Welcome to LookChem.com Sign In|Join Free

Article Doi

Thermolyses of cis- and trans-2,2,3,4-Tetramethyloxetane

DOI: 10.1039/f19848000691

Source and publish data:

Journal of the Chemical Society, Faraday Transactions 1: Physical Chemistry in Condensed Phases p. 691 - 698 (1984)

Update date:2022-08-28

Topics:

Authors:

Hammonds, PaulHammonds, Paul

Holbrook, Kenneth A.Holbrook, Kenneth A.

Carless, Howard A. J.Carless, Howard A. J.

Read Full Text PDF DownLoad Join now for total 90,000,000 free articles

Article abstract of DOI:10.1039/f19848000691

The thermolyses of cis- and trans-2,2,3,4-tetramethyloxetane were studied at temperatures between 408.0 and 477.0 deg C and initial reactant pressures from 5.0 to 10.0 Torr.Both compounds undergo parallel unimolecular reactions producing either 2-methylbut-2-ene and acetaldehyde or but-2-ene and acetone .For the trans isomer the following rate expressions were found: log10(ka/s-1)=(14.50+/-0.35)-(237.0+/-4.18 kJ mol-1)/2.303 RT log10(kb/s-1)=(15.00+/-0.40)-(261.5+/-5.02 kJ mol-1)/2.303 RT.The ratio of cis-but-2-ene to trans-but-2-ene was 0.25+/-0.02.For the cis isomer the corresponding rate expressions are: log10(k'a/s-1)=(13.90+/-0.76)-(229.0+/-10.0 kJ mol-1)/2.303 RT log10(k'b/s-1)=(14.10+/-0.83)-(246.6+/-10.9 kJ mol-1)/2.303 RT.The ratio of cis-but-2-ene to trans-but-2-ene in this case was 3.45+/-0.30.All error limits are the 95 percent confidence limits.Comparison of the Arrhenius parameters with those for other oxetane decompositions and with thermochemical estimates make it unlikely that both paths procced via biradical intermediates.It is suggested that for both isomers the data are consistent with a biradical path for the production of but-2-ene but that the major path to 2-methylbut-2-ene is a concerted reaction involving a twisted activated complex.

View More

Products guided by the article

Product name:Polymethane

Cas No:27936-85-2

27936-85-2

R&D Labs maybe for 27936-85-2

Relevant to this article

Hot Product