Sulfenamides are usually prepared by the reaction of sulfenyl chlorides and amines:
:RSCl  +  RNH   →   RSNR  +  HCl
The S-N bond formation generally obeys standard bimolecular nucleophilic substitution rules, with the basic nitrogen centre being the nucleophile.  Primary sulfenamide formation as shown above occurs with the reaction of the sulfenyl halide with ammonia.  Additionally primary as well as secondary and tertiary amines form sulfenamides through reaction with, thiols, disulfides, and sulfenyl thiocyanates. In one illustrative synthesis, triphenylmethanesulphenyl chloride and butylamine react in benzene at 25 C:
:PhCSCl  +  2BuNH  →  PhCSN(H)Bu + BuNHCl
Many other routes to sulfenamides are known, starting from thiols and disulfides. 
:RSSR  +  2RNH  + Ag   →  RSNR  +  AgSR  + R'NH