Reactions of dialkylmagnesium-salt mixtures with ketones: increasing the ratio of addition to reduction

Reactions of dialkylmagnesium-salt mixtures with ketones: increasing the ratio of addition to reduction
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二烷基镁盐混合物与酮的反应:增加加成与还原的比例

DOI:
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发表时间:
1990
期刊:
影响因子:
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通讯作者:
J. Destephano
J. Destephano
中科院分区:
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文献类型:
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作者:
H. G. Richey;J. Destephano

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在酮和二烷基镁化合物的反应中伴随加成的酮还原成仲醇可以通过首先向二烷基镁化合物中加入适当的盐来减少。在有利的盐和反应物化学计量下,在二丙基镁与二异丙基酮或二叔丁基酮的反应中消除了还原。在二叔丁基镁和二叔丁基酮的反应中,还原总是占主导地位,尽管也会发生一些加成。观察到具有显著效果的盐是甲醇钾、(Me2NCH2)2CHOK、甲醇钠、甲醇锂、叔丁醇锂、四丁基溴化铵和苄基三乙基氯化铵
The reduction of the ketone to a secondary alcohol that accompanies addition in reactions of ketones and dialkylmagnesium compounds can be lessened by first adding an appropriate salt to the dialkylmagnesium compound. With favorable salts and reactant stoichiometries, reduction is eliminated in reactions of dipropylmagnesium with diisopropyl ketone or di-tert-butyl ketone. In reactions of di-tert-butylmagnesium and di-tert-butyl ketone, reduction always predominates, although some addition does occur. Salts observed to have significant effects are potassium methoxide, (Me 2 NCH 2 ) 2 CHOK, sodium methoxide, lithium methoxide, lithium tert-butoxide, tetrabutylammonium bromide, and benzyltriethylammonium chloride