Three derivatives of the novel (E)-2-cyano-N-(4-ethoxyphenyl)-3-methylthio-3-(substituted-amino)acrylamides 3-5 were selectively synthesized by the one-pot reaction of 2-cyano-N-(4-ethoxyphenyl)acetamide (2) with substituted isothiocyanates and methyl iodide in DMF containing potassium hydroxide as a basic catalyst. The stereochemistry and the structures of the synthesized compounds were confirmed by single crystal X-ray diffraction, IR, H-1-NMR, C-13-NMR, mass spectroscopy, and elemental analyses.