化学学报 ›› 1987, Vol. 45 ›› Issue (12): 1207-1210. 上一篇    下一篇

研究论文

二乙基膦酰乙酸乙酯阴离子参与脂肪族SRN1反应

洪琳;杨克   

  1. 杭州大学化学系
  • 发布日期:1987-12-15

Participation of the diethylphosphonoacetate anion in the aliphatic SRN 1 reaction

HONG LIN;YANG KE   

  • Published:1987-12-15

二乙基膦酰乙酸乙酯阴离子与对硝基苄基衍生物的反应中发生烷基化和烷氧基化.结果表明,离去基团的离去性能降低,SN2烷基化或烷氧基化受抑制,而是有利于SRN 1途径,使烷基化容易发生.在对硝基苄基氯化物与阴离子反应时,得到P,P'-二硝基苯代乙烯,当不存在电子转移抑制剂或只存在间二硝基苯时,二苯代乙烯通过SRN 1机理形成,在对二硝基苯时,以SN 2消除反应机理.

关键词: 乙酸酯, 反应机理, 乙酸乙酯, 氯代烃, 膦酸酯类, 溴代烃, 重排反应, 硝基苯, 苄基, 阴离子

In the reaction of the anion of Et diethylphosphonoacetate with p-nitrobenzylic derivatives either C-alkylation or O-alkylation may occur. Results showed that with decreasing ability of the leaving group from iodo, Br, Cl, OAc to N+(CH3)3I-, the SN2 O-alkylation or C-alkylation was inhibited, and the SRN 1 path, leading to C-alkylation, was facilitated. In the reaction of p-nitrobenzyl chloride with the anion, p,p'-dinitrostilbene was obtained. In the absence of electron transfer inhibitors or presence of only m-dinitrobenzene, the stilbene might be formed through SRN1 mechanism. In the presence of p-dinitrobenzene the mechanism might change to an SN2-elimination type.

Key words: ACETIC ACID ESTER, REACTION MECHANISM, ETHYL ACETATE, CHLOROHYDROCARBON, PHOSPHONIC ACID ESTER, BROMOHYDROCARBON, REARRANGEMENT REACTION, NITROBENZENE, BENZYL GROUP, ANION

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