Isomerization of n‐hexyl and s‐octyl radicals by 1,5 and 1,4 intramolecular hydrogen atom transfer reactions

S. Dóbé, T. Bérces, F. Réti, F. Márta

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Abstract

n‐Hexyl and s‐octyl radical isomerizations by intramolecular hydrogen atom shift have been studied in the presence of high methyl radical concentration where isomerized alkyl radicals reacted predominantly by combination and disproportionation reactions with methyl radicals. By assuming the rate coefficient of 1‐hexyl radical recombination to be equal to that of ethyl self‐combination, the rate coefficient of log(k1/s−1) = (9.5 ± 0.3) – (11.6 ± 0.3) kcal mol−1/RT ln 10 has been derived for the 6sp isomerization of n‐hexyl radicals, 1‐hexyl → 2‐hexyl (1). Investigation of s‐octyl radical isomerization was complicated by fast interconversion between 3‐octyl, 2‐octyl, and 4‐octyl radicals. Use of the methyl trapping technique and systematic variation of methyl radical concentration made possible the determination of log(k2/s−1) = (9.4 ± 0.7) − (11.2 ± 1.0) kcal mol−1/RT ln 10 for the 6ss isomerization of 3‐octyl and the estimation of log(k3/s−1) = 10.5–17 kcal mol−1/RT ln 10 for the 5ss isomerization of 2‐octyl radicals, where 3‐octyl → 2‐octyl (2), and 2‐octyl → 4‐octyl (3).

Original languageEnglish
Pages (from-to)895-921
Number of pages27
JournalInternational Journal of Chemical Kinetics
Volume19
Issue number10
DOIs
Publication statusPublished - 1987

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Isomerization
isomerization
Hydrogen
hydrogen atoms
Atoms
Genetic Recombination
methyl radical
coefficients
trapping
shift

ASJC Scopus subject areas

  • Biochemistry
  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry

Cite this

Isomerization of n‐hexyl and s‐octyl radicals by 1,5 and 1,4 intramolecular hydrogen atom transfer reactions. / Dóbé, S.; Bérces, T.; Réti, F.; Márta, F.

In: International Journal of Chemical Kinetics, Vol. 19, No. 10, 1987, p. 895-921.

Research output: Contribution to journalArticle

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abstract = "n‐Hexyl and s‐octyl radical isomerizations by intramolecular hydrogen atom shift have been studied in the presence of high methyl radical concentration where isomerized alkyl radicals reacted predominantly by combination and disproportionation reactions with methyl radicals. By assuming the rate coefficient of 1‐hexyl radical recombination to be equal to that of ethyl self‐combination, the rate coefficient of log(k1/s−1) = (9.5 ± 0.3) – (11.6 ± 0.3) kcal mol−1/RT ln 10 has been derived for the 6sp isomerization of n‐hexyl radicals, 1‐hexyl → 2‐hexyl (1). Investigation of s‐octyl radical isomerization was complicated by fast interconversion between 3‐octyl, 2‐octyl, and 4‐octyl radicals. Use of the methyl trapping technique and systematic variation of methyl radical concentration made possible the determination of log(k2/s−1) = (9.4 ± 0.7) − (11.2 ± 1.0) kcal mol−1/RT ln 10 for the 6ss isomerization of 3‐octyl and the estimation of log(k3/s−1) = 10.5–17 kcal mol−1/RT ln 10 for the 5ss isomerization of 2‐octyl radicals, where 3‐octyl → 2‐octyl (2), and 2‐octyl → 4‐octyl (3).",
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AU - Márta, F.

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