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合成了一系列3酰胺基氮取代的NAD(P)H模型物,测定了其与5硝基异喹啉正离子的二级反应速率常数,并与模型物的氧化还原电势进行了比较.实验结果表明,模型物3位酰基氧一方面可离域二氢吡啶环上N的电子;另一方面负电性的3位酰基氧在反应过渡态中又可引起分子内和分子间的两种静电作用;3位酰基的电子效应对模型物动力学反应性的影响是这两种效应综合作用的结果
A series of NAD (P) H models substituted with 3-amido nitrogen were synthesized and the second order reaction rate constants with 5-nitroisoquinoline positive ions were determined and compared with the redox potential of the model compounds . The experimental results show that the 3-acyl oxygen species of the model can dissociate from the electron on the dihydropyridine ring on the one hand; on the other hand, the negatively charged 3-acyl oxygen can cause intramolecular and intermolecular Two kinds of electrostatic interactions; 3-acyl electron effect on the kinetic reactivity of the model is the result of the combined effects of these two effects