3,5-Dinitro-N-(4’-benzo-15-crown-5)-benzamide derivatives. Synthesis and properties

Four new derivatives of benzo-15-crown-5 (4 - 7) were synthesized from 4'-amino-benzo-15- crown-5 (3) and 2-chloro-3,5-dinitrobenzoic acid (1) or its chloride (2): the amide 4 resulted from 2 and 3, and the arylamine 5 from 1 and 3. A compound with two crown ether cavities (6) resulted from 3 and 4. Nucleophilic substitution with methoxyamine converted 4 into 7. Structures were confirmed by 1 H-NMR, 13 C-NMR, and IR-ATR spectroscopy. Geometries of the the new compounds are presented. The hydrophobic character of 5, 6, and 7 was measured by reverse-phase thin-layer chromatography (RP-TLC). The yellow-orange compound 7, in the solid state and in acetonitrile solution becomes deeper-colored in the presence of solid lithium or sodium hydroxides. Stability constants of the corresponding supramolecular complexes 8 (from 7 with LiOH or NaOH) were determined. The supramolecular complex 8 (with Na + ) was also obtained in solid state and was characterized by 1 NMR, IR-ATR and UV-vis spectroscopy.