139778-28-2Relevant articles and documents
Kinetics of peroxodisulphate oxidation of ortho-substituted N,N-dimethylanilines, and the mechanism of Boyland-Sims oxidation
Srinivasan, Chockalingam,Perumal, Subbu,Arumugam, Natesan
, p. 1855 - 1858 (1985)
The kinetics of oxidation of some ortho-substituted N,N-dimethylanilines by peroxodisulphate have been studied in 50percent (v/v) aqueous ethanol containing 0.025 mol/dm3 phosphate buffer (pH 7).The reaction is second-order overall, and first-order in each reactant.The rate is not influenced by the presence of free-radical inhibitor allyl acetate.An increase in the polarity of the medium enhances the rate.The reactivities of ortho-substituted anilines lie in the order o-H > Me ca.MeO > F > Br > Cl > NO2.Multiple regression analysis of the rate data reveals that the rate is susceptible to significant electronic and steric effects.All these observations are rationalised on the basis of attack of the oxidant at the ipso-position of the amine.Correlation analysis of reactivity data from the literature also indicates that the mechanism involves ipso-attack and not attack on nitrogen.
Substituent Effects in the Oxidation of N,N-Dimethylanilines by Peroxydisulphate
Srinivasan, C.,Perumal, S.,Arumugam, N.
, p. 160 - 161 (2007/10/02)
The kinetics of oxidation of meta- and para-substituted N,N-dimethylanilines by peroxydisulphate in 50percent aq. ethanol (v/v) using the phosphate buffer (pH 7) have been investigated at three temperatures.The reaction is accelerated by electron-releasing and retarded by electron-withdrawing substituents.An excellent correlation between logarithms of second order rate constants and ?(+) (ρ(+) = -0.765, r = 0.998) excludes the attack on the ortho-carbon atom and supports the idea of initial ipso attack by the peroxydisulphate ion.
