METHOD FOR OBTAINING 4,4'-BINAPHTHYL-1,1',8,8'-TETRACARBOXYLIC ACID FROM HALOGENACENAPHTHENES Russian patent published in 2018 - IPC C07D311/92 C07D311/76 

FIELD: technological processes; chemistry.

SUBSTANCE: invention relates to a method for the preparation of dianhydride 4,4'-binaphthyl-1,1',8,8'-tetracarboxylic acid, which can be used to produce polyimide materials used in the manufacture of fuel cell membranes, solid polymer electrolytes. Process for the preparation of dianhydride 4,4'-binaphthyl-1,1',8,8'-tetracarboxylic acid is carried out using 5-haloacenaphthene as a starting compound, which is subjected to a condensation reaction carried out in an organic amide solvent in an inert gas atmosphere in the presence of a catalyst mixture containing anhydrous nickel halide (II), zinc powder and triphenylphosphine, after which the resulting 4,4'-diacenaphthene is oxidized with sodium bichromate in glacial acetic acid and the resulting dianhydride 4,4'-binaphthyl-1,1',8,8'-tetracarboxylic acid is recovered, where the condensation reaction is carried out using 5-haloene-phenene selected from the group of the following compounds: 5-bromoacenaphthene, 5-iodoacenaphthene and 5-chloroacenaphthene, and is carried out in the presence of a catalytic mixture containing 0.2–0.4 moles of nickel halide (II), 0.2–0.4 moles of triphenylphosphine, 2–4 moles of activated zinc powder, based on 1 mole of halogenacenaphthene and an inert gas flow preheated with stirring up to 80–100 °C for 10–40 minutes, after which a haloacenaphthene solution is added to it in an organic dry amide solvent, the reaction mixture is maintained at 80–100 °C for 6–12 hours, evaporated to dryness, a low-boiling chlorine-containing organic solvent is added, and the resulting solution is acidified with hydrochloric acid, filtered, the organic filtrate is dried, the chlorinated solvent is evaporated, the residue is dissolved in a monohydric alcohol, boiled under stirring, and 4,4'-diacenaphtene recovered by filtering is dried in vacuum at 150–200 °C, after which it is dissolved with stirring in glacial acetic acid, and sodium dichromate is added to it at a rate of 8–12 moles of bichromate per 1 mole of the resulting 4,4'-diacenaphtene, then the reaction mass is boiled for 8–12 hours, cooled to 100–110 °C, poured into distilled water and aged for 4–10 hours, the precipitated residue of the desired product is filtered off, washed with cold water and dried in vacuum.

EFFECT: maximum yield of the target product is 75 %.

5 cl, 5 ex