氯苄基膦酸二乙酯与醛、酮的反应——α-氯代苯乙烯衍生物的制备

THE PREPARATION OF THE DERIVATIVES OFa-CHLOROSTYRENE BY THE REACTION OF DIETHYL CHLOROBENZYLPHOSPHONATE WITH ALDEHYDES AND KETONES

Horner-Emmons反应在各类烯烃的台成中得到广泛应用,但通过该反应制备卤代烯烃的报导却相对较少。Bergmann、Zimmer和山口彰宏等曾先后报导了氟苄基膦酸二乙酯、对硝基氯苄基膦酸二苯醋以及对硝基溴或碘苄基膦酸二乙酯与芳香醛的反应,但反应中均使用了较强的碱,如RLi、NaH和NaOR。

The derivatives ofα-chlorostyrene have been prepared in good yields by the phase transfer catalytic reaction of diethyl chlorobenzylphos-phonate with aldehydes and ketones under the solid-liquid two phase systems.The polyethylene glycol(PEG)was used as the phase transfer catalysts.PhClCHP■(OEt)_(2)+RC■RKOH(s)→PEGPhC1C=CRR'+-OP■(OEt)_(2).