【作者】 陈利标；

【导师】 张兴；

【作者基本信息】 西北农林科技大学 ， 农药学， 2007， 硕士

【摘要】 为了进一步研究鬼臼毒素类化合物结构和杀虫活性的关系,结合近年来杂环农药的发展趋势,本论文在前期研究的基础上设计合成了28种C环修饰鬼臼毒素衍生物,其中18种为含杂环的化合物。合成化合物通过IR、MS、1H NMR和13C NMR对其结构进行确证。同时还收集了3种鬼臼毒素类似物。测试了这31种化合物对3龄粘虫幼虫的拒食活性。取得如下结果:1.经过文献调研确定:28种合成的化合物中18种含杂环的衍生物为未见报道的新化合物,而其他10种C环修饰的化合物是已报道过的化合物。2.鬼臼毒素4位引入杂环可以得到比母体化合物活性更高的化合物。4α-吲哚-3-酸-4-脱氧鬼臼酯(I4)其24h AFC50(拒食中浓度)为0.36mg·mL-1,是母体化合物鬼臼毒素拒食毒力的2.03倍,是引入杂环后唯一活性高于母体化合物鬼臼毒素的化合物。其他4位引入杂环后的鬼臼毒素衍生物活性都有所降低。3.18种含杂环的鬼臼毒素衍生物中,4β位与母体分别以酯键、酰胺键、硫酯键相连引入杂环时,以酯键相连时对粘虫幼虫的拒食活性最高。4.在合成的所有化合物中24h和48h拒食活性均高于母体化合物鬼臼毒素的只有α-阿朴苦鬼臼毒素(C9),其24h和48h对粘虫幼虫的拒食毒力分别是母体化合物鬼臼毒素的1.30和2.70倍。而β-阿朴苦鬼臼毒素24h拒食活性与鬼臼毒素相当,48h的拒食毒力则是鬼臼毒素的1.78倍,说明C环不饱和可以提高鬼臼毒素的拒食活性。5.测定了鬼臼毒素4位和2位不同构型的化合物对3龄粘虫幼虫的拒食活性。结果表明:(1)4位为α构型时比4位为β构型时对3龄粘虫幼虫的拒食活性要高;(2)2位为β构型时比2位为α构型时对3龄粘虫幼虫的拒食活性要高。上述研究结果表明:对鬼臼毒素进行结构修饰可以发现比鬼臼毒素活性更高的化合物;鬼臼毒素杀虫活性结构与抗肿瘤结构有所不同,其作用机制有待进一步研究。更多还原

【Abstract】 Aiming to study the insecticidal activity , 28 podophyllotoxin derivatives were synthesized based on earlier stage work .Their chemical structure were confirmed by IR,MS,1H-NMR and 13C-NMR.And another 3 podophyllotoxin analogues were collected. The antifeedant activities of 31 compounds against the 3rd-instar larvae of Mythimna separataduring 24h and 48h were assayed with leaf-disk method. The results showed as follows:1. Among the 28 synthesized compounds ,18 compounds which contained heterocyclic ring were new compounds .2. The C4 contained heterocyclic ring of podophyllotoxin derivatives can get higher antifeedant activity than podophyllotoxin . The 24h AFC50(concentration for 50% antifeedant activity) against the 3rd larvae of Mythimna separata of 4α-1H-indole-3-acetic acid-4- deoxy- podophyllotoxin ether (I4) was 0.36mg·ml-1 which was 1/2.06 of podophyllotoxin .And the others had lower activity than podophyllotoxin .3. The antifeedant activity of those compounds which 4βcontained ether bond with heterocyclic ring were the highest in the 18 compounds contained heterocyclic ring.4. The antifeedant activities ofα-Apopicropodophyllin was the only one higher than podophyllotoxin in all of synthesized compounds against the 3rd-instar Mythimna separata during both 24h and 48h. Its 24h and 48h AFC50 against the 3rd larvae of Mythimna separata was respectively 1/1.30 and 1/2.70 of podophyllotoxin. The 24h antifeedant activities ofβ-Apopicropodophyllin was equal to that of podophyllotoxin against the 3rd-instar Mythimna separata ,but 48h AFC50 was 1/1.78 of podophyllotoxin. The results showed that: not saturation of C ring of podophyllotoxin analogues had very higher activities than others.5. The antifeedant activities of compounds which had different configuration of C4 and C2 were assayed against the 3rd-instar Mythimna separata .The result showed that: (1) The activity of C4α-configuration podophyllotoxin derivatives were higher than theirβ-configuration analogues (2) The activity of C2β-configuration podophyllotoxin derivatives were higher than theirα-configuration derivatives.更多还原