(Z)-N-(2,6-二氧-5-苯基-1,2,3,5,6,7,8,9-八氢-4H-色烯并[2,3-d]嘧啶-4-亚基)-4-甲基苯磺酰胺类化合物的设计、合成及生物活性

Design,synthesis and biological activity of novel(Z)-N-(2,6-dioxo-5-phenyl-1,2,3,5,6,7,8,9-octahydro-4 H-chromeno[2,3-d]pyrimidin-4-ylidene)-4-methylbenzenesulfonamide compounds

为开发新型高效的除草化合物,设计、合成了29个(Z)-N-(2,6-二氧-5-苯基-1,2,3,5,6,7,8,9-八氢-4H-色烯并[2,3-d]嘧啶-4-亚基)-4-甲基苯磺酰胺类衍生物(Ⅵaa~Ⅵbc),通过熔点,核磁共振氢谱、碳谱和高分辨质谱表征确认其结构。利用X-射线单晶衍射确定化合物Ⅵan的空间构型。以稗草和苘麻为供试杂草,通过平皿法测定目标化合物的除草活性。在200 mg/L下,目标化合物对稗草的抑制率均超过70%,其中化合物Ⅵak高达85%;目标化合物对苘麻的抑制效果略低。化合物Ⅵak对稗草种子萌发的抑制中浓度(IC_(50))为113 mg/L。作物安全性试验表明,在500和1000 mg/L下,化合物Ⅵak对玉米、水稻和油菜均有不同程度的药害,但对大豆的药害程度最小,明显低于对照药剂苄嘧·丙草胺。透射电子显微镜观察显示,经化合物Ⅵak处理后,稗草叶绿体断裂、分散,大部分叶绿体被膜由长条形变为椭圆形,叶绿体内出现嗜锇颗粒,内囊体基粒片层消失,基质堆叠散乱,其内部有大量体积较大的囊泡。酶活性测定结果表明,化合物Ⅵak在50~450 mg/L下对过氧化氢酶(CAT)活性和过氧化氢(H_(2)O_(2))含量均表现出先缓慢上升后平稳的趋势,由此推断化合物Ⅵak可能是通过破坏稗草叶绿体结构与影响CAT活性和H_(2)O_(2)含量抑制稗草生长的,有望成为杀稗剂开发的先导化合物。

To discover new and highly effective herbicidal compounds,29(Z)-N-(2,6-dioxo-5-phenyl-1,2,3,5,6,7,8,9-octahydro-4H-chromeno[2,3-d]pyrimidin-4-ylidene)-4-methylbenzenesulfonamide derivatives(Ⅵaa-Ⅵbc)were designed and synthesized.The structures of these compounds were characterized by melting point,1H NMR,13C NMR,and HRMS.The spatial configuration of compoundⅥan was determined using X-ray single crystal diffraction.The herbicidal activity of these compounds was tested using the plate method with barnyard grass and piemarker as target weeds.The target compounds exhibited inhibition rates of over 70%against barnyard grass,with compound Ⅵak showing 85% inhibition at a concentration of 200 mg/L,but the inhibitory effect on the piemarker was slightly lower.The inhibitory medium concentration(IC_(50))of compoundⅥak on seed germination of barnyard grass was 113 mg/L.Crop safety experiments showed that compoundⅥak at a dosage of 500 or 1000 mg/L caused varying degrees of phytotoxicity to maize,rice,and rapeseed.However,the phytotoxicity to soybean was the lowest among these crops and significantly lower than the control herbicide bensulfuronmethyl·pretilachlor.Transmission electron microscopy showed that the chloroplasts of barnyard grass were broken and dispersed,most chloroplast envelope changed from elongated to oval,osmophilic particles appeared in the chloroplast,the lamella of the inner capsule disappeared,and the matrix stack was scattered,including a large number of large vesicles when barnyard grass seeds were treated with compoundⅥak.The enzyme activity assay showed that compoundⅥak at 50-450 mg/L showed a trend of slow increase to CAT acitivity and H2O2 content at first and then stable.It can be concluded that compoundⅥak may inhibit the growth of barnyard grass by destroying chloroplast structure and affecting CAT activity and H_(2)O_(2) content,thus providing lead compounds for the development of barnyard grass.