Derivatization of Coumarins at the Benzenoid Ring in Aqueous Medium

Abstract

Some 6‐disubstituted, 8‐disubstituted, and/6,8‐disubstituted compounds have been prepared from coumarin, 7‐methylcoumarin, and 3,4‐benzocoumarin. The Reimer–Tiemann reaction, Lederer–Manasse reaction, bromination using molecular bromine as well as 2,4,4,6‐tetrabromocyclohex‐2,5‐dien‐1‐one, Elbs reaction, and diazocoupling have been carried under controlled conditions to obtain various derivatives. Further, several reactions of aldehyde derivatives of these coumarins have been carried on to prepare important functional compounds including some heterocycles. It is noteworthy that these aldehydes behave as phenolic aldehydes under alkaline conditions to undergo the Dakin reaction. The reactions are mostly carried in aqueous media involving a dianionic intermediate and hence fulfill one important criterion of green chemistry.