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|Title:||Kinetics and mechanism of the oxidation of diols by butyltriphenylphosphonium dichromate|
Kinetic isotope effect
|Abstract:||The oxidation of four vicinal, four non-vicinal diols and one of their monoethers by butyltriphenylphosphonium dichromate (BTPPD), in dimethylsulfoxide (DMSO), resulted in the formation of corresponding hydroxyaldehyde as a main product of the oxidation. The reactions are of first order with respect to BTPPD, however, second order dependence is obtained with respect to each the diol and hydrogen ion. The oxidation of [1,1,2,2-<sup>2</sup>H<sub>4</sub>]ethanediol exhibited primary kinetic isotope effect (<i style="">k</i><sub>H</sub>/<i style="">k</i><sub>D</sub> = 6.61 at 298 K). The temperature dependence of the kinetic isotope effect suggested the symmetrical transition state in the rate-determining step. The rate constants of oxidation of four vicinal diols show excellent correlation with Taft’s <img src='/image/spc_char/sum.gif' border=0> <img src='http://www.niscair.res.in/jinfo/sigma.gif' border=0><sup>*</sup> values with negative reaction constant, <img src='http://www.niscair.res.in/jinfo/rho.gif' border=0><sup>*</sup>. The rate of oxidation of ethanediol has been determined in nineteen different solvents. An analysis of the solvent effect indicates the importance of the cation-solvating power of the solvents. A suitable mechanism has been postulated involving the formation of chromate ester in a pre-equilibrium.|
|Appears in Collections:||IJC-B Vol.50B(07) [July 2011]|
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