1. bookVolume 15 (2013): Issue 3 (September 2013)
Journal Details
License
Format
Journal
eISSN
1899-4741
ISSN
1509-8117
First Published
03 Jul 2007
Publication timeframe
4 times per year
Languages
English
access type Open Access

Kinetic investigation of oxidation of aromatic anils by magnesium monoperoxyphthalate in aqueous acidic medium

Published Online: 20 Sep 2013
Volume & Issue: Volume 15 (2013) - Issue 3 (September 2013)
Page range: 55 - 60
Journal Details
License
Format
Journal
eISSN
1899-4741
ISSN
1509-8117
First Published
03 Jul 2007
Publication timeframe
4 times per year
Languages
English
Abstract

The kinetics of oxidation of aromatic anils to benzaldehyde and azobenzene by magnesium monoperoxyphthalate (MMPP) has been studied in aqueous acetic acid medium. The low dielectric constant of the medium facilitates the reactivity. It has been found that ionic strength of the reaction has no significant effect on rate. The added acrylonitrile has no effect on the reaction rate indicating the absence of free radical mechanism. The added Mn(II) decreases the rate of the reaction, which indicates the involvement of two-electron transfer. Highly negative ΔS# values indicate a structured transition state. The deviation of Hammett plot is noted and a non-linear concave downward curve is obtained for the anils with substituents in the aniline moiety. The observed break in the log kobs versus σ is attributed to the transition state whereas the non-linear concave upward curve is observed for the substituents in the benzaldehyde moiety and a non-linear concacve upward curve is observed for the substituents in the combination of aniline and benzaldehyde moiety and a suitable mechanism is proposed

Keywords

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