The chromic acid oxidation of aliphatic secondary alcohols—substituent effects and the mechanism

1970 ◽  
Vol 71 (1) ◽  
pp. 1-8 ◽  
Author(s):  
N. Venkatasubramanian ◽  
G. Srinivasan
Keyword(s):  
Chromic Acid ◽  
Substituent Effects ◽  
Acid Oxidation ◽  
Secondary Alcohols ◽  
Chromic Acid Oxidation

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.

THE CHROMIC ACID OXIDATION OF ARYL TRIFLUOROMETHYL ALCOHOLS: ISOTOPE AND SUBSTITUENT EFFECTS

1964 ◽  
Vol 42 (2) ◽  
pp. 439-446 ◽  
Author(s):  
Ross Stewart ◽  
Donald G. Lee
Keyword(s):  
Acetic Acid ◽  
Acid Solution ◽  
Chromic Acid ◽  
Isotope Effects ◽  
Acetic Acid Solution ◽  
Substituent Effects ◽  
Acid Oxidation ◽  
Unimolecular Decomposition ◽  
Chromic Acid Oxidation ◽  
Deuterium Isotope Effects

The mechanism of the chromic acid oxidation of eight aryltrmuoromethylcarbinols has been studied in acetic acid solution. Electron-donating substituents accelerate the reaction and a good correlation of rate with σ+ values has been found. The rho value is −1.01. Deuterium isotope effects for the oxidation of five of these compounds have been determined and the magnitude of the isotope effect has been found to correlate inversely with the ease of oxidation of the alcohol.The results are interpreted in terms of a unimolecular decomposition of the chromate ester of the alcohol.

Aqueous chromic acid oxidation of secondary alcohols in diethyl ether: A convenient undergraduate organic chemistry experiment

1979 ◽  
Vol 56 (3) ◽  
pp. 203 ◽  
Author(s):  
Kerry L. Thompson ◽  
S. Krishnamurthy ◽  
Thomas Nylund ◽  
M. Ravindranathan
Keyword(s):  
Organic Chemistry ◽  
Diethyl Ether ◽  
Chromic Acid ◽  
Acid Oxidation ◽  
Secondary Alcohols ◽  
Chromic Acid Oxidation ◽  
Chemistry Experiment

Kinetic Isotope Effect in the Chromic Acid Oxidation of Secondary Alcohols

2000 ◽  
Vol 77 (8) ◽  
pp. 1042 ◽  
Author(s):  
Charles E. Harding ◽  
Christopher W. Mitchell ◽  
Jozsef Devenyi
Keyword(s):  
Isotope Effect ◽  
Kinetic Isotope Effect ◽  
Chromic Acid ◽  
Acid Oxidation ◽  
Secondary Alcohols ◽  
Chromic Acid Oxidation ◽  
Kinetic Isotope

Direct Observation of Intermediates in the Chromic Acid Oxidation of Secondary Alcohols

1967 ◽  
Vol 89 (2) ◽  
pp. 455-457 ◽  
Author(s):  
Kenneth B. Wiberg ◽  
Hans. Schafer
Keyword(s):  
Direct Observation ◽  
Chromic Acid ◽  
Acid Oxidation ◽  
Secondary Alcohols ◽  
Chromic Acid Oxidation

THE CHROMIC ACID OXIDATION OF ARYL TRIFLUOROMETHYL ALCOHOLS: ISOTOPE AND SUBSTITUENT EFFECTS

1965 ◽  
Vol 43 (11) ◽  
pp. 3128-3128
Author(s):  
Ross Stewart ◽  
Donald G. Lee
Keyword(s):  
Chromic Acid ◽  
Substituent Effects ◽  
Acid Oxidation ◽  
Chromic Acid Oxidation

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