Abstract
A new series of benzo-substituted macrocyclic diamides were prepared by nucleophilic reaction of the appropriate dipotassium salts with the corresponding bis(halo) compounds in refluxing DMF. Treatment of the novel macrocyclic diamides with Lawesson's reagent in refluxing toluene led to the formation of the corresponding macrocyclic dithiodiamides in good yields. Molecular orbital calculations were performed at the semi-empirical level AM I on some of the studied macrocycles. Thermodynamic functions show that the most stable structures in gas phase that have internal amine groups are less in energy than the other ones that have internal carbonyl groups. The solvent polarity does not appreciably affect the stability trend of the three conformers of each compound due to their comparable dipole moments. A complete and thorough survey of proton affinity (PA) and proton detachment energies (PDE) on each of the possible sites has been performed. (C) 2007 Elsevier Ltd. All rights reserved.