The reaction of amino-imidazoles, -pyrazoles and -triazoles with α,β-unsaturated nitriles

Abstract

The reactions of α,β-unsaturated nitriles (1, 9, 12) as bielectrophiles with aminoazoles (2, 4, 6) as binu-cleophiles were investigated. Acrylonitrile (1) reacts almost exclusively in a chemoselective Michael-type addition yielding the substituted azoles 3, 5 and 7, respectively. Cinnamonitriles 9a,b behave in a similar way, but the free CN group adds a second molecule 4 yielding 10a,b and its cyclocondensation product 11a,b as minor component. The attempted formation of azolopyrimidines is best achieved by the reaction of the benzylidenemalononitriles 12a - f with 2 or 4. The process is chemo- and regioselective. The structure determinations were based on NMR measurements including DEFT, COSY, ROESY, HMQC and HMBC techniques and correct earlier suggestions.