三光气法合成2,6-二氟苯甲酰基异氰酸酯

摘要 2,6-二氟苯甲酰基异氰酸酯(DFBI)是合成苯甲酰脲类杀虫剂的重要中间体,使用光气合成DFBI的工艺危险性很大,使用草酰氯的合成工艺成本较高。三光气(BTC)是剧毒的光气和双光气的绿色替代品,不仅毒性低、使用安全方便,而且反应条件温和、计量准确、价格低廉。采用BTC与2,6-二氟苯甲酰胺(FBA)反应合成DFBI,研究了单一因素对合成DFBI的影响。实验结果表明,以氯苯为溶剂,投料n(BTC)：n(FBA)=1.0：1.5,BTC分2次均等投料,第1阶段冷光气化-5 ℃反应1 h,第2阶段热光气化126~128 ℃反应4 h的较适宜条件下,产品收率达到86.4%。BTC可以较稳定、安全地使用,易于工业化。

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	张天永
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	李彬
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	张朋飞

关键词：三光气 2,6-二氟苯甲酰胺二氟苯甲酰异氰酸酯氯苯

Abstract： 2,6-Difluorobenzoyl isocyanate (DFBI) is an important intermediate for the synthesis of benzoyl urea pesticides. The synthetic process of DFBI with phosgene is very dangerous, and the cost of preparation of DFBI using oxalyl chloride is high. Bis(trichloromethyl) carbonate (BTC) is a green substitute for the highly toxic phosgene and diphosgene. It not only is low in toxicity, safe and convenient to use, but also has mild reaction conditions, accurate measurement and low price. The DFBI was synthesized by the reaction of BTC with 2,6-difluorobenzamide (FBA), and the effect of single factor on the synthesis of DFBI was studied. The experimental results show that the optimal conditions are as follows: Chlorobenzene is used as the solvent, the molar ratio of feeding is n(BTC)∶n(FBA)=1.0∶1.5, BTC is equally fed in two times, and the first stage of cold-phosgenation is reacted at -5 ℃ for 1 h, the second stage of thermal-phosgenation is reacted at 126—128 ℃ for 4 h, and the product yield could reach 86.4%. BTC can be used stably and safely, and the process is easy to industrialize.

Keywords： triphosgene 2,6-difluorobenzamide difluorobenzoyl isocyanate chlorobenzene

Received 2022-04-14;

Corresponding Authors: 李彬,副教授,E-mail:libin@tju.edu.cn;姜爽,副教授,E-mail:shuangjiang@tju.edu.cn。 Email: libin@tju.edu.cn;shuangjiang@tju.edu.cn

About author: 张天永(1966-),男,教授,博士生导师,现从事精细化学品制备方面的研究。

引用本文:

张天永, 鞠雯超, 姜爽, 李彬, 刘余峰, 张朋飞.三光气法合成2,6-二氟苯甲酰基异氰酸酯[J]. 化学工业与工程, 2024,41(4): 13-19

ZHANG Tianyong, JU Wenchao, JIANG Shuang, LI Bin, LIU Yufeng, ZHANG Pengfei.Synthesis of 2,6-difluorobenzoyl isocyanate by triphosgene method[J]. Chemcial Industry and Engineering, 2024,41(4): 13-19

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