Abstract
Solvolysis rate constants for methylchloroformate, methylthionochloroformate, methylthiolchloroformate and methyldithiochloroformate have been determined conductometrically in methanol, ethanol and ethanol-water mixtures and activation parameters have been derived. Results show that methylchloroformate solvolyzes through $S_N2$ process while methyldithiochloroformate solvolyzes by $S_N1$ process in all the solvent systems. The rate of hydrolysis decreased in the order, $CH_3S(CS)Cl>CH_3S(CO)Cl>CH_3O(CS)Cl>CH_3O(CO)Cl$ which corresponds to the order of decreasing $S_N1$ character. In methanol, $CH_3S(CS)Cl$ solvolyzed via the $S_N1$ mechanism while the others solvolyzed via the $S_N2$ process. In ethanol, however, $S_N2$ character was dominant for all the compounds, except methyldithiochloroformate, for which $S_N1$ character was still strong enough to accelerate the rate of ethanolysis. In ethanol-water mixtures, $CH_3S(CS)Cl$ and $CH_3S(CS)Cl$ solvolyzed via $S_N2$ process in ethanol-rich region while the $S_N1$ character increased greatly in water-rich region for the solvolysis of these compounds. The order of $S_N1$ character for solvolysis in water-rich region was the same as the order of hydrolysis rate.
메탄올, 에탄올 및 에탄올-물 혼합용매중에서 메틸클로로휘메이트, 메틸티올클로로휘메이트, 메틸티오노클로로휘메이트 및 메틸디티오클로로휘메이트의 가용매분해반응에 대한 속도상수를 전기전도도법으로 구하고 활성화 파라미터를 계산하였다. 결과로 메틸클로로휘메이트는 항상 $S_N2$ 메카니즘으로 반응하며, 가수분해 순위는 $CH_3S(CS)Cl>CH_3S(CO)Cl>CH_3O(CS)Cl>CH_3O(CO)Cl$ 로 $S_N1$ 반응성이 감소하고, 메탄올에서는 $CH_3S(CS)Cl$은 $S_N1$으로, 기타는 $S_N2$로 반응하고, 에탄올에서는 모두 $S_N2$로 반응하나 아직도 메틸클로로디티오휘메이트는 $S_N1$ 반응성이 어느정도 작용함을 알았다. 또한 에탄올-물 혼합용매에서 물함량이 큰 부분에서는 티오치환체의 $S_N1$ 반응성이 증가하며 메틸클로로디티오휘메이트는 $S_N1$으로 반응함을 알았다. 에탄올-물 혼합용매중에서 $S_N1$ 반응성의 순위는 가수분해속도의 순위와 같았다.
