Autocatalyzed oxidation of d-glucitol by alkaline copper (III) periodate complex: A kinetic and mechanistic approach

被引：6

作者：

Patil, Shreekant M. ^{[1
]}

Bagoji, Atmanand M. ^{[1
]}

Konnur, Santosh B. ^{[1
]}

Nandibewoor, Sharanappa T. ^{[1
]}

机构：

[1] Karnatak Univ, Dept Studies Chem, Dharwad 580003, Karnataka, India

来源：

JOURNAL OF PHYSICAL ORGANIC CHEMISTRY | 2021年 / 34卷 / 03期

关键词：

autocatalysis; d‐ glucitol; diperiodatocuprate (III); kinetics; mechanism; oxidation; DIPERIODATOCUPRATE(III) COMPLEX; CATALYZED OXIDATION; ALCOHOLS; MEDIA; METAL;

D O I：

10.1002/poc.4146

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

An autocatalyzed oxidation of d-glucitol (DG) by diperiodatocuprate (III) (DPC) in aqueous alkaline medium at a constant ionic strength of 0.06 mol dm(-3) was studied spectrophotometrically. An autocatalysis was observed by one of the products formed, that is, Cu (II). A 1:2 stoichiometry (DG : DPC) exhibited reaction between the DG and DPC in an aqueous alkaline medium. The reaction was of first order in [DPC] when [DPC] < < [DG], while the order with respect to [DG] and [OH-] was less than unity, whereas periodate had retarding effect on the rate of reaction. Ionic strength had a negligible effect on the rate of reaction. The main reaction products were identified by the spot tests and spectroscopic analysis. The product, Cu (II), catalyzed the reaction with a fractional order. A composite mechanism involving uncatalyzed and autocatalyzed reaction paths was proposed. The activation parameters with respect to slow step of the mechanism and also the thermodynamic quantities were determined and discussed.

引用

页数：11

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