29791-12-6Relevant articles and documents
Stefani et al.
, p. 4732,4734 (1961)
Montague
, p. 513 (1973)
Radical-Stabilization-Energy - the MMEVBH Force Field
Roth, Wolfgang R.,Staemmler, Volker,Neumann, Martin,Schmuck, Carsten
, p. 1061 - 1118 (2007/10/02)
Making use of the VB method of Malrieu et al. a force field has been developed, which allows to calculate heats of formation of hydrocarbons (conjugated and non-conjugated olefins, radicals and diradicals) with high accuracy.With this method radical stabilization energies (RSE) for a great number of delocalized radicals are calculated and compared with experimental values, derived from shock-tube measurements of dissociation energies or from rotational barriers of substituted olefins.A detailed analysis of the RSE with respect to structure, substituents, strain, and aromaticity is presented. - Key Words: Resonance energy / Heats of formation / Single pulse shock tube / Intrisic rotational barrier
The Reactions of t-Butoxyl with Unsaturated Hydrocarbons: Structure and Reactivity of Allylic Radicals
Cuthbertson, Matthew J.,Rizzardo, Ezio,Solomon, David H.
, p. 1957 - 1973 (2007/10/02)
A radical trapping technique employing 1,1,3,3-tetramethylisoindolin-2-yloxyl (1) as scavenger has been used to study the reactions of t-butoxy radicals with propene, 2-methylpropene, but-1-ene, (E)- and (Z)-but-2-ene, 3-methylbut-1-ene, buta-1,3-diene and 2-methylbuta-1,3-diene.Relative rates of double bond addition and of allylic hydrogen abstraction have been measured and are discussed, as are the relative stabilities of the products formed.The allylic radicals generated in these systems react with (1) mainly by coupling at the more substituted terminus of the radical ? system.Substituent effects on this regioselectivity may be explained in terms of the electrophilicity of (1).