Correlations of the Specific Rates of Solvolysis of Aromatic Carbamoyl Chlorides, Chloroformates, Chlorothionoformates, and Chlorodithioformates Revisited

doi:10.3390/i8040346

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Int. J. Mol. Sci. 2007, 8(4), 346-362; doi:10.3390/i8040346

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Correlations of the Specific Rates of Solvolysis of Aromatic Carbamoyl Chlorides, Chloroformates, Chlorothionoformates, and Chlorodithioformates Revisited

Dennis N. Kevill ¹^,* , Fumie Koyoshi ² and Malcolm J. D’Souza ²^,*

¹ Department of Chemistry and Biochemistry, Northern Illinois University, DeKalb, Illinois 60115-2862, USA ² Department of Chemistry, Wesley College, 120 N. State Street, Dover, Delaware 19901-3875, USA

* Authors to whom correspondence should be addressed.

Received: 22 March 2007 / Accepted: 24 April 2007 / Published: 30 April 2007

(This article belongs to the Section Physical Chemistry, Theoretical and Computational Chemistry)

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Abstract: Additional specific rates of solvolysis are determined for phenyl chloroformate.These values are combined with literature values to give a total of 49 data points, which areused within simple and extended Grunwald-Winstein treatments. Literature values are alsobrought together to allow treatments in more solvents than previously for three N-aryl-N-methylcarbamoyl chlorides, phenyl chlorothionoformate, phenyl chlorodithioformate, andN,N-diphenylcarbamoyl chloride. For the last two listed, moderately strong evidence for ameaningful inclusion of a term governed by the aromatic ring parameter (I) was indicated.No evidence was found requiring inclusion of this parameter for ionization reactions withonly one aromatic ring on the nitrogen of carbamoyl chlorides or for the solvolyses of thechloroformate or chlorothionoformate proceeding by an addition-elimination (association-dissociation) mechanism.

Keywords: solvolysis; carbamoyl chlorides; chloroformates; chlorothionoformates; chlorodithioformates; Grunwald-Winstein equation; aromatic ring parameter (I).

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MDPI and ACS Style

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.

AMA Style

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. International Journal of Molecular Sciences. 2007; 8(4):346-362.

Chicago/Turabian Style

Kevill, Dennis N.; Koyoshi, Fumie; D’Souza, Malcolm J. 2007. "Correlations of the Specific Rates of Solvolysis of Aromatic Carbamoyl Chlorides, Chloroformates, Chlorothionoformates, and Chlorodithioformates Revisited." Int. J. Mol. Sci. 8, no. 4: 346-362.

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