52497-67-3Relevant academic research and scientific papers
Kinetic studies of the reaction of some nitrosoalkanes with nitrogen dioxide
Gowenlock, Brian G.,King, Boyd,Pfab, Josef,Witanowski, Michal
, p. 483 - 485 (2007/10/03)
The rates of the oxidation of some nitrosoalkanes (CH3)2C(CH2X)NO by nitrogen dioxide in carbon tetrachloride have been studied by stopped-flow techniques, and have been found to exhibit second order kinetics. Arrhenius parameters have been determined for the cases of X = H, CH3, C(CH3)3, C6H5, NO2, Cl and OCOCH3. Electron withdrawing substituents are found to decrease significantly the rates, which are generally much faster than the corresponding oxidation of nitrosoarenes. The results obtained are discussed with reference to the Hammett σ constants of the substituents X, and the atomic charges at the nitrogen atom as given by the TNDO/2 method, the geometries of the molecules having been optimised by the PM3 semi-empirical method.
Decomposition Rates of Some trans-2-Nitroso-1-phenylethane Dimers in Solution
Lundkvist, Gunilla,Jonsson, Ulf,Lindeke, Bjoern
, p. 1377 - 1382 (2007/10/02)
The rate of decomposition of some trans-α-alkyl-substituted 2-nitroso-1-phenylethane dimers including one deuterium-substituted analogue, has been measured spectrophotometrically in the temperature range 15-60 deg C in ethanol, ethanol-water, cyclohexane, carbon tetrachloride, and chloroform.From studies in ethanol the rate constant of monomer formation, k1, the Arrhenius parameters, and the heat and entropy of activation were evaluated.The observed rate constant, kobs, evaluated from a first-order plot of the decomposition of the secondary C-nitroso dimers decreased with increasing initial concentrations and with increasing size of the α-alkyl substituent.C-Nitroso dimers with one α-hydrogen decomposed up to 1 200 times faster in ethanol than in non-polar solvents.The decomposition rate of one dimer without α-hydrogens was comparatively independent of the solvent used.However, the addition of water to the ethanol solutions had a stabilizing effect on both types of dimers.The isotope effect, kH/kD, was shown to be 2-5 on k1, and 3-5 on kobs for the dimer of 2-nitroso-1-phenylpropane.
Oxidation of Hydroxylamine Derivatives. VI. Anodic Oxidation of N-Alkyl-β-hydroxyhydroxylamines in Aqueous Buffer Solution
Ozaki, Shigeko,Nishiguchi, Susumu,Masui, Masaichiro
, p. 2609 - 2616 (2007/10/02)
Anodic oxidation of N-alkylhydroxylamines with and without a β-hydroxy group was studied by cyclic voltammetry and controlled potential electrolysis in aqueous buffer solution of pH 8.8.The hydroxylamines with a β-hydroxy group were oxidized initially to the corresponding nitroxides and gave the final products via two routes; i) cleavage of the (α)C-(β)C bond to give aldehydes and oximes, and ii) disproportionation of the nitroxides to form the nitroso compounds.The hydroxylamines without a β-hydroxy group did not undergo cleavage of the (α)C-(β)C bond and gave nitroso compounds.Substituents on the α and β carbons affected the product distribution.When a phenyl group or two methyl groups were present on the (β)C, or one methyl group was present on both (α)C and (β)C, (α)C-(β)C bond cleavage was predominant. Keywords - N-alkyl-β-hydroxyhydroxylamine; anodic oxidation; C-C bond fission; C-nitroso compound; aldehyde; oxime; azoxy compound
