Articles

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

  • Qin Weiyan ,
  • Liu Bo ,
  • You Jun ,
  • Ma Jing ,
  • Li Xiang ,
  • L? Chengcheng
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  • 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 date: 2012-01-12

  Revised date: 2020-02-28

  Online published: 2012-03-31

Supported by

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

Abstract

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.

Cite this article

Qin Weiyan , Liu Bo , You Jun , Ma Jing , Li Xiang , L? Chengcheng . One-Pot Synthesis of 2-Amino-5-halogenated-N,3-dimethylbenzamides[J]. Chinese Journal of Organic Chemistry, 2012 , 32(05) : 896 -899 . DOI: 10.6023/cjoc1201123

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