SU405859A1 - THE METHOD OF OBTAINING 5YAS - ("- CHLORBENZOIL) -1,4-BENZENE,? YAS- (n ^ OXYBENZOIL) -1,4-BENZENE AND / OR 5YAS- (L-AMINO- - Google Patents

Description

This invention relates to a process for the preparation of b < / RTI > c- (benzoyl) -1,4-benzene derivatives, namely, bass - (/ g-chlorobenzoyl) -, 5ys - (/ g-oxybenzoyl) - and / or bis- (p-aminobenzoyl ) -1,4-benzene used in the synthesis of highly heat-resistant polymers. A known method for producing 1,4- and 1,3-bis (ha-hydroxybenzoyl) benzenes is by rearranging the terepharyl esters of tere- and psophthalic acids in the presence of aluminum chloride in carbon disulfide, followed by distilling off the solvent by the end of the reaction and heating the resulting reaction complex to 185-195 C. The yield of the target products is 38%. The disadvantage of this method is the low yield of the target products and the use of high-boiling solvent. The purpose of the invention, an increase in the yield of the target product, is achieved due to the fact that the dichlorohydride of terephthalic acid is treated with chlorobenzene in the presence of Friedl Crafts catalysts, for example ferric chloride, at 100-250 ° C, the resulting bc (- / g-chlorobenzoyl A) -1,4-benzene is isolated by known methods or is subjected to alkaline hydrolysis or ammonium monolysis in the presence of a catalyst — salts or oxides of media; forming bis (p-oxybenzoyl) -1,4-benzene or bis - (- - aminobenzoyl) 1,4-benzene is isolated by known techniques. The proposed method is simple to perform and allows to obtain the desired products with a yield of 75-99%. Example 1. A stainless steel autoclave was charged with 40.6 g (0.2 mol) of terephthalic acid dichlorohydride, 225.1 g (2.0 mol) of chlorobenzene and 2.4 g of anhydrous ferric chloride, heated under intensive displacement to 220- 230 ° C and maintained at this temperature for 7-8 hours. Then 70% chlorobenzene is distilled off, cooled to -5 ° C, the crystals are filtered off, washed on the acetone filter, and 53.2 g (75.0%) bis - (d-chlorobenzoyl) -1,4-benzene are obtained. t. pl. 252.0-252.5 ° С (dioxane). Found,%: C 67.15; And 3.72; C1 19.19. C2oHi2O2Cl2. Calculated,%: C 67.60; And 3.38; C1 19.95. Example 2. 15 g (0.0423 mol). Bis- {n, -chlorobenzoyl) -1,4-benzene, 6.77 g (0.1: 69-mol) of caustic soda, 1.4 g of copper monochloride ( CuCl) and 85 ml of water are loaded into a stainless steel autoclave, transferred for 1.5-2.0 hours at 220-230 ° C, filtered and acidified with cold water with a 5% hydrochloric acid solution to pH 3-4. The precipitated crystals of the dioxy derivative are filtered off, dissolved in vacuo, and 13.5 g (99.1%) are obtained.

b "c- (Ag-hydroxybenzoyl) -1,4-benzene, t. pl. 288-289 ° C.

Found,%: C 74.92; H 4.48.

C2oHi4O4.

Calculated,%: C 75.47; H 4.41.

Example 3. In the autoclave load 25 g (0,0705 mol) of bis- (p-chlorobenzoyl) -1,4-benzene, 75 ml of water, 3.52 g (0.035 mol) of copper monochloride, 75 ml of liquid ammonia, with vigorous stirring heated to 210-220 ° C and maintained at this temperature for 1.5-2.0 hours. The precipitate is separated, washed on the filter with plenty of water and dried in vacuo. 20.2 g (91.0%) of bis - (g-aminobenzoyl) -1,4-benzene were isolated, m.p. 280 ° C (decomp., Ethanol).

Found,%: C 76.03; H 5.40.

CjoHieOaNj.

Calculated,%: C 75.95; H 5.07.

Subject matter of the invention;

The method of obtaining bis - (/ g-chlorobenzoyl) -1,4 benzene, byb- (p-hydroxybenzoyl) -1,4-benzene and / or b "c- (p-aminobenzoyl) -1,4-benzrla, that, in order to increase the yield of the target products, terephthalic acid dichloride is treated with chlorobenzene in the presence of Friedl-Crafts catalysts, such as ferric chloride, at 100-250 ° C, the resulting bis- (phlorbenzoyl) -1,4-benzene is isolated by known techniques or subjected to to alkaline hydgolysis or ammonolysis in the presence of: a catalyst — salts or oxides of copper, forming the bs, respectively, b c - (/ r-hydroxybenzoyl) 1, 4-benzene or byb - ("- aminobenzoyl) -1,4-benzene is isolated by known methods.