Some applications of13CNMR spectroscopy in heterocyclic structure assignments

Abstract

The usefulness of13CNMR spectral data in solving otherwise intractable structural problems in heterocyclic chemistry is illustrated with ring systems such as imidazoles, pyrazoles, thiazoles, pyrimidines, benzodioxoles, benzodioxanes, benzoxazines, benzothiazines, quinoxalines, imidazopyrazoles, imidazothiazoles, pyridobenzoxazines, thiazolobenzimidazoles, thiazinobenzimidazoles, pyrimidobenzimidazoles, naphthodioxanes and perimidines. For example, using both chemical shifts and coupling constants, especially the one across three bonds, it has been possible to assign unique structures to the addition products of acetylenedicarboxylic esters to a variety of dinucleophiles such as thioureas, guanidines, 2-aminophenol, 2-aminothiophenol, 1,8-dihydroxy and 1,8-diaminonaphthalenes and 8-hydroxy-1,2,3,4-tetrahydroquinoline. These parameters also allow easy differentiation of isomeric imidazoles arising from N-alkylation of nitroimidazoles or nitration of imidazoles and of isomeric pyrazoles obtained from the reaction of hydrazines with ethoxymethylene derivatives of 1,3-dicarbonyl compounds.