European Journal of Chemistry 2011, 2(2), 130-135 | doi: https://doi.org/10.5155/eurjchem.2.2.130-135.405 | Get rights and content

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Detailed analysis for the solvolysis of isopropenyl chloroformate


Malcolm John D’Souza (1,*) , Kevin Edward Shuman (2) , Arnold Ochieng Omondi (3) , Dennis Neil Kevill (4)

(1) Department of Chemistry, Wesley College, Dover, DE, 19901, USA
(2) Department of Chemistry, Wesley College, Dover, DE, 19901, USA
(3) Department of Chemistry, Wesley College, Dover, DE, 19901, USA
(4) Department of Chemistry & Biochemistry , Northern Illinois University, DeKalb, IL, 60115, USA
(*) Corresponding Author

Received: 10 Feb 2011 | Revised: 24 Feb 2011 | Accepted: 28 Feb 2011 | Published: 30 Jun 2011 | Issue Date: June 2011

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 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).2_2_130_135_800


Keywords


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

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DOI: 10.5155/eurjchem.2.2.130-135.405

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Funding information


NIH-NCRR-INBRE, grant # 2 P2O RR016472-010

Citations

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[1]. Malcolm D'Souza, Aaron Givens, Peter Lorchak, Abigail Greenwood, Stacey Gottschall, Shannon Carter, Dennis Kevill
Kinetic Studies that Evaluate the Solvolytic Mechanisms of Allyl and Vinyl Chloroformate Esters
International Journal of Molecular Sciences  14(4), 7286, 2013
DOI: 10.3390/ijms14047286
/

[2]. Gui Taek Lim, Yeong Ho Lee, Zoon Ha Ryu
Further Kinetic Studies of Solvolytic Reactions of Isobutyl Chloroformate in Solvents of High Ionizing Power Under Conductometric Conditions
Bulletin of the Korean Chemical Society  34(2), 615, 2013
DOI: 10.5012/bkcs.2013.34.2.615
/

[3]. Dennis Neil Kevill, Chang-Bae Kim, Malcolm John D’Souza
Correlation of the rates of solvolysis of α-bromoisobutyrophenone using both simple and extended forms of the Grunwald-Winstein equation and the application of correlation analysis to related studies
European Journal of Chemistry  9(1), 1, 2018
DOI: 10.5155/eurjchem.9.1.1-6.1680
/

[4]. T. Bentley
Calculated Third Order Rate Constants for Interpreting the Mechanisms of Hydrolyses of Chloroformates, Carboxylic Acid Halides, Sulfonyl Chlorides and Phosphorochloridates
International Journal of Molecular Sciences  16(12), 10601, 2015
DOI: 10.3390/ijms160510601
/

[5]. Malcolm J. D’Souza, Olivia N. Hampton, Brett M. Sansbury, Dennis N. Kevill
Evaluation of Electronic Effects in the Solvolyses ofp-Methylphenyl andp-Chlorophenyl Chlorothionoformate Esters
Journal of Chemistry  2013, 1, 2013
DOI: 10.1155/2013/248534
/

[6]. Malcolm J. D’Souza, Jaci A. Knapp, Gabriel A. Fernandez-Bueno, Dennis N. Kevill
Use of Linear Free Energy Relationships (LFERs) to Elucidate the Mechanisms of Reaction of a γ-Methyl-β-alkynyl and an ortho-Substituted Aryl Chloroformate Ester
International Journal of Molecular Sciences  13(1), 665, 2012
DOI: 10.3390/ijms13010665
/

[7]. Jin Burm Kyong, Yelin Lee, Malcolm John D'Souza, Brian Patrick Mahon, Dennis Neil Kevill
Correlation of the rates of solvolysis of tert-butyl chlorothioformate and observations concerning the reaction mechanism
European Journal of Chemistry  3(3), 267, 2012
DOI: 10.5155/eurjchem.3.3.267-272.624
/

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How to cite


D’Souza, M.; Shuman, K.; Omondi, A.; Kevill, D. Eur. J. Chem. 2011, 2(2), 130-135. doi:10.5155/eurjchem.2.2.130-135.405
D’Souza, M.; Shuman, K.; Omondi, A.; Kevill, D. Detailed analysis for the solvolysis of isopropenyl chloroformate. Eur. J. Chem. 2011, 2(2), 130-135. doi:10.5155/eurjchem.2.2.130-135.405
D’Souza, M., Shuman, K., Omondi, A., & Kevill, D. (2011). Detailed analysis for the solvolysis of isopropenyl chloroformate. European Journal of Chemistry, 2(2), 130-135. doi:10.5155/eurjchem.2.2.130-135.405
D’Souza, Malcolm, Kevin Edward Shuman, Arnold Ochieng Omondi, & Dennis Neil Kevill. "Detailed analysis for the solvolysis of isopropenyl chloroformate." European Journal of Chemistry [Online], 2.2 (2011): 130-135. Web. 27 Feb. 2021
D’Souza, Malcolm, Shuman, Kevin, Omondi, Arnold, AND Kevill, Dennis. "Detailed analysis for the solvolysis of isopropenyl chloroformate" European Journal of Chemistry [Online], Volume 2 Number 2 (30 June 2011)

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