Ministry of Agriculture Key Laboratory of Molecular Biology of Crop Pathogens and Insects, Institute of Pesticide and Environmental Toxicology, Zhejiang University, Hangzhou, People's Republic of China.
J Agric Food Chem. 2011 May 11;59(9):4836-50. doi: 10.1021/jf2001926. Epub 2011 Apr 14.
Milbemycins have received considerable interest in agricultural chemistry due to a special action mode, extremely high activity against arachnoide pests, low toxicity to mammals, and environmentally benign characteristics. Two series of novel milbemycin analogues (4Ia-6IIc) containing alkyl and aryl groups at the 4'- and 13-positions were designed and synthesized by five schemes. These analogues were identified by (1)H NMR, (13)C NMR, and elemental analysis (or HRMS). Their insecticidal activities against carmine spider mite, oriental armyworm, and black bean aphid were evaluated. The results showed that all of the title compounds had low acaricidal activity against carmine spider mite. However, most of them exhibited good insecticidal activities against oriental armyworm and black bean aphid at a concentration of 200 mg L(-1). The most potent substituents of 2,2-dimethylbutanoyl (4Ib), phenylacetyl (4IIm), and (Z)-1-(methoxyimino)-1-phenylacetyl (4IIn) exhibited the highest larvicidal activities, and its insecticidal LC(50) values against oriental armyworm were 0.250, 0.204, and 0.350 mg L(-1), while its insecticidal LC(50) values against black bean aphid were 0.150, 0.070, and 0.120 mg L(-1), respectively. These substituents provided some hints for further investigation on structure modification.
米尔贝霉素因其特殊的作用模式、对蛛形纲害虫极高的活性、对哺乳动物的低毒性和环境友好的特性，在农业化学领域受到了广泛关注。本研究设计并合成了两个系列含有烷基和芳基的新型米尔贝霉素类似物（4Ia-6IIc），其在 4′和 13 位分别带有烷基和芳基取代基。通过五种方案得到了这些类似物，并用（1）H NMR、（13）C NMR 和元素分析（或高分辨质谱）对其进行了鉴定。评估了这些类似物对朱砂叶螨、东方粘虫和烟粉虱的杀虫活性。结果表明，所有标题化合物对朱砂叶螨均具有较低的杀螨活性。然而，在 200 mg/L 的浓度下，大多数化合物对东方粘虫和烟粉虱表现出良好的杀虫活性。2,2-二甲基丁酰基（4Ib）、苯乙酰基（4IIm）和（Z）-1-（甲氧基亚氨基）-1-苯乙酰基（4IIn）是最有效的取代基，其对东方粘虫的幼虫致死活性最高，其杀虫 LC50 值分别为 0.250、0.204 和 0.350 mg/L，对烟粉虱的杀虫 LC50 值分别为 0.150、0.070 和 0.120 mg/L。这些取代基为进一步的结构修饰研究提供了一些线索。
