%0 Journal Article
%T Detailed analysis for the solvolysis of isopropenyl chloroformate
%A Malcolm John D¡¯Souza
%A Kevin Edward Shuman
%A Arnold Ochieng Omondi
%A Dennis Neil Kevill
%J European Journal of Chemistry
%D 2011
%I 
%R 10.5155/eurjchem.2.2.130-135.405
%X The specific rates of solvolysis (including those obtained from the literature) of isopropenyl chloroformate (1) are analyzed using the extended Grunwald-Winstein equation, involving the NT scale of solvent nucleophilicity (S-methyldibenzothiophenium ion) combined with a YCl scale based on 1-adamantyl chloride solvolysis. A similarity model approach, using phenyl chloroformate solvolyses for comparison, indicated a dominant bimolecular carbonyl-addition mechanism for the solvolyses of 1 in all solvents except 97% 1,1,1,3,3,3-hexafluoro-2-propanol (HFIP). An extensive evaluation of the outcomes acquired through the application of the extended Grunwald-Winstein equation resulted in the proposal of an addition-elimination mechanism dominating in most of the solvents, but it is proposed that a superimposed unimolecular (SN1) type ionization is making a significant contribution in 97-70% HFIP, and 97% 2,2,2-trifluoroethanol (TFE).
%K Solvolysis
%K Grunwald-Winstein equations
%K Isopropenyl chloroformate
%K Chlorocarbonate
%K Addition-elimination
%K Ionization
%U http://www.eurjchem.com/index.php/eurjchem/article/view/405