高等学校化学学报 ›› 2019, Vol. 40 ›› Issue (8): 1637-1642.doi: 10.7503/cjcu20190069

• 有机化学 • 上一篇    下一篇

硒催化羰基化合成1,3,4-噻二唑-2-氨基甲酸酯

张晓鹏, 牛雪利, 高贺梅, 范学森, 张贵生   

  1. 河南师范大学化学化工学院, 河南省有机功能分子与药物创新重点实验室, 精细化学品绿色制造河南省协同创新中心, 绿色化学介质与反应教育部重点实验室, 新乡 453007
  • 收稿日期:2019-01-23 修回日期:2019-06-01 出版日期:2019-08-10 发布日期:2019-08-02
  • 通讯作者: 张晓鹏,男,博士,副教授,主要从事有机合成方面的研究.E-mail:zhangxiaopengv@sina.com E-mail:zhangxiaopengv@sina.com
  • 基金资助:
    国家自然科学基金(批准号:21772033,U1604285)和高等学校学科创新引智计划(批准号:D17007)资助.

Selenium-catalyzed Carbonylation to 1,3,4-Thiadiazol-2-ylcarbamates

ZHANG Xiaopeng, NIU Xueli, GAO Hemei, FAN Xuesen, ZHANG Guisheng   

  1. Henan Key Laboratory of Organic Functional Molecules and Drug Innovation, Collaborative Innovation Center of Henan Province for Green Manufacturing of Fine Chemicals, Key Laboratory of Green Chemical Media and Reactions, Ministry of Education, School of Chemistry and Chemical Engineering, Henan Normal University, Xinxiang 453007, China
  • Received:2019-01-23 Revised:2019-06-01 Online:2019-08-10 Published:2019-08-02
  • Supported by:
    Supported by the National Natural Science Foundation of China(Nos. 21772033, U1604285) and the "111" Project, China(No. D17007).

摘要: 以非金属硒作为催化剂,以CO替代剧毒光气作为羰基化试剂,以O2作为氧化剂,通过2-氨基-1,3,4-噻二唑与醇以"一锅法"方式发生硒催化氧化羰基化反应,提出了一种成本低、原子经济性高、合成路线简短及环境相对友好的合成1,3,4-噻二唑-2-氨基甲酸酯类化合物的新方法.研究了反应温度、醇的用量、压力及碱的种类等对合成1,3,4-噻二唑-2-氨基甲酸酯的影响,在优化反应条件下,2-氨基-1,3,4-噻二唑可与一系列醇顺利发生羰基化反应,以45%~90%的收率得到1,3,4-噻二唑-2-氨基甲酸酯类化合物.

关键词: 硒催化, 羰基化, 1,3,4-噻二唑-2-氨基甲酸酯, 2-氨基-1,3,4-噻二唑

Abstract: 1,3,4-Thiadiazol-2-ylcarbamates are an important class of heterocyclic compounds with remarkable medical and agromedical applications due to their pharmacological and biological activities such as antimicrobial, antibacterial, and analgesic effects as well as protein kinase CK2 and acetohydroxy acid synthase inhibition effects. In order to develop an economical, eco-friendly and convenient approach to these target compounds, herein, a facile one-pot selenium-catalyzed carbonylation protocol was studied. The optimal reaction conditions were obtained through investigating the effects of main factors on the carbonylation reaction such as reaction temperature, ethanol dosage, pressure and kind of bases. With cheap and readily available nonmetal selenium as the catalyst, carbon monoxide instead of virulent phosgene as the carbonylation reagent, oxygen as the oxidant, the selenium-catalyzed oxidative carbonylation reaction of 1,3,4-thiadiazol-2-amine proceeded smoothly with a series of alcohols especially with those less hindered ones under the optimized conditions in one-pot manner, affording the corresponding products 1,3,4-thiadiazol-2-ylcarbamates in moderate to good yields. Thus, a new economical, eco-friendly and convenient approach to 1,3,4-thiadiazol-2-ylcarbamates featured with simple and readily available catalyst and raw materials, low cost, high atomic economy, one-pot and phosgene-free manners, and no emission of corrosive wastes has been developed. The probable reaction mechanism was also proposed at the end of this paper.

Key words: Selenium catalysis, Carbonylation, 1,3,4-Thiadiazol-2-ylcarbamate, 1,3,4-Thiadiazol-2-amine

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