A stepwise procedure has been developed for the synthesis of 3,6‐unsymmetrically disubstituted‐ or 3‐monosubstituted‐1,2,4,5‐tetrazines, based upon the facile substitution either of an alkylthio group in 3,6‐bis(alkylthio)‐1,2,4,5‐tetrazines (1) and (2) by nitrogen nucleophiles, particularly by hydrazine, or of a bromo group, obtained by oxidation of a hydrazino group or by an independent synthesis, by carbon nucleophiles. The ultraviolet‐visible spectra and some nuclear magnetic resonance properties are discussed.

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data of the cyclic (1)-(IV) and of the open chain sulphonyl anions (v)-(Ix) are reported in Tables 1 and 2 respectively, together with chemical shift values of the corresponding precursors. AND D*SCUSSIONlH N.m.r. Spectra of Szclpkonyl Aniorts.-Dimethyl sulphoxide was chosen as solvent for the anionic species

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