Novel, Metal-Free, Superacid-Catalyzed “Click” Reactions of Isatins with Linear, Nonactivated, Multiring Aromatic Hydrocarbons

Abstract

A novel series of linear, high-molecular-weight polymers was synthesized by one-pot, metal-free superacid-catalyzed reaction of isatins (1a−d) with linear, nonactivated, multiring aromatic hydrocarbons: biphenyl (A), p-terphenyl (B), p-quaterphenyl (C), 2-(4-biphenylyl)-6-phenylbenzoxazole (D), 9H-fluorene (E), 9,9-dimethyl-9H-fluorene (F), 2,2′-[2,5-bis(trifluoromethyl)-1,4-phenylene]bis(9,9-dimethyl-9H-fluorene) (G), oligo-9,9-bis(2,6-ethylhexyl)-9H-fluorene (H), biphenol (I), and bi-2-napththol (J). The reactions were performed at room temperature in the Bronsted superacid trifluoromethanesulfonic acid (CF3SO3H, TFSA) and in a mixture of TFSA with methylene chloride or TFA tolerant of hydroxyl, carboxy, and cyano groups. The polymers obtained were soluble in most common organic solvents, and flexible transparent films could be cast from the solutions. 1H and 13C NMR analyses of the polymers synthesized revealed their linear structure with para-substitution in the phenylene fragments of the main chain. ...