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:S,S)-bis(trans-cyclohexane-1,2-diamine)copper(II) with formaldehyde and nitroethane in aqueous base yields the macrocyclic molecular cation (4,15-dimethyl-4,15-dimethyl-4,15-dinitro-2,6,13,17-tetraazatricyclo[16.4.0.0(7,12)]docosane)copper(II) with two -NH-CH2-C(Me)(NO2)-CH2-NH- links completing the macrocycle, as well as the molecular cation [N,N'-bis(2-aminocyclohexyl)-2-methyl-2-nitropropane-1,3-diamine]copper(II) with a single such link inserted. The rigid polycylic macrocycle, based on a 14-membered tetraazacycloalkane (cyclam) frame, may exist as a number of isomers. Spectroscopic and chiroptical 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.