- RATE CONSTANTS FOR THE FORMATION OF OXIRANES BY γ-SCISSION IN SECONDARY β-t-BUTYLPEROXYALKYL RADICALS
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Rate constants for the title reactions have been determined from the ratios of oxirane to peroxide obtained in the reductons of β-bromoalkyl t-butyl peroxides with tributyltin hydride.At ca. 298 K the rate constants are 0.32, 1.12, 1.96, 2.0 and 6.2E6 s-1 for β-t-butylperoxy derivatives of trinorbornan-2-yl (exo) cyclohexyl, 1-methylpropyl , cyclopentyl and 1-ethylbutyl, respectively.The results are discussed in terms of steric and electronic effects in the transition state leading to ring closure of the radicals.
- Bloodworth A. J.,Courtneidge, J. L.,Davies, Alwyn G.
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p. 523 - 528
(2007/10/02)
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