| DOI | Resolve DOI: https://doi.org/10.1021/ja00753a037 |
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| Author | Search for: Bowman, D.F.1; Search for: Brokenshire, J.L.1; Search for: Gillan, T.1; Search for: Ingold, K. U.1 |
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| Affiliation | - National Research Council of Canada
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| Format | Text, Article |
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| Abstract | The self-reactions of methyl, isopropyl, tert-butyl, and phenyl nitroxides in solution have been examined by epr spectroscopy. The reaction is a disproportionation to yield a hydroxylamine and a nitroso compound: 2RNHO· → RNHOH + RNO. Rate constants for this reaction have been measured in several solvents. In benzene at 25° the rate constants are in the range 4 × 107 to 3 × 106 M-1 sec-1. For R = phenyl and R = tert-butyl the reaction was shown to be reversible and the equilibrium constants were measured over a range of temperature. The measured enthalpy change for the reaction with R = tert-butyl is in good agreement with that calculated (for R = CH3) from the heats of formation of the various species involved. Evidence is presented for hydrogen bonding of methyl nitroxide in methanol. The rate constant for the slow conversion of phenyl nitroxide to azoxybenzene has also been measured over a range of temperature in benzene. |
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| Publication date | 1971 |
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| In | |
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| Language | English |
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| Peer reviewed | Yes |
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| NPARC number | 21276710 |
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| Export citation | Export as RIS |
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| Report a correction | Report a correction (opens in a new tab) |
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| Record identifier | c283ecce-5503-4c2c-8f14-0de25da501ad |
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| Record created | 2015-10-13 |
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| Record modified | 2020-03-13 |
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