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

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

以蒽醌为原料,经Schmidt重排为5,6-二氢-二苯并[b,e]氮杂-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-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-6,11二酮(4u)对芦笋茎枯病菌有良好的杀菌活性,在50μg/m L浓度下抑制率达96.3%,与对照药剂百菌清基本相当(在50μg/m L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.

A series of novel 2-（alkylaminosulfonyl）-5,6-dihydro-dibenzo[b,e]azephine-6,11-dione derivatives were synthe-sized 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 spec-trometry （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 50μg/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.