Nonlinear Hammett Relationships in the Reaction of Peroxomonosulfate Anion (HOOSO3-) with meta- and para-Substituted Anilines in Alkaline Medium

[img]PDF - Authorized users only
Language: English
104Kb
Title:Nonlinear Hammett Relationships in the Reaction of Peroxomonosulfate Anion (HOOSO3-) with meta- and para-Substituted Anilines in Alkaline Medium
Creators:
Meenakshisundaram, Subbiah
Sockalingam, Ramanathan
Journal or Publication Title:
Collection of Czechoslovak Chemical Communications, 66, 6, pp. 897-911
Uncontrolled Keywords:Solvent effects, Nitroso compounds, Amines, Oxidations, Nonlinear Hammett plot, Peroxomonosulfate, Substituent effects, Aniline

Abstract

The HOOSO<sub>3</sub><sup>-</sup> oxidation of eleven <i>meta</i>- and <i>para</i>-substituted anilines to the corresponding nitrosobenzenes at pH ≈ 11 was characterized by the rate equation <i>v</i> = <i>kK</i>[OX][An]/(1 + <i>K</i>[An]). Formation constant of the reactive intermediate and its rate of decomposition were evaluated separately for ascertaining the structure-reactivity relationships. Under the experimental conditions the dianion, <sup>-</sup>O-O-SO<sub>3</sub><sup>-</sup> is probably the effective electrophile. Kinetic data can be rationalized by a bimolecular process which involves the attack of nucleophilic nitrogen atom on the peroxidic oxygen. The highlight of the study is the opposite curvatures observed in the nonlinear Hammett plots of first-order rate constant <i>k</i> and the "equilibrium" constant <i>K</i>, being concave downward and upward, respectively. <p>

Title:Nonlinear Hammett Relationships in the Reaction of Peroxomonosulfate Anion (HOOSO3-) with meta- and para-Substituted Anilines in Alkaline Medium
Creators:
Meenakshisundaram, Subbiah
Sockalingam, Ramanathan
Uncontrolled Keywords:Solvent effects, Nitroso compounds, Amines, Oxidations, Nonlinear Hammett plot, Peroxomonosulfate, Substituent effects, Aniline
Divisions:Life and Chemical Sciences > Institute of Organic Chemistry and Biochemistry > Collection of Czechoslovak Chemical Communications
Journal or Publication Title:Collection of Czechoslovak Chemical Communications
Volume:66
Number:6
Page Range:pp. 897-911
ISSN:0010-0765
E-ISSN:1212-6950
Publisher:Institute of Organic Chemistry and Biochemistry
Related URLs:
URLURL Type
http://dx.doi.org/10.1135/cccc20010897UNSPECIFIED
ID Code:1830
Item Type:Article
Deposited On:06 Feb 2009 17:13
Last Modified:06 Feb 2009 16:13

Citation

Meenakshisundaram, Subbiah; Sockalingam, Ramanathan (2001) Nonlinear Hammett Relationships in the Reaction of Peroxomonosulfate Anion (HOOSO3-) with meta- and para-Substituted Anilines in Alkaline Medium. Collection of Czechoslovak Chemical Communications, 66 (6). pp. 897-911. ISSN 0010-0765

Repository Staff Only: item control page