Grignard reagents in toluene solutions
Grignard reagents in toluene solutions
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甲苯溶液中的格氏试剂
DOI：
10.1002/aoc.333
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发表时间：
2002
影响因子：
3.9
通讯作者：
A. Tuulmets
中科院分区：
文献类型：
--
作者：
Meeri Sassian;D. Panov;A. Tuulmets
在甲苯中，在1或0.5当量的各种有机碱（醚和胺）的存在下，由氯代烷烃和氯苯制备格氏试剂。具有平均单溶剂化的试剂可以从伯或仲烷基氯化物和氯苯以高产率获得。乙醚是最有效的给体，因为它为试剂提供非常少量的碱。研究了正丁基氯化镁在乙醚中的反应动力学，以及格氏试剂在甲苯中与乙醚的单溶剂化反应动力学。部分溶剂化试剂的反应活性大大超过常规格氏试剂。单和半溶剂化的正丁基氯化镁在甲苯中与酮，醛，和两个酯的加成和还原反应的产率进行了测定。部分溶剂化的试剂提供的加成产物（叔醇）的产率优于，或至少相当于，用常规的格氏试剂得到的那些。
Grignard reagents were prepared from chloroalkanes and chlorobenzene in toluene in the presence of one or 0.5 equivalents of various organic bases (ethers and amines). Reagents with an average monosolvation can be obtained in high yields from primary or secondary alkyl chlorides and chlorobenzene. Diethyl ether is the most effective donor, in that it affords the reagents with a very small content of base. The kinetics of the reactions of n-butylmagnesium chloride in diethyl ether, and of this Grignard reagent monosolvated with the ether in toluene, with alkylalkoxysilanes were investigated. Reactivity of the partially solvated reagent greatly exceeds that of the conventional Grignard reagent. Yields of addition and reduction reactions of mono- and semi-solvated n-butylmagnesium chlorides in toluene with a ketone, an aldehyde, and two esters were determined. The partially solvated reagents afford the addition products (tertiary alcohols) in yields better than, or at least comparable to, those obtained with the conventional Grignard reagents.