SU558900A1 - Biphenyl derivatives with bridging groups as monomers for the production of heat-resistant polymers - Google Patents

Description

(54) DERIVED DIFF AS A MONO 1 The invention relates to new compounds - diphenip derivatives with bridging groups of the general formula where Y is an oxygen atom or a methylene group. These diphenyl derivatives with bridging groups can be used as monomers in the synthesis of heat-resistant polymers. Other monomers of this type, diacetyl-substituted keto-phenylenes, are known, on the basis of which they obtain fiberglass plastics that do not have high strength characteristics at high temperatures tl. Diacetyl-aromatic compounds capable of polycyclotrimerization with the formation of spatial polymers are known (Schigty polymers of this type have 5% weight loss at 380A in air with MOXIC GROUPS FOR GETTING THERMAL-RESISTANT LIMETERS 2,430 ° C10% at 440-47 ° C, Steam-pegaeted glass heat-resistant, 1440 ° C, 10% C, 10% at 440-47O ° C, Steam-resistant, thermally dimer-resistant thermimeters have been obtained. Based on these polymers, they are capable of operation at 300 ° C for 15–170 hours, prc 35O ° C, 2O hours.These polymers obtained on the basis of known diacegylaromatics have insufficient thermal stability. are monomers to obtain heat-resistant polymeric materials capable of operating at temperatures above 30 ° C-35 ° C and maintaining high strength characteristics under these conditions. Compounds of the general formula where Y is an oxygen atom or methylene group J are obtained by acylation of dibenzofuran or fluorene, taken in excess, of heptafluoric acid dichloride in the presence of aluminum chloride, followed by acetyping of half acetic acid chloroacetyl by the reaction of Friedel-Krafgs. Example 1, Obtaining 1,4-bis- (2-dibenzofurylcarbonip) benzene (1) in the melt. In flasks, equipped with a stirrer and a reflux condenser, 86.0 g (0.51 mol) of dibenzofran and 34 g (0.26 mol) of aluminum chloride are prevented and the mixture is heated to 85 ° C. 13.0 g (0.064 mol) of gerephthalic acid dichloride are heated to the mixture gradually with stirring over a period of 5 hours. Heating is continued until hydrogen chloride is released (2 hours). The reaction mixture is heated with 50 ml of dioxane, 10O ml of diethyl ether is added. The precipitated precipitate is repeatedly stratified with ether, then with hot toluene and pyridine. Crude yield 27 g. After recrystallization from toluene, 19.8 g of compound 1 are obtained (66.5% of the theoretical), m.p. 280-293 ° C. Found.,%: C 82.84; H 4.25; O 12.9 Calculated,%: C 82.39; H 3.89; About 13 B and the K-spectrum, the following absorption bands were detected, cm: 1653-1645 (carbonyl group), 1593 (benzene core), 1245 (ether oxygen). The onset temperature for the thermo-oxidative degradation of compound 1 in oxygen is C. Example 2. Preparation of 1,4-bis (2-dibenzofurylcarbonyl) benzene (1) in a solution of methylene chloride. To skoyi 1OO ml of methylene chloride, 10 g (0.05 mol) of terephthalic acid dichloride and 42 g (0.025 mol) of dibenzofuran when cooled to –2 ° C. while stirring, 27 g (0.2 mol) chloride, x; o aluminum are gradually added. After cessation of the release of hydrogen chloride, the reaction mixture is poured into dilute hydrochloric acid mixed with ice, the precipitate is filtered off, washed with water, ethyl alcohol, and extracted with ether. The yield of the crude compound 1 is 13.7 g. After recrystallization from pyridine, 11.3 g of compound 1 (47.7% of TeOf-ethical) are obtained, t, pl. 276-290 ° C. Found,%: C 82.70; H 4.07; O 13.2 S.GN804 Calculated,%: C 82.39; H 3.89; 013.7 Example 3. Preparation of 1,4-bis (8-acetyl-2-dibenzofurylcarbonyl) benzene (2). To a mixture of 50 ml of carbon disulfide, 8.1 g of 0.104 mol) of acetyl chloride and 34.5 g of 0.26 mol) of aluminum chloride are gradually added with stirring 10.7 g of 0.023 mol) of compound 1. The reaction mixture is heated to boiling point 3 hour. Carbon disulfide is removed by extraction. The complex of acetylated product with aluminum chloride is suspended in air, decomposed with dilute hydrochloric acid mixed with ice, filtered off, washed with water, and alcohol. Crude yield 2-11.7 g; After recrystallization from pyridine, 4.8 g of product 2 are obtained, mp. 319-321 ° C. Found,%: C, 77.32; H 4.33; About 18.36. Calculated,%: C 78.53; H4, OZ; 017.44 The following absorption bands were observed in the IR spectrum of compound 2, cm: 1667 (acetyl group), 1648 (carbonyl group of benzophenone type), 1590 (benzene core), 1245 (ether oxygen). Example 4. Obtaining 1,4-bis- (2-fluorenylcarbonyl) benzene (3). To a mixture of 27 g of carbon disulfide, 5.6 g (0.042 mol) of aluminum chloride and 7.0 g (О, 042 mol) of fluorene, 1.4 g, (0.007 mol) of terephthalic acid dichloride was added. After the termination of the release of hydrogen chloride, the precipitated complex of the adhytylated product with aluminum chloride is filtered off, dried in air and decomposed with dilute hydrochloric acid mixed with ice, filtered off again, washed with water and dried. After recrystallization from toluene, 2.0 g (61.7% of theory) of compound 3 are obtained, m.p. 294-ZOO C. Found,%: C 87.32; H 4.99; About 9.5; NWO 66. Calculated,%: C 88j28; H 4.79; 06.92; NWO, 0. .. The following absorption bands of YaSm were detected in the IR spectrum: .i1646 (carbonyl group of benzophenone type), 1610, 1500 (benzene cores), 830 (2-substituted fluorene). Example 5. Preparation of 1,4-bis- (7-acetyp-2-fluoreylcarbonyl) benzene (4) To a mixture of 2.0 g (0.043 mol) of compound 3, 4.0 g (0.03 mol) of aluminum chloride when cooled while stirring, 6.7 g (O, O85 mol) of acetyl chloride was added. The mixture is then heated for 3 hours at 40 ° C. Compound 4 is isolated, csc is indicated in Example 2. The yield of the crude compound 4 is 2.1 g. After recrystallization from pyridine, 1, О g (41.5% og of georegical) prod, -kta,

square ZO8-312 ° C. Found,%: C 82.78;

H 5.15; 012.07 ..

38 26 4

Calculated,%: C 83.5; H4.79; About 11.71.

The following absorption bands, 1676 (acetyl group), 1646 (carbonyl group, benophenone type), 1607, 1496 (beisole cores), 822, 825 (2,7-substituted fluorene), were found in the IR spectrum.

Claims (2)

1. Forward number 201268О / 04, cl. C 07 C 43/20, C 07 C 49/76, C 07 C 69/82, 05.04.74. 2. For the number 2O11473 / 04, cl. C 07 C 49/76, 04.O4.74.