ESR spin-trap study of the radicals present during the thermolysis of some bis(tert-alkylperoxy)alkanes and bis(tert-alkylperoxy)cycloalkanes.

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https://doi.org/10.1002/(SICI)1097-458X(200003)38:3<183::AID-MRC614>3.0.CO;2-L
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ESR spectroscopy, radicals, reaction mechanisms, peroxides, spin trap

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ESR spin-trap study of the radicals present during the thermolysis of some bis(tert-alkylperoxy)alkanes and bis(tert-alkylperoxy)cycloalkanes. / Mekarbane, Pierre G.; Tabner, Brian J.
In: Magnetic Resonance in Chemistry, Vol. 38, No. 3, 03.2000, p. 183-191.

Research output: Contribution to Journal/Magazine › Journal article › peer-review

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@article{736bb215f68448eda6a9bea702c66189,

title = "ESR spin-trap study of the radicals present during the thermolysis of some bis(tert-alkylperoxy)alkanes and bis(tert-alkylperoxy)cycloalkanes.",

abstract = "The thermolysis of three bis(tert-alkylperoxy)alkanes and two 1,1-bis(tert-alkylperoxy)cycloalkanes was undertaken at various temperatures between 333 and 383 K and the radicals generated trapped employing DMPO, DEPMPO, PBN-d14 and TTBNB. The appropriate tert-alkoxyl radical was trapped during the thermolysis of all five peroxides and underwent -scission to give the appropriate alkyl radical and ketone. Although the appropriate sister O-centred 1-(tert-alkylperoxy)alkoxyl radicals (3) were not trapped, adducts of the radicals derived from them via -scission were observed. The ethyl radical was trapped during the thermolysis of 2,2-bis(tert-butylperoxy)butane (1a) and the ethoxycarbonylmethyl radical during the thermolysis of both ethyl-3,3-bis(tert-butylperoxy)butyrate (1b) and ethyl 3,3-bis(tert-amylperoxy)butyrate (1c), thus establishing the thermolysis scheme for these bis(tert-alkylperoxy)alkanes. In the case of 1,1-bis(tert-butylperoxy)cyclohexane (2a) it has been established that the sister O-centred [1-(tert-butylperoxy)cyclohexyl]oxyl radical (6a) undergoes a rapid ring-opening reaction to give the 5-(tert-butylperoxycarbonyl)pentyl radical (7a).",

keywords = "ESR spectroscopy, radicals, reaction mechanisms, peroxides, spin trap",

author = "Mekarbane, {Pierre G.} and Tabner, {Brian J.}",

year = "2000",

month = mar,

doi = "10.1002/(SICI)1097-458X(200003)38:3<183::AID-MRC614>3.0.CO;2-L",

language = "English",

volume = "38",

pages = "183--191",

journal = "Magnetic Resonance in Chemistry",

issn = "0749-1581",

publisher = "John Wiley and Sons Ltd",

number = "3",

}

RIS

TY - JOUR

T1 - ESR spin-trap study of the radicals present during the thermolysis of some bis(tert-alkylperoxy)alkanes and bis(tert-alkylperoxy)cycloalkanes.

AU - Mekarbane, Pierre G.

AU - Tabner, Brian J.

PY - 2000/3

Y1 - 2000/3

N2 - The thermolysis of three bis(tert-alkylperoxy)alkanes and two 1,1-bis(tert-alkylperoxy)cycloalkanes was undertaken at various temperatures between 333 and 383 K and the radicals generated trapped employing DMPO, DEPMPO, PBN-d14 and TTBNB. The appropriate tert-alkoxyl radical was trapped during the thermolysis of all five peroxides and underwent -scission to give the appropriate alkyl radical and ketone. Although the appropriate sister O-centred 1-(tert-alkylperoxy)alkoxyl radicals (3) were not trapped, adducts of the radicals derived from them via -scission were observed. The ethyl radical was trapped during the thermolysis of 2,2-bis(tert-butylperoxy)butane (1a) and the ethoxycarbonylmethyl radical during the thermolysis of both ethyl-3,3-bis(tert-butylperoxy)butyrate (1b) and ethyl 3,3-bis(tert-amylperoxy)butyrate (1c), thus establishing the thermolysis scheme for these bis(tert-alkylperoxy)alkanes. In the case of 1,1-bis(tert-butylperoxy)cyclohexane (2a) it has been established that the sister O-centred [1-(tert-butylperoxy)cyclohexyl]oxyl radical (6a) undergoes a rapid ring-opening reaction to give the 5-(tert-butylperoxycarbonyl)pentyl radical (7a).

AB - The thermolysis of three bis(tert-alkylperoxy)alkanes and two 1,1-bis(tert-alkylperoxy)cycloalkanes was undertaken at various temperatures between 333 and 383 K and the radicals generated trapped employing DMPO, DEPMPO, PBN-d14 and TTBNB. The appropriate tert-alkoxyl radical was trapped during the thermolysis of all five peroxides and underwent -scission to give the appropriate alkyl radical and ketone. Although the appropriate sister O-centred 1-(tert-alkylperoxy)alkoxyl radicals (3) were not trapped, adducts of the radicals derived from them via -scission were observed. The ethyl radical was trapped during the thermolysis of 2,2-bis(tert-butylperoxy)butane (1a) and the ethoxycarbonylmethyl radical during the thermolysis of both ethyl-3,3-bis(tert-butylperoxy)butyrate (1b) and ethyl 3,3-bis(tert-amylperoxy)butyrate (1c), thus establishing the thermolysis scheme for these bis(tert-alkylperoxy)alkanes. In the case of 1,1-bis(tert-butylperoxy)cyclohexane (2a) it has been established that the sister O-centred [1-(tert-butylperoxy)cyclohexyl]oxyl radical (6a) undergoes a rapid ring-opening reaction to give the 5-(tert-butylperoxycarbonyl)pentyl radical (7a).

KW - ESR spectroscopy

KW - radicals

KW - reaction mechanisms

KW - peroxides

KW - spin trap

U2 - 10.1002/(SICI)1097-458X(200003)38:3<183::AID-MRC614>3.0.CO;2-L

DO - 10.1002/(SICI)1097-458X(200003)38:3<183::AID-MRC614>3.0.CO;2-L

M3 - Journal article

VL - 38

SP - 183

EP - 191

JO - Magnetic Resonance in Chemistry

JF - Magnetic Resonance in Chemistry

SN - 0749-1581

IS - 3

ER -

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