Intramolecular Reaction of tert‐Butyl‐NNO‐Azoxy and Cyano Groups – Novel Synthesis of Pyridazine, 1,2,3‐Triazepine, and Furan Rings

Abstract

A reaction of (tert‐butyl‐NNO‐azoxy)acetonitrile with N,N‐dimethylacetamide dimethylacetal afforded 2,4‐bis(tert‐butyl‐NNO‐azoxy)‐3‐methylpent‐2‐enedinitrile 9 as a main product. This compound cyclized on silica gel surface with the loss of isobutylene to give 6‐amino‐5‐(tert‐butyl‐NNO‐azoxy)‐4‐methylpyridazine‐3‐carbonitrile 2‐oxide 10. On the contrary, the cyclization of dinitrile 9 in protic solvents resulted in quite different products: furan, 1,2,3‐triazepine, and pyridazine derivatives were among them. These reactions are the first examples of intramolecular reactions of (tert‐butyl‐NNO‐azoxy) and cyano groups. The structures of products under investigation were confirmed by X‐ray diffraction analysis.