Kinetics and mechanism of the oxidation of primary alcohols by sodium N-chloroethylcarbamate

✍ Scribed by Suman Mittal; Vinita Sharma; Kalyan K. Banerji

• Publisher: John Wiley and Sons
• Year: 1986
• Tongue: English
• Weight: 423 KB
• Volume: 18
• Category: Article
• ISSN: 0538-8066
• DOI: 10.1002/kin.550180607

✦ Synopsis

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 ap-dideuterioethanol exhibited a primary kinetic isotope, kH/kD = 2.11 at 298 K. The value of solvent isotope effect k(H,O)/k(D,O) = 2.23 at 298 K. Addition of ethyl carbamate does not affect the rate. (EtOC(0H)NHCl)-has been postulated as the reactive species. Plots of (log k z + Ho) against (Ho + log[H+I) are linear with the slope, 6, 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 electronwithdrawing and electron-donating groups are more than that of methanol. A concerted mechanism involving transfer of a hydride ion from the C -H bond of the alcohol to the oxidant and removal of a proton from the 0 -H group by a water molecule has been proposed.