摘要
桑树是传统栽桑养蚕产业的物质基础。近年来斜纹夜蛾对桑树的危害逐渐加重,传统化学药剂防治容易造成环境污染,致使害虫产生抗药性,亟需开发新型绿色桑园防治药剂。以天然产物莰烯为起始原料,通过硼氢化-氧化反应将莰烯双键修饰生成羟基,在N,N'-二环己基碳酰亚胺和二甲基氨基吡啶催化下与甲酸等羧酸发生酯化反应,采用硅胶柱层析纯化,单体结构经^(1)H-NMR谱鉴定,并采用叶碟法测定拒食活性。结果表明,成功制备11种莰烯酯类衍生物,对斜纹夜蛾均表现出一定的拒食活性,其中3b~3j共9种化合物未见报道。当莰烯的双键结构被破坏,其酯类衍生物对斜纹夜蛾的拒食活性下降,说明莰烯的双键对拒食活性起到关键作用。分析莰烯酯类衍生物的拒食活性构效关系,发现2位上的羟基被酯基取代和3位上的氢原子被甲基取代的活性均降低,但延长3位上的烷基链拒食活性会增强。另外,3c和3d、3e和3f是两对同分异构体,其甲基支链的产生会降低拒食活性。这些结果为莰烯结构修饰制备新型杀虫剂提供了一定的指导,为桑园用药的研发提供了新的思路。
Mulberry is the material foundation of the sericulture industry.In recent years,the harm of Spodoptera litura to mulberry trees has been increasing gradually.It is easy to cause environmental pollution and pest resistance problems by using traditional chemical insecticides.Thus it is urgent to develop new green insecticides for mulberry tree.The natural product camphene was used as the starting material.The carbon-carbon double bond of camphene was modified into hydroxyl group by hydroboration oxidation reaction.Then it was esterified with carboxylic acid by using N,N'-dicyclohexyl carbon(DCC)and dimethylaminonaphthalene(DMAP)as catalyzer.The monomers were purified by silica gel column chromatography,and the structures of the compounds were confirmed by ^(1)H-NMR.Finally,the antifeedant activities of these compounds were determined by leaf disc method.The results showed that 11 camphene ester derivatives were successfully prepared in the experiment,and all the 11 compounds showed some antifeedant activity.Among them,9 compounds(3b-3j)have not been reported before.When the carbon-carbon double bond of camphene was broken,the antifeedant activity of its ester derivatives decreased,indicating that the carbon-carbon double bond of camphene played a key role in the antifeedant activity.The structural-activity relationship of antifeedant activity of camphene ester derivatives was analyzed.It was found that the antifeedant activity decreased when the hydroxyl at position 2 was substituted by ester group and the hydrogen at position 3 was substituted by methyl group.However,the antifeedant activity increased when the alkyl chain at position 3 was prolonged.In addition,3c and 3d,3e and 3f were two pairs of isomers,and the production of their methyl branches would reduce the antifeeding activity.These results provide certain guidance for the preparation of new insecticides by modifying the structure of camphene,and provide a new direction for the research and development of mulberry garden medicine.
作者
王鹏源
涂清波
郑绍军
盛晟
吴福安
王俊
Wang Pengyuan;Tu Qingbo;Zheng Shaojun;Sheng Sheng;Wu Fuan;Wang Jun(School of Biotechnology,Jiangsu University of Science and Technology,Zhenjiang Jiangsu 212000,China;Sericultural Research Institute,Chinese Academy of Agricultural Sciences,Zhenjiang Jiangsu 212100,China)
出处
《蚕业科学》
CAS
CSCD
北大核心
2021年第5期416-422,共7页
ACTA SERICOLOGICA SINICA
基金
财政部和农业农村部国家现代农业产业技术体系项目(CARS-18)。
关键词
构效关系
莰烯
酯类衍生物
斜纹夜蛾
Structure-activity relationship
Camphene
Ester derivative
Spodoptera litura
