scholarly journals Permanganate oxidation of aromatic alcohols in acid solution

1969 ◽  
Vol 47 (17) ◽  
pp. 3199-3205 ◽  
Author(s):  
Fariza Banoo ◽  
Ross Stewart
Keyword(s):  
Sulfuric Acid ◽  
Acid Solution ◽  
Acidity Function ◽  
Effect Of Substituents ◽  
Tertiary Alcohols ◽  
Permanganate Oxidation ◽  
Carbonium Ion ◽  
Aromatic Alcohols ◽  
Rapid Reaction ◽  
Rate Controlling Step

The mechanism of the permanganate oxidation of di- and tri-arylcarbinols has been studied in aqueous sulfuric acid. With both kinds of alcohols the rate-controlling step in solutions more acidic than H0 −0.50 was found to be the ionization of the carbinol to give the carbonium ion followed, it is believed, by rapid reaction with permanganate ion to form the ester which decomposes rapidly to products. In the case of the tertiary alcohols the decomposition probably proceeds via a 1,2-aryl shift. The effect of substituents is correlated with σ+ in both cases, ρ+ being −1.02 and −1.39 for the secondary and tertiary series. The acidity function which governs both reactions is H0. Tri(p-tolyl)carbinol is exceptional in that its oxidation in solutions more acidic than HR −2.6 is second-order and is governed by the HR acidity function.

Chromic acid oxidation of aromatic alcohols

1969 ◽  
Vol 47 (17) ◽  
pp. 3207-3212 ◽  
Author(s):  
Ross Stewart ◽  
Fariza Banoo
Keyword(s):  
Chromic Acid ◽  
Acid Oxidation ◽  
Secondary Alcohols ◽  
Tertiary Alcohols ◽  
Chromic Acid Oxidation ◽  
Hydride Shift ◽  
Rate Of Reaction ◽  
Aromatic Alcohols ◽  
Reaction Constant ◽  
Rate Controlling Step

The mechanism of the chromic acid oxidation of di- and tri-aryl carbinols has been studied in 80 wt% acetic acid containing sulfuric acid. The reactions are cleanly second-order and give benzophenones in the case of the secondary alcohols and benzophenones plus phenols in the case of the tertiary alcohols. Electron-donating substituents in the tertiary alcohol appear predominantly in the phenol component and the rate-controlling step is believed to be a 1,2-aryl shift. The reaction constant for the migration is ρ+ = −1.44 and that for the overall reaction is ρ+ = −0.879. The presence of manganous ions does not alter these values although it lowers the overall rate of reaction. Although an analogous 1,2-hydride shift mechanism can be written for the oxidation of the secondary alcohols, there are enough points of difference between the oxidations of the secondary and tertiary systems to make this appear unlikely.

Protonation of conjugated carbonyl groups in sulfuric acid solution. I. Adaptation of the amide acidity function HA for protonation of the carbonyl group in non-Hammett bases

1968 ◽  
Vol 46 (14) ◽  
pp. 2469-2470 ◽  
Author(s):  
R. I. Zalewski ◽  
G. E. Dunn
Keyword(s):  
Sulfuric Acid ◽  
Acid Solution ◽  
Carboxylic Acids ◽  
Carbonyl Group ◽  
Sulfuric Acid Solution ◽  
Acidity Function ◽  
Carbonyl Groups ◽  
Aliphatic Aldehydes

The protonation of a number of aromatic and α,β-unsaturated aliphatic aldehydes, ketones, and carboxylic acids in sulfuric acid has been found to obey the HA acidity function, rather than H0.

Simple theoretical models of elimination reactions on polar catalysts; Dehydration reactivity of secondary alcohols on acidic and basic catalysts

1985 ◽  
Vol 50 (4) ◽  
pp. 920-929 ◽  
Author(s):  
Jiří Sedláček
Keyword(s):  
Experimental Data ◽  
Quantum Chemical ◽  
Theoretical Models ◽  
Aliphatic Alcohols ◽  
Secondary Alcohols ◽  
Carbonium Ion ◽  
Dehydration Reactions ◽  
Aromatic Alcohols ◽  
Basic Catalysts ◽  
Simple Models

CNDO/2 calculations for simple models of adsorption and dehydration reactions of secondary aliphatic and aromatic alcohols on polar catalysts are presented. The models involve selected stages of elimination mechanisms of various types (E1, E2 and E1cB elimination). Calculated quantum chemical quantities were correlated with reported experimental data. It is shown that reactivities for the series of substituted phenylethanols correlate very well with the ease of carbonium ion formation. In the case of aliphatic alcohols, calculated quantities correlate generally with the reactivities on SiO2 and are in anticorrelation with the reactivities on Al2O3.NaOH.

Fundamental Measurements of the Friction on an Atomically-Flat Terrace of Au(100) in Sulfuric Acid Solution under Potential Control Using Electrochemical Atomic Force Microscope

2006 ◽  
Vol 512 ◽  
pp. 395-398
Author(s):  
Nobumitsu Hirai ◽  
Tatsuya Tooyama ◽  
Toshihiro Tanaka
Keyword(s):  
Aqueous Solution ◽  
Sulfuric Acid ◽  
Silicon Nitride ◽  
Acid Solution ◽  
Atomic Force Microscope ◽  
Friction Force ◽  
Potential Range ◽  
Potential Control ◽  
Atomic Force ◽  
Atomically Flat

Potential dependence of the friction force between an atomically-flat terrace of Au(100) single crystal and a tip attached to a silicon nitride cantilever of electrochemical atomic force microscope (EC-AFM) have been investigated qualitatively in 0.05 M H2SO4 aqueous solution. It is found that the friction force gains when the potential increases in the potential range between −400 mV and 400 mV vs Hg/Hg2SO4 electrode.

scholarly journals Continuos Operation of Chromium (VI) Recovery from Sulfuric Acid Solution by Liquid Surfactant Membrane.

1991 ◽  
Vol 17 (6) ◽  
pp. 1104-1109 ◽  
Author(s):  
Yasushige Mori ◽  
Shingo Hibin ◽  
Hideyuki Uemae ◽  
Masataka Tanigaki ◽  
Wataru Eguchi
Keyword(s):  
Sulfuric Acid ◽  
Acid Solution ◽  
Sulfuric Acid Solution ◽  
Chromium Vi
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