高等学校化学学报

高等学校化学学报 ›› 1994, Vol. 15 ›› Issue (11): 1639.

• 论文 • 上一篇    下一篇

2,5-二甲氧基苯基烷基酮与t-BuMgCl反应的机理研究

龚跃法, 赵成学, 蒋锡夔   

  1. 1. 华中理工大学化学系, 武汉, 430074;
    2. 中国科学院上海有机化学研究所, 上海
  • 收稿日期:1993-11-27 修回日期:1994-02-18 出版日期:1994-11-24 发布日期:1994-11-24
  • 通讯作者: 龚跃法,男,30岁,博士,副教授.
  • 作者简介:龚跃法,男,30岁,博士,副教授.
  • 基金资助:

    国家自然科学基金

A Mechanistic Study on Reactions of Alkyl 2,5-Dimethoxyphenyl Ketones with t-Butylmagnesium Chloride

GONG Yue-Fa, ZHAO Cheng-Xue, JIANG Xi-Kui   

  1. 1. Chemistry Department , Huazhong university of Science and Technology, Wuhan, 430074
    2. Shanghai Institute of Organic Chemistry, Academia Sinica
  • Received:1993-11-27 Revised:1994-02-18 Online:1994-11-24 Published:1994-11-24

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摘要： 2,5-二甲氧基苯基烷基酮1_(a-d)(烷基分别为甲基、乙基、异丙基和叔丁基)与t-BuMgCl反应后,主要生成了1,2-加成产物、1.6-共轭加成产物及还原产物,产物及其分布在不同程度上受酮的结构、反应介质以及金属镁中过渡金属杂质的含量等因素的影响。据此,提出了反应的可能机理。

关键词: 二甲氧基苯基烷基酮, 格氏反应, 单电子转移

Abstract: Reactions of alkyl 2, 5-dimethoxyphenyl ketones with t-butylmagnesium chloride were shown to yield the 1, 2-adducts, 1, 6-adducts, and the corresponding alcohols as the major products.The product distributions were found largely dependent on the alkyl group of the ketone and the solvent used. The bulkier the alkyl group . the more favoured the formation of the 1.6-adduct or the alcohol. On the other hand, the formation of the 1, 6adducts became a more important pathway when the reactions were carried out in tetrahydrofuran than in ether.In addition. the trace amount of transition metals in magnesium alsoshowed a little effect on the product distribution. Based on the experimental observations, we suggested that the above reactions, initiated by a single electron transfer, would possiblyundergo via the intermediates, radical ion pairs and radical pair, and the final product distributions greatly depended on the nature of the generated intermediates in each of the reactions.

Key words: Alkyl dimethoxyphenyl ketone.Grignard reaction, Single electron transfer

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