Kinetics and Mechanistic Study of the Ruthenium(III) Catalysed Oxidative Decarboxylation of L‐Proline by Alkaline Heptavalent Manganese (Stopped flow technique)

Abstract

The kinetics of ruthenium(III) catalysed oxidation of L-Proline by permanganate in alkaline medium at a constant ionic strength has been studied spectrophotometrically using a rapid kinetic accessory. The reaction between permanganate and L-Proline in alkaline medium exhibits 2:1 stoichiometry (KMnO4: L-Proline). The reaction shows first order dependence on [permanganate] and [ruthenium(III)] and apparent less than unit order dependence each in L-Proline and alkali concentrations. Reaction rate increases with increase in ionic strength and decrease in solvent polarity of the medium. Initial addition of reaction products did not affect the rate significantly. A mechanism involving the formation of a complex between catalyst and substrate has been proposed. The activation parameters were computed with respect to the slow step of the mechanism and discussed.

Kinetics of Os(VIII) Catalyzed Oxidation of 2-Pyrrolidine Carboxylic Acid in Alkaline Medium using Sodium Periodate as Oxidant: A Mechanistic Approach

“…The reaction product was found to be L-glutamic acid. However, earlier studies reveal that the products were 4-amino butyric acid [3], 4-amino butaraldehyde [26], and keto acids [27]. The 4-amino butaraldehyde is the most unpredictable product, as L-proline oxidizes through a pyrrolidine ring cleavage without decarboxylation.…”

Osmium(VIII) Catalyzed Oxidative Cleavage of Pyrrolidine Ring in l-Proline by Hexacyanoferrate(III) in Alkaline Media

“…The reaction product was found to be L-glutamic acid. However, earlier studies reveal that the products were 4-amino butyric acid, 14 4-amino butaraldehyde, 29 and keto acids. 30 The 4-amino butaraldehyde is the most unpredictable product, as L-proline oxidizes through a pyrrolidine ring cleavage without decarboxylation.…”