TRANSHALOGENATION IN CHLOROETHYNYL DERIVATIVES OF NITROGEN-CONTAINING HETEROCYCLIC-COMPOUNDS

1. Haloethynyl-N-methyldiazoles and haloethynyl-N-methyltriazoles in the presence of NaNH2 in liquid ammonia isomerize with a shift of the halogen atom to a free site on the heterocycle having enhanced acidity. The replacement of halogen by metal (sodium) proceeds competitively. 2. The relationship between the competing reactions is determined by the nature of the halogen, polarization of the haloethynyl group, acidity of the unsubstituted ring carbons, and halophilicity of the heteroaryl anions which corresponds to intermediate organosodium compounds. © 1980 Plenum Publishing Corporation.