13252-72-7Relevant academic research and scientific papers
Solvent hydrogen bonding and structural influences on the CrVI oxidation of anilines in aqueous acetic acid medium
Bhuvaneshwari,Elango
experimental part, p. 242 - 249 (2010/04/26)
The oxidation of meta- and para-substituted anilines by CrVI oxidant, imidazolium fluorochromate (IFC), in aqueous acetic acid mixtures of varying compositions in the presence of p-toluenesulfonic acid (PTS) is first order in IFC and PTS. Michaelis-Menten type kinetics is observed with all of the anilines. The IFC oxidation of 15 meta- and para-substituted anilines at 299-322 K complies with the isokinetic relationship but not to any of the linear free energy relationships. The isokinetic temperature lies within the experimental range. The rate data failed to correlate with macroscopic solvent parameters such as relative permittivity, εr, and ionizing power, Y, correlation of rate data with Kamlet-Taft solvatochromic parameters (hydrogen bond donor acidity, α, hydrogen bond acceptor basicity, β, and dipolarity/polarizability, π*) is linear which suggests that the specific solute-solvent interactions play a dominating role in governing the reactivity.
Effect of solvent on the rate of oxidation of substituted anilines with nicotinium dichromate in aqueous-acetic acid media
Bhuvaneshwari,Elango
, p. 999 - 1005 (2007/10/03)
Mechanistic studies on the oxidation of 15 para- and meta-substituted anilines by nicotinium dichromate in water-acetic acid medium of varying mole fractions have been performed. The reaction can be characterized by the experimental rate equation, -d[oxidizing agent]/dt = Kk [substrate] [HCrO 4-]/(1 + K [substrate]) The addition of p-toluenesulfonic acid enhances the reaction. The oxidation substituted anilines at 299-322 K complies with the isokinetic relationship but not to any of the linear free energy relationships, the isokinetic temperature lies within the experimental range. Correlation of rate data with Kamlet-Taft solvatochromic parameters (α, β, π*) suggests that the specific solute-solvent interactions play a major role in governing the reactivity.
Mechanism and reactivity in perborate oxidation of anilines in acetic acid
Karunakaran, Chockalingam,Kamalam, Ramasamy
, p. 2011 - 2018 (2007/10/03)
Perborate but not percarbonate in acetic acid generates peracetic acid on standing and the peracetic acid oxidation of anilines is fast. The oxidation with a fresh solution of perborate in acetic acid is smooth and second order but the specific oxidation rate increases with increasing [perborate]0 or [boric acid]. Perborate on dissolution affords hydrogen peroxide and a borate; the latter assists the former in the oxidation. The oxidation rates of anilines under identical conditions do not conform to any of the linear free energy relationships but the reaction rates of molecular anilines do. Perborate oxidation proceeds via two reaction paths but the overall oxidation rates of molecular anilines conform to structure reactivity relationships; the transition states do not differ significantly. Analysis of the oxidation rates of perborate and percarbonate reveals that while perborate oxidation is faster than percarbonate it is at least as selective as the latter.
Flow cell electrosynthesis of phenylhydroxylamines. In situ reaction with arenesulfonyl chlorides. A convenient route to arenesulfinic acids synthesis.
Moinet, C.,Raoult, E.
, p. 214 - 221 (2007/10/02)
First, electrosyntheses of phenylhydroxylamines in a flow cell fitted with porous cathode and two counter-electrodes are described.Good yields are attained when electrolyses are performed in buffered aqueous organic or aqueous media.Reaction between p-toluenesulfonyl chloride and N-(3-chloro-4-methylphenyl)hydroxylamine, at the outlet of the cell, leads to a N-sulfonylated phenylhydroxylamine (N-addition); hydrolysis of this latter occurs in aqueous basic media to give the corresponding nitrosobenzene and sodium p-toluenesulfinate.As a result, some arenesulfinic acids have been directly obtained after reaction of arenesulfonyl chloride with sodium salt of 3-hydroxylaminobenzoate and 3-hydroxylaminobenzenesulfonate in aqueous phosphate buffer (pH 7).Next, an examination of the reaction of p-toluenesulfonyl chloride with phenylhydroxylamine in organic solvent, in the presence of triethylamine or of sodium carbonate, shows the importance of experimental conditions to control N-addition or O-addition.Addition of some arenesulfonyl chlorides to phenylhydroxylamine, in ether or dichloromethane containing sodium carbonate, gives only the N-sulfonylated phenylhydroxylamines.These compounds lead to nitrosobenzene and arenesulfinate anions in aqueous basic media.Aliphatic or aromatic sulfinic acids can be prepared in this way.
