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The kinetics and mechanisms of the gas phase elimination of 4-(methylthio)-1-butyl acetate and 1-chloro-4-(methylthio)-butane

✍ Scribed by Gabriel Chuchani; Ignacio Martin; Rosa M. Dominguez

Publisher: John Wiley and Sons
Year: 1987
Tongue: English
Weight: 351 KB
Volume: 19
Category: Article
ISSN: 0538-8066
DOI: 10.1002/kin.550190802

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✦ Synopsis

The gas phase elimination of 4-(methylthio)-l-butyl acetate and l-chloro-4-(methy1thio)-butane has been investigated in a seasoned, static reaction vessel over the temperature range of 310dlO"C and the pressure range of 46-193 Torr. The presence of the inhibitors pmpene, cyclohexene, andior toluene had no effect on the rates. The reactions are homogeneous, unimolecular, and obey a first-order rate law. The rate coefficients are given by the following Arrhenius equations: for 4-(methylthiol-l-butyl acetate, log kl(s' '1 = (12.32 f 0.29) -(192.1 2 3.6) W/mo1/2.303RT; for 1-chloro-4imethylthiol-butane. log kits ') = (12.23 f 0.591 -(175.7 5 6.81 kJ/mo1/2.303RT.

The CH,S substituent in 1-chloro-4-~methylthiol-butane has been found to participate in the elimination reaction, where tetrahydrothiophene and methyl chloride formation may result from an intimate ion-pair type of mechanism. The yield of a cyclic product in gas phase reactions provides additional evidence of an intimate ion pair mechanism through neighboring group participation in gas phase elimination of special types of organic halides.

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