Next Article in Journal
Plant Nucleotide Binding Site–Leucine-Rich Repeat (NBS-LRR) Genes: Active Guardians in Host Defense Responses
Previous Article in Journal
Digoxin Downregulates NDRG1 and VEGF through the Inhibition of HIF-1α under Hypoxic Conditions in Human Lung Adenocarcinoma A549 Cells
Article Menu

Export Article

Open AccessArticle
Int. J. Mol. Sci. 2013, 14(4), 7286-7301; doi:10.3390/ijms14047286

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

1
Department of Chemistry, Wesley College, 120 N. State Street, Dover, DE 19901-3875, USA
2
Department of Chemistry and Biochemistry, Northern Illinois University, DeKalb, IL 60115-2862, USA
These authors contributed equally to this work.
*
Authors to whom correspondence should be addressed.
Received: 16 February 2013 / Revised: 26 March 2013 / Accepted: 28 March 2013 / Published: 2 April 2013
(This article belongs to the Section Physical Chemistry, Theoretical and Computational Chemistry)
View Full-Text   |   Download PDF [291 KB, uploaded 19 June 2014]   |  

Abstract

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 (NT) and solvent ionizing power (YCl). 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.
Keywords: allyl chloroformate; vinyl chloroformate; mechanisms; solvolysis; nucleophilicity; ionizing power; π electron cloud; Grunwald-Winstein equation; Linear Free Energy Relationships (LFERs) allyl chloroformate; vinyl chloroformate; mechanisms; solvolysis; nucleophilicity; ionizing power; π electron cloud; Grunwald-Winstein equation; Linear Free Energy Relationships (LFERs)
Figures

This is an open access article distributed under the Creative Commons Attribution License (CC BY 3.0).

Scifeed alert for new publications

Never miss any articles matching your research from any publisher
  • Get alerts for new papers matching your research
  • Find out the new papers from selected authors
  • Updated daily for 49'000+ journals and 6000+ publishers
  • Define your Scifeed now

SciFeed Share & Cite This Article

MDPI and ACS Style

D'Souza, M.J.; Givens, A.F.; Lorchak, P.A.; Greenwood, A.E.; Gottschall, S.L.; Carter, S.E.; Kevill, D.N. Kinetic Studies that Evaluate the Solvolytic Mechanisms of Allyl and Vinyl Chloroformate Esters. Int. J. Mol. Sci. 2013, 14, 7286-7301.

Show more citation formats Show less citations formats

Related Articles

Article Metrics

Article Access Statistics

1

Comments

[Return to top]
Int. J. Mol. Sci. EISSN 1422-0067 Published by MDPI AG, Basel, Switzerland RSS E-Mail Table of Contents Alert
Back to Top