Determination of Reactivities by MO Theory (). Theoretical Studies on Acid Catalyzed Displacement Reactions at Carbonyl Carbon

[摘要] The CNDO/2 MO method has been used to study gas phase reactions of protonated acetaldehyde with alcohols and protonated acetic acid with alcohols respectively by optimizing state geometries. Results showed that the former is predicted to proceed by alkyl-O cleavage and the latter by acyl-O cleavage. It has also been found using eigenvector properties of reactants that the former should be a charge controlled while the latter an orbital controlled reaction. According to the calculated activation energies assuming the transition states proposed by Caserio et al., the predicted reactivity order for alcohols agreed with the experiments for the latter but the order predicted was the reverse of the experimental one for the former.

[学科分类] 化学（综合）