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

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.


1943 ◽  
Vol 16 (3) ◽  
pp. 660-667 ◽  
Author(s):  
V. L. Burger ◽  
W. E. Donaldson ◽  
J. A. Baty

Abstract A method for the direct determination of rubber is reported. This method utilizes the property of rubber hydrocarbon when oxidized by chromic acid to form definite and reproducible amounts of acetic acid. This determination has been reduced to a comparatively simple laboratory procedure, whose accuracy (in the absence of interferences) is 1 to 2 per cent.



1968 ◽  
Vol 46 (3) ◽  
pp. 441-449 ◽  
Author(s):  
Donald G. Lee ◽  
William L. Downey ◽  
R. Michael Maass

The rate law for oxidation of 2-propanol by chromic acid in aqueous acetone solutions has been found to be V = k3 [Cr(VI)| [2-propanol]ho, with the magnitude of k3 being over 700 times as great in 93.3% acetone as it is in water. In other respects (primary deuterium isotope effect, Hammett "rho" value, and salt effects) the general features of the reaction strongly resemble those observed in aqueous acetic acid solutions.



1962 ◽  
Vol 27 (1) ◽  
pp. 294-296 ◽  
Author(s):  
Yoshiro Ogata ◽  
Hiroyuki Akimoto


1971 ◽  
Vol 74 (11) ◽  
pp. 2328-2333
Author(s):  
Nobuaki FUJIWARA ◽  
Kosaku KATO ◽  
Mitsuyoshi NAKAO ◽  
Futoru YOSHIMURA


1971 ◽  
Vol 26 (5) ◽  
pp. 383-385 ◽  
Author(s):  
C. Goswami ◽  
K. K. Banerji

The kinetics of chromic acid oxidation of propanaldehyde, butyraldehyde and isobutyraldehyde in aq. acetic acid have been studied. The product of the oxidation is the corresponding carboxylic acid. The reaction is of first order with respect to each the acid chromate ion, HCrO4⊖, and the aldehyde but of second order to hydrogen ion. The rate increases with proportion of acetic acid in the solution. The activation parameters for the oxidation and enolisation reactions have been evaluated. The rate of enolisation under similar condition is less than that of oxidation. A mechanism in which the first step is the rapid reversible formation of a chromate ester followed by a hydrideion transfer in the rate determining step has been suggested.



1952 ◽  
Vol 74 (11) ◽  
pp. 2707-2709 ◽  
Author(s):  
Yoshiro Ogata ◽  
Atsuo Fukui ◽  
Sadao Yuguchi


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