3-苯甲酰基-4-羟基香豆素衍生物的合成、晶体结构及其除草活性研究  

Synthesis,Crystal Structure and Herbicidal Activity of 3-Benzoyl-4-hydroxycoumarin Derivatives

作　　者：刘斌[1] 谢龙观[1] 徐效华[1] 李永红[1] 

机构地区：[1]南开大学元素有机化学研究所元素有机化学国家重点实验室,天津300071

出　　处：《有机化学》2011年第12期2067-2073,共7页Chinese Journal of Organic Chemistry

基　　金：国家自然科学基金(No.0872070)资助项目

摘　　要：利用活性叠加的原理,设计合成了带有三酮类结构的3-苯甲酰基-4-羟基香豆素衍生物.用~1H NMR,^(13)C NMR,HRMS和X-ray单晶衍射对其进行了结构鉴定.用平皿小杯法和盆栽法评价了其对双子叶植物油菜和单子叶植物稗草的抑制活性.结果显示,目标化合物表现出与香豆素相似的活性,只对油菜有很好的抑制活性,苯甲酰基的接入能一定程度上提高4-羟基香豆素对油菜的活性.部分化合物对油菜表现出良好的活性,其中,3-(2-硝基-4-甲磺酰基苯甲酰基)-4-羟基香豆素(21)对油菜根长的抑制活性好于甲基磺草酮,10μg/mL时,抑制率能达到87.6%,但盆栽活性比甲基磺草酮差.目标化合物虽然具有与三酮除草剂类似的结构,但并不表现出明显的白化作用,具有与三酮类除草剂不同的作用模式.化合物21对双子叶植物油菜表现出很好的选择性,可以作为开发新型选择性除草剂的先导结构,继续结构优化.3-Benzoyl-4-hydroxycoumarin derivatives were designed by combination of coumarin and trike- tone structure. Twenty one target compounds were synthesized. Their structures were elucidated by 1H NMR, 13C NMR and HRMS techniques. Furthermore, the structure of 3-（2,4-dichlorobenzoyl）-7-methoxyl- 4-hydroxycoumarin （15） was determined by X-ray single crystal diffraction. Their herbicidal activities against Brassica campestris and Echinochloa crusgalli were eualuated. The results indicated that the target compounds pocessed similar activity with 4-hydroxycoumarin, only active toward Brassica campestris. The addition of benzoyl group to 4-hydroxycoumarin could enhance their activities against Brassica campestris to some extent. 3-（2-Nitro-4-mesylbenzoyl）-4-hydroxycoumarin （21） displayed better in-vitro activity against Brassica campestris than mesotrione, with 87.6% inhibition under 10 ~tg/mL. But it showed worse in-vivo activity than mesotrione. Target compounds showed no bleaching action, displaying a different mode of action with triketone herbicides. Since compound 21 was active selectively to Brassica campestris, it could be a leading compound for developing selective herbicide.

关 键 词：香豆素 合成 晶体结构 除草活性 

分 类 号：TQ450[化学工程—农药化工]