【作者】 丛杉；

【导师】 沈德隆；

【作者基本信息】 浙江工业大学 ， 农药学， 2007， 硕士

【摘要】 拟除虫菊酯类杀虫剂有着广谱、高效、环境友好等特点，符合当代农药发展要求；乙氰菊酯作为一种拟除虫菊酯类杀虫剂，在具备上述优点的同时，对水生生物低毒，这使其在水稻害虫防治方面比其他同类杀虫剂有着优势。国内对乙氰菊酯的需求日益增加，而目前我国尚无该化合物的原药生产厂家，且无关于其合成的研究报道；因此，对乙氰菊酯合成路线的探索有着重要的现实意义。本文在查阅总结文献资料的基础上，完成了乙氰菊酯的合成路线设计并对原有工艺方法进行了改进。以对羟基苯乙酸为起始原料，经Williamson醚化、酯化、Claisen酯缩合、Aldol缩合、卡宾加成、酯水解六步反应得到了重要中间体乙氰菊酸；由间苯氧基苯甲醛经加成反应得到氰醇；最后由菊酸与氰醇缩合得到的最终产物经核磁、质谱、红外等方法进行结构测定，确定为目标产物乙氰菊酯，产品总收率约35％，含量大于90％。在该合成路线中，合成了对乙氧基苯乙酸、对乙氧基苯乙酸乙酯、2-(4-乙氧基苯基)-3-羰基丁二酸二乙酯、2-(4-乙氧基苯基)丙烯酸乙酯、2，2-二氯-1-(4-乙氧基苯基)环丙烷甲酸乙酯、2，2-二氯-1-(4-乙氧基苯基)环丙烷甲酸及3-苯氧基-α-氰基苄醇七个中间体化合物，各化合物的结构及纯度均经分析测定。本文对目标产物及各中间体化合物的不同合成方法做出了评价并对反应条件做出了一定的优化，最终确定的乙氰菊酯合成工艺原料廉价易得，工艺操作简便，反应条件温和，收率与文献报道值相比有较大的提高，具有较高的工业应用价值。更多还原

【Abstract】 Pyrithriods are a group of insecticides characterized as broad-spectrum, efficient and pro-environmental, which is in accordance with the demand of our society to the development of modem pesticides. Cycloprothrin, as a member of this group, shows priority to other congeneric compounds in the use against paddy pests for its lower toxicity to hydrophily animals. The need of Cycloprothrin in our country is growing rapidly, while there is neither domestic manufacturer nor report about the synthesis of this compound. So researching work in the synthesis of the title compound is of great, significance.This paper, based on summarization of references, has accomplished the design of the synthetic route of Cycloprothrin and improved the reported technics. 4-Hydroxybenzeneacetic was employed as inceptive material, via a six-step reaction including Williamson etherization,esterfication, Claisen condensation, Aldol condensation, carbene addition,and hydrolyzation, an important intermediate compound—2,2-dichloro-1- (4-ethyoxy phenyl) cyclopropanecarboxylic acid was obtained. After another intermediate compound—(RS)-α-Cyano-3-phenoxybenzyl alcohol was made from 3-phenoxybenzaldehyde, the two intermediate compounds were condensed to generate the final product, which was identified by means of ~1H-NMR, MS, IR to be the target compound—Cycloprothrin, with the total yield of about 35% and the purity of 90% or more.In this paper, besides the title compound another seven intermediate compounds were also obtained, including 4-Ethoxyphenylacetic acid, Ethyl-4-ethoxy phenyl acetate, Diethyl-(4-ethoxyphenyl)oxobutanedioic acid, Ethyl-2-(4-ethoxyphenyl)propenoate, Ethyl-2,2-Dichloro-1-(4-ethy-oxyphenyl) cyclopropanecarboxylic acid, 2,2-dichloro-1-(4-ethyoxy phenyl) cyclopropanecarboxylic acid and (RS)-α-Cyano-3-phenoxyben-zyl alcohol. The structure and purity of each of these compounds above were also confirmed.Different synthetic methods were compared in this paper and the reaction conditions were also studied and optimized, which offered a satisfactory result for the synthesis process. A feasible technics to the synthesis of Cycloprothrin was at last established, characterized by low cost, cheap and easily gained materials and convenient operating process.The new technics has. gained a higher yield compared with the reported route and possesses a broad foreground of industrialization.更多还原