A Stable Phenoxy Radical Inert to Oxygen

Coppinger, Galvin M.

doi:10.1021/ja01559a073

Cited by 157 publications

(58 citation statements)

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“…They all are characteristically colored and show an absorption band in the infrared near 1560 cm-1; they differ rnarkcdly from the colorless, dimeric quinol ethers which have a doublet at 1660 and 1640 cm-1 in the infrared spectrum 145,471. Because of resonance stabilization, unsubstituted phenoxyl radicals (38) have a longer lifetime than alkyl o r aryl radicals and do not tend to attack the solvent or to initiate olefin polymerization as readily.…”

Section: Stable Phenoxy Radicalsmentioning

confidence: 99%

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Phenol Oxidation Reactions

Musso¹

1963

Angew. Chem. Int. Ed. Engl.

109

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Dedicated to Professor Dr. Hans Brockmann on the occasion of his 60th birthdayThe use of well-known phenol oxidation reactions for the preparation of compounds arising from C-C and C-0 coupling has recently received increased attention. A selection from the large number of products obtainable by oxidation of mono-and polyhydric phenols and a discussion of the reaction mechanisms indicate the scope of this method. The formation of hydroxyphenylquinones and orceine dyes from resorcinol derivatives is explained. The synthesis of natural products by way of phenol oxidations is briejiy discussed.

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Section: Stable Phenoxy Radicalsmentioning

confidence: 99%

“…In all the cases cited, silver oxide, lead dioxide, and manganese dioxide in slightly polar solvents, electrochemical oxidation [59], or potassium ferricyanide in alkaline solution afford phenoxyl radicals (38) in the first reaction step, which usually undergo further reactions very rapidly.…”

Section: Oxidizing Agents and Coupling Mechanismsmentioning

confidence: 99%

Phenol Oxidation Reactions

Musso¹

1963

Angew. Chem. Int. Ed. Engl.

109

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“…1,2 This stability stems from both steric hindrance induced by the bulky tert-butyl groups and efficient delocalization of the unpaired electron all along the conjugated system. It is widely used as an EPR standard and serves as a radical scavenger/antioxidant, and, as such, it has numerous biological applications.…”

Section: Introductionmentioning

confidence: 99%

Photophysics of the galvinoxyl free radical revisited

Grilj

Zonca

Daku

et al. 2012

Phys. Chem. Chem. Phys.

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The photophysical properties of the free neutral radical galvinoxyl were studied by a combination of femtosecond time-resolved spectroscopy and quantum chemical calculations. The electronic absorption spectrum is dominated by an intense band at 430 nm that is ascribed to the D 9,10 ' D 0 transitions. Upon photoexcitation at 400 nm, the population of the D 9,10 states decays within less than 200 fs to the electronic ground state. This ultrafast internal conversion does not involve intramolecular modes with large amplitude motion as the measured dynamics does not show any significant dependence on the environment, but is most probably facilitated by a high density of electronic states of different character. Depending on the solvent, a weak transient band due to the galvinoxylate anion is also observed. This closed-shell species, which is fluorescent although its deactivation is also dominated by non-radiative decay, is generated upon biphotonic ionization of the solvent and electron capture. The ultrashort excited-state lifetime of the galvinoxyl radical precludes photoinduced disproportionation previously claimed to be at the origin of the formation of both anion and cation.

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“…Galvinol 1 and its radical derivative galvinoxyl 2 have been known and studied for a long time [1,2]. This is related to the excellent stability of the radical 2 [2], the usefulness of sterically hindered radicals and parent compounds [3], their conducting properties [4], and their chemical reactivity [5].…”

Section: Introductionmentioning

confidence: 99%

The Molecular and Crystal Structures of Galvinol Derivatives

Senge

2012

Zeitschrift Für Naturforschung B

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Galvinols are interesting, sterically hindered compounds that serve as precursors for the generation of stable galvinoxyl radicals. In order to elucidate their basic structural chemistry and the influence of steric effects on their conformation a comparative analysis of several galvinol derivatives was undertaken. The aryl and quinoid subunits could clearly be identified, and substituents at the connecting methine bridge were found to influence the conformation of the molecules. As a result of the sterically hindered residues the molecules pack mainly through weak van der Waals interactions without formation of hydrogen bonds. The observation of different crystal forms and packing for galvinols and their conformational flexibility will impact current solid-state applications and provides unambiguous structural data for theoretical calculations.

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A Stable Phenoxy Radical Inert to Oxygen

Abstract: This corresponds to the loss of three hydrogens from the starting phenol.Compound II is a radical. Magnetic suscepti-

Cited by 157 publications

References 0 publications

Phenol Oxidation Reactions

Phenol Oxidation Reactions

Photophysics of the galvinoxyl free radical revisited

The Molecular and Crystal Structures of Galvinol Derivatives

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