Oxidation Studies of Industrially Important Aliphatic and Cyclic Alcohols

Abstract

The oxidation of industrially important aliphatic and cyclic studies has been studied using inorganic and organic oxidants. The kinetic, thermodynamic and mechanistic aspects of the oxidation of alcohols have been investigated. Transition metal ions have been effectively used to oxidize alcohols to aldehydes/ketones.

Oxidation of alcohols is an industrially important reaction yielding several useful products. Organic oxidants have been routinely used to oxidize alcohols to carbonyl compounds but inorganic oxidants have rarely been used. Literature survey also shows that transition metal ions of the first series have been sparingly used to catalyze the oxidation of alcohols.

This chapter describes the first order kinetics of the oxidation of straight  chain and branched aliphatic alcohols and cyclic alcohols by a variety of inorganic and organic oxidizing agents - Ce(IV) in acidic medium and K₂S₂O₈ in acidic medium, N-Bromosuccinimide in alkaline medium and N-Chloro 4-methylbenzenesulphonamide, sodium salt  in alkaline medium. The dependence of the oxidation rate on alcohol and oxidant concentrations, ionic strength of reaction medium and temperature has been studied in detail. The thermodynamic activation parameters of the oxidation process have been determined from the variation of oxidation rate with temperature and interpreted in terms of the molecular dynamics of the oxidation process.

Suitable reaction mechanisms have been suggested for the oxidation of alcohols in the presence and absence of transition metal ions. For each series of alcohols under study, the sequence of oxidation rates has been explained on the basis of their steric, structural and isomeric factors, ring size and chain length. The sequence of catalytic efficiency of the transition metal ions has been determined for each series of alcohols under study and correlated with the theoretically expected sequence.