Synthetic Route to Phenyl Diazenes and Pyridazinium Salts from Phenylazosulfonates

J Org Chem. 2021 May 7;86(9):6228-6238. doi: 10.1021/acs.joc.1c00013. Epub 2021 Apr 26.

Abstract

The synthesis of pyridazinium salts was achieved from readily available phenylazosulfonates in a single reaction step. The reaction proceeds via the formation of short-lived phenyldiazenes, which-owing to the strongly acidic conditions-are partially protonated. The phenyldiazenes then undergo a rapid cycloaddition to furans to give pyridazinium salts via elimination of water. The fact that the pyridazinium synthesis shows a low sensitivity toward oxygen, although phenyldiazenes occur as intermediates, can be explained by the very fast cycloaddition step and the partial protonation of the phenyldiazene.