
Journal of the Chemical Society. Perkin transactions II p. 1377 - 1382 (1986)
Update date:2022-08-05
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Lundkvist, Gunilla
Jonsson, Ulf
Lindeke, Bjoern
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.
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