Seven new benzyl (3–9) and four new phenethyl (10–13) amino analogues of ansa- macrolide rifampicin (1) were synthesized using the optimised method of reductive amination. Structures of 3–13 in solution were determined by 1D and 2D NMR and FT-IR methods whereas the energetically most favoured conformation of amino analogues was calculated with the use of the PM5 method. Spectroscopic and semi-empirical studies ...