Free radical addition to olefins. Part 10. - Addition of dibromofluoromethyl radicals to fluoroethylenes

John P. Sloan; John M. Tedder; John C. Walton

doi:10.1039/F19736901143

Free radical addition to olefins. Part 10. - Addition of dibromofluoromethyl radicals to fluoroethylenes

John P. Sloan, John M. Tedder, John C. Walton^*

^*Corresponding author for this work

Research output: Contribution to journal › Article › peer-review

Abstract

The gas phase photochemical addition of tribromofluoromethane to a series of fluoro-olefins has been studied over a range of temperatures. The products included those from addition of dibromofluoromethyl radicals to the olefins as well as cyclopropanes from addition of bromofluorocarbene. The mechanism of the reaction is discussed, and Arrhenius parameters for the addition of dibromofluoromethyl radicals are derived from competitive experiments with each olefin and ethylene. CFBr₂·+E^k2→CFBr ₂E· E_2-E₂(C₂H₄) log A₂ - log A₂(C₂H₄) CH ₂=CHF 0.32 -0.38 CH₂=CF₂ 0.80 - 0.46 CHF=CH₂ 2.33 - 0.41 CHF=CF₂ 4.31 1.15 CF ₂=CH₂ 8.1 1.52 CF₂=CHF 5.6 1.40 Activation energies, relative to ethylene, in kcal mol^-1, A-factors in l. mol^-1 s^-1 (1 cal = 4.184 J).

Original language	English
Pages (from-to)	1143-1152
Number of pages	10
Journal	Journal of the Chemical Society, Faraday Transactions 1: Physical Chemistry in Condensed Phases
Volume	69
DOIs	https://doi.org/10.1039/F19736901143
Publication status	Published - 1 Dec 1973

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title = "Free radical addition to olefins. Part 10. - Addition of dibromofluoromethyl radicals to fluoroethylenes",

abstract = "The gas phase photochemical addition of tribromofluoromethane to a series of fluoro-olefins has been studied over a range of temperatures. The products included those from addition of dibromofluoromethyl radicals to the olefins as well as cyclopropanes from addition of bromofluorocarbene. The mechanism of the reaction is discussed, and Arrhenius parameters for the addition of dibromofluoromethyl radicals are derived from competitive experiments with each olefin and ethylene. CFBr2·+Ek2→CFBr 2E· E2-E2(C2H4) log A2 - log A2(C2H4) CH 2=CHF 0.32 -0.38 CH2=CF2 0.80 - 0.46 CHF=CH2 2.33 - 0.41 CHF=CF2 4.31 1.15 CF 2=CH2 8.1 1.52 CF2=CHF 5.6 1.40 Activation energies, relative to ethylene, in kcal mol-1, A-factors in l. mol-1 s-1 (1 cal = 4.184 J).",

author = "Sloan, \{John P.\} and Tedder, \{John M.\} and Walton, \{John C.\}",

year = "1973",

month = dec,

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doi = "10.1039/F19736901143",

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volume = "69",

pages = "1143--1152",

journal = "Journal of the Chemical Society, Faraday Transactions 1: Physical Chemistry in Condensed Phases",

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T1 - Free radical addition to olefins. Part 10. - Addition of dibromofluoromethyl radicals to fluoroethylenes

AU - Sloan, John P.

AU - Tedder, John M.

AU - Walton, John C.

PY - 1973/12/1

Y1 - 1973/12/1

N2 - The gas phase photochemical addition of tribromofluoromethane to a series of fluoro-olefins has been studied over a range of temperatures. The products included those from addition of dibromofluoromethyl radicals to the olefins as well as cyclopropanes from addition of bromofluorocarbene. The mechanism of the reaction is discussed, and Arrhenius parameters for the addition of dibromofluoromethyl radicals are derived from competitive experiments with each olefin and ethylene. CFBr2·+Ek2→CFBr 2E· E2-E2(C2H4) log A2 - log A2(C2H4) CH 2=CHF 0.32 -0.38 CH2=CF2 0.80 - 0.46 CHF=CH2 2.33 - 0.41 CHF=CF2 4.31 1.15 CF 2=CH2 8.1 1.52 CF2=CHF 5.6 1.40 Activation energies, relative to ethylene, in kcal mol-1, A-factors in l. mol-1 s-1 (1 cal = 4.184 J).

AB - The gas phase photochemical addition of tribromofluoromethane to a series of fluoro-olefins has been studied over a range of temperatures. The products included those from addition of dibromofluoromethyl radicals to the olefins as well as cyclopropanes from addition of bromofluorocarbene. The mechanism of the reaction is discussed, and Arrhenius parameters for the addition of dibromofluoromethyl radicals are derived from competitive experiments with each olefin and ethylene. CFBr2·+Ek2→CFBr 2E· E2-E2(C2H4) log A2 - log A2(C2H4) CH 2=CHF 0.32 -0.38 CH2=CF2 0.80 - 0.46 CHF=CH2 2.33 - 0.41 CHF=CF2 4.31 1.15 CF 2=CH2 8.1 1.52 CF2=CHF 5.6 1.40 Activation energies, relative to ethylene, in kcal mol-1, A-factors in l. mol-1 s-1 (1 cal = 4.184 J).

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DO - 10.1039/F19736901143

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SN - 0300-9599

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JO - Journal of the Chemical Society, Faraday Transactions 1: Physical Chemistry in Condensed Phases

JF - Journal of the Chemical Society, Faraday Transactions 1: Physical Chemistry in Condensed Phases

ER -

Free radical addition to olefins. Part 10. - Addition of dibromofluoromethyl radicals to fluoroethylenes

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