Kinetic Studies that Evaluate the Solvolytic Mechanisms of Allyl and Vinyl Chloroformate Esters

International Journal of Molecular Sciences

Malcolm J. D’Souza¹  Aaron F. Givens¹  Peter A. Lorchak¹  Abigail E. Greenwood¹  Stacey L. Gottschall¹  Shannon E. Carter¹ 

[1] Department of Chemistry, Wesley College, 120 N. State Street, Dover, DE 19901-3875, USA

关键词: allyl chloroformate;    vinyl chloroformate;    mechanisms;    solvolysis;    nucleophilicity;    ionizing power;    π electron cloud;    Grunwald-Winstein equation;    Linear Free Energy Relationships (LFERs);   

DOI  :  10.3390/ijms14047286

来源: mdpi

【 摘 要 】

At 25.0 °C the specific rates of solvolysis for allyl and vinyl chloroformates have been determined in a wide mix of pure and aqueous organic mixtures. In all the solvents studied, vinyl chloroformate was found to react significantly faster than allyl chloroformate. Multiple correlation analyses of these rates are completed using the extended (two-term) Grunwald-Winstein equation with incorporation of literature values for solvent nucleophilicity (N_T) and solvent ionizing power (Y_Cl). Both substrates were found to solvolyze by similar dual bimolecular carbonyl-addition and unimolecular ionization channels, each heavily dependent upon the solvents nucleophilicity and ionizing ability.

【 授权许可】

CC BY   
© 2013 by the authors; licensee MDPI, Basel, Switzerland