氯化亚铜催化的月桂烯氢氯化反应的研究(Ⅲ)——烯丙基型氯化物的酯化反应

STUDY ON Cu 2Cl 2 CATALYZED HYDROCHLORINATION OF MYRCENE(Ⅲ) ——Esterification of the Allyl type Chlorides

研究月桂烯氢氯化反应产物中里哪基氯、香叶基氯和橙花基氯３种烯丙型氯化物与醋酸钠的酯化反应。重点考察了催化剂、反应温度和氯化物组成对酯化反应产物分布的影响。结果表明：（１）在氯化亚铜催化剂存在下，３种烯丙基型氯化物与醋酸钠在醋酸溶剂中均可转化成醋酸里哪酯，酯化反应选择性达９６％以上；（２）在三乙胺催化剂存在下，３种烯丙基型氯化物与醋酸钠反应可转化成相应的醋酸酯，但里哪基氯酯转化生成醋酸里哪酯的选择性明显低于香叶基氯和橙花基氯，且伴随有消除副产物生成；（３）低温有利于醋酸里哪酯的生成，温度升高有利于醋酸里哪酯向醋酸香叶基酯和醋酸橙花酯的生成；在优化反应条件下，醋酸里哪酯的选择性达９６．５％。

The esterification of linalyl, geranyl and neryl chlorides with NaOAc were studied. Effects of catalysts, reaction temperature and the compositions of myrene hydrochlorides on the distribution of esters were investigated in detail. Results showed that all three allyl type chlorides can be esterified with sodium acetate in acetic acid to yield linalyl acetate with 96% or more selectivity when catalyzed by Cu 2Cl 2. In the presence of Et 3N, the three allyl type chlorides were converted to their acetates respectively. Linalyl acetate can be obtained with 96 5% selectivity under the optimum conditions.