普罗托品类生物碱的合成及其杀虫活性

目的]对小果博落回中分离的普罗托品、隐品碱和别隐品碱中的十元氮杂环和苯环进行结构修饰,合成了17种普罗托品类生物碱,在确认其结构的基础上考查其体外杀虫活性。方法]首先,采用ESI-MS、1H NMR和13C NMR等波谱技术对目标化合物的结构进行表征;接着,以伊维菌素为阳性对照,采用浸虫法分别测定了目标化合物在0.5、1 g/L时对兔痒螨和小麦红蜘蛛的体外杀灭活性。结果]大多数化合物对兔痒螨和小麦红蜘蛛均显示了一定程度的杀灭活性。其中,待测物1的活性最佳,其对兔痒螨的致死率达71.7%;对小麦红蜘蛛的致死率为60.0%,校正致死率达57.1%。结论]对目标化合物的结构及其杀虫活性进行分析,发现向十元氮杂环引入C=C键可显著提高该类化合物的杀螨活性;向13位引入羰基可提高它们杀灭小麦红蜘蛛的活性。为普罗托品类杀虫剂的研发提供了一定的理论依据。

Synthesis and Insecticidal Activity of Protopine Compounds

Aims] By modifying the ten-membered nitrogen heterocyclic rings and phenyl rings of protopine,cryptopine, and allocryptopine isolated from Macleaya microcarpa, 17 derivatives of this kinds were successfully synthesized with good yields. Their insecticidal activities in vitro were investigated on the basis of determining the chemical structure of all prepared compounds. Methods] Firstly, the structures of synthesized compounds were confirmed by the spectra of ESI-MS,1 H NMR and13 C NMR. Then, using ivermectin as positive control, the insecticidal activities of the prepared compounds against P. cuniculi and T. cinnbarinus were examined by immersion method at the concentrations of 0.5 and 1 g/L, respectively. Results] Most of the tested compounds showed different degrees of insecticidal activity for the tested insects. Among of them, whether for P. cuniculi or for T. cinnbarinus, compound 1 exhibited the highest activity and its lethality rates were 71.7 and 60.0%, respectively. Furthermore, its corrected lethality rate against the latter was 57.1%. Conclusions] We analyzed the relationship between the structure and insecticidal activity of the target compounds. It was found that the acaricidal activity of the corresponding compounds could be significantly improved by introducing C=C bond into the ten-membered nitrogen heterocycle. The insecticidal activity against T. cinnbarinus could be slightly enhanced via introduction of carbonyl group into 13 position. The present research will provide a theoretical basis for the research and development of protopine insecticides.