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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@article{06a8f7a31db142e3a9db8fa4c16747d6,

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.",

author = "David Laurie and Nonhebel, \{Derek C.\} and Suckling, \{Colin J.\} and Walton, \{John C.\}",

year = "1993",

month = jun,

day = "25",

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

language = "English",

volume = "49",

pages = "5869--5872",

journal = "Tetrahedron",

issn = "0040-4020",

publisher = "Elsevier",

number = "26",

}

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.

UR - https://www.scopus.com/pages/publications/0027322734

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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