二烷基苯基磷(膦)酸酯重排和水解反应的结构效应

本文用分子力学(MM)和量子化学(MNDO)方法研究了各种不同磷(膦)酸酯的Csp^2-O-P重排反主尖和碱性水解反应的结构效反应.计算结果表明,随着底物分子中C-P键数目的增多,发生重排反主尖的活化能也增加,这与实验结果完全一致.但由于计算得到的各类磷(膦)酸酯碱性水解反应的活化能同实验结果相矛盾,这可能是由于底物同过渡态之间溶剂化能的差别所致.

The structure effects on Scp^2-O-P rearrangement reactions and alkaline -hydrolysis reactions for phosphinates,phosphonates and phosphates

The structure effects on the rearrangement and alkaline-hydrolysis reactions forphosphinates. phosphonates and phosphates are investigated by MM and MNDO methods.The calculation results indicate that the activation energles of the rearrangement reactionsIncrease with the increasing number of C-P bonds in the substrates, that is consistant withthe experimental results. On the contrary, the calculation activation energies for the alka-line-hydrolysis reactions of these series of compounds are opposite to the experimental re-sults, which can be explained by the difference of the solvent effects between the substrateand the transition state.