Work

A thermal [1,3] sigmatropic rearrangement: thermolysis of 2,2-bis(ethylthio)-3,3-dimethyl-4-pentenal

Year: 1981

Type: article

Abstract: 2,2-Bis(ethylthio)-3,3-dimethyl-4-pentenal was found to quantitatively isomerize to 2,2-bis(ethylthio)-5-methyl-4-hexenal over a wide temperature range (130–170 °C). This rearrangement can formally be regarded as a [1,3] sigmatropic shift. The reaction, which could be conveniently monitored by 1Hmr spectroscopy, was found to obey first order kinetics. The substantial positive entropy of activation (+ 61.5 J deg−1 mol−1) for the reaction and the negligible solvent effect (decane vs. DMF) are both consistent with a proposed diradical pathway.

Source: Canadian Journal of Chemistry

DOI: 10.1139/v81-455

Authors: Gordon S. Bates, S. Ramaswamy

Institutions: University of British Columbia, National Research Council Canada

Language: English

Topic: Photolysis and Reactive Intermediates

Subfield: Physical and Theoretical Chemistry

Field: Chemistry

Domain: Physical Sciences

Open Access status: bronze

Funder: Natural Sciences and Engineering Research Council of Canada

OpenAlex ID: W2073680201

FWCI: 0.358

Cites: 2

Cited by: 6

Related to: 10