Enols and thioenols of substituted cyanomonothiocarbonylmalonamides: structures, enolization vs. thioenolization, equilibria and conformations

Condensation of organic isothiocyanates with cyanoacetamides gave 24 N- and N'-substituted cyanomonothiocarbonylmalonamides in different tautomeric ratios i.e., amide-thioamides (TMA)R3NHCSCH(CN)CONR1R2 (12), thioamide-enols of amides (E) R3NHCSC(CN)=C(OH)NR1R2 (11)or amide-thioenols (TE) R3NHC(SH)=C(CN)CONR1R2 (13). The equilibrium constants (K(thioenol) =TE]/TMA] and K(enol) = E]/TMA]) in solution depend on R1, R2, R3 and the solvent. The %(E + TE)for NR1R2 increases in the order NMe2 < NHMe < NH2. The (K(thioenol) + K(enol)) in various solvents follows the order CCl4 > CDCl3 > C6D6 > THF-d8 > (CD3)2CO > CD3CN > DMF-d7 > DMSO-d6. The delta(OH) values are 16.46-17.43 and the delta(SH) values are 3.87-5.26 ppm in non polar solvents, e.g.,CDCl3 and 6.34-6.97 ppm in THF-d8 and CD3CN. An intramolecular O-H...O hydrogen bond leads to the preferred Z-configuration of the enols, and an N-H...O bond stabilizes the thioenols' preferred E-configuration with a non-bonded SH in solution. X-Ray crystallography revealed that systems with high %(E + TE) in solution mostly display the enols 11 in the solid state and systems with lower %(E +TE) in solution display structure 12. The differences in delta(OH), delta(NH), K(enol) and crystallographic data for analogous enol and thioenol systems are compared.