Kinetics and mechanism of oxidation of aliphatic aldehydes by pyridinium chlorochromate

Citation
S. Saraswat et al., Kinetics and mechanism of oxidation of aliphatic aldehydes by pyridinium chlorochromate, I J CHEM A, 40(6), 2001, pp. 583-587
Citations number
30
Language
INGLESE
art.tipo
Article
Categorie Soggetti
Chemistry
Journal title
INDIAN JOURNAL OF CHEMISTRY SECTION A-INORGANIC BIO-INORGANIC PHYSICAL THEORETICAL & ANALYTICAL CHEMISTRY
ISSN journal
0376-4710 → ACNP
Volume
40
Issue
6
Year of publication
2001
Pages
583 - 587
Database
ISI
SICI code
0376-4710(200106)40:6<583:KAMOOO>2.0.ZU;2-T
Abstract
Oxidation of six aliphatic aldehydes by pyridinium chlorochromate (PCC), in dimethyl sulphoxide (DMSO), to the corresponding carboxylic acids, is firs t order each in PCC, the aldehyde and hydrogen ion. The oxidation of deuter iated acetaldehyde, MeCDO, exhibits a substantial primary kinetic isotope e ffect (k(H)/k(D) = 6.12 at 288 K). The oxidation of acetaldehyde has been s tudied in nineteen different organic solvents. The solvent effect has been analysed using Taft's and Swain's multiparametric equations. The rate const ants correlate well with Taft's sigma* values; reaction constants being neg ative. A mechanism involving transfer of hydride ion has been suggested.