Synthesis and Reactions of 2-Arylhydrazinotropones. II. Synthesis of 5-Aryltropolones and B-Ring-Open Colchicine Analogues via Benzidine Type Rearrangement of 2-(2-Arylhydrazino)tropones

Article abstract of DOI:10.1246/bcsj.62.128

Treatment of a wide variety of 2-(2-arylhydrazino)tropones with ethanolic acid at 50-80 deg C readily gave the benzidine type rearrangement products, 2-amino-5-(4-aminoaryl)tropones, besides minor amounts of byproducts of various type.The main products were conveniently led to the corresponding 5-aryltropolones.Similarly, 2-(2-arylhydrazino)tropones bearing an isopropyl and isopropenyl group at the 4-position afforded 4-substituted 2-amino-5-(4-aminoaryl)tropones as the main products, which were also led to 4-substituted 5-(4-acetamidoaryl)- and 5-(4-methoxyaryl)tropolones.Structural assignments of these products were made on the basis of 1H NMR and other spectral data as well as of chemical transformations to known 5-phenyltropolone and also to 2-acetamido-8-hydroxy-10,10-dimethylcycloheptinden-7(10H)-one.This synthetic scheme may possibly be utilized for a convenient synthesis of B-ring-open analogues of colchicine.