Anionoradikale, IV. Über radikalische und nicht‐radikalische Alkalimetalladdukte aromatischer Azoxyverbindungen

Kauffmann, Thomas; Hage, S. M.; Ruckelshauss, G.

doi:10.1002/cber.19671000423

Cited by 5 publications

(2 citation statements)

References 10 publications

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“…It was observed that the initially formed radical anion intermediate does not undergo further reaction and the starting material was recovered unchanged in appreciable yields, on work-up. However, the reaction of 26 with sodium in tetrahydrofuran resulted in the cleavage of this molecule, and a small quantity of 2-nitrophenol (28) was isolated from this run.…”

Section: Scheme IVmentioning

confidence: 99%

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Alkali metal reduction of aromatic nitro compounds

Kalyanaraman¹,

George²

1973

J. Org. Chem.

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The reaction of nitrobenzene with lithium in tetrahydrofuran gave a mixture of products consisting of azobenzene, 2-anilinoazobenzene, 2,2'-and 2,4'-dianilinoazobenzenes, anilinodibenzopyridazine, and unidentified polymeric azo compounds. Similar products were obtained from the reaction of nitrosobenzene with lithium, whereas the reaction of azoxybenzene gave exclusively azobenzene. It has been suggested that radical anion intermediates are involved in these reactions. Substituted nitro compounds react in a manner analogous to that of nitrobenzene, whereas nitroamlines are unchanged under similar conditions. Compounds such as 4-bromoazoxybenzene and 2-chloronitrobenzene undergo both deoxygenation and dehalogenation reactions on treatment with lithium in THE. 2,2'-Dinitrobiphenyl, on the other hand, gave dibenzopyridazine and a trace of carbazole on treatment with lithium in ether solvents. Under similar conditions, however, 2,2 '-dinitrodiphenyl ether did not give any cyclized product.Aromatic nitro compounds, in general, are reduced in basic medium to the corresponding azoxy, azo, and hydrazo derivatives, whereas they are converted to the corresponding amines under strongly acidic conditions or under catalytic hydrogenation.2The deoxygenation of nitro and nitroso compounds have been brought about by several reagents to give a variety of products depending on the reaction conditions and the nature of the reagents.8 Aryl nitro compounds, for example, have been reduced to the corresponding azo derivatives in fairly good yields by metal hydrides4-6 and thallium.7The reaction of nitrobenzene with sodium in liquid ammonia is very complex and may warrant further investigation.8 However, sodium amalgam has been reported to reduce aromatic nitro compounds to the corresponding azoxy and azo compounds.2 Luka-shevich® had observed the formation of mono-and disodium adducts of nitrobenzene, as well as nitrosobenzene in ether solvents. Addition of alkali metals to nitro compounds in aprotic solvents has been reported to give rise to radical anion intermediates and several groups of workers have examined the esr spectra of some of these intermediates.10 We previously examined the electronic spectra of the radical anions of a few nitrobenzene derivatives and some

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Section: Scheme IVmentioning

confidence: 99%

“…-Acylation of Metal Enolatesla Herbert 0. House,* Robert A. Auerbach, Martin Gall,111 and Norton P. Peet School of Chemistry, Georgia Institute of Technology, Atlanta, Georgia 30882 Received August 28, 1972 From a spectroscopic examination of metal enolates, the mercury(II) salts of ketones are found to exist as a-…”

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confidence: 99%

Alkali metal reduction of aromatic nitro compounds

Kalyanaraman¹,

George²

1973

J. Org. Chem.

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Anionoradikale, V. Radikalbildung und Fragmentierung bei Einwirkung von dispergiertem Natrium auf Verbindungen mit PC‐, PN‐ und SO‐Doppelbindung

1973

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Bei der Einwirkung von dispergiertem Natrium in einem inerten Losnngsmittel bei Raumtemperatur auf Fluorenylidentriphenylphosphoran, N-Phenyltriphenylphosphinimin und Diplicnylsulfoxid erfolgtc jcweils Abspaltung eines Phenylrestes und Bildung eines stabilen Radikals. Aus Fluorcnylidentriphenylphosphoran cntstand sehr wahrscheiiilich das neutrale Fluorenyldiphenylphosphin-Radikal 3, B U S N-Phenyltriphcnylphosphinimin ein Phosphorstickstoff-Radikal, bei dem es sich urn das Anionoradikalll oder dasNeutralradikall2 handelt. Ob das aus Diphenylsulfoxid erhaltene Radikal das Mononatriumaddukt des Diphenylsulfoxids ist, was mit dem ESR-Spektrum vereinbar ware, ist noch zweifelhaft. -Produkte, die bei der Hydrolyse sowie bei der Sauerstoffoxidation der radikalischen Losungen entstanden sind, wurden grofitenteils identifiziert. Treatment of fluorenylidenetriphenylphosphorane, N-phenyltriphenylphosphine imine and diphenyl sulfoxide with sodium dispersed in an inert solvent at room temperature led in each case to the formation or a stable radical and splitting off of a phenyl residue. The neutral fluorenyldiphenylphosphine radical 3 was most probably produced from fluorenylidenetriphenylphosphorane. N-Phenyltriphenylphosphine imine afforded a phosphorus-nitrogen radical, which is either the anionic radical 11 or the neutral radical 12. It is still doubtful whether the radical gained from diphenyl sulfoxide is the monosodium adduct, which would be in accordance with the ESR. -The products which were obtained in the hydrolysis as well as in the oxygenation of the radical solutions have largely been identified.

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Alkali metal additions to unsaturated systems

Kalyanaraman

George

1973

Journal of Organometallic Chemistry

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Anionoradikale, IV. Über radikalische und nicht‐radikalische Alkalimetalladdukte aromatischer Azoxyverbindungen

Cited by 5 publications

References 10 publications

Alkali metal reduction of aromatic nitro compounds

Alkali metal reduction of aromatic nitro compounds

Anionoradikale, V. Radikalbildung und Fragmentierung bei Einwirkung von dispergiertem Natrium auf Verbindungen mit PC‐, PN‐ und SO‐Doppelbindung

Alkali metal additions to unsaturated systems

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