New methods to synthesize phthalaldehyde and its diacetals

Abstract

A new synthesis of phthalaldehyde that avoided formation of HBr involved treatment of 1,2-bis(dibromomethyl)benzene with trimethyl orthoformate (1: 6, 90 °C, 10 mol.% ZnCl2) to obtain acyclic diacetal without admixture of cyclic one (1,3-dimethoxy-1,3-dihydrobenzo-[c]furan) followed by hydrolysis to give the target dialdehyde. Phthalaldehyde reacted with CH(OMe)3 in the presence of trifluoroacetic acid to yield exclusively cyclic diacetal. Acyclic diacetal was phosphorylated by treatment with secondary chlorophosphines and by the reaction with PCl3 followed by treatment with PIII acid ester.