Density functional theory studies on the mechanism of ozonolysis of butyl vinyl ether

The reaction mechanism of ozonolysis of three isomers of butyl vinyl ether ( n -Bve、 em -Bve and t -Bve) has been studied using the density functional theory (DFT) at the BHandHLYP/6-31+G(d,p) and MPWB1K/6-31+G(d,p) levels of theory. The geometries for the reactants, the transition states and the products are completely optimized. All the transition states are verified by the vibrational analysis and the instrisic reaction coordinate (IRC) calculations. The pathway of rearranging to isomer is preferred to the pathway of decomposing to OH for the n -butyl, em -butyl and t -butyl substituted carbonyl oxide compounds. Our computations produce the large exothermicity of the three cycloaddition reactions. According to our calculation, the ozone- n -Bve reaction is faster than the ozone- t -Bve reaction, the ozone- em -Bve reaction is slower than the ozone- t -Bve reaction. The calculated results are in good agreement with the available experiment data.