Detailed analysis for the solvolysis of isopropenyl chloroformate

Malcolm John D’Souza; Kevin Edward Shuman; Arnold Ochieng Omondi; Dennis Neil Kevill

doi:10.5155/eurjchem.2.2.130-135.405

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Published: Jun 30, 2011

DOI: https://doi.org/10.5155/eurjchem.2.2.130-135.405

Keywords:

Solvolysis, Grunwald-Winstein equations, Isopropenyl chloroformate, Chlorocarbonate, Addition-elimination, Ionization

Section

Research Article

Issue

Vol. 2 No. 2 (2011): June 2011

Dates

Received 2011-02-10
Accepted 2011-02-24
Published 2011-06-30

Malcolm John D’Souza

Department of Chemistry, Wesley College, Dover, DE, 19901, USA

Kevin Edward Shuman

Department of Chemistry, Wesley College, Dover, DE, 19901, USA

Arnold Ochieng Omondi

Department of Chemistry, Wesley College, Dover, DE, 19901, USA

Dennis Neil Kevill

Department of Chemistry & Biochemistry , Northern Illinois University, DeKalb, IL, 60115, USA

Abstract

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 N_T scale of solvent nucleophilicity (S-methyldibenzothiophenium ion) combined with a Y_Cl 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 (S_N1) type ionization is making a significant contribution in 97-70% HFIP, and 97% 2,2,2-trifluoroethanol (TFE). 2_2_130_135_800

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D’Souza, M. J.; Shuman, K. E.; Omondi, A. O.; Kevill, D. N. Detailed Analysis for the Solvolysis of Isopropenyl Chloroformate. Eur. J. Chem. 2011, 2, 130-135.

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