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|Title:||Kinetics and mechanism of oxidation of aliphatic aldehydes by pyridinium bromochromate|
Sharma, Pradeep K
Banerji, Kalyan K
|Abstract:||The oxidation of six aliphatic aldehydes by pyridinium bromochromate (PBC), to the corresponding carboxylic acids, is first order each in PBC and the aldehyde. The reaction is catalysed by H+; the H+ dependence has the form, kobs = a + b [H+]. Oxidation of deuterated acetaldehyde (MeCDO) showed the presence of a substantial kinetic isotope effect (kH/kD=6.40 at 288 K). Oxidation of acetaldehyde is studied in 19 organic solvents. The solvent effect has been analysed using Taft's and Swain's multiparametric equations. The rate constants correlate well with Taft's o* constants; reactions being negative. A mechanism involving transfer of a hydride ion has been suggested.|
|Appears in Collections:||IJC-A Vol.35A(07) [July 1996]|
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