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Pure Appl. Chem. 76(9), 1691-1703, 2004

Pure and Applied Chemistry

Vol. 76, Issue 9

Monocyclic and cascade rearrangements of furoxans

N. N. Makhova, I. V. Ovchinnikov, A. S. Kulikov, S. I. Molotov, and E. L. Baryshnikova

N.D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, Moscow 119991, Russia

Abstract: Monocyclic rearrangements of azoles are extensively studied as alternative methods for the preparation of new heterocyclic systems. The present work is devoted to investigation of monocyclic and cascade rearrangements of 1,2,5-oxadiazole 2-oxide (furoxan) derivatives. It was found during investigations that rearrangements of furoxan ring had some peculiarities in comparison with analogous rearrangements of other azoles. Therefore, three different kinds of rearrangements were found. The first of them occurred through a dinitroso-ethylene intermediate and resulted in the synthesis of 1,2,3-triazole 1-oxides [oximes of 5-acetyl-4-phenyl(methyl)-2-phenyl-2H -1,2,3-triazole 1-oxides and 2-(furoxan-4-yl)-4-nitro-5-R-2H -1,2,3-triazole 1-oxides ]by thermal recyclization accordingly of 3-methyl-4-acetyl(benzoyl)furoxans phenylhydrazones and 3,3'-(R)-disubstituted-4,4'-azofuroxans. The latter reaction was performed in an oxidizing medium. The second kind of rearrangement (classical variant) was the synthesis of new azoles containing the 1-nitroalkyl substituent. These rearrangements were performed using three examples: base-induced interconversion of furoxanyl ketone phenylhydrazones into 5-(1-nitroalkyl)-2H-1,2,3-triazole derivatives and of 1-alkyl(aryl)-3-(furoxan-4-yl)amidines into 1-substituted 3-(1-nitroalkyl)-1,2,4-triazoles as well as a thermally induced rearrangement of 4-thioureido-3-R-furoxans into derivatives of 5-amino-3-(1-nitroalkyl)-1,2,4-thiadiazole including (5-amino-1,2,4-thiadiazol-3-yl)nitro-formaldehyde arylhydrazones (where R =N=N ľAr). Rearrangements of the third kind were those of the cascade type. Three new cascade rearrangements of azofuroxan derivatives [3,3'-azo-4,4'-bis(acetylamino)furoxans, 3-arylazo-4-acetylaminofuroxans, and 3-arylazo-4-(3- ethoxycarbonylureido)furoxans] into 4-amino-5-nitro-2H-1,2,3-triazole derivatives were discovered. These three reactions were assumed to include two consecutive (cascade) rearrangements: a 1,2,4-oxadiazole ring was formed at the first step and then transformed into a 1,2,3-triazole ring with the participation of an azo group.

*Plenary lecture presented at the XVII Mendeleev Congress on General and Applied Chemistry, Kazan, Tatarstan, Russia, 21 -26 September 2003. Other presentations are published in this issue, pp. 1605-1798.


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