Issue 12, 1982

Electron spin resonance studies of the radicals formed from C-nitroso compounds and olefins. Part 2.—Reactions of fluoro-olefins with 2,4,6-trichloronitrosobenzene and with nitrosobenzene

Abstract

The dark reactions of a number of fluoro-olefins with 2,4,6-trichloronitrosobenzene and with nitrosobenzene have been investigated. The fluoro-olefins CF2CFCl, CF2CFBr, CF2CFI and CF2CCl2 gave free radicals, but none were detected with CF2CH2, CF2CFH, CF2CFCF3 or CFClCFCl. The temperature at which the reactions are allowed to occur is a critical factor in determining the type of radical produced: at least two radicals are formed for each olefin studied. A temperature-dependent e.s.r. spectrum was found for the reaction between CF2CFBr and nitrosobenzene in iso-octane: activation parameters for the interconversion process of the radical PhN([grphic omitted])CF2CFBr— about the CF2—N(O) bond were found to be 21.8 ± 1.0 kJ mol–1, 23.8 ± 1.1 kJ mol–1 and 6.6 ± 0.6 J mol–1 K–1 for the free energy, enthalpy and entropy, respectively, at 298 K.

Similarly, a temperature-dependent spectrum was detected from the reaction of CF2CFBr with 2,4,6-trichloronitrosobenzene in CFCl3: the slow limit could not be reached but the enthalpy of activation for interconversion of the radical ArN(O)CF2CFBr— was estimated to be 21 ± 5 kJ mol–1.

Article information

Article type
Paper

J. Chem. Soc., Faraday Trans. 1, 1982,78, 3499-3508

Electron spin resonance studies of the radicals formed from C-nitroso compounds and olefins. Part 2.—Reactions of fluoro-olefins with 2,4,6-trichloronitrosobenzene and with nitrosobenzene

L. H. Sutcliffe and A. Zilnyk, J. Chem. Soc., Faraday Trans. 1, 1982, 78, 3499 DOI: 10.1039/F19827803499

To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.

Spotlight

Advertisements