“一锅法”合成2-氨基-N,3-二甲基-5-卤代苯甲酰胺

doi:10.6023/cjoc1201123

有机化学 ›› 2012, Vol. 32 ›› Issue (05): 896-899.DOI: 10.6023/cjoc1201123 上一篇下一篇

研究论文

“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

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

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).

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摘要/Abstract

报道了从3-甲基-2-氨基苯甲酸出发一锅三步合成2-氨基-N,3-二甲基-5-卤代苯甲酰胺的方法. 3-甲基-2-氨基苯甲酸(1)与固体光气反应生成中间体8-甲基-2H-3,1-苯并噁嗪-2,4(1H)-二酮(2), 化合物2 与甲胺水溶液发生胺解反应生成2-氨基-N,3-二甲基苯甲酰胺(3), 3 再与氯代丁二酰亚胺(NCS)、溴代丁二酰亚胺(NBS)或碘代丁二酰亚胺(NIS)发生芳香亲电取代反应生成目标产物2-氨基-N,3-二甲基-5-卤代苯甲酰胺(4～6). 整个反应过程不需分离中间产品, 最终产物经减压浓缩除去有机溶剂后, 直接从水中析出针状晶体, 总收率达到87%～94%, 较文献报道的分步法收率提高30%以上. 该方法工艺操作简单、反应条件温和、反应时间短、收率高, 是一条环境友好的绿色合成路线.

关键词: 3-甲基-2-氨基苯甲酸, 固体光气, 邻甲酰氨基苯甲酰胺

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

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秦伟艳, 刘波, 由君, 马静, 李香, 吕程程. “一锅法”合成2-氨基-N,3-二甲基-5-卤代苯甲酰胺[J]. 有机化学, 2012, 32(05): 896-899.

Qin Weiyan, Liu Bo, You Jun, Ma Jing, Li Xiang, L? Chengcheng. One-Pot Synthesis of 2-Amino-5-halogenated-N,3-dimethylbenzamides[J]. Chin. J. Org. Chem., 2012, 32(05): 896-899.

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“一锅法”合成2-氨基-N,3-二甲基-5-卤代苯甲酰胺

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

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