In the reaction of 4-ethoxycarbonylmethyl-1,2,4-triazoline-5-thione derivatives (Ia,b) with the primary amines the corresponding amides (IIa,b-IVa,b) have been formed. These amides were then undergone to reduction with LiAlH4 leading to the formation of corresponding amines (Va,b-VIIa,b). Then by means of the reaction with acetic anhydride these amines were transformed into corresponding acetylamine derivatives of 1,2,4-triazoline-5-thione (VIIIa,b-Xa,b).