21228-90-0Relevant articles and documents
Oxidation and Oxidative Carbonylation of Methane and Ethane by Hexaoxo-μ-peroxodisulfate(2-) Ion in Aqueous Medium. A Model for Alkane Oxidation through the Hydrogen-atom Abstraction Pathway
Lin, Minren,Sen, Ayusman
, p. 892 - 893 (2007/10/02)
In aqueous medium, at 105-115 deg C, SO4 radical-anion (generated from S2O82-) was found to abstract a hydrogen atom from methane and ethane to form the corresponding alkyl radicals which could be trapped efficiently by carbon monoxide, the resultant acyl radicals being ultimately converted into the homologous carboxylic acids.
Group Transfers III. Consequences of the Application of the Marcus Equation
Lewis, Edward S.
, p. 259 - 262 (2007/10/02)
The rates of many group transfers are well described by the Marcus equation.Alkyl transfers in the solvent sulfolane, the formal transfers of R+ from one nucleophile to another, fit almost within experimental error.In these fairly slow reactions the Marcus quadratic term is negligible.Neglect of this term leads to absence of Reactivity Selectivity principle correlations.It leads to a scale of nucleophilicities and one of methylating power.In contrast, many nonalkyl transfers have much lower intrinsic barriers, and neglect of the quadratic term is unjustifiable.For alkyl transfers there is no general correlation between rate and equilibrium constants.When closely related series, such as a Hammett variation in the leaving group or nucleophile are studied, there is generally a rate-equilibrium LFER.From the slope of this rate-equilibrium LFER, the charge, δ, on the transferring group is calculated.The variation in this charge, which is structurally plausible, gives a new perspective on the rates of SN2 reactions, including benzylic, and α-halocarbonyl systems.
