Three-electron oxidations. VI. Chromic acid cooxidation of cyclobutanol and oxalic acid. The chromium(V) oxidation of cyclobutanol
The chromic acid cooxidation of cyclobutanol and oxalic acid yields only cyclobutanone and carbon dioxide with the CO/sub 2/: cyclobutanone ratio varying from 1: 1 to 4: 1 depending on the initial ratio of the two substrates. The chromic acid oxidation in the presence of oxalic acid thus provides a quantitative method of converting cyclobutanol to cyclobutanone with complete suppression of ring cleavage side reactions. The chromium(V) oxidation of cyclobutanol yields cyclobutanone. The deuterium isotope effect of the reaction is k/sub H//k/sub D/ = 4.96. Cyclobutanol is only 2.3 times more reactive toward chromium(V) than isopropyl alcohol. A mechanism for the chromium (V) oxidation is proposed which is analogous to the mechanism of the chromium(VI) oxidation of alcohols and involves reversible formation of an ester intermediate and carbon- hydrogen bond cleavage in the rate-limiting step. The presence of either acrylonitrile or acrylamide leads to polymer formation during the oxidation; however, with acrylonitrile, a constant 1: 1 ratio of cyclobutanone: carbon dioxide is formed, whereas in the presence of acrylamide, the ratio of the two products is a function of the initial concentration of the substrates. The difference between the two monomers is interpreted in terms of different reactivity of the polymer radical toward oxidation. All results obtained in this study are fully consistent with the earlier proposed three-electron mechanism for the cooxidation reaction. (auth)
- Research Organization:
- Univ. of Illinois, Chicago
- Sponsoring Organization:
- USDOE
- NSA Number:
- NSA-29-018116
- OSTI ID:
- 4319861
- Journal Information:
- J. Amer. Chem. Soc., v. 96, no. 2, pp. 534-539, Journal Name: J. Amer. Chem. Soc., v. 96, no. 2, pp. 534-539; ISSN JACSA
- Country of Publication:
- Country unknown/Code not available
- Language:
- English
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