrogen at room temperature
15. 15
    세척washed with 5% sodium sulfate and with saturated aqueous sodium bicarbonate
16. 16
    세척The organic layers were washed with brine
17. 17
    건조dried over anhydrous sodium sulfate
18. 18
    여과filtered
19. 19
    농축concentrated in vacuo
20. 20
    기타chromatographed on Silica Gel eluting with ethyl acetate in hexane

실험 절차

A twice hexane washed suspension of 15.0 g (312 mmol) sodium hydride (50% in mineral oil) in 600 ml of dry dimethyl sulfoxide was heated under nitrogen at 60° C. for 1.5 hour, cooled to 15° C., and treated portionwise over 15 min with 60 g (140 mmol) of 3-carboxypropyl triphenylphosphonium bromide. The bright red solution was stirred at room temperature for 1 hour, then treated with 9.6 ml (93 mmol) of cyclohexanone in 100 ml of dry tetrahydrofuran, stirred 1 hour at room temperature, 2 hours at 40°-45° C., cooled to 0° C., quenched with 10 ml of water, diluted with 600 ml of ice water containing 50 ml of concentrated sulfuric acid and 250 ml of brine, and extracted with ethyl acetate. The combined organic layers were washed with brine, dried over anhydrous sodium sulfate, filtered, and concentrated in vacuo. The resulting yellow oil was dissolved in 500 ml of acetonitrile, degassed, treated with 25 ml (143 mmol) of diisopropylethylamine and 50 ml (792 mmol) of methyliodide, stirred for 18 hours under nitrogen at room temperature, diluted with 250 ml of ethyl acetate, washed with 5% sodium sulfate and with saturated aqueous sodium bicarbonate. The organic layers were washed with brine, dried over anhydrous sodium sulfate, filtered, concentrated in vacuo, and chromatographed on Silica Gel eluting with ethyl acetate in hexane to give 11.43 g (68%) of the title compound as a pale yellow oil.

출처