One-pot synthesis of fluorinated 2-amino-pyrimidine-N-oxides. Competing pathways in the four-atom side-chain rearrangements of 1,2,4-oxadiazoles |
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Authors: | Silvestre Buscemi Andrea Pace Nicolò Vivona |
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Institution: | a Dipartimento di Chimica Organica ‘E. Paternò’, Università degli Studi di Palermo, Viale delle Scienze - Parco d'Orleans II, I-90128 Palermo, Italy b Dipartimento di Chimica e Chimica industriale, Università di Genova, Via Dodecaneso 31 - I-16146 Genova, Italy |
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Abstract: | Trifluoromethylated 2-amino-pyrimidine N-oxides have been synthesized by reaction of the 3-amino-5-methyl-1,2,4-oxadiazole with trifluoromethyl-β-diketones in the presence of perchloric acid, followed by hydrolysis. In this ring-to-ring transformation an initial formation of (unisolated) 1,2,4-oxadiazole-pyrimidinium salts, and subsequent ring-opening at the oxadiazole moiety occurs. Isolation of 2-(hydroxyamino)-pyrimidine from the reaction mixture evidenced the presence of a competing pathway where the N(4) nitrogen of the oxadiazole is involved in the formation of a regioisomeric pyrimidinium salt. The effect of the trifluoromethyl group on the product distribution is discussed. By X-ray analysis, the crystal structure of two different N-oxide regioisomers has been unambiguously ascertained. |
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Keywords: | Pyrimidine N-oxides 1 2 4-oxadiazole Fluorinated heterocycles Side-chain rearrangement |
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