Reactions of Organoalkali Compounds with Nitro Compounds: A New Synthesis of Nitroxides

Hoffmann, Alexander; Feldman, Allan M.; Gelblum, Ernestine

doi:10.1021/ja01058a021

Cited by 67 publications

(17 citation statements)

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“…A degassed sample gave a more complex spectrum in which each of the three lines was split into nine lines with intensity ratios 1 :2:4:6:6:6:4:2: 1. Hyperfine splitting by aryl hydrogens when oxygen is kept out of a sample containing phenyl-tert-butyl nitroxide radicals has been reported by others and our values of the hyperfine constants, a H~r l h o = aHPaTa = 2aHmefa = 1.91 G, are in good agreement with those in the literature (12,13). These epr results suggest that 3 decomposes by a radical pathway and that the radical trapped by nitrosobenzene is the tert-butyl radical.…”

Section: Spin Trappingsupporting

confidence: 92%

Synthesis and radical decomposition of α-hydroxydiazenes. II. tert-Butylazodiphenylcarbinol

Yeung¹,

Warkentin²

1976

Can. J. Chem.

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tert-Butylazodiphenylcarbinol (Ph2C(OH)N=NCMe3, 3) decomposes in oxygen-free benzene by the unimolecular radical mechanism characteristic of most azo compounds. In benzene or in carbon tetrachloride, with or without air present, decomposition of 3 is also induced by radicals through abstraction of hydroxyl hydrogen in concert with the formation of nitrogen. Radicals which induce decomposition of 3 include trichloromethyl, tert-butyl, phenylthiyl, tert-butylperoxy and possibly oxygen. The failure of inhibitors like thiophenol to stop chain decomposition of 3 is interpreted in terms of the thermochemistry of induced decomposition.

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Section: Spin Trappingsupporting

confidence: 92%

Synthesis and radical decomposition of α-hydroxydiazenes. II. tert-Butylazodiphenylcarbinol

Yeung¹,

Warkentin²

1976

Can. J. Chem.

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“…The di-t-butylnitroxide radical was synthesized by the technique of Hoffmann et al [4]. The radical was estimated to be 97 per cent pure from the constant wave N.M.R.…”

Section: Methodsmentioning

confidence: 99%

Electron spin relaxation in concentrated solutions of a nitroxide radical

1975

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We have determined the transverse electron spin relaxation time of the di-t-butylnitroxide radical in a series of concentrated solutions at four different frequencies. Spin-lattice relaxation times were determined at two frequencies.The relaxation times are interpreted in terms of contributions from electronnuclei hyperfine interactions and electron-electron dipolar interactions. The dipolar interaction appears to arise from the formation of associated radical pairs. This interaction dominates the relaxation times in the more concentrated samples. The experimental data have been analysed to obtain estimates of the dipolar correlation times, the average electron-electron separation and the population of radical pairs.

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“…However, it is known to be formed in the reactions of t-BuNO-, with sodiunz metal (20) or with organo-alkali co~npounds (21) and also in its electrochemical reduction (22). These all involve thc radical anion of t-BLINO-, which is assumed to bc unstable leacling t o the formkltion of 8.…”

mentioning

confidence: 99%

Spin trapping of radicals formed during radiolysis of aqueous solutions. Direct electron spin resonance observations

Sargent¹,

Gardy²

1976

Can. J. Chem.

103

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Can. J. Chem. 54, 275 (1976). It is shown that e,,,,, He, and OH formed by the radiolysis of water by 3 MeV electrons are trapped by nitroso and nitrone compounds to give nitroxides with well defined esr spectra. Three spin trapping agents were used, nitroso-t-butane, phenyl-t-butyl nitrone, and 5,s'-dimethyl pyrroline-I-oxide. The latter was shown to be an excellent con~pound for these studies. Complications due to the instability of some of the nitroxides were overcome by coupling the electron accelerator to the esr spectron~eter to permit direct observation of the spectra. On a montrC que les e,,,,,, Ha, et OH formts par radiolyse de I'eau par des Clectrons B 3 MeV sont captCs par des composes nitroso et nitrone et conduisent B des nitroxydes avec des spectres rpe bien dtfinis. On a utilise trois agents de piCgeage; L e nitroso t-butane, la phtnyl t-butyl nitrone et la dimethyl-5,5' pyrroline oxyde-I. On a n~o n t r i que ce dernier composC est excellent pour ces ttudes. On a CliminC les con~plications dues a I'instabilitC de q~~elques nitroxydes en couplant directement I'acctICrateur d'Clectron au spectromktre de rpe pour permettre une observation directe du spectre.[Traduit par le journal]

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Reactions of Organoalkali Compounds with Nitro Compounds: A New Synthesis of Nitroxides

Cited by 67 publications

References 0 publications

Synthesis and radical decomposition of α-hydroxydiazenes. II. tert-Butylazodiphenylcarbinol

Synthesis and radical decomposition of α-hydroxydiazenes. II. tert-Butylazodiphenylcarbinol

Electron spin relaxation in concentrated solutions of a nitroxide radical

Spin trapping of radicals formed during radiolysis of aqueous solutions. Direct electron spin resonance observations

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