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Even mild biological reducing agents such as cysteine (in the presence of traces of ferric ion) and ascorbic acid will reduce nitroxides to the corresponding hydroxylamine
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0026652023
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Even though nitroxides possess a visible chromophore of their own, their characteristic red color is due to an absorption with a very low extinction coefficient centered around 460 nm. For example, the visible absorption spectrum in hexane for di-tert-butylnitroxide shows a maximum at 465 nm with log ε = 0.95 The extinction coefficient for the absorption giving rise to the color of the diamagnetic azulene-containing spin adducts described herein is between 1 and 2 orders of magnitude greater. See: Smith, P. A. S. Open-Chain Nitrogen Compounds; W. A Benjamin, Inc.: New York, 1965; Vol. 2, p 105 and references cited therein.
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27
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85033822320
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-
note
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+ + 1) 356.2226, found 356.2230.
-
-
-
-
28
-
-
85033819225
-
-
note
-
+ + 1) 572.3852, found 572.3853.
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-
-
-
29
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85033831134
-
-
note
-
1H NMR and TLC comparison with an authentic sample) when the thermolysis is conducted in the presence of an equimolar concentration of benzophenone. In toluene solution, benzophenone is preferentially attacked by carbanions (organolithium derivatives) in the presence of equimolar concentrations of nitrone 1 (R = OEt).
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-
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30
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0000932162
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1H NMR spectra of the violet and green products formed at room temperature when nitrone 1 (R = OEt, 10 mg. 100 mM in benzene) is subjected to conditions for the generation of the 4-bromophenyl radical (according to the Gokel modification of the Gomberg-Bachmann reaction), their structures have been assigned as the corresponding hydroxylamine (violet) and nitrone (green) resulting from disproportionation of the expected intermediate nitroxide radical. That these products are also formed in 9:1 benzene-t-BuOH argues strongly against their being artifacts formed via the involvement of aryl carbanion intermediates. See: Beadle, J. R : Korzeniowski, S. H.; Rosenberg, D. E., Garcia-Slanga, B. J ; Gokel, G. W J. Org. Chem. 1984, 49, 1594
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85033816253
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note
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-4 M) is unchanged in 98:1:1 EtOAc-HOAc-water after 10 h at 90 °C in a sealed tube. Spin trapping studies of 1 with active oxygen radicals have not yet been conducted. See also ref 18b.
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