Gabriel Synthesis of Hexakis(aminomethyl)benzene and Its Derivatization

Abstract Hexakis(aminomethyl)benzene, which is a key precursor for various hexa‐substituted functional molecules, was synthesized by Gabriel synthesis. Nucleophilic substitution of hexakis(bromomethyl)benzene with potassium phthalimide gave hexakis(phthalimidemethyl)benzene in excellent yield. Hydrazinolysis of the phthalimide moieties of hexakis(phthalimidemethyl)benzene afforded a mixture of hexakis(aminomethyl)benzene and 2,3‐dihydrophthalazine‐1,4‐dione. Pure hexakis(aminomethyl)benzene was isolated as its hexahydrochloride upon treating the mixture with HCl. Hexakis‐amides and hexakis‐tosylamide were prepared from hexahydrochloride of hexakis(aminomethyl)benzene in good to high yields. Alkyl‐substituted hexakis‐amide shows extremely high solubility in non‐polar organic solvents like chloroform and n ‐hexane. Density functional theory calculation of the structure of hexakis‐amide show that all substituents were oriented to the same side ( aaaaaa conformation) via intramolecular hydrogen bonding.