Mechanism Interpretation of Thermal Decomposition Reactions of Vinyl Ethers in Gas Phase Using DFTMethod

Abstract: The mechanism thermal decompositions of propyl vinyl ether (PVE), isopropyl vinyl ether (IPVE)and butyl vinyl ether (BVE) compounds were investigated in the gas phase using density functional theory (DFT). The DFT calculations for the decomposition of considered ethers were performed at B3LYP/6-31G level of theory. Changes in thermodynamic functions including∆H‡ , ∆S‡ and ∆G‡were also determined and interpreted. The calculation results revealed that thermal decompositions of PVE, BVE and IPVE species occur via a proton transfer mechanism, where formation of a hydrogen bridge between a hydrogen atom of the alkyl group and the extreme carbon atom of the vinyl group is responsible for the decomposition reaction.The theoretical results compare rather well with the experimental findings available in the literature.

Keywords:

DFT , vinyl ethers , proton transfer mechanism , decomposition , rate constant