Synthesis and properties of bis-dinitrophenyl derivatives of 1,7,10,16-tetraoxa-4,13-diazacyclooctadecane (Kryptofix 22)

Six new crown ethers derivatives (3a"f) with two symmetrical branches were synthesized (by S N Ar type reaction) starting from Kryptofix 22 (1) and different reactive aryl halides (2a-f); 4,13-bis(2',6'-dinitrophenyl)-1,7,10,16-tetraoxa-4,13-diazacyclooctadecane (3a), 4,13-bis(2',4'-dinitrophenyl)-1,7,10,16-tetraoxa-4,13-diazacyclooctadecane (3b), 4,13-bis[(2',6'-dinitro-4'-trifluoromethyl)phenyl]-1,7,10,16-tetraoxa-4,13-diazacyclooctadecane (3c), 4,13-bis[(2',4'-dinitro-6'-trifluoromethyl)phenyl]-1,7,10,16-tetraoxa-4,13-diazacyclooctadecane (3d), 4,13-bis[(4'-cyano-2',6'-dinitro)phenyl]-1,7,10,16-tetraoxa-4,13-diazacyclooctadecane (3e) and 4,13-bis[(6'-cyano-2',4'-dinitro)phenyl]-1,7,10,16-tetraoxa-4,13-diazacyclooctadecane (3f). Compounds 3a-f were characterized by spectral analyses (MS, 1 H- and 1 3 C-NMR, VIS), and their chromatographic behaviour was investigated by TLC and RP-TLC. The compounds 3a-f gave with Dragendorff reagent (KBiI 4 ) an intense red colour and also quenched the fluorescence of anthracene, anthracene-9,10-dipropionic acid disodium salt, carbazole, tryptophan, indole-3-acetic acid, and phenothiazine.