Kinetics and mechanism of oxidation of n-butylamine and 1,3-propanediamine by potassium ferrate

Abstract

KEYWORDSThe kinetics of oxidation of n-butylamine and 1,3-propanediamine by home-made potassium ferrate(VI) at different conditions has been studied spectrophotometrically in the temperature range of 283.2-298.2 K. The results show first order dependence on potassium ferrate (VI) and on each reductant. The observed rate constant (kobs) decreases with the increase of [OH -], and the reaction rate has a negative fraction order with respect to [OH -]. A plausible mechanism is proposed and the rate equations derived from the mechanism was shown to fit all the experimental results. The rate constants of the rate-determining step and the thermodynamic activation parameters are calculated.

Oxidation and Reduction

“…A similar synthesis of 1,1 -binaphthyl-2,2 -diamines from 2-naphthylamines was also described. 126 The alkaline Fe(VI) oxidations of 2-methoxy-and 2-ethoxy-ethanol 127 and isobutylamine and 1,4-butanediamine 128 were first order in Fe(VI) and substrates. In the case of alcohol k obs decreased with increasing [OH − ], there being a negative fractionalorder dependence in [OH − ] in the case of amines.…”

“…274 Cinnamyl cinnamate derivatives were obtained in good to excellent yields by esterification of α,β-unsaturated aldehydes, including aromatic aldehydes, with cinnamyl bromides in the presence of DBU, K 2 CO 3 , THF, and t-BuOH using either atmospheric O 2 or MnO 2 as the oxidant and N-heterocyclic carbene (NHC) as the catalyst. The use of 18 275 The synthesis of isoindolinones (128) from N-tosylbenzamides (129) and t-butyl acrylate was achieved in high yields using O 2 as oxidant and Pd(OAc) 2 as catalyst in the presence of 4,7-diphenyl-1,10-phenanthroline and toluene. Aliphatic alkenes with electron-rich and electron-deficient alkenes or conjugated alkenes could also be used.…”