Dibenzo[b,e][1,4]diazepin-1-ones and their Ring-Opened Derivatives: Revisited Synthesis, 2D NMR and Crystal Structure

Abstract

The synthesis of 2,3,4,5,10,11-hexahydro-1H-dibenzo[b,e][1,4]diazepin-1-ones was revisited and a catalyst-free method was established, by exploring the reactivity of 3-[(2-aminoaryl)amino]dimedones towards carbonylated electrophiles. 2D NMR and single-crystal X-ray diffraction studies were used to characterize the structures unequivocally and to review the mechanism leading to the formation of supposed positional isomers. The action of 3-[(2-aminoaryl)amino]dimedones on chromene-3-carboxylic acid, fumaryl, and oxalyl chloride has led to dibenzo[b,e][1,4]diazepin-1-one ring opening to produce novel Z-configured enaminone and linear diamides.