Abstract
Møller-Plesset MP2/6-31G method was used to examine the gas-phase elimination of 2-substituted alkyl ethyl N, N-dimethylcarbamates. The results of these calculations support a concerted non-synchronous six-membered cyclic transition state mechanism for carbamates containing a C β–H bond at the alkyl side of the ester. These substrates produce the N, N-dimethylcarbamic acid and the corresponding olefin. The unstable intermediate, N, N-dimethylcarbamic acid, rapidly decomposes through a four-membered cyclic transition state to dimethylamine and CO 2 gas. Correlation of the logarithm of theoretical rate coefficients against original Taft's σ* values gave an approximate straight line ( ρ*=−1.39, r=0.9558 at 360 °C). In addition to this fact, when log k rel is plotted against the theoretical log k rel for 2-substituted ethyl N, N-dimethylcarbamates a reasonable straight line ( r=0.9919 at 360 °C) is obtained, suggesting similar mechanism.
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