Über oxydative Spaltung der Hydrazone und über Derivate des Oxyhydrazins

Bergmann, Max; Ulpts, Reinhold; Witte, Charlotte

doi:10.1002/cber.19230560317

Cited by 12 publications

(3 citation statements)

References 4 publications

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“…The diimide monoxide produced by this reaction has also been obtained by the peracid oxidation of benzaldehyde phenylhydrazone, XIV (18 as the reaction medium). This behavior is not ine expected when substances like XVIII, XIV, and X I X are present.…”

Section: H~cg-c=n-n-cgh~~---h~cg-n~-cm?-cgh:mentioning

confidence: 98%

The Stable Alkylation Products of Organonitrosohydroxylamines

George¹,

Kierstead²,

Wright³

1959

Can. J. Chem.

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The stable alkylation products of alkyl and aryl nitrosohydroxylan~ir~es seem to exist in a hitherto unknown structure, the diimide dioxide linkage. The alternative possibility is the alkyl diazotate monoxide structure, but the latter cannot account for the pure methane evolved when the substances are treated with methyl halide Grignard reagent. T h e principal products of this reaction with Grignard reagents are diirnide monoxides formed subsequently by addition of an equivalent of reagent with elimination of the original alkoxy group a s its magnesium salt. Nitration of N-methyl-N'-phenyldiimide dioxide shows that in salt-forming media (nitric-sulphuric) the NpOzR group is electrically negative, but dipole moment studies show that it is highly degenerate. This resonance stabilization is not ~~nexpected in view of the high stability of the diimide dioxides in acidic media.The first i~itrosohydroxylamii~es were prepared (1) by reaction of nitric oxide with substances contailling an active methylene group in presence of ethanolic sodium hydroxide. Typical is the reaction with acetone which may be postulated as follows:The second, more orthodox, method of preparation involved the nitrosation of a n arylhydroxylamine (2), and led to the preparation of salts such as ammonium phenyl~~itrosohydroxylaminate (cupferron). The free acids are rather unstable.When the silver salts of these nitrosohydroxylamines (11, NI = Ag) are treated with alkyl iodides two products, designated a and P, are formed. The P isomers may be desig-,hT=O N=O Me1 R-N

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Section: H~cg-c=n-n-cgh~~---h~cg-n~-cm?-cgh:mentioning

confidence: 98%

The Stable Alkylation Products of Organonitrosohydroxylamines

George¹,

Kierstead²,

Wright³

1959

Can. J. Chem.

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“…In two cases (benzaldehyde phenylhydrazone and furfural phenylhydrazone, table 1), the carbon-nitrogen double bond has been oxidized to the oxirane group by perbenzoic acid (54) but in other instances a different type of reaction has been reported. Bergmann, Ulpts, and Witte (54) oxidized benzanil with perbenzoic acid in ether solution and obtained nitrobenzene and benzaldehyde.…”

Section: Miscellaneousmentioning

confidence: 99%

Organic Peracids.

Swern¹

1949

Chem. Rev.

244

108

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“…Bergmann and coworkers reported in 1923 that oxidation of benzaldehyde Nphenylhydrazone 76 with perbenzoic acid led to the unlikely structure 77. 79 After several more misassignments, 80-82 the correct structure of the "Bergmann oxide" was finally established as The activation energy for breaking the central C-C bond of 78 was a remarkably low 14 kcal/mol, indicating that α-azoxy radicals 79 are particularly stable. These radicals were observed by ESR in a hot toluene solution of 78; in fact, the ESR spectra of many hydrazonyloxides have been analyzed in detail.…”

Section: α-Azoxy Radicalsmentioning

confidence: 99%

The free radical chemistry of the azoxy group

Engel¹,

Duan²,

Shu-Lin³

et al. 2003

Arkivoc

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The azoxy functional group, though relatively uncommon, is found in several natural products and in liquid crystalline compounds. Azoxyalkanes are generally very stable to heat and light and are not subject to attack by radicals. Intramolecular radical reactions, however, can lead to cyclic aminyl nitroxides and hydrazyls, which rearrange further or undergo fragmentation. The azoxy group greatly stabilizes an attached carbon-centered radical but the chemistry of the resulting α-azoxy radicals is not completely understood.

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Über oxydative Spaltung der Hydrazone und über Derivate des Oxyhydrazins

Cited by 12 publications

References 4 publications

The Stable Alkylation Products of Organonitrosohydroxylamines

The Stable Alkylation Products of Organonitrosohydroxylamines

Organic Peracids.

The free radical chemistry of the azoxy group

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