It has been found that despite the presence of three active amino moieties of carbamoylguanidine, it adds to sulfonyl chloride by the amino group, not the carbamoyl groups, to give monosulfonamides. Being 1,3-dipolar compounds, the arylsulfonylcarbamoylguanidines obtained readily add to polarophiles, such as chloroacetonitrile and benzoin, to form imidazolylsulfonamides or make pyrimidinylsulfonamides by reacting with arylidene malonodinitrile. A study of the reactivity of sulfonyl-2-carbamoylguanidine in the N-alkylation reaction has revealed that the reaction proceeds exceptionally via the replacement of the hydrogen atom at the sulfonamide nitrogen. Examination of some sulfonyl-N-carbamoylguanidine derivatives has shown their high rust-preventing and tribological properties in lubricating oils and greases, as well as antimicrobic activity.