S. Mittal, Vinita Sharma, K. Banerji
Jun 1, 1986
Citations
0
Influential Citations
3
Citations
Journal
International Journal of Chemical Kinetics
Abstract
The oxidation of primary alcohols by sodium N-chloroethylcarbamate in acid solution, results in the formation of corresponding aldehydes. The reaction is first order with respect to the oxidant and alcohol. The rate increases with an increase in acidity. The oxidation of α,α-dideuterioethanol exhibited a primary kinetic isotope, kH/kD = 2.11 at 298 K. The value of solvent isotope effect k(H2O)/k(D2O) = 2.23 at 298 K. Addition of ethyl carbamate does not affect the rate. (EtOC(OH)NHCl)+ has been postulated as the reactive species. Plots of (log k2 + Ho) against (Ho + log[H+]) are linear with the slope, ϕ, having values from 1.78–1.87. This suggested a proton abstraction by water in the rate-determining step. The rates of oxidation of alcohols bearing both electron-withdrawing and electron-donating groups are more than that of methanol. A concerted mechanism involving transfer of a hydride ion from the CH bond of the alcohol tothe oxidant and removal of a proton from the OH group by a water molecule has been proposed.