102617-52-7Relevant academic research and scientific papers
Investigations on the Selectivity of the β-Scission of Alkyl-Radicals, II - Selectivity of the β-Fragmentation of α-(Methoxycarbonyl)alkyl Radicals
Metzger, Juergen O.,Klenke, Kurt
, p. 875 - 879 (2007/10/02)
The rate of β-scission of α-(methoxycarbonyl)alkyl radicals 3 and 9, generated by addition of cycloalkyl radicals to appropriate methyl 2-methylenealkanoates 1 and methyl (E)-2-alkenoates 8, resp., has been measured relative to the hydrogen transfer from cycloalkanes.The rate of β-scission increases with increasing stability of the leaving radical R*.Polar effects reversing the stability sequence have also been observed, e.g. the more stable (methoxycarbonyl)methyl radical leaves more slowly than a less stable secondary alkyl radical.
Thermal Addition of Alkanes to Alkenes, II. Addition of Cyclohexane to Acrylate in a Free Radical Chain Reaction
Hartmanns, Joerg,Klenke, Kurt,Metzger, Juergen O.
, p. 488 - 499 (2007/10/02)
Alkanes can be added to alkenes in a thermally initiated reaction.Kinetic studies on the addition of cyclohexane to phenyl acrylate clearly revealed that a radical chain reaction is involved.The results can only be satisfactorily explained in terms of a symproportionation of the alkane and the alkene to give two alkyl radicals.This initiation reaction is very slow (220C: ki 610-13lmol-1s-1, t1/2 3104a).Kinetic isotopic effects of the initiation reaction and of the H-transfer reaction from cyclohexane to alkyl radical 6b have been measured. β-Scission of the intermediate adduct radicals has been measured as well.Quite normal reaction rates are observed near the critical point of cyclohexane.
