论文部分内容阅读
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。
In this paper, we proposed a stereospecific synthesis method for insecticide “off aphid net” and its geometrical isomers. Using phosphorus oxychloride and ethyl acetoacetate in the presence of tributylamine, 1-methyl-2-ethoxycarbonyl) -phosphoryl dichloride E body, and then esterified to “off aphids net” E body. The Z-body was obtained by the reaction of trichlorosulfuron (or dialkoxyphosphoryl chloride) with the ethyl acetoacetate enolate sodium salt, and the results of nuclear magnetic resonance spectroscopy showed that the E or Z body contents All above 95%. The activity of these geometric isomers indicates the relationship between the spatial structure and activity of the insecticide molecules. The different geometric isomers of the same chemical composition have a difference of about 20 times in their activity. The same geometry with different chemical composition, such as “off aphids net” E and ethyl thiosulfate off net E body activity, about 2.5 times worse. Visible spatial configuration on the activity of these pesticide molecules in the chemical composition of the impact is much larger.