Issue 8, 2006
From the journal:

Organic & Biomolecular Chemistry

Rate and product studies in the solvolyses of N,N-dimethylsulfamoyl and 2-propanesulfonyl chlorides

Dennis N. Kevill,*a   Byoung-Chun Park,a   Kyoung-Ho Park,a   Malcolm J. D'Souza,b   Lamia Yaakoubd,b   Stacey L. Mlynarskib  and  Jin Burm Kyongc  

* Corresponding authors

a Department of Chemistry and Biochemistry, Northern Illinois University, DeKalb, Illinois, USA

b Department of Chemistry, Wesley College, 120 N. State Street, Dover, Delaware, USA

c Department of Chemistry, Hanyang University, Ansan, Kyunggi-do, Korea

Abstract

Contrary to earlier suggestions of an SN1 pathway for solvolyses of N,N-dimethylsulfamoyl chloride (1), an extended Grunwald–Winstein equation treatment of the specific rates of solvolysis in 32 solvents shows an appreciable sensitivity towards changes in both solvent nucleophilicity and solvent ionizing power. The actual values are very similar to those obtained in earlier studies of the solvolyses of sulfonyl and phosphoryl chlorides, solvolyses which are believed to proceed by an SN2 pathway. The observation of similar selectivities in aqueous-alcohol solvents further supports this assignment. In a recent report, an addition–elimination (association–dissociation) pathway was proposed for solvolyses of 2-propanesulfonyl chloride (2). A severe multicollinearity problem has been removed by the addition of several specific rates of solvolysis in fluoroalcohol-containing solvents. The new analyses using the extended Grunwald–Winstein equation lead to sensitivities similar to those for 1 and the previously studied related compounds, and these solvolyses are also best described as following an SN2 pathway.

Graphical abstract: Rate and product studies in the solvolyses of N,N-dimethylsulfamoyl and 2-propanesulfonyl chlorides

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Article information

DOI
https://doi.org/10.1039/B518129A
Article type
Paper
Submitted
21 Dec 2005
Accepted
23 Feb 2006
First published
16 Mar 2006

Org. Biomol. Chem., 2006,4, 1580-1586

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Rate and product studies in the solvolyses of N,N-dimethylsulfamoyl and 2-propanesulfonyl chlorides

D. N. Kevill, B. Park, K. Park, M. J. D'Souza, L. Yaakoubd, S. L. Mlynarski and J. B. Kyong, Org. Biomol. Chem., 2006, 4, 1580 DOI: 10.1039/B518129A

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