The mechanisms for thermal and photochemical isomerizations of N-substituted 2-halopyrroles:: Syntheses of N-substituted 3-halopyrroles

Halopyrroles, N-substituted 2-halopyrroles were prepared by halogenation of N-substituted pyrroles with NBS, NCS, or surfuryl chloride. N-Substituted 3-halopyrroles were synthesized by acid-catalyzed thermal and photochemical isomerization reactions of N-substituted 2-halopyrroles. Both the thermal and photochemical reactions were acid-catalyzed. For the acid-catalyzed isomerization, a mechanism of [1,3] bromine shift followed by deprotonation is operated. For the acid-catalyzed photoisomerization, an excited triplet state of 2-protonated N-benzyl-2-halopyrrole produces an intermediate N-substituted pyrrole complex with halonium ion which is equilibrated with N-substituted pyrrole plus halonium ion, and then the halonium ion newly adds to 3-position of N-substituted pyrrole followed by deprotonation to afford N-benzyl-3-halopyrrole.