Ab initio and DFT studies on the elimination kinetics 2-substituted ethyl N, N-dimethylcarbamates [(CH 3) 2NCOOCH 2CH 2Z, Z=CH 2C 6H 5, C 6H 5, C(CH 3) [dbnd6]CH 2] in the gas phase

Abstract

The theoretical studies on the elimination kinetics of 2-substituted ethyl N, N-dimethylcarbamates [(CH 3) 2NCOOCH 2CH 2Z, Z=CH 2C 6H 5, C 6H 5, C(CH 3) CH 2] in the gas phase were carried out using the ab initio MP2/6-31G and DFT RMPWP91/6-31G(d,p) levels of theory. These carbamates produce N, N-dimethylcarbamic acid and the corresponding substituted olefin in a rate determining step. On the basis of these calculations, the mechanism appears to be concerted, asynchronous, through a six-membered cyclic transition state structure. The acidity of the benzylic and allylic β-hydrogen is believed to be responsible for faster elimination rates.