新型蒎烯杂环植物源杀虫活性化合物的设计合成及构效关系研究

In the previous study, the insecticidal and antibacterial activity of pinene derivatives was studied. On this basis, pinene can be chemical modified with heterocyclic structure to design some kinds of novel, efficient pinene-based heterocyclic botanical insecticides. With the further study of the insecticidal activity of pinene-based heterocyclic compounds against Ostrinia furnacalis and Bemisia tabaci, compounds with higher activity would be screened. Meanwhile, the quantitative structure-activity relationships (QSAR) of pinene-based heterocyclic compounds and the insecticidal activity are performed by quantum chemistry softwares. According to the established QSAR model, some significant descriptors contributing to insecticidal activity would be revealed. The structure-activity relationships study would enhance the understanding of the insecticidal activity action mechanism of pinene-based heterocyclic compounds. The theory obtained from this study would provide guidance in the further design of pinene-based botanical insecticides, and the higher value applications of turpenine in bio-pesticide field will be achiveved.

在前期蒎烯衍生物的合成及抑菌、杀虫活性研究工作的基础上，本课题拟以天然产物蒎烯为原料，经化学改性修饰，引入高活性的杂环结构，制备安全、高效的新型蒎烯基杂环植物源杀虫剂。深入研究蒎烯基杂环杀虫剂对亚洲玉米螟和烟粉虱的杀虫活性，筛选出高活性的药剂分子，同时选用量子化学软件建立蒎烯基杂环分子对应于杀虫活性的QSAR模型，从分子结构的水平来揭示药剂的结构描述符与杀虫活性之间的关系，进一步促进对蒎烯基杂环分子杀虫作用机制的理解，从而为更加安全高效的新型蒎烯基植物源杀虫剂的设计合成提供理论指导，进而实现松节油在生物农药领域的高值化利用。

本课题以天然产物蒎烯为原料，经化学改性修饰，引入高活性的杂环结构，制备了蒎烯基噻二唑席夫碱，蒎烯基噻二唑酰胺，蒎烯基杂环肟酯、枯茗酸酯、枯茗酸酰胺等五系列40余种衍生物。在此基础上，对松脂衍生物进行了杀虫、抑菌活性测试，筛选出性能优良的药剂分子。杀虫结果表明，丙酸脱氢枞醇酯对胡萝卜微管蚜具有较好的杀虫活性（100 μg/mL，致死率：90%），马来海松酸异丙酯和二氢枞醇对孑孓具有较好的杀虫活性（10μg/mL，致死率：90%）。β-蒎烯酰基硫脲衍生物对孑孓具有较好的杀虫活性（10 μg/mL，致死率：90%）。抑菌结果表明，脱氢枞基（对三氟甲基）苯甲醛亚胺，脱氢枞基对氟苯甲醛亚胺, 脱氢枞基对氯苯甲醛亚胺对小麦赤霉菌的半数抑制浓度分别为 0.0807，0.0474，0.0885 mg/mL，去氢枞酸，脱氢枞基（对三氟甲基）苯甲醛亚胺，脱氢枞基对氟苯甲醛亚胺, 脱氢枞基间氟苯甲醛亚胺对番茄灰霉菌的半数抑制浓度分别为0.0407，0.0855，0.0867，0.0805 mg/mL。通过分子的最低能量计算和几何优化、结构描述符的计算建立了三个松节油衍生物杀虫、抑菌的定量构效关系模型。研究结果表明，几何，拓扑和静电类描述符对活性具有重要的影响，其中分子体积，极性和静电势能等分子特性对农用活性发挥重要作用。研究成果为更加安全高效的新型蒎烯基植物源杀虫剂的设计合成提供理论指导，进而实现松节油在生物农药领域的高值化利用。