Chin. J. Org. Chem. ›› 2012, Vol. 32 ›› Issue (05): 896-899.DOI: 10.6023/cjoc1201123 Previous Articles     Next Articles

Articles

“一锅法”合成2-氨基-N,3-二甲基-5-卤代苯甲酰胺

秦伟艳, 刘波, 由君, 马静, 李香, 吕程程   

  1. 哈尔滨理工大学化学与环境工程学院 绿色化工技术黑龙江省高校重点实验室 哈尔滨 150040
  • 收稿日期:2012-01-12 修回日期:2020-02-28 发布日期:2012-03-31
  • 通讯作者: 秦伟艳 E-mail:qinweiyan@hrbust.edu.cn
  • 基金资助:

    国家自然科学基金(No. 21101045)资助项目.

One-Pot Synthesis of 2-Amino-5-halogenated-N,3-dimethylbenzamides

Qin Weiyan, Liu Bo, You Jun, Ma Jing, Li Xiang, L? Chengcheng   

  1. Key Laboratory of Green Chemical Engineering and Technology of College of Heilongjiang Province, College of Chemical and Environmental Engineering, Harbin University of Science and Technology, Harbin 150040
  • Received:2012-01-12 Revised:2020-02-28 Published:2012-03-31
  • Supported by:

    Project supported by the National Natural Science Foundation of China (No. 21101045).

The synthetic method of 2-amino-5-halogenated-N,3-dimethylbenzamides is reported from 2-amino-3-methylbenzoic acid by three steps in one pot. Firstly, 8-methyl-2H-3,1-benzoxazine-2,4(1H)-dione (2) was synthesized by using 2-amino-3-methylbenzoic acid (1) and bis(trichloromethyl) carbonate. Secondly, 2-amino-N,3-dimethyl-benzamide (3) was prepared through the aminolysis of compounds 2 and aqueous methylamine. Lastly the target products 2-amino-5-halogenated- N,3-dimethylbenzamides (4 ~ 6) were obtained by using 3 and N-chlorosuccinimide (NCS), N-bromosuccinimide (NBS) or N-iodosuccinimide (NIS) through electrophilic aromatic substitution. This whole process does not need to separate the middle products, and the needlelike crystals of the target product can be directly separated from water after evaporating the organic solvent under reduced pressure. The overall yield was 87%~94%, at least 30% higher than using the substep methods which reported by early literatures. This method gets the advantages of simple work-up procedure, milder conditions, shorter reaction time, higher yield and environ-mental friendliness, which is a green synthetic route.

Key words: 2-amino-3-methylbenzoic acid, bis(trichloromethyl) carbonate, anthranilic diamides