氢同位素分离效应在催化加成反应中的作用——高比度〔4,5-~3H〕去甲斑蝥素的合成

THE ROLE OF HYDROGEN ISOTOPE EFFECT IN CATALYTIC ADDITION REACTION——SYN-THESIS OF (4,5-~3H)-EXO-CIS-3,6-EPOXYHEXA-HYDROPHTHALIC ANHYDRIDE

摘要: 本文描述了借助催化加成反应制备高比度4,5-~3H去甲斑蝥素的化学合成法。同时,为了说明氚丰度对于~3H-去甲斑蝥素比度的影响,在不同氚丰度条件下,进行了催化加成反应。阐明了钯催化剂对氢同位素的分离效应。对氕-氚体系而言,分离效应和温度的关系符合lgα_(H-T)=-0.04+138/T的公式。氢同位素的分离效应是导致实际比度较相应丰度条件下应得比度为低的主要因素。所得实验结果和理论分析数据获得了较好的符合。

Abstract: Hydrogen isotope effect is found in the catalytic addition reaction-synthesis of (4.5-(?)H)-exp-cis-3,6-epoxyhexahydrophthalic anhydride and the isotope separation factor is related to the temperature by the equation lgαH-T = 0.04 ±138/T. Theoretical values of specific activities of the 3H-labelled compound calculated from the equation agree well with experimental values. The agreement proves that hydrogen isotope effect does exist on the palladium catalyst.