An ab initio study on the molecular elimination reactions of methacrylonitrile

Ab initio quantum chemical molecular orbital calculations have been performed for the unimolecular decomposition of methacrylonitrile (CH3C(CN)=CH2), especially for HCN and H-2 molecular elimination channels. Structures and energies of the reactants, products, and relevant species along the individual reaction pathways were determined by MP2 gradient optimization and MP4 single point energy calculations. Direct four-center elimination of HCN and three-center elimination of H-2 channels were identified. In addition, H or CN migration followed by HCN or H-2 elimination channels via the methylcyanoethylidene intermediate was also identified. Unlike the case of crotonitrile previously studied, in which the dominant decomposition process was the direct three-center elimination of HCN, the most important reaction pathway should be the direct three-center elimination of H-2 in the case of methacrylonitrile.