高等学校化学学报 ›› 1981, Vol. 2 ›› Issue (2): 176.

• 论文 • 上一篇    下一篇

某些乙烯基磷酸酯类杀虫剂几何异构体的研究(Ⅱ)——杀虫剂“灭蚜净”及其类似物几何异构体的立体专一性合成

邵瑞链, 董希阳, 张春造   

  1. 南开大学元素有机化学研究所
  • 收稿日期:1980-03-19 出版日期:1981-04-24 发布日期:1981-04-24

STUDY OF GEOMETRIC ISOMERS OF SOME VINYLPHOSPHATE INSECTICIDES——II——THE STEREOSPECIFIC SYNTHESIS OF THE O,O-DIMETHYL-O-(1-ETHOXYCARBONYL-1-PROPEN-2-YL) PHOSPHATE INSECTICIDE (MIE-YA-JING) AND ITS ANALOGUES

Shao Ruilian, Dong Xiyang, Zhang Chunzao   

  1. Institute of Elemento- Organic Chemistry, Nankai University, Tianjin
  • Received:1980-03-19 Online:1981-04-24 Published:1981-04-24

摘要: 本文提出了杀虫剂“灭蚜净”及其类似物几何异构体的立体专一性合成方法,用三氯氧磷和乙酰乙酸乙酯在三丁胺存在下反应,可得O-(1-甲基-2-乙氧甲酰基乙烯基)-磷酰二氯E体,进而酯化得“灭蚜净”E体。用三氯硫磷(或二烷氧基磷酰氯)与乙酰乙酸乙酯烯醇钠盐反应可得Z体,经核磁共振谱测定,所得灭蚜净及其类似物的E体或Z体含量均在95%以上。这些几何异构体的活性说明了杀虫剂分子中空间结构与活性的关系,同一化学组成的不同几何异构体其活性相差20倍左右。而同一几何构型不同化学组成,如“灭蚜净”E体和乙基硫代灭蚜净E体活性相比,约差2.5倍。可见空间构型对活性的影响,在这些杀虫剂分子中要比化学组成上的影响来得大。

Abstract: The present report deals with the stereospecific synthesis of the O, O-dimethyl-O-(1-ethoxycarbonyl-1-propen-2-yl) phosphate, an insecticide named Mie-Ya-jing in Chinese. The reaction of phosphorus oxychloride with ethyl acetoacetate in the presence of tributylamine yeilded specifically the E-stereoisomer as the key intermediate, from which E-stereoisomer "Mie-Ya-jing" was prepared by treating with excess of methyl alcohol. It seems that there is a relationship between the steric factors of the base and the E/Zratio obtained. The Z-stereoisomer was synthesized by the action of dimethyl phosphoryl Chloride on ethyl sodioacetoacetate. The other two Mie-Ya-jing derivatives were similarly prepared. The E-isomer proved to be more toxic to insects than the corresponding Z-isomers.

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