- Intramolecular Reactions of o-Alkoxy- and o-Alkylthio-benzyl Radicals
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We report new gas-phase reactions of o-substituted benzyl radicals produced by flash vacuum pyrolysis of 2,3-dihydro-1,3,2-benzoxazaphosph(V)oles (4)-(6), dibenzyl sulphone (8), and dibenzyl oxalates (9)-(11).Both o-ethoxy- and o-methoxy-benzyl radicals rearrange to o-tolualdehyde via intramolecular hydrogen transfer, as shown by experiments using 2-methoxybenzyl radicals. o-Methylthiobenzyl radicals do not give the corresponding thioaldehyde, but produce a mixture of benzocyclobutene and isomeric dihydrobenzothiophens by novel rearrangement reactions. o-Ethylthio- and o-propylthio-benzyl radicals give o-methylstyrene and o-propenyltoluenes respectively as major products.
- Cadogan, J. I. G.,Husband, James B.,McNab Hamish
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p. 697 - 702
(2007/10/02)
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