Kinetics of oxidation of some active methylene compounds by thallium(III) perchlorate in acetic acid-water medium

Gupta, OP; Gupta, HD; Sharma, VK; Sharma, K

HERO ID

4937125

Reference Type

Journal Article

Year

2004

HERO ID 4937125
In Press No
Year 2004
Title Kinetics of oxidation of some active methylene compounds by thallium(III) perchlorate in acetic acid-water medium
Authors Gupta, OP; Gupta, HD; Sharma, VK; Sharma, K
Journal Oxidation Communications
Volume 27
Issue 1
Page Numbers 105-115
Abstract The kinetics of Tl(III) perchlorate oxidation of some active methylene compounds viz. ethyl acetoacetate and diethyl malonate has been studied in acetic acid-water mixture in the presence of perchloric acid. <br> <br>The reactions show first order in oxidant while the order in both the esters vary from one to zero. The order with respect to hydrogen ion is one for ethyl acetoacetate oxidation while one to zero in malonic ester oxidation. Added Cl- inhibits the rate of reactions. The effect of variation of ionic strength of the medium has been investigated. The stoichiometry of the title reaction is found to be 1:2. The activation parameters have been evaluated. Based on these finding a probable mechanism has been proposed.
Wosid WOS:000220796100014
Is Certified Translation No
Dupe Override No
Is Public Yes
Keyword ethyl acetoacetate (EAA); diethyl malonate (DEM); acid-catalysed; thallium(III) perchlorate; enol intermediate