87671-71-4Relevant academic research and scientific papers
Intramolecular Reactions of o-Alkoxy- and o-Alkylthio-benzyl Radicals
Cadogan, J. I. G.,Husband, James B.,McNab Hamish
, p. 697 - 702 (2007/10/02)
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.
The Reactivity of Organophosphorus Compounds. Part 35. Pyrolysis of 3-Aryl- and 3-Alkyl-2,3-dihydro-1,3,2-benzoxazaphosph(V)oles
Cadogan, J. I. G.,Husband, James B.,McNab, Hamish
, p. 1489 - 1495 (2007/10/02)
Pyrolysis of 2,2-diphenyl-2-methoxy derivatives of the title compounds in the gas phase gives phosphinates or phosphinamidates derived from the substrate by formal loss of methylene.Control experiments show that the reaction involves radical cleavage initiated by rupture of the oxazaphosph(V)ole ring.Pyrolysis of 3-aryl-2,2-dimethoxy-2-phenyl derivatives of the title compounds under similar conditions results in the formation of 3-aryl-2,3-dihydro-2-oxo-2-phenyl-1,3,2-benzoxazaphospholes.No significant products could be isolated from 2,2,2-trimethoxy derivatives, though vigorous conditions were required for their complete breakdown.The pyrolysis of the corresponding 2,2-diphenyl-2-ethoxy, 2,2-diethoxy-2-phenyl, and 2,2,2-triethoxy compounds gave higher yields of similar products, possibly via a six-centre concerted elimination.
