METAL-DIRECTED SYNTHESIS OF MACROCYCLIC TETRAAMINES WITH PENDANT NITRO OR AMINE GROUPS, BASED ON TRANS-CYCLOHEXANE-1,2-DIAMINE

Reaction of R,R:S,S-, R,R:R,R(or :S,S)-bis(trans-cyclohexane-1,2-diami ne)copper(II) with formaldehyde and nitroethane in aqueous base yields the macrocyclic molecular cation etraazatricyclo[16.4.0.0(7,12)]docos ane)copper(II) with two -NH-CH2-C(Me)(NO2)-CH2-NH- links completing th e macrocycle, as well as the molecular cation yl)-2-methyl-2-nitroprop ane-1,3-diamine]copper(II) with a single such link inserted. The rigid polycylic macrocycle, based on a 14-membered tetraazacycloalkane (cyc lam) frame, may exist as a number of isomers. Spectroscopic and chirop tical properties of the isolated complexes are reported. Reduction of the nitro groups with zinc in aqueous acid produces the corresponding molecules with primary amine (or ammonium) pendants in good yield, as metal-free hydrochloride salts.