Reactions of 3-methylthio, 3-mercapto and 3-alkylamino-6-chloro-7-R1-1,1-dioxo-1,4,2-benzodithiazines (Ia-b, IIa, IIIa-e and IVa-b) with amines were investigated. Respective 1,3-dialkyl-2-(4-chloro-2-mercapto-5-R1-benzenesulphonyl)guanidines possessing equal (Va-i) or unequal (VIa-c) alkyl substituents at the 1,3-positions were obtained. Some observations regarding the influence of molar ratio, as well the kind of amines used on the course of reactions were presented. Finally, the probable mechanisms of these reactions were discussed.