硒催化3,4-二氯苯胺和甲醇氧化羰基化合成灭草灵

doi:10.3724/SP.J.1095.2014.30521

摘要/Abstract

摘要： 报道了一种绿色、简易的合成灭草灵的方法，首次以廉价易得且能循环使用的非金属硒作催化剂，以CO替代剧毒光气作羰基化试剂，通过3,4-二氯苯胺和甲醇经“一锅法”的硒催化氧化羰基化反应来直接合成灭草灵。考察了压力、3,4-二氯苯胺和甲醇用量比、催化剂硒粉用量、溶剂种类、时间、温度及助催化剂种类对反应的影响规律，获得了实施该反应的较优条件。即，在100 mL高压反应釜中：压力3 MPa(n(CO)∶n(O2)=9∶1)，3，4-二氯苯胺5 mmol，CH3OH 75 mmol，Se 0.25 mmol，乙酸乙酯10 mL，时间5 h，温度130 ℃，三乙胺10 mmol。在此条件下，目标产物灭草灵的收率为67%。该方法具有步骤简短、方法绿色和操作方便等优点。

关键词: 硒催化, 二氯苯胺, 氧化羰基化, 灭草灵

Abstract: A green and facile approach to swep is reported in this paper. With cheap, easily available and recyclable nonmetal selenium as the catalyst and CO instead of virulent phosgene as the carbonylation reagent, swep was obtained directly for the first time by one-pot selenium-catalyzed oxidative carbonylation of 3,4-dichloroaniline with methanol. The effects of reaction pressure, molar ratio of 3,4-dichloroaniline to methanol, content of selenium, solvent, reaction time, reaction temperature and co-catalyst on the reaction were investigated. The optimal reaction conditions for preparing the target product swep with a yield of 67% are as followings when the reaction is conducted in a 100 mL autoclave:the reaction pressure is 3 MPa(n(CO)∶n(O2)=9∶1), contents of 3,4-dichloroaniline, methanol, selenium, ethyl acetate and triethylamine are 5 mmol, 75 mmol, 0.25 mmol, 10 mL and 10 mmol, respectively, the reaction time is 5 h, and the reaction temperature is 130 ℃. This method has the merits of short synthetic route, green approach and easy operation.

Key words: selenium-catalyzed, dichloroaniline, oxidative carbonylation, swep

中图分类号:

O625.6

张晓鹏, 王岩, 赵骁, 王焕, 刘晓宁, 张贵生. 硒催化3,4-二氯苯胺和甲醇氧化羰基化合成灭草灵[J]. 应用化学, DOI: 10.3724/SP.J.1095.2014.30521.

ZHANG Xiaopeng*, WANG Yan, ZHAO Xiao, WANG Huan, LIU Xiaoning, ZHANG Guisheng. Selenium-catalyzed Oxidative Carbonylation of 3,4-Dichloroaniline and Methanol to Swep[J]. Chinese Journal of Applied Chemistry, DOI: 10.3724/SP.J.1095.2014.30521.

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