ИСТИНА

We investigated the catalytic N-heteroarylation of some adamantane-containing amines using dihalopyridines. We found out that symmetrical 2,6- and 3,5-dihalopyridines successfully produced mono- and diamino derivatives depending on the stoichiometry of starting compounds. Generally, better results were obtained with 2,6-dichloropyridines in comparison with 2,6-dibromopyridines. Unsymmetrical 2,3- and 2,5-dihalopyridines did not produce corresponding diamino derivatives even upon reacting with great excesses of adamantaneamines. However, the catalytic substitution of the halogen atom at -carbon atom was in many cases successful, and again better results were achieved with less active dichloropyridines. The most interesting fact is the possibility to synthesize N,N-bis(5-halopyridin-2-yl) derivatives of adamantane-containing amines in yields up to 95% using 2,5-dihalopyridines taken in a 4-fold excess. Catalytic substitution of chlorine in dichloroquinolines proceeds faster in positions 2 and 4 allowing to obtain corresponding chloroquinolinyl substituted amines. Diamination of 4,7- and 4,8-dichloroquinolines with the excess of 1-(2-ethoxy)adamantane afforded diaminosubstituted quinolines in high yields while diamination of 2,6- and 2,8-isomers was not selective.