第 51 卷第 5 期 Vol. 51 No. 5 2021 年 10 月 Oct 2021

所属栏目：农药及中间体 中间体3，5-二氯-2-戊酮的绿色合成工艺开发

丁亚伟1，张绍勇2，杨丙连1* （1. 上海泰禾化工有限公司，上海 201612；2. 湖州师范学院，浙江省媒介生物学与病原控制重点实验室，浙江 湖州 313000）

摘　要：α-乙酰基-γ-丁内酯与氯气在无溶剂条件下发生氯化反应，得到α-氯-α-乙酰基-γ-丁内酯和副产氯化氢，α-氯-α-乙酰基-γ-丁内酯在少量水和氯化氢的存在下进行开环、氯代和脱羧反应得到3,5-二氯-2-戊酮。对氯气投料比、反应温度、氯化氢用量等因素进行优化。优化工艺条件为，第一步反应：氯化温度为0~5 ℃、n（氯气）∶n（α-乙酰基-γ-丁内酯）=1.07∶1.00；第二步反应：水解、脱羧及氯化温度为90 ℃、n（氯化氢）∶n（α-氯-α-乙酰基-γ-丁内酯）=0.7∶1.0，n（水）∶n（α-氯-α-乙酰基-γ-丁内酯）=0.8∶1.0，通入氯化氢4 h，此条件下，收率达95.2%。

关键词：α-乙酰基-γ-丁内酯；α-氯-α-乙酰基-γ-丁内酯；3，5-二氯-2-戊酮

中图分类号：S482.2　　文献标识码：A　　文章编号：1009-9212（2021）05-0027-04

Synthesis of 3,5-Dichloro-2-pentanone

DING Ya-wei1, ZHANG Shao-yong2, YANG Bing-lian1* (1. R&D Center of CAC Shanghai International Trading Co.,Ltd., Shanghai 201612, China; 2. Key Laboratory of Vector Biology and Pathogen Control of Zhejiang Province, College of Life Sciences, Huzhou University, Huzhou 313000, China)

Abstract：The reaction between α-acetyl-γ-butyrolactone and chlorine gas under solvent-free conditions gives α-chloro-α-acetyl-γ-butyrolactone and the by-product hydrogen chloride. Then, α-chloro-α-acetyl-γ-butyrolactone undergoes ring opening reaction and decarboxylation reactions in the presence of a small amount of water and hydrogen chloride to obtain 3,5-dichloro-2-pentanone. The reaction conditions including chlorine feed ratio, reaction temperature, hydrogen chloride dosage and other factors were optimized. The optimized process conditions were as followings: the chlorination temperature was in a range from 0 ℃ to 5 ℃; the amount of chlorine gas was 1.07 times of α-chloro-α-acetyl-γ-butyrolactone in molar mass; the temperature of hydrolysis, decarboxylation and chlorination was of 90 ℃; the amount of hydrogen chloride was 0.7 times of α-chloro-α-acetyl-γ-butyrolactone in molar mass; the amount of water was 0.8 times of α-chloro-α-acetyl-γ-butyrolactone in molar mass; and the yield was 95.2%.

Key words：α-acetyl-γ-butyrolactone; α-chloro-α-acetyl-γ-butyrolactone; 3,5-dichloro-2-pentanone

作者简介：丁亚伟（1985—），男，河南夏邑人，工程师，主要从事农药及中间体合成研究（E-mail：yawei.ding@163.com）。

联 系 人：杨丙连，高级工程师，主要从事农药及中间体合成研究（E-mial：bingliany@126.com）。

收稿日期：2021-08-03