N-TOSYLATED POLYAZA[N](1,4)NAPHTHALENOPHANES - SYNTHESIS AND CONFORMATIONAL STUDIES

N-Tosylated polyaza[n](1,4)naphthalenophanes containing from 3 to 6 nitrogen atoms and from 9 to 18 atoms in the saturated bridge can be prepared in high yields from 1,4-bis(bromomethyl)naphthalene and the appropriate N-tosylated polyamine chains. NMR data and molecular mechanics calculations suggest the prevalence of conformations in which the polyamine bridge is located above the aromatic ring. Variable-temperature NMR experiments show that internal rotation of the aromatic ring is not allowed, on the NMR time scale, even at 180 degrees C for naphthalenophanes having chain lengths of 12 or less. For naphthalenophanes with chain lengths of 14 or 15 atoms, the rotational barrier is on the order of 12 kcal mol(-1) as calculated from VT-NMR data.