Oxidation of aliphatic aldehydes by benzimidazolium fluorochromate in non aqueous medium – A kinetic and mechanistic study

The oxidation of seven aliphatic aldehydes by benzimidazolium fluorochromate (BIFC) in dimethyl sulphoxide (DMSO) leads to the formation of the corresponding carboxylic acids. The reaction is first order in BIFC. The Michaelis–Menten type kinetics was observed with respect to the aldehyde. The react...

Full description

Saved in:
Bibliographic Details
Published in:Arabian journal of chemistry 2017-05, Vol.10 (S2), p.S2115-S2123
Main Authors: Asghar, Basim H., Mansoor, S. Sheik, Mohamed Hussain, A., Saleem Malik, V., Aswin, K., Sudhan, S.P.N.
Format: Article
Language:English
Subjects:
Aliphatic aldehyde
Benzimidazolium fluorochromate
Kinetics
Oxidation
Solvent effect
Citations: Items that this one cites
Items that cite this one
Online Access:Get full text
Tags: Add Tag
No Tags, Be the first to tag this record!
Description
Summary:The oxidation of seven aliphatic aldehydes by benzimidazolium fluorochromate (BIFC) in dimethyl sulphoxide (DMSO) leads to the formation of the corresponding carboxylic acids. The reaction is first order in BIFC. The Michaelis–Menten type kinetics was observed with respect to the aldehyde. The reaction is catalysed by hydrogen ions. The hydrogen-ion dependence has the form: kobs=a+b[H+]. The oxidation of deuterated acetaldehyde, CH3CDO, exhibited a substantial primary kinetic isotope effect (kH/kD=6.05 at 303K). Oxidation of acetaldehyde has been studied in eighteen different organic solvents. Various thermodynamic parameters are discussed along with isokinetic temperature. The solvent effect has been analysed using multi parametric equations. A mechanism involving transfer of hydride ion has been suggested. The linear isokinetic correlation implies that all the aldehydes are oxidized by the same mechanism.
ISSN:1878-5352
1878-5379
DOI:10.1016/j.arabjc.2013.07.043