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These ANRORC-like rearrangements appear determined by the presence of the perfluoroalkyl group at C-5 of the oxadiazole.9 The Addition of the Nucleophile on the C-5 is followed by Ring Opening and then Ring Closure by attack of the β nucleophilic center of the bidentate reagent (hydrazine or hydroxylamine) at the C-3 of the initial oxadiazole ring, a molecule of hydroxylamine being displaced in the final step.
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As previously observed,15c,16,17 the presence of an XH moiety at C-3 of the 1,2,4-oxadiazole heterocycle is needed for the ring photo. isomerization to occurr, and this is valid for both fluorinated and nonfluorinated substrates. Therefore, in the presence of a base, the involvement of deprotonated species from 3-N-methylaminooxadiazoles 9 in the reaction pathway cannot be excluded. In this context, it is worthy to note that the NH moiety of the starting oxadiazole is expected to show a significant acidity in the excited state and could be efficiently deprotonated.
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In an independent experiment, aminolysis on representative 3-methoxy-triazole 22a in the presence of methylamine left the starting material unchanged, thus excluding that compounds 11-15 could be formed by an aminolysis reaction of the first formed compounds 22 with the employed amines.
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48
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2942535048
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For the open-chain compound 23, one could anticipate different tautomeric hydrogen-bonded structure or ring-chain equilibria. However, this structural aspect has not been developed in this study.
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49
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This observation explains low yields of 3-amino- (or 3-N-alkylamino-)1,2,4-oxadiazoles obtained in the irradiation of 3-perfluoroalkanoylamino furazans in the presence of ammonia or aliphatic primary amines (see Scheme 1).6
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