Structure and tautomerism of azo coupling products from N-alkylenaminones derived from acetylacetone and benzoylacetone in solid phase and in solution

Abstract

A series of azo coupling products have been prepared by reaction of substituted benzenediazonium tetrafluoroborates with N-alkyl 4-aminopent-3-en-2-ones or 3-amino-1-phenylbut-2-en-1-ones. The structure and tautomerism of the reaction products were studied by means of single-crystal X-ray study and by NMR spectroscopy in deuteriochloroform solution. The azo coupling products obtained from 4-methylaminopent-3-en-2-ones (3a–i) exist in CDCl3 solution as E/Z isomer mixtures with the Z isomer strongly predominating. The major isomer is a mixture of enamino–azo and imino–hydrazo tautomers with the former predominating. The proportion of the azo form depends on substitution of the benzene ring of the diazonium salt and decreases in the order of MeO > Me > Br > NO2. The position of tautomeric equilibrium is practically unaffected by switching from 4-methylaminopent-3-en-2-ones to 3-methylamino-1-phenylbut-2-en-1-ones. In the solid phase, the azo form always predominates; substitution of diazonium salt and at N3 nitrogen does not significantly affect the position of the tautomeric equilibrium. The azo coupling products always exist in the form of a single Z isomer. All determined structures, in the solid state, consist of a mixture of the two tautomeric forms, amino–diazenyl and imino–hydrazone, in ratios ranging from 82/18 to 91/9%. The weighed superimposition of both the hydrogen-bonded N1N2–C1C2–N3H/ HN1–N2C1–C2N3 heterodienic fragments, however, do not allow to clarify the effects of the para-substituents at the N1-phenyl ring both on the N1⋯N3 hydrogen-bond distances and on the bond lengths in the heterodienic systems within the series 3a–c,f and 4a–c,e,f.