SU789496A1 - Para-phenylglyoxalylbenzamino derivatives as monomers for synthesis of polyamidophenylquinoxalines - Google Patents

Description

benzoic acid or its chlorohydride in an organic solvent.

As diamines, m-phenylenediamine, 4,4-diamino) enyloxide is used, and 4.4, 4-triaminotriphenylmethane is used as triamines. p-Phenylglyoxalylbenzoic acid is synthesized by oxidation of p-phenylacetylbenoic acid with a quantitative yield.

The acylation of di- and triamines by p-phenylglyoxylbenzoic acid or its acid chloride is carried out using organic solvents at known temperatures in order to temperature. boiling point of the selected solution. When using p-phenylglyoxalylbenzene acid, the process is carried out in the presence of PCCj or SOC8a. The use of anide-type solvents allows the reaction time to be reduced to 0.5 h. The yield of the target products in all cases is close to quantitative.

Synthesis of polyamidophenylquinbxalines based on the proposed monomers is carried out according to well-known methods and produces polymers capable of forming strong and flexible films and fibers. The properties of polymers obtained on the basis of the proposed bis- (a tdiketone) are similar to those on the properties of polymers obtained on the basis of monomers of a similar chemical structure.

The advantage of the proposed bis- and tris- (ot-diketones) is the simplicity of their synthesis, the greater availability of the starting materials and the high yields of the target products.

Example 1. The resulting 1,3-bis- (p-phenylglyoxylbenzamino) 0 benzene

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to a solution of 1.08 g (0.01 mol) of freshly-distilled m-phenylenediamine in 12 ml of dry N, M-dimethylacetamide, while cooling in an ice bath and in vigorous stirring, add 5.45 g (0.02 mol ) p-Lenylglyoxalylbenzoyl chloride. The cooling is removed and stirring is continued at room temperature for 0.5 h, after which the reaction solution is heated to BO-C, 2 to 3 ml of water is added until a slight turbidity of the solution and is observed. 1,3-bis- (p-phenylglyoxalylbenzamino) benzene is allowed to crystallize. The precipitated white crystals are filtered off, washed with alcohol and dried.

Yield: 99% of theoretical; melting point: 258-259 ° C.

Elemental analysis:

Found,%: C 74.72; H 4.09; N 4.91.

Cr NOA M „0,

Calculated,%: C, 74.47; H 4.17; M 4.8

Based on the obtained 1,3-bis- (p-phenylglyoxylbenzamino) -benzene and 3,3,4,4-tetraamino di-enyloxide, polyamide-phenylquinoxaline was synthesized with a viscosity of 0.5% solution in m-cresol of 1.68 dl / g and glass transition temperature of 290 ° C.

Example 2. Preparation of 4,4-bis- (p-phenylglyoxalylbenzamino) -diphenyloxide

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A mixture of 5.45 g (0.02 mol) of p-Lenilglyoxylbenzoic acid chloride, 2.0 g (0.01 mol) of 4,4-diaminodiphenyl oxide and 200 ml of dry toluene is refluxed for 5 hours until the evolution of hydrogen chloride stops. . The precipitate is filtered off, washed with alcohol, dried and recrystallized from dimethylformamide containing 10% water.

Yield 5.5 g (82% of the theoretical), T 242-244 “C,

Elemental analysis:

Found,%: C 74.63; H 4.37; N 4.39.

41 2v H

Calculated,%; C, 74.99; H 4.19;

N 4.16.

Polycondensation of the obtained 4,4-bis- (p-phenylglyoxalylbenzamino) diphenyloxide and 3.3, 4, 4-tetraaminodiphenyloxide in m-cresol synthesizes polyamide-phenylquinoxaline with a viscosity of 1.22 dl / g. The polymer is dissolved in m-cresol, N-methyl pyrrolidone and does not dissolve in chloroform. Glass transition temperature of 268 ° C polymer.

Claims (1)

Example 3. Preparation of 4.4, 4-tris- (p-phenylglyoxalylbenzamino) triphenylmethane to solution i., 89 g (0.01 mol) of tri-4-amino-enyl) methane in 35 ml of N-methylpyrrolidone at room temperature and stirring under an argon atmosphere, 8.18 g (0.03 mol) of p-phenylglyoxalylbenzoyl chloride is added. Stirring is continued for 2 hours. Then the reaction mass is poured into water. The precipitated creamy precipitate is filtered off, washed with alcohol, dried under vacuum for 2 hours, dissolved in acetone and reprecipitated in alcohol. A yellow amorphous powder is obtained with a 94% yield and a decomposition temperature in the 137-142® C. capillary. Elemental analysis: Found,%: C 76.91; H 4.79; N 4.12. Sb4 H4, NjO, e 77.02; H 4.34; Calculated,%: N 4.21. Based on the obtained tris (about-tone of tone) and 3,3, 4,4-tetraag- "indodiphenyloxide, synthesized cross-linked polyamido phenylquinoxaline, which does not melt to its decomposition temperature and does not dissolve in all tested solvents, including concentrated sulfuric acid acid. The results of elemental analysis, IR spectroscopy, the pathway for the synthesis of p-phenylglyoxalylbenzamine derivatives, and their successful use for the synthesis of polymers, allow us to conclude that the new compounds are consistent. formulas given. The formula of the invention is Phenylglyoxalylbenzamino derivative of the general formula V-C - C). ONH) TI, and 41 /. / h R is a divalent or trivalent radical; o-, n 2 or 3, monomers for the synthesis of polyamidofeinoxalines. Sources of Inmaracia, taye into account in the examination. j BTOpCKoe certificate of the USSR 1130, cl. C 07 C 49/12, 1971.. Patent QlA 3746687, 260-50, 1973.