Evaluation of the olefinic double bond influence in the unimolecular homogeneous gas phase elimination of alkenyl acetates

Abstract

Martin et al.analogous to those shown in Figure 3 for the decomposition of the hydroxylamines formed in the reactions involving primary and secondary amines.This heuristic model offers explanations for both the unusually great importance of the R-loss route in the 0 + TMA reaction and the fact that the H20 loss route was not observed in the same reaction. The latter route would require the loss of two primary hydrogens in sequential steps, each of which involves a competition with a second pathway which is probably energetically favored. These six studies have begun to reveal details of the mechanism of O + amine reactions under essentially collision-free conditions following the formation of an energy-rich adduct. Recognizing that an excited amine IV-oxide is the first intermediate in this reaction, we have shown in this study that amine IV-oxides with 60-70 kcal/mol of internal energy decompose not only along the path of lowest free-energy increase, but to a very great extent by other routes which have not been observed before.