Termination reactions of C5-C12 cycloalkyl radicals and carbenes

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Abstract

Reactions of C5-C12 cycloalkyl radicals and carbenes produced during radiolysis, vacuum-u.v. photolysis, and decomposition of cycloalkanone p-tosylhydrazones were investigated. The disproportionation to combination ratios of radicals are ca. 1 and agree with the ratios of linear secondary radicals. The disproportionation of smaller cycloalkyl radicals yields cis-cycloalkenes and cycloalkanes; from C9 and C10 cis- and trans-cycloalkenes and cycloalkanes and from C11 and C 12 trans-cycloalkenes and cycloalkanes are produced. Both atoms of H2 given off in the elimination reaction from excited cycloalkane molecules originate from the same carbon atom and in this process carbenes are formed. Rearrangement of small (C6, C6) and large (C 11, C13) cycloalkylcarbenes in the solvent of the given cycloalkane occurs by 1,2-hydrogen migration. C7-C10 carbenes rearrange both by hydrogen atom migration and transannular insertion.

Original languageEnglish
Pages (from-to)1449-1451
Number of pages3
JournalJournal of the Chemical Society, Perkin Transactions 2
Issue number9
DOIs
Publication statusPublished - 1984

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Cycloparaffins
Atoms
Hydrogen
Radiolysis
carbene
Photolysis
Carbon
Vacuum
Decomposition
Molecules

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

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abstract = "Reactions of C5-C12 cycloalkyl radicals and carbenes produced during radiolysis, vacuum-u.v. photolysis, and decomposition of cycloalkanone p-tosylhydrazones were investigated. The disproportionation to combination ratios of radicals are ca. 1 and agree with the ratios of linear secondary radicals. The disproportionation of smaller cycloalkyl radicals yields cis-cycloalkenes and cycloalkanes; from C9 and C10 cis- and trans-cycloalkenes and cycloalkanes and from C11 and C 12 trans-cycloalkenes and cycloalkanes are produced. Both atoms of H2 given off in the elimination reaction from excited cycloalkane molecules originate from the same carbon atom and in this process carbenes are formed. Rearrangement of small (C6, C6) and large (C 11, C13) cycloalkylcarbenes in the solvent of the given cycloalkane occurs by 1,2-hydrogen migration. C7-C10 carbenes rearrange both by hydrogen atom migration and transannular insertion.",
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AU - Wojnárovits, László

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N2 - Reactions of C5-C12 cycloalkyl radicals and carbenes produced during radiolysis, vacuum-u.v. photolysis, and decomposition of cycloalkanone p-tosylhydrazones were investigated. The disproportionation to combination ratios of radicals are ca. 1 and agree with the ratios of linear secondary radicals. The disproportionation of smaller cycloalkyl radicals yields cis-cycloalkenes and cycloalkanes; from C9 and C10 cis- and trans-cycloalkenes and cycloalkanes and from C11 and C 12 trans-cycloalkenes and cycloalkanes are produced. Both atoms of H2 given off in the elimination reaction from excited cycloalkane molecules originate from the same carbon atom and in this process carbenes are formed. Rearrangement of small (C6, C6) and large (C 11, C13) cycloalkylcarbenes in the solvent of the given cycloalkane occurs by 1,2-hydrogen migration. C7-C10 carbenes rearrange both by hydrogen atom migration and transannular insertion.

AB - Reactions of C5-C12 cycloalkyl radicals and carbenes produced during radiolysis, vacuum-u.v. photolysis, and decomposition of cycloalkanone p-tosylhydrazones were investigated. The disproportionation to combination ratios of radicals are ca. 1 and agree with the ratios of linear secondary radicals. The disproportionation of smaller cycloalkyl radicals yields cis-cycloalkenes and cycloalkanes; from C9 and C10 cis- and trans-cycloalkenes and cycloalkanes and from C11 and C 12 trans-cycloalkenes and cycloalkanes are produced. Both atoms of H2 given off in the elimination reaction from excited cycloalkane molecules originate from the same carbon atom and in this process carbenes are formed. Rearrangement of small (C6, C6) and large (C 11, C13) cycloalkylcarbenes in the solvent of the given cycloalkane occurs by 1,2-hydrogen migration. C7-C10 carbenes rearrange both by hydrogen atom migration and transannular insertion.

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