The Formation of the Azoxy-group in the Oxidation of Compounds with Nitrogen–Nitrogen Bonds

Yandovskii, V. N.; Gidaspov, B. V.; Целинский, И. В.

doi:10.1070/rc1981v050n02abeh002554

Cited by 18 publications

(3 citation statements)

References 181 publications

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“…Reactions of nitric oxide with carbanions were originally reported by Traube more than a century ago and have been extended to a series of carbanions derived from ketones by Yandovskii et al several decades later. − Traube's characterization of products, performed with techniques available in the 1890s, need careful scrutiny. Nevertheless, the phenomenological core of his results remains remarkably accurate.…”

Section: Introductionmentioning

confidence: 99%

Synthesis of Diazeniumdiolates from the Reactions of Nitric Oxide with Enolates

Arulsamy

Bohle

2005

J. Org. Chem.

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[reaction: see text] Reactions of nitric oxide with enolates derived from aliphatic methyl ketones containing alpha-methylene or alpha-methine groups and with enolates derived from alpha,alpha'-dimethylene or alpha,alpha'-dimethine ketones yield mono- or bis(diazeniumdiolate) products. Diazeniumdiolation occurs in the following order: alpha-methine > alpha-methylene > alpha-methyl. The amount of the base used alters the extent of diazeniumdiolation and the course of the reaction. Mono- and bis(diazeniumdiolate)-substituted methyl ketones are cleaved in the presence of excess base before and after the subsequent diazeniumdiolation of the alpha-methyl group. Similar to the trihalogenated methyl groups in the base-assisted halogenation reactions of methyl ketones, the bis(diazeniumdiolate)-substituted alpha-methylene and alpha-methyl groups act as leaving groups in the presence of excess base. The reaction of nitric oxide with a (approximately 20:80, cis/trans) mixture of 2,6-cyclohexananone yields the cis and trans isomers of 2,6-dimethylcyclohexanone-2,6-bis(diazeniumdiolate) in 12.9% and 57.6% yield. Single-crystal X-ray diffraction data determined for potassium cis-2,6-dimethylcyclohexanone-2,6-bis(diazeniumdiolate), cis-14b, reveal that the N(2)O(2-) substituent is planar with considerable delocalization of a double bond over the anionic four-atom group. Except for one of the diazeniumdiolate products, namely, potassium propanoate 2,2-bis(diazeniumdiolate), 8b, all are stable in neutral and basic aqueous media. Compound 8b slowly decomposes in neutral aqueous solution releasing nitrous oxide and nitric oxide gases but is stable in basic aqueous media. Differential scanning calorimetry data measured for the diazeniumdiolate products indicate that they decompose exothermally with most of them undergoing explosive decomposition at moderately high temperatures (181-274 degrees C).

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Section: Introductionmentioning

confidence: 99%

Synthesis of Diazeniumdiolates from the Reactions of Nitric Oxide with Enolates

Arulsamy

Bohle

2005

J. Org. Chem.

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“…Azoxy compounds are of increasing importance on account of their biological activity, but the radical chemistry of azoxyalkanes is largely undeveloped . Presently we report the intramolecular addition of a β-carbon radical 1 to azoxy oxygen followed by fragmentation 2 → 3 , as shown in Scheme .…”

Section: Introductionmentioning

confidence: 88%

Radical Cyclization and Fragmentation of Azoxy Compounds

Engel

Wang

et al. 1999

J. Am. Chem. Soc.

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Photolysis of azoazoxyalkane 9 and thermolysis of β-azoxyperester 13 afford β-azoxy radicals 1 and 14, respectively. One reaction pathway of these radicals is cyclization to azoxy oxygen to form cyclic hydrazyl radicals 2 and 16 that fragment to a ketone or aldehyde plus hydrazonyl radical 3. The analogous hydrazyl radical 6 need not be invoked in the case of γ-azoxy radical 5, which instead undergoes a rare solution phase β-scission to lose ethylene. Surprisingly, the same β-scission was found in the 3,3-dimethyl-4-pentenyl radical (34), a hydrocarbon analogue of 5.

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“…GOPl: 212 mg (1.00 mmol) of 6, 600 mg (3.45 mmol) of MCPBA, 2 d at 5 12(13)-0xide (14a,b), 3a, t-4a, t-8a, t-9a)-A2-Octahydro-r-4, c-9-azo-t-I, t-2, t-6, t-7-diepoxy-c-5, c-8-etheno-lH-cyclopenta(b)naphthalene 12(13)-oxide (15a,b): -4a, t-aa, t-9a, t-10a)-A2-Dodecahydro-c-9,c-10-azor-I,c-4, t-5, t-8 (t-4a, t-8a, t-9a, t-l0a)-Perhydro-c-9,c-l0-azo-r-l,c-4…”

Section: T-3a T-4a T-8a T-9a)-a2-0ctahydro-r-4 C-9-azo-t-5 T-8-mmentioning

confidence: 99%

Azo bridges from azines. XV. Oxygenation of Unsaturated Cyclic Azo Compounds with peracids

Hünig

Schmitt

1996

J. Prakt. Chem.

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Azo bridges in compounds 3, 6, 11, 16, 20 and 22 are chemospecifically oxidized with MCPBA to the corresponding azoxy derivatives 4, 7, 12, 17, 21, and 23 in the presence of one or two (20, 22) double bonds even if these are located in a close parallel position to the azo bridge (6, 11, 20, 22). The order of reactivity of different olefinic moieties towards MCPBA was found to be bicycloheptene > bicyclooctene, cyclopentene. Thus, epoxy/azoxides 5, 8, 13, 14, and 19 as well as bisepoxy/azoxides 10 and 15 were obtained. If both the azo and the olefinic bridge are part of a bicycloheptane system (24) the azo group can be no longer oxidized chemospecifically (25 + 26).

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The Formation of the Azoxy-group in the Oxidation of Compounds with Nitrogen–Nitrogen Bonds

Cited by 18 publications

References 181 publications

Synthesis of Diazeniumdiolates from the Reactions of Nitric Oxide with Enolates

Synthesis of Diazeniumdiolates from the Reactions of Nitric Oxide with Enolates

Radical Cyclization and Fragmentation of Azoxy Compounds

Azo bridges from azines. XV. Oxygenation of Unsaturated Cyclic Azo Compounds with peracids

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