Effect of acetylene structure on the rates and products of addition of 4-chlorobenzenesulfenyl chloride

George H. Schmid, Agnieszka Modro, Frederick Lenz, Dennis G. Garratt, Keith Yates

Research output: Contribution to journalArticle

Abstract

The rates and products of addition of 4-chlorobenzenesulfenyl chloride to acetylene and 12 alkyl-substituted derivatives have been determined in 1,1,2,2-tetrachloroethane at 25°C. The effect of the alkyl groups on the rate of addition to 10 of the 13 alkynes can be correlated by means of the Taft equation: log k2 = -4.47Σσ* + 1.64. The three compounds that do not lie on the line contain tert -butyl substituents. Polar effects of the substituents on the rates are dominant and steric effects are important only for tert -butyl groups. The product regiochemistry, however, is determined by the steric bulk of the substituent. The results are consistent with a mechanism involving bridged thiirenium ion-like rate and product determining transition states.

Original languageEnglish (US)
Pages (from-to)2331-2336
Number of pages6
JournalJournal of Organic Chemistry
Volume41
Issue number13
StatePublished - 1976
Externally publishedYes

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Acetylene
Alkynes
Chlorides
Ions
Derivatives
1,1,2,2-tetrachloroethane

ASJC Scopus subject areas

  • Organic Chemistry

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Effect of acetylene structure on the rates and products of addition of 4-chlorobenzenesulfenyl chloride. / Schmid, George H.; Modro, Agnieszka; Lenz, Frederick; Garratt, Dennis G.; Yates, Keith.

In: Journal of Organic Chemistry, Vol. 41, No. 13, 1976, p. 2331-2336.

Research output: Contribution to journalArticle

Schmid, George H. ; Modro, Agnieszka ; Lenz, Frederick ; Garratt, Dennis G. ; Yates, Keith. / Effect of acetylene structure on the rates and products of addition of 4-chlorobenzenesulfenyl chloride. In: Journal of Organic Chemistry. 1976 ; Vol. 41, No. 13. pp. 2331-2336.
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AU - Yates, Keith

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