Multinuclear magnetic resonance study of the structure and tautomerism of azide and iminophosphorane derivatives of chloropyridazines

Some azido- and iminophosphorane derivatives of 3,6-dichloro- and 3,4,5,6-tetrachloropyridazine were synthesized and studied by means of NMR measurements. Based on multinuclear data (chemical shifts, coupling constants) for compounds containing the azide group, no potentially possible tetrazole-azide equilibrium can be observed, even under acidic conditions. An unusual substitution of a chlorine atom (in position 4) of tetrachloropyridazine in the reaction with hydrazine was demonstrated by NMR measurements of two newly synthesized compounds containing azido- and iminophosphorane groups. Using multinuclear magnetic resonance data, the sites of ethylation and protonation of azido- and iminophosphorane derivatives of chloropyridazines were established. In the case of the tetrazolopyridazines, ethylation occurs at the N1' and N2' atoms, whereas for monocyclic compounds it takes place at the N1 and/or N2 atoms of the pyridazine ring. Preferred sites of protonation are the N1' atom of the tetrazole ring and the N1 atom of the pyridazine ring. Moreover, the structures of potassium salts of 6-(3-cyano-1-triazeno)tetrazolo[1,5-b] pyridazine and its amido derivative were established using NMR data, especially N-15 NMR chemical shifts. Copyright (C) 2002 John Wiley Sons, Ltd.