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Special Issue "Grunwald-Winstein Equations – 60 Years & Counting"

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A special issue of International Journal of Molecular Sciences (ISSN 1422-0067). This special issue belongs to the section "Physical Chemistry, Theoretical and Computational Chemistry".

Deadline for manuscript submissions: closed (30 June 2009)

Special Issue Editor

Guest Editor
Prof. Dr. Malcolm D´Souza

Department of Chemistry, Wesley College, 120 N. State Street, Dover, DE 19901-3875, USA
Website | E-Mail
Fax: +1 302-736-2301
Interests: chemical kinetics; solvolysis; LFERs (Linear Free Energy Relationships); QSARs (Quantitative Structure Activity Relationships); database user-needs analysis (database building)

Special Issue Information

Dear Colleagues,

The IJMS has agreed to publishe a special issue commemorating the 60th anniversary of the original Grunwald-Winstein Equation. In recent years several papers have highlighted its usefulness in Physical Organic Chemistry, especially appreciating its contribution in providing information utilized in the determination of mechanisms of reaction of useful organic compounds.

I now strongly urge you to take advantage of this forum provided by IJMS, to submit your research articles or review commentaries on LFER’s, and studies on solvent interactions, for possible publication in this journal during 2008.

Thank you,
Malcolm J. D’Souza
Guest Editor

Leading Papers and Reviews

  • D’Souza, M. J.; Reed, D.; Koyoshi, F.; Kevill, D. N. Consideration of the Factors Influencing the Specific Rates of Solvolysis of p-Methoxyphenyl Chloroformate. Int. J. Mol. Sci. 2007, 8, 788-796
  • Kevill, D. N.; Koyoshi, F.; D’Souza M. J. Correlations of the Specific Rates of Solvolysis of Aromatic Carbamoyl Chlorides, Chloroformates, Chlorothionoformates, and Chlorodithioformates Revisited. Int. J. Mol. Sci. 2007, 8, 346-362
  • Kyong, J. B.; Chan, J. R.; Kim, Y.-G.; Kevill, D. N. Rate and Product Studies with 2-Adamantyl Fluoroformate Under Solvolytic Conditions. J. Phys. Org. Chem. 2007, 20, 525-531
  • Kevill, D. N.; Ryu, Z. H.; Niedermeyer, M. A.; Koyoshi, F.; D’Souza, M. J. Rate and Product Studies in the Solvolyses of Methanesulfonic Anhydride and a Comparison with Methanesulfonyl Chloride Solvolyses. J. Phys. Org. Chem. 2007, 20, 431-438
  • Fujita, M.; Mishima, E.; Okuyama, T. Solvolysis of Methoxy-Substituted Diaryliodonium Tetrafluoroborates: Attempted Generation of a Stabilized Aryl Cation. J. Phys. Org. Chem. 2007, 20, 241-244
  • Kevill, D. N.; Koh, H. J. Correlation of the Rates of Solvolysis of Diphenylphosphinyl Chloride Using an Extended Form of the Grunwald-Winstein Equation. J. Phys. Org. Chem. 2007, 20, 88-92
  • Creary, X.; O'Donnell, B. D.; Vervaeke, M. Homoallyl-Cyclopropylcarbinyl Cation Manifold. Trimethylsilyl versus Aryl Stabilization. J. Phys. Org. Chem. 2007, 9, 3360-3368
  • Kevill, D. N.; Kyong, J. B. Intramolecular Nucleophilic Assistance in the Solvolyses of Benzyl Derivatives: Solvolyses of o-Nitrobenzyl Bromide and Tosylate. J. Phys. Org. Chem. 2007, 210-215
  • Berger, S. T. A.; Seeliger, F. H.; Hofbauer, F.; Mayr, H. Electrophilicity Parameters for 2-Benzylidene-indan-1,3-diones-A Systematic Extension of the Benzhydrylium Based Electrophilicity Scale. Org. Biomol. Chem. 2007, 18, 3020-3026
  • Lee, S. H.; Rhu, C. J.; Kyong, J. B.; Kim, D. K.; Kevill, D. N. Correlation of the Rates of Solvolysis of Isopropyl Fluoroformate Using the Extended Grunwald-Winstein Equation. Bull. Korean Chem. Soc. 2007, 28, 657-661
  • Liu, K. –T.; Chang, L. –W. ; Chin, C. –P. Kinetic Evidence for the Solvent Intervention in the Solvolysis of Tertiary Benzylic Benzoates. Chin. J. Chem. 2006, 24, 1238-1241
  • Bentley, T. W. Additivity Rules Using Similarity Models for Chemical Reactivity: Calculation and Interpretation of Electrofugality and Nucleofugality. Chem. Eur. J. 2006, 12, 6514-6520
  • Bentley, T. W.; Garley, M. S. Correlations and Predictions of Solvent Effects on Reactivity: Some Limitations of Multi-Parameter Equations and Comparisons with Similarity Models Based on One Solvent Parameter. J. Phys. Org. Chem. 2006, 19, 341-349
  • Kevill, D. N.; Park, B. C.; Park, K. H.; D’Souza, M. J.; Yaakoubd, L.; Mlynarski, S. L.; Kyong, J. B. Rate and Product Studies in the Solvolyses of N,N-dimethylsulfamoyl and 2-Propanesulfonyl Chlorides. Org. Biomol. Chem. 2006, 4, 1580-1586
  • D’Souza, M. J.; Boggs, M.E.; Kevill, D. N. Correlation of the Rates of Solvolysis of 2-Furancarbonyl Chloride & Three Naphthoyl Chlorides. J. Phys. Org. Chem. 2006, 173-178
  • Denegri, B.; Streiter, A.; Juri, S.; Ofial, A. R.; Kronja, O.; Mayr, H. Kinetics of the Solvolyses of Benzhydryl Derivatives: Basis for the Construction of a Comprehensive Nucleofugality Scale. Chem. Eur. J. 2006, 12, 1648-1656
  • Kevill, D. N.; Ryu, Z. H. Additional Solvent Ionizing Power Values for Binary Water-1,1,1,3,3,3-Hexafluoro-2-propanol Solvents. Int. J. Mol. Sci. 2006, 7, 451-455
  • Kyong, J. B.; Ryu, S. H.; Kevill, D. N. Rate and Product Studies of Solvolyses of Benzyl Fluoroformate. Int. J. Mol. Sci. 2006, 7, 186-196
  • Kevill, D. N.; Goken, E. G.; Park, B. C. Correlation of the Specific Rates of Solvolysis of Trimethylsilylmethyl Trifluoromethanesulfonate Using a Two-term Grunwald-Winstein Equation. J. Chem. Res. 2006, 173-175
  • Fujio, M.; Umezaki, Y.; Alam, Md. A.; Kikukawa, K.; Fujiyama, R.; Tsuno, Y. The β-Silicon Effect. II. Substituent Effects on the Solvolysis of 1-Aryl-2-(aryldimethylsilyl)ethyl 3,5-Dinitrobenzoates. Bull. Chem. Soc. Jap. 2006, 79, 1091-1099

Keywords

  • Grunwald-Winstein equation
  • solvolysis
  • LFER (Linear Free Energy Relationship)
  • mechanisms of reaction
  • rates of reaction
  • solvent nucleophilicity
  • solvent ionizing power
  • aromatic ring parameter
  • correlation
  • correlation coefficient
  • nucleophilic salvation
  • transition state
  • unimolecular
  • bimolecular
  • kinetics
  • substituent effects
  • carbocations
  • solvent effects
  • nucleophilic substitution
  • activation parameters
  • electrofugality
  • electrophilicity
  • association-dissociation mechanism (AN + DN)
  • SN2 (ANDN) or SN1 (DN)
  • selectivity
  • leaving group effects
  • solvent polarity
  • salt effect
  • sulfonyl transfer reactions
  • nucleophilicity
  • ionizing power
  • log (k/ko)
  • acyl chlorides
  • alcoholysis
  • rate ratio
  • general-base catalysis
  • correlation analysis
  • Kinetic Solvent Isotope Effect (KSIE)
  • N scales
  • Y scales
  • I scale
  • product selectivity
  • regression Analysis (or, multiple regression)
  • rate constants
  • free energy (or, thermodynamic properties)
  • variation in transition state structure

Published Papers (5 papers)

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Research

Open AccessArticle Corrrelation of the Specific Rates of Solvolysis of Ethyl Fluoroformate Using the Extended Grunwald-Winstein Equation
Int. J. Mol. Sci. 2009, 10(3), 929-941; doi:10.3390/ijms10030929
Received: 15 February 2009 / Revised: 27 February 2009 / Published: 2 March 2009
Cited by 5 | PDF Full-text (196 KB) | HTML Full-text | XML Full-text
Abstract
The specific rates of solvolysis of ethyl fluoroformate have been measured at 24.2 °C in 21 pure and binary solvents. These give a satisfactory correlation over the full range of solvents when the extended Grunwald-Winstein equation is applied. The sensitivities to changes in
[...] Read more.
The specific rates of solvolysis of ethyl fluoroformate have been measured at 24.2 °C in 21 pure and binary solvents. These give a satisfactory correlation over the full range of solvents when the extended Grunwald-Winstein equation is applied. The sensitivities to changes in the NT solvent nucleophilicity scale and the YCl solvent ionizing power scale, and the kF/kCl values are very similar to those for solvolyses of n-octyl fluoroformate, consistent with the addition step of an addition-elimination pathway being rate-determining. For methanolysis, a solvent deuterium isotope effect of 3.10 is compatible with the incorporation of general-base catalysis into the substitution process. For five representative solvents, studies were made at several temperatures and activation parameters determined. The results are also compared with those reported earlier for ethyl chloroformate and mechanistic conclusions are drawn. Full article
(This article belongs to the Special Issue Grunwald-Winstein Equations – 60 Years & Counting)
Figures

Open AccessArticle Correlation of the Rates of Solvolysis of Two Arenesulfonyl Chlorides and of trans-β-Styrenesulfonyl Chloride — Precursors in the Development of New Pharmaceuticals
Int. J. Mol. Sci. 2008, 9(12), 2639-2657; doi:10.3390/ijms9122639
Received: 21 November 2008 / Revised: 16 December 2008 / Accepted: 17 December 2008 / Published: 17 December 2008
Cited by 9 | PDF Full-text (358 KB) | HTML Full-text | XML Full-text
Abstract
Additional specific rates of solvolysis have been determined, mainly in fluoroalcohol containing solvents, for benzenesulfonyl chloride (1) and p-nitrobenzenesulfonyl chloride (2). For trans-β-styrenesulfonyl chloride (3), a study has been carried out in 43 pure and binary solvents, covering a wide range of
[...] Read more.
Additional specific rates of solvolysis have been determined, mainly in fluoroalcohol containing solvents, for benzenesulfonyl chloride (1) and p-nitrobenzenesulfonyl chloride (2). For trans-β-styrenesulfonyl chloride (3), a study has been carried out in 43 pure and binary solvents, covering a wide range of hyroxylic solvent systems. For the specific rates of solvolyses of each of the three substrates, a good correlation was obtained over the full range of solvents when the extended Grunwald-Winstein equation was applied. The sensitivities to changes in solvent nucleophilicity and solvent ionizing power are similar to values determined earlier and an SN2 process is proposed. For 3, kinetic solvent isotope effects of 1.46 for kH2O/kD2O and 1.76 for kMeOH/kMeOD were determined. These are also compared to literature values for other sulfonyl chlorides. Full article
(This article belongs to the Special Issue Grunwald-Winstein Equations – 60 Years & Counting)
Open AccessArticle Extended Grunwald-Winstein Analysis - LFER Used to Gauge Solvent Effects in p-Nitrophenyl Chloroformate Solvolysis
Int. J. Mol. Sci. 2008, 9(11), 2231-2242; doi:10.3390/ijms9112231
Received: 27 October 2008 / Revised: 9 November 2008 / Accepted: 12 November 2008 / Published: 13 November 2008
Cited by 14 | PDF Full-text (233 KB) | HTML Full-text | XML Full-text
Abstract
Specific rates of solvolysis at 25oC for p-nitrophenyl chloroformate (1) are analyzed using the extended (two-term) Grunwald-Winstein equation. For 39 solvents, the sensitivities (l = 1.68±0.06 and m = 0.46±0.04) towards changes in solvent nucleophilicity (l) and
[...] Read more.
Specific rates of solvolysis at 25oC for p-nitrophenyl chloroformate (1) are analyzed using the extended (two-term) Grunwald-Winstein equation. For 39 solvents, the sensitivities (l = 1.68±0.06 and m = 0.46±0.04) towards changes in solvent nucleophilicity (l) and solvent ionizing power (m) obtained, are similar to those previously observed for phenyl chloroformate (2) and p-methoxyphenyl chloroformate (3). The observations incorporating new kinetic data in several fluoroalcohol-containing mixtures, are rationalized in terms of the reaction being sensitive to substituent effects and the mechanism of reaction involving the addition (association) step of an additionelimination (association-dissociation) pathway being rate-determining. The l/m ratios obtained for 1, 2, and 3, are also compared to the previously published l/m ratios for benzyl chloroformate (4) and p-nitrobenzyl chloroformate (5). Full article
(This article belongs to the Special Issue Grunwald-Winstein Equations – 60 Years & Counting)
Figures

Open AccessArticle The Influence of Carbon-Carbon Multiple Bonds on the Solvolyses of Tertiary Alkyl Halides: a Grunwald-Winstein Analysis
Int. J. Mol. Sci. 2008, 9(9), 1704-1716; doi:10.3390/ijms9091704
Received: 17 June 2008 / Revised: 4 August 2008 / Accepted: 26 August 2008 / Published: 4 September 2008
Cited by 4 | PDF Full-text (125 KB) | HTML Full-text | XML Full-text
Abstract
The influence of carbon-carbon multiple bonds on the solvolyses of 3-chloro-3-methylbutyne (1), 2-chloro-2-phenylpropane (2), 2-bromo-2-methyl-1-phenylpropane (3), 4-chloro-4-methyl-2-pentyne (4) and 2-chloro-2-methylbutane (5) is critically evaluated through the extended Grunwald-Winstein equation. Substrates 1, 3 and 5 lead to correlations with unexpected negative sensitivity, h,
[...] Read more.
The influence of carbon-carbon multiple bonds on the solvolyses of 3-chloro-3-methylbutyne (1), 2-chloro-2-phenylpropane (2), 2-bromo-2-methyl-1-phenylpropane (3), 4-chloro-4-methyl-2-pentyne (4) and 2-chloro-2-methylbutane (5) is critically evaluated through the extended Grunwald-Winstein equation. Substrates 1, 3 and 5 lead to correlations with unexpected negative sensitivity, h, to changes in the aromatic ring parameter, I. It is claimed that I is not a pure parameter, reflecting also some solvent nucleophilicity, NOTs, character. In substrates 2 and 4 the possibility of rearside solvation is reduced due to steric hindrance and/or cation stabilization and the best found correlations involve only the solvent ionizing power, Y, and I. Full article
(This article belongs to the Special Issue Grunwald-Winstein Equations – 60 Years & Counting)
Open AccessArticle Concerted Solvent Processes for Common Sulfonyl Chloride Precursors used in the Synthesis of Sulfonamide-based Drugs
Int. J. Mol. Sci. 2008, 9(5), 914-925; doi:10.3390/ijms9050914
Received: 9 April 2008 / Revised: 19 May 2008 / Accepted: 19 May 2008 / Published: 24 May 2008
Cited by 14 | PDF Full-text (283 KB) | HTML Full-text | XML Full-text
Abstract
Specific rates of solvolysis in hydroxylic solvents available for the solvolysis of 2-thiophenesulfonyl chloride and phenylmethanesulfonyl chloride are supplemented by determining the values in fluoroalcohol-containing solvents. The data sets are then correlated using the extended Grunwald-Winstein equation. For both substrates, it is found
[...] Read more.
Specific rates of solvolysis in hydroxylic solvents available for the solvolysis of 2-thiophenesulfonyl chloride and phenylmethanesulfonyl chloride are supplemented by determining the values in fluoroalcohol-containing solvents. The data sets are then correlated using the extended Grunwald-Winstein equation. For both substrates, it is found that a single correlation controls the influence of solvent over the full range of solvent composition. The sensitivities to solvent nucleophilicity and solvent ionizing power are compared to values available for other substrates. Three of these previous studies are upgraded by the incorporation of additional specific rate values from the recent literature. With a methyl, isopropyl, benzyl, aromatic or heteroaromatic group as the R group of RSO2Cl, a concerted SN2 mechanism is proposed for the solvolysis. Full article
(This article belongs to the Special Issue Grunwald-Winstein Equations – 60 Years & Counting)

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