Theoretical calculations on the mechanism of the elimination kinetics of allyl cyclohexyl-, -amine, -sulfide, -ether, and allyl ethyl ether in the gas phase

Abstract The mechanism of the gas-phase elimination allyl cyclohexyl amine, allyl cyclohexyl sulfide, allyl cyclohexyl ether, and allyl ethyl ether has been studied by using ab initio combined methods CBS-QB3, and Density Functional Theory CAM-B3LYP, MPW1PW91, PBE1PBE, M06, and M062X. Products formation is described below: Theoretical calculations of these reactions support the unimolecular process of these gas-phase eliminations. These thermal decompositions undergo a retro-ene type of mechanism and proceed through a non-planar concerted six-membered cyclic transition structure. The energy of activation follow the order allyl ethyl ether (187.0 kJ/mol) > N-allyl cyclohexyl amine (171.7 kJ/mol) > allyl cyclohexyl ether (170.5 kJ/mol) > allyl cyclohexyl sulfide (137.9 kJ/mol). The polarization of C 5 –Z 6 bond, and the electronegativity of the heteroatom (O, N) increases the reaction rate compared to allyl ethyl ether. Conversely, the S atom is positively charged and its electronic effect causes a high dissymmetry in the TS geometry, which appear to accelerate the decomposition. The rate determining step of these substrates is the change in hybridization from sp 3 to sp 2 reflected in the bond order in C 3 –C 4 . Calculated kinetic and thermodynamic parameters from the M06/6-311++G(d,p) level of theory are in reasonable good agreement with the experimental values.