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碱催化7,7-二甲基-2-亚甲基双环[3.1.1]庚-6-酮开环反应研究

发表时间:2017-01-15  浏览量:1489  下载量:374
全部作者: 朱玉娟,何玲,李卫东
作者单位: 重庆大学药学院
摘 要: 2,2,4-三甲基-3-环己烯-1-酸(2a)是一种重要的有机合成中间体。研究7,7-二甲基-2-亚甲基双环[3.1.1]庚- 6-酮(13)在KOH、叔丁醇钾(t-BuOK)和六甲基二硅基氨基钾(KHMDS)等碱性条件下的环丁酮开环反应,发现该反应在KHMDS条件下能高效完成,直接高区域选择性得到不饱和酸(2a),同时在t-BuOK的作用下会生成相应的酯。推测该反应过程中的质子化是分子内的1,5-σ氢迁移过程。
关 键 词: 有机化学;7,7-二甲基-2-亚甲基双环[3.1.1]庚-6-酮;环丁酮;水解开环;1,5-σ氢迁移
Title: Base cleavage of 7,7-dimethyl-2-methylenebicyclo[3.1.1]heptan-6-one
Author: ZHU Yujuan, HE Ling, LI Weidong
Organization: School of Pharmaceutical Sciences, Chongqing University
Abstract: 2,2,4-trimethyl-3-cyclohexene-1-carboxylic acid (2a) is an important synthetic intermediate in organic synthesis. Basic cleavage of 7,7-dimethyl-2-methylenebicyclo[3.1.1]heptan-6-one (13) with potassium hydroxide, potassium t-butoxide (t-BuOK), potassium bis(trimethylsilyl)amide (KHMDS) was studied in this work and confirmed that KHMDS was the most efficient base, providing 2,2,4-trimethyl-3-cyclohexene-1-carboxylic acid (2a) with high regioselectivity respectively. Cleavage of 13 with potassium t-BuOK afforded the corresponding esters simultaneously. The protonation was speculated to process through a 1,5-σ proton shift to produce 2a.
Key words: organic chemistry; 7,7-dimethyl-2-methylenebicyclo[3.1.1]heptan-6-one; cyclobutanone; hydrolytic cleavage; 1,5-σ proton shift
发表期数: 2017年1月第1期
引用格式: 朱玉娟,何玲,李卫东. 碱催化7,7-二甲基-2-亚甲基双环[3.1.1]庚-6-酮开环反应研究[J]. 中国科技论文在线精品论文,2017,10(1):69-75.
 
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