Quantum chemical study of 5,5-dimethyl-1,3-dioxane isomerization to 2,2-dimethyl-3-methoxypropanal, - the general reaction scheme

Abstract

The results of quantum chemical simulation by B3PW91 method in the 6-31G(d,p) basis for formation of 2,2-dimethyl-3-methoxypropanal from 5,5- dimethyl- 1,3- dioxane in the presence of proton are given. The proposed reaction scheme involves protonation of the parent molecule - formation of the oxonium ion, breaking of C-0 bond with receipt of alkoxycarbenium ion, rearrangement of the alkoxycarbenium ion by two successive 1,3-displacement or 1,5 displacement of positive charge, deprotonation of the oxycarbenium ion with formation of the reaction product. Data on the structure and energy characteristics of molecular products, ions, and transition states are obtained not only for the states characterized minimum Gibbs energy (G298, δG298, δG# 298), but also for possible conformers and transitions between them. Based on the calculations, an energy diagram is drawn up in accordance with the general reaction scheme.Comparison of the estimated activation barriers (δG# 298) for implementation of the reaction in two stages (1,3-migrations) and one-stage 1,5-migration showed that they are comparable in size, the difference is about 2 kcal/mol. Since conversion of 5,5- dimethyl- 1,3- dioxane to 2,2-dimethyl-3-methoxypropanal is an endothermal reaction with heat absorption of 3.4 kcal/mol, it can be assumed that in real conditions transformation of ions as per the reaction coordinate will include both two-stage and one-stage conversion of alkoxycarbenium ion to the oxycarbenium ion.