有机化学 ›› 2014, Vol. 34 ›› Issue (12): 2493-2498.DOI: 10.6023/cjoc201407004 上一篇    下一篇

研究论文

2-(烃基胺磺酰基)-5,6-二氢-二苯并[b,e]氮杂(艹卓)-6,11-二酮的合成与杀菌活性

肖炎双, 张建军, 闫晓静, 董燕红, 袁会珠, 梁晓梅, 王道全   

  1. 中国农业大学应用化学系 北京 00193;
    中国农业科学院植物保护研究所 北京 100193
  • 收稿日期:2014-07-03 修回日期:2014-08-20 发布日期:2014-08-29
  • 通讯作者: 梁晓梅 E-mail:liangxiaomeim@163.com

Synthesis and Fungicidal Activity of 2-Alkylaminosulfonyl-5,6-dihydro-dibenzo[b,e]azephine-6,11-dione

Xiao Yanshuang, Zhang Jianjun, Yan Xiaojing, Dong Yanhong, Yuan Huizhu, Liang Xiaomei, Wang Daoquan   

  1. Department of Applied Chemistry, China Agricultural University, Beijing 100193;
    Institute of Plant Protection, Chinese Academy of Agricultural Sciences, Beijing 100193
  • Received:2014-07-03 Revised:2014-08-20 Published:2014-08-29

以蒽醌为原料, 经Schmidt重排为5,6-二氢-二苯并[b,e]氮杂(艹卓)-6,11-二酮, 再经氯磺酰化和胺化合成了一系列新颖的2-(烃基胺磺酰基)-5,6-二氢-二苯并[b,e]氮杂(艹卓)-6,11-二酮. 结构经1H NMR, 13C NMR和高分辨质谱确证. 初步的生测结果表明, 它们对棉花立枯病菌、油菜菌核病菌和芦笋茎枯病菌具有一定的杀菌活性. 其中, 2-(3-三氟甲基-4-溴苯基胺磺酰基)-5,6-二氢-二苯并[b,e]氮杂(艹卓)-6,11二酮(4u)对芦笋茎枯病菌有良好的杀菌活性, 在50 mg/mL浓度下抑制率达96.3%, 与对照药剂百菌清基本相当(在50 mg/mL浓度下的抑制率为98.8%). 初步的构效关系分析指出, 氟原子的引入有利于杀菌活性的提高.

关键词: 5,6-二氢-二苯并[b,e]氮杂(艹卓)-6,11-二酮, 2-(烃基胺磺酰基)-5,6-二氢-二苯并[b,e]氮杂(艹卓)-6,11-二酮, 合成, 杀菌活性

A series of novel 2-(alkylaminosulfonyl)-5,6-dihydro-dibenzo[b,e]azephine-6,11-dione derivatives were synthesized starting from anthraquinone by Schmidt rearrangement to 5,6-dihydro-dibenzo[b,e]azephine-6,11-dione, followed by chlorosulfonylation and amination. Their structures were confirmed by 1H NMR, 13C NMR and high-resolution mass spectrometry (HRMS). The preliminary bioassay showed that compounds have some fungicidal activity against Rhizoctonia solani, Sclerotinia sclerotiorum and Phomopsis asparagi. Among them, 2-(3-trifluoromethyl-4-bromophenylaminosulfonyl)-5,6-dihydro-dibenzo[b,e]azepine-6,11-dione (4u) has good fungicidal activity against Phomopsis asparagi and the inhibition rate reached 96.3% at 50 mg/mL, and is comparable with commercial fungicide chlorothalonil. The preliminary structure-activity relationship analysis indicated that introduction of fluorine is favorable to the increase of the activity.

Key words: 5,6-dihydro-dibenzo[b,e]azephine-6,11-dione, 2-(alkylaminosulfonyl)-5,6-dihydro-dibenzo[b,e]azephine-6,11-dione, synthesis, fungicidal activity