Ring opening of oxiranylmethyl and 3-methyl-3-oxetanylmethyl radicals

David Laurie; Derek C. Nonhebel; Colin J. Suckling; John C. Walton

doi:10.1016/S0040-4020(01)87953-9

Ring opening of oxiranylmethyl and 3-methyl-3-oxetanylmethyl radicals

David Laurie^*, Derek C. Nonhebel, Colin J. Suckling, John C. Walton

^*Corresponding author for this work

School of Chemistry

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

Abstract

Oxiranylmethyl and 3-methyl-3-oxetanylmethyl radicals were generated from the corresponding bromides and their rearrangements to allyloxyl and 2-methylprop-2-enyloxymethyl radicals respectively, were studied by kinetic EPR spectroscopy. The former radical was shown to ring open with a rate constant o≫ 4 x 10⁸ s^-1 at 25°C. The following kinetic parameters were measured for ring opening of the latter radical: k(25°C) = 8.9 x 10² s^-1, log[A/s^-1] = 13.97, E/kJ mol^-1 = 63.3. Comparison of this data with that of related radicals supported the proposal that the transition state for β-scission of three-membered and four-membered cycloalkylmethyl radicals has dipolar character.

Original language	English
Pages (from-to)	5869-5872
Number of pages	4
Journal	Tetrahedron
Volume	49
Issue number	26
DOIs	https://doi.org/10.1016/S0040-4020(01)87953-9
Publication status	Published - 25 Jun 1993

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10.1016/S0040-4020(01)87953-9

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title = "Ring opening of oxiranylmethyl and 3-methyl-3-oxetanylmethyl radicals",

abstract = "Oxiranylmethyl and 3-methyl-3-oxetanylmethyl radicals were generated from the corresponding bromides and their rearrangements to allyloxyl and 2-methylprop-2-enyloxymethyl radicals respectively, were studied by kinetic EPR spectroscopy. The former radical was shown to ring open with a rate constant o≫ 4 x 108 s-1 at 25°C. The following kinetic parameters were measured for ring opening of the latter radical: k(25°C) = 8.9 x 102 s-1, log[A/s-1] = 13.97, E/kJ mol-1 = 63.3. Comparison of this data with that of related radicals supported the proposal that the transition state for β-scission of three-membered and four-membered cycloalkylmethyl radicals has dipolar character.",

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year = "1993",

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doi = "10.1016/S0040-4020(01)87953-9",

language = "English",

volume = "49",

pages = "5869--5872",

journal = "Tetrahedron",

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TY - JOUR

T1 - Ring opening of oxiranylmethyl and 3-methyl-3-oxetanylmethyl radicals

AU - Laurie, David

AU - Nonhebel, Derek C.

AU - Suckling, Colin J.

AU - Walton, John C.

PY - 1993/6/25

Y1 - 1993/6/25

N2 - Oxiranylmethyl and 3-methyl-3-oxetanylmethyl radicals were generated from the corresponding bromides and their rearrangements to allyloxyl and 2-methylprop-2-enyloxymethyl radicals respectively, were studied by kinetic EPR spectroscopy. The former radical was shown to ring open with a rate constant o≫ 4 x 108 s-1 at 25°C. The following kinetic parameters were measured for ring opening of the latter radical: k(25°C) = 8.9 x 102 s-1, log[A/s-1] = 13.97, E/kJ mol-1 = 63.3. Comparison of this data with that of related radicals supported the proposal that the transition state for β-scission of three-membered and four-membered cycloalkylmethyl radicals has dipolar character.

AB - Oxiranylmethyl and 3-methyl-3-oxetanylmethyl radicals were generated from the corresponding bromides and their rearrangements to allyloxyl and 2-methylprop-2-enyloxymethyl radicals respectively, were studied by kinetic EPR spectroscopy. The former radical was shown to ring open with a rate constant o≫ 4 x 108 s-1 at 25°C. The following kinetic parameters were measured for ring opening of the latter radical: k(25°C) = 8.9 x 102 s-1, log[A/s-1] = 13.97, E/kJ mol-1 = 63.3. Comparison of this data with that of related radicals supported the proposal that the transition state for β-scission of three-membered and four-membered cycloalkylmethyl radicals has dipolar character.

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U2 - 10.1016/S0040-4020(01)87953-9

DO - 10.1016/S0040-4020(01)87953-9

M3 - Article

AN - SCOPUS:0027322734

SN - 0040-4020

VL - 49

SP - 5869

EP - 5872

JO - Tetrahedron

JF - Tetrahedron

IS - 26

ER -

Ring opening of oxiranylmethyl and 3-methyl-3-oxetanylmethyl radicals

Abstract

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