含氮五元杂环酮的拟除虫菊酯的合成、结构和生物活性

Synthesis, Structure and Biological Activities of Pyrethroids with Ni- trogen Containing Five-Membered Heterocyclic Ketone Moieties

以1-对乙氧基-2,2-二氯环丙烷甲酸(1a)和3-(2-氯-3,3,3-三氟-1-丙烯)-2,2-二甲基环丙烷甲酸(1b)为原料,经酰氯化反应得到酰氯,再以三乙胺为缚酸剂,分别与2-烷酮、2-噻唑烷酮、2-噻唑硫酮、1-乙酰基-2-咪唑烷酮、1-甲磺酰基-2-咪唑烷酮反应,得到10个新的含氮五元杂环酮的拟除虫菊酯.化合物结构经1HNMR,IR,MS和元素分析进行表征.并用X-ray单晶衍射测定了化合物3-(1-对乙氧基-2,2-二氯环丙烷甲酰)-2-噁唑烷酮(4a-1)的晶体结构.对合成的化合物进行了初步的生物活性测试,结果表明,在试验浓度下部分目标化合物对黄瓜灰霉病菌具有一定得防效作用;其中,化合物(4a-1)和3-(3-(2-氯-3,3,3-三氟-1-丙烯)-2,2-二甲基环丙烷甲酰)-2-噻唑烷酮(4b-3)对粘虫也分别有50%及90%的杀虫活性.

Ten new pyrethroids with nitrogen containing five-membered heterocyclic ketone moieties were synthesized by the reaction of 1-（4-ethoxyphenyl）-2,2-dichlorocyclopropane-1-carboxylic acid （1a） or 3-（2-chloro-3,3,3-trifluoro-1-propenyl）-2,2-dimethylcyclopropane-1-carboxylic acid （lb）, with thionyl chloride, and then condensation reaction with 2-oxazolidinone, 2-thiazolidinethione, 2-thiazolidinone, 1-acetylimidazolidin-2-one and 1-（methylsulfonyl）imidazolidin-2-one respectively in the presence of triethylamine. Their structures were confirmed by ^1H NMR, IR, Mass Spectra and elemental analysis. The crystal structure of 3-（1-（4-ethoxyphenyl）-2,2-dichlorocyclopropylcarbonyl）oxazolidin-2-one （4a-1） was determined by X-ray diffraction analysis. The preliminary bioassay showed that some of the compounds exhibited certain fungicidal activities against Botrytis cinerea, 4a-1 and 3-（3-（2-chloro-3,3,3-trifluoroprop-1-enyl）-2,2-dimethylcyclopropylcarbonyl）thiazolidin-2-one （4b-3） exhibited 50% and 90% inhibition activities against Mythimnaseparate respectively.