Nucleophilic Cleavage of Phosphate Triesters in Dialkylammonium Bilayer Membranes
作者:Yoshio Okahata、Hirotaka Ihara、Toyoki Kunitake
DOI:10.1246/bcsj.54.2072
日期:1981.7
on the reaction of p-nitrophenyl phosphates with hydroxamate nucleophiles in water in the presence of dialkylammonium bilayer membranes. With ethyl bis(p-nitrophenyl) phosphate, clean second order kinetics was observed for all the hydroxamate nucleophiles, two equivalents of p-nitrophenol being released in most cases. In contrast, a complex kinetics was observed for octadecylbis(p-nitrophenyl)phosphate
在二烷基铵双层膜的存在下,对磷酸对硝基苯酯与异羟肟酸盐亲核试剂在水中的反应进行了研究。对于双(对硝基苯基)磷酸乙酯,所有异羟肟酸酯亲核试剂均观察到干净的二级动力学,在大多数情况下释放了两当量的对硝基苯酚。相反,观察到十八烷基双(对硝基苯基)磷酸酯的复杂动力学。长链异羟肟酸酯对这种长链底物的第二次切割过程受基质膜流动性的影响,在 Arrhenius 图中在 2C16N+2C1 膜的相变温度 (Tc) 附近存在一个拐点区域。在高于和低于 Tc 的温度下,活化能分别为 14 和 21 kcal/mol。