Solid supramolecular complexes of potassium salts of N-methoxynitroanilinederivatives and methoxyamino-3,5-dinitropyridine with 18-crown-6 ether

Reactions of substituted N-methoxynitroaniline derivatives (1) or 2-methoxy amino-3,5-dinitropyridine (2) with potassium hydroxide afford the correspon ding potassium salts (K(+)A(-)) in high yield. After dissolution of these s alts in dichloromethane in the presence of 18-crown-6 ether (18-C-6), the a ddition of petroleum ether led to the precipitation of the corresponding so lid supramolecular complexes of the type [18-C-6 . . .K](+)A(-), having the stoichiometry 1:1:1. The UV/vis and H-1 NMR spectra are discussed. A barri er of DeltaG(not equal) = 15.3 +/- 0.2 kcal/mol for rotation about the Ar-N bond has been determined for N-methoxy-2-cyano-4,6-dinitroaniline. The sup ramolecular complex [18-C-6 . . .K](+)A(-) derived from 2 has been N-methyl ated with methyl iodide to afford 3, and N-arylated with 2chloro-3,5-dinitr opyridine to afford 4. The conformations of compounds 3 and 4 have been cal culated.