Chloromethylation of β-Chloroethylbenzene and the Preparation of p-Vinylbenzyl Alcohol1
Chloromethylation of β-Chloroethylbenzene and the Preparation of p-Vinylbenzyl Alcohol1
复制标题
β-氯乙苯的氯甲基化及对乙烯基苯甲醇的制备1
DOI：
10.1021/jo01066a015
复制
发表时间：
1961
影响因子：
3.6
通讯作者：
E. C. Chapin
中科院分区：
文献类型：
--
作者：
J. Abramo;E. C. Chapin
/S-氯乙苯的氯甲基化得到了/3-氯乙基氯化物的混合物，其异构体分布为74±3%对位和26±3%邻位。没有认真尝试检测偏异构体，尽管它可能只有少量存在。这种混合物结晶得到纯的对位异构体，而分馏得到邻位异构体的样品。沸点较高的产物经鉴定为双(氯甲基1)/3-氯乙苯和双(/3-氯乙基)二苯甲烷。邻位和对位异构体转化为邻位和对位/S氯乙基苯乙酸乙酯。醇碱将对氯乙酸苄酯转化为对乙烯基苯甲醇，类似的处理使邻位异构体转化为异色胺。异色曼的形成是基于分子中乙酸苄酯部分的快速皂化和氯原子的亲核置换。
Chloromethylation of/S-chloroethylbenzene gave a mixture of/3-chloroethylbenzyl chlorides having an isomer distribution of 74±3% para and 26±3% ortho. No serious attempt was made to detect the meta isomer, although it could have been present only in small amount. Crystallization of this mixture gave the pure para isomer and fractional distillation afforded a sample of the ortho isomer. Higher boiling products obtained were identified as bis (chloromethy 1)-/3-chloroethylbenzene and bis (/3-chloroethyl) diphenylmethane. The ortho and para isomers were converted to ortho-and para-/S-chloroethylbenzyl acetate. Alcoholic base converted p-(^-chloroethyl) benzyl acetate to p-vinylbenzyl alcohol while similar treatment con-verted the ortho isomer to isochroman. The formation of isochroman is explained on the basis of a rapid saponification of the benzyl acetate portion of the molecule followed by nucleophilic displacement of the chlorine atom.