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Supramolecular Interactions In Biologically Relevant Compounds. 2-Pyrazineformamide Thiosemicarbazones And Some Products Of Their Cyclization

A. Castiñeiras, I. Garcia-Santos, Silvia Nogueiras, I. Rodríguez-González, Raúl Rodríguez-Riobó
Published 2014 · Chemistry

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Abstract Reaction of 2-cyanopyrazine with thiosemicarbazide or N-methylthiosemicarbazide afforded the (Z)-2-(amino(pyrazin-2-yl)methylene)hydrazinecarbothioamide (HPzAm4DH) and (Z)-2-(amino(pyrazin-2-yl)methylene)-N-methylhydrazine carbothioamide (HPzAm4M), respectively. (2Z,N′E)-N′-(4-Oxothiazolidin-2-ylidene)pyrazine-2-carbohydrazonamide (HPzAmot, 5) and (2Z,N′E)-N′-(3-methyl-4-oxothiazolidin-2-ylidene)pyrazine-2-carbohydrazonamide (MPzAmot, 7) have been synthesized from these thiosemicarbazones with chloroacetic or bromoacetic acids, using a conventional synthetic methodology and microwave-assisted organic reaction enhancement. The crystal structures of the thiosemicarbazones and their solvates [HPzAm4DH⋅1/2 MeOH (1), HPzAm4DH⋅H2O (2), HPzAm4M (3), HPzAm4M⋅2H2O (4)] and the 1,3-thiazolidin-4-ones (5 and 7) have been studied by X-ray diffractometry. All of the compounds were characterized by elemental analysis, mass spectrometry, FT-IR and 1H and 13C NMR spectroscopy. Several by-products have also been isolated in a crystalline form, namely 3-((Z,E)-N′-(4-oxothiazolidin-2-ylidene)carbamohydrazonium-yl)pyrazin-1-ium dibromide monohydrate, (H3PzAmot)Br2⋅H2O (6), 2-((5-(pyrazin-2-yl)-1H-1,2,4-triazol-3-yl)thio)acetic acid, (H2Pz124ttAc) (8), 2-amino-5-(pyrazin-2-yl)-1,3,4-thiadiazol-3-ium chloride monohydrate, (HPz134tda)Cl⋅H2O (9), and 2-(methylamino)-5-(pyrazin-2-yl)-1,3,4-thiadiazol-3-ium chloride N-methyl-5-(pyrazin-2-yl)-1,3,4-thiadiazol-2-amine solvate, (HMPz134tda)Cl⋅(MPz134tda) (10). The structures of these compounds were also analyzed by X-ray diffractometry. The microwave-assisted organic reaction method for synthesis is easy, convenient, and ecofriendly when compared to the traditional synthetic methods. Crystal analysis revealed that the compounds have extended 3D supramolecular networks through high levels of H-bonding and weak molecular interactions between the molecular moieties and solvent molecules. The novel synthons, which are sustained by N H⋯N and N H⋯O hydrogen bonding and other weak interactions, have been shown to assemble with 1,3-thizolidine-4-ones, 1,2,4-trizole, or 1,3,4-thiadiazole derivatives in a zigzag or herringbone architecture.
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