SU365352A1 - METHOD OF OBTAINING SUBSTITUTED 2-OXYBENZOPHENONES - Google Patents

Description

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The invention relates to the field of producing substituted 2-hydroxybenzophenones, which can be used as light stabilizers for polymers and as complexing agents for various non-ferrous metals.

A known method for the preparation of substituted 2-hydroxybenzophenol, for example 4-chloro-2-hydroxy-4-octyloxnbenzophenone, is that 4-chloro-2,4-hydroxybenzophenone is treated with n-octyl bromide and sodium bicarbonate in absolute butyl alcohol at boiling point. The product yield 30-40%.

In a known manner, only alkoxy-substituted 2-hydroxybenzophenones can be obtained; the output of the products in a known way pizok.

The purpose of the invention is to increase the yield and expansion of the range of products obtained.

According to the proposed method, using the known reaction, new compounds described in the literature are obtained.

The method consists in the fact that the substituted 2-oxediphenylmethanes are boiled in the liquid phase by boiling with an oxidizing agent, preferably a chromium mixture or selenium dioxide, followed by separation of the target product by known methods. Yield 65-70%.

Example 1. Getting 4-octoxy-2-hydroxybenzophenone.

To a solution of 11.2 g (0.1 g mol) of selenium dioxide in 100 ml of dioxane and 2 ml of water was added 31.2 g (0.1 g mol) of 4-octoxy-2-oxydiphenylmethag1a and heated for 10 hours at boiling point . The precipitated selenium is filtered off and the filtrate is distilled in vacuo after distillation;

Received 22.5 g of the final product. Yield 69.1%; t., ,, 200-203 ° С (3 mm of mercury.).

111-spectrum (droplet between glasses) Y with, | 1626 cm F-spectrum and - transition

. „Ak with 320 NM.

In the treatment of the obtained Cstone hydroxyl. In practice, the corresponding oxime is formed with a quantitative yield.

PRI mme R 2. Obtaining 4-butyl-2-hydroxybenzophenone.

To a solution of 24.0 g (0.1 g-mol) of 2-oxn-G-butnidiphenylmethane in 50 ml of acetone to a dose of a 75.0 g solution of sodium bichromate in 30 ml of water. 100 g of 77% -non sulfuric acid is added to the obtained mixed mixture and temperature and the mixture is left overnight at room temperature, and then the mixture is heated for 4 hours at a temperature of kinen. After cooling, the organic layer is separated and after removal of the solvent it is distilled in vacuo.

16.6 g of the final product were obtained. Yield 65.5%; m.p. 140-145 ° C (1.5 mm, Hg. Art.).

IR spectrum (droplet between glasses) Y 1633 c. “-. UV spectrum n-transition

 them.

BUT

 itaKc

When the obtained ketone is treated with hydroxylamine, a corresponding oxime is formed with a quantitative yield.

UV spectrum l varnish 308 nm.

Example 3. Obtaining 2,4-dioxybenzophenone.

To a solution of 11.2 g (0.1 g mol of selenium dioxide in 100 ml of donoxane and 2 ml of water was added 20.0 g (0.1 g mol) of 2,4-dioxydiphenyl methane and heated for 10 hours at boiling point. filtered off. The solvent was distilled off. The resulting precipitate was dried in vacuo.

15.2 g of the final product were obtained. Output 71 o; t ,,., 134-136 ° C. IR spectrum (drop between the glasses) with about 1630 s. UV spectrum P - L transition Lmax 328 nm.

By treating the resulting ketone with hydroxylamine, a corresponding oxime is formed with a practically quantitative yield.

UV spectrum I., a, nm.

Example 4. Obtaining 4-chloro-2-hydroxybenzophenone.

To a solution of 21.9 g (0.1 g mol} 4-chloro-2-oxydiphenylmethane in 50 ml of acetone was added; a solution of 75.0 g of sodium bichromate in 30 ml of water. To the mixture obtained with stirring and at a temperature of 0 ° C, drop by drop 1:00 g of 77% sulfuric acid and leave the mixture overnight at room temperature, and then heated for 4 hours at boiling point. After cooling, the organic layer is separated, the solvent is distilled off.

Received 15.9 g of the final product. Yield 68.3%; t ,,., 56-58 ° C. IR spectra (droplets between glasses) with о-1628 cm. UV spectrum /, max. 322 nm transition.

Example B. Preparation 4-7 / 5 | 2g-octyl-2-hydroxybenzophenone.

To a solution of 11.2 g (0.1 g-mol) of herring dioxide g 1.00 m.A of dioxane and 2 ml of water were added 29.6 g (0.1 g-mol) of 5-7reg-Octyl-2-oxydiphenylmethane and heated for 10 hours at boiling point. The precipitated selenium is filtered off and the filtrate is distilled under vacuum after the solvent has been distilled off.

21.1 g of the final product were obtained, yield 65.0%; t. cues. 140 ° C (1 mm. Hg. Art.). Selenium can be regenerated into selenium oxide by the action of nitric acid.

When the obtained product was oximated by a known method, 5-g / 7r-octyl-2-hydroxybenzophenone oxime was obtained practically in quantitative yield; UV spectrum (in methanol)

max 324 nm.

Example 6. To a solution of 29.6 g (0.1 g mol), 5-t / 7g-octyl-2-oxydiphenylmethane in 50 ml of acetone, a solution of 75.0 g of sodium dichromate in 30 ml of water is added. Under stirring at 0 ° C, 100 g of 77% sulfuric acid are added dropwise to the mixture and the mixture is left overnight at room temperature, and then heated and after removal of the solvent, it is distilled in vacuo.

15.1 g of the final product were obtained, yield 48.7%; m.p. 10 (mmHg); UV spectrum (in methanol) A „ac 360 nm.

Subject invention

Claims (2)

1. A process for the preparation of substituted 2-hydroxybenzophenones, characterized in that in order to increase the yield and expand the range of the products obtained, the substituted 2-oxydiphenylmethanes are oxidized by boiling in the liquid phase by the action of oxidizing agents, followed by separation of the target products by known methods. 2. A method according to claim 1, characterized in that chromium blend or selenium dioxide is used as oxidizing agents.