Electron spin resonance study of the fragmentation of some cyclic and acyclic dialkoxyalkyl radicals. The mechanism of 1,2-rearrangement of β-acyloxyalkyl radicals
- 1 January 1975
- journal article
- research article
- Published by Royal Society of Chemistry (RSC) in Journal of the Chemical Society, Perkin Transactions 2
- No. 1,p. 77-84
- https://doi.org/10.1039/p29750000077
Abstract
The di-t-butoxymethyl radical and a series of 1,3-dioxolanyl and 1,3-dioxanyl radicals have been generated and studied by e.s.r. spectroscopy in soulution. All of these radicals undergo β-scission under appropriate conditions, β-acyloxyalkyl radicals resulting from the 1,3-dioxolanyl radicals. The kinetics of β-scission of these dialkoxyalkyl radicals have been measured, and it is found that the di-t-butoxymethyl radical decomposes much more readily than the analogous cyclic 4,4,5,5-tetramethyldioxolanyl radical undergoes ring opening. The relevance of these results to the mechanism of vicinai rearrangement of β-acyloxyalkyl radicals is discussed. The rate constant for addition of the di-t-butoxymethyl radical to nitrosobutane is found to be about 106 l mil–1S–1 at 40° in benzene.Keywords
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