Correlation analysis of reactivity in the oxidation of anilines by nicotinium dichromate in nonaqueous media

✍ Scribed by D. S. Bhuvaneshwari; K. P. Elango

• Publisher: John Wiley and Sons
• Year: 2006
• Tongue: English
• Weight: 128 KB
• Volume: 38
• Category: Article
• ISSN: 0538-8066
• DOI: 10.1002/kin.20199

✦ Synopsis

Abstract

The kinetics of oxidation of 15 para‐ and meta‐substituted anilines by nicotinium dichromate (NDC) in different organic solvent media in the presence of p‐toluenesulfonic acid (TsOH) has been investigated. The rate of the reaction is zero order with respect to substrate, first order in NDC, and is found to increase with increase in [TsOH]. The various thermodynamic parameters for the oxidation have been reported and discussed along with the validity of the isokinetic relationship. The specific rate of oxidizing species‐anilines reaction (k~2~) correlates with Hammett's substituent constants affording negative reaction constants. The effect of para‐ and meta‐substituents on the oxidation rates confirms to Swain et al.'s substituent constants F and R, both with negative reaction constants. The rate data failed to correlate with macroscopic solvent parameters such as ε~r~ and E while showing satisfactory correlation with Kamlet–Taft's solvatochromic parameters (α, β, and π*). © 2006 Wiley Periodicals, Inc. Int J Chem Kinet 38: 657–665, 2006