RU2330029C1 - METHOD OF OBTAINING DERIVATIVES 3-AROILANTRA-(1,9-cd)ISOXAZOLE-6-ONE - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: invention relates to the method of obtaining the derivatives 3-aroilanra-(1,9-cd)isoxazole-6-one of the general formula

where X - hydrogen, halogen or the lowest alkyl, which are used as intermediate products in synthesis of derivatives 7,8-phthalylclaridone used as dyes for various polymeric materials and polyester fibres. The essence of the method lies in boiling 1(triazene-N-sulfonate)-2-aroihtranquonine in spirit solution of alkali with the subsequent neutralisation by acetic acid.

EFFECT: simpler technology and safer process.

1 cl, 2 tbl, 3 ex

Description

The invention relates to chemistry and technology of intermediate products and organic dyes and can be used at enterprises of the aniline-dye industry to obtain anthraquinone dyes.

Known starting materials for the preparation of 7,8-phthaloyl acridones are 1-nitroantraquinone-2-carboxylic acid and various aromatic amines. For example, 3-methyl-7,8-phthaloyl acridone is prepared by reacting 1-nitroantraquinone-2-carboxylic acid with p-toluidine (Patent 262469, Germany, 1915, Frdl., Bd 2. S.687).

The disadvantage of this method is the inaccessibility of the starting products, the formation of by-products in the condensation process, the low yield of the resulting dye.

The closest in technological essence and the achieved result is a method for producing 3-aroylantra [1,9-cd] isoxazole-6-ones, based on heating the corresponding 1-azido-2-aroylanthraquinones in organic solvents (Gornostaev L.M., Levdansky V .A., Arnold E.V. // Chemistry of heterocyclic compounds, 1983, No. 1, pp. 22-25; USSR Patent 857128, 1981, bull.

The disadvantage of obtaining 1-azido-2-aroylanthraquinones is the use of nitric acid or its alkali metal salts, which can form explosive mixtures both with air (nitric acid) and in the presence of heavy metals (heavy metal azides are explosive), which makes the process unsafe.

The problem solved by the invention is to create a new method for producing derivatives of 3-aroylanthra [1,9-cd] isoxazol-6-one.

The technical result is the simplification of process technology and the expansion of the range of target products.

The specified technical result is achieved in the development of a new method for producing derivatives of 3-aroylanthra [1,9-cd] isoxazole-6-one of the general formula I

where X is hydrogen, halogen or an alkyl group, which consists in the fact that 1- (triazene-N-sulfonate) -2-aroylanthraquinone of the general formula II

boil in an alcohol solution of alkali, followed by neutralization with acetic acid.

The inventive product: derivatives of 3-aroylanthra [1,9-cd] isoxazol-6-one of the formula I

where X - has the above meanings.

Reagent: 1- (triazene-N-sulfonate) -2-aroylanthraquinone of formula II

Reaction conditions: boiling in an alcohol solution of alkali.

The proposed method allows to obtain derivatives of 3-aroylanthra [1,9-cd] isoxazol-6-one with a high yield of 1- (triazene-N-sulfonate) -2-aroylanthraquinones not previously used for this purpose.

The composition and structure of the obtained 3-aroilantra [1,9-cd] isoxazol-6-ones were determined using elemental analysis and physicochemical methods.

Example 1. 3-Aroylantra [1,9-cd] isoxazol-6-one

4.57 g (0.01 mol) of 1- (triazene-N-sulfonate) -2-aroylanthraquinone is refluxed with stirring in 50 ml of ethyl alcohol containing 0.4 g (0.01 mol) of sodium hydroxide , for 0.5-1 hours. The reaction mass is cooled to 10-15 ° C, neutralized with acetic acid, diluted with 50-60 ml of water and the precipitated crystals are filtered off, washed on the filter with 20-25 ml of water, dried at room temperature. The product yield was 2.83 g (87%). _Mp = 248-250 ° C. Found,%: N 4.53; 4.37. C ₂₁ H ₁₁ NO ₃ . Calculated,%: N 4.31.

Example 2. 3-Aroylanthra [1.9-cd] isoxazol-6-one

4.57 g (0.01 mol) of 1- (triazene-N-sulfonate) -2-aroylanthraquinone is refluxed with stirring in 40 ml of ethyl alcohol containing 0.4 g (0.01 mol) of potassium hydroxide for 40 minutes. The reaction mass is cooled to 10-15 ° C, neutralized with acetic acid, diluted with 50-60 ml of water and the precipitated crystals are filtered off, washed on the filter with 20-25 ml of water, dried at room temperature. The product yield was 2.86 g (88%). _Mp = 248-250 ° C. Found,%: N 4.20; 4.41. C ₂₁ H ₁₁ NO ₃ . Calculated,%: N 4.31.

The synthesis of the remaining 3-aroylantra [1,9-cd] isoxazol-6-ones is carried out similarly, their characteristics are shown in table 1.

Table 1
Characteristics of 3-aroylanthra [1.9-cd] isoxazole-6-ones No. p / p Deputy X * T _pl . ° C Found N,% Formula Calculated N,% Exit % one N 248-250 4.53; 4.37 C ₂₁ H ₁₁ NO ₃ 4.31 87 2 CH ₃ 261-263 4.25; 4.07 C ₂₂ H ₁₃ NO ₃ 4.13 84 3 Cl 300-302 4.01; 3.80 C ₂₁ H ₁₀ ClNO ₃ 3.89 89 four Br 285-287 3.37; 3,51 C ₂₁ H ₁₀ BrNO ₃ 3.46 85 * - the temperature at which decomposition of substances begins

The synthesis of the starting 1- (triazen-N-sulfonate) -2-aroylanthraquinones used to produce 3-aroylanthra [1,9-cd] isoxazol-6-ones is carried out as follows.

Example 3. 1- (Triazene-N-sulfonate) -2-aroylanthraquinone

A solution of 3.27 g (0.01 mol) of 1-amino-2-aroylanthraquinone in 100 ml of acetic acid is diazotized at 5-10 ° C with a solution of nitrosyl sulfuric acid prepared from 0.83 g (0.012 mol) of sodium nitrite and 10 ml of 95 % sulfuric acid, within 2 hours. Then the reaction mass is diluted with 10-15 ml of water, activated carbon is added and filtered from impurities. Then, 1.43 g (0.012 mol) of sulfamic acid sodium salt and 0.098 g (0.012 mol) of sodium acetate are added to the filtrate with stirring and cooling. It is kept for 15-20 minutes with stirring, then the reaction mixture is diluted with 100-150 ml of cold water, the precipitated crystals of 1- (triazene-N-sulfonate) -2-aroylanthraquinone are filtered off, washed on a filter with cold water, dried at room temperature. The product yield was 4.04 g (89%). _Mp = 121 ° C. Found,%: N 9.31, 9.12; S 6.88, 7.09. C ₂₁ H ₁₂ N ₃ O ₆ SNa. Calculated,%: N 9.19; S 7.00.

The synthesis of the remaining 1- (triazene-N-sulfonate) -2-aroylanthraquinones is carried out under similar conditions. Characteristics of the obtained compounds are shown in table 2.

The starting 1-amino-2-aroylanthraquinones were prepared in a known manner by acylating aromatic hydrocarbons with 1-amino-2-anthraquinonecarboxylic acid chloride in the presence of aluminum chloride (Dokunikhin N.S., Shein S.M., Boguslavskaya I.L. // ZhORKh . 1964. T.34. S.1565).

The obtained derivatives of 3-aroylanthra [1,9-cd] isoxazole-6-one can be used in basic organic synthesis to obtain derivatives of 7,8-phthaloyl acridone, used as dyes for various polymeric materials and polyester fibers.

table 2
Characteristics of 1- (triazene-N-sulfonate) -2-aroylanthraquinones No. p / p Deputy X ^* T _pl ° C Found Formula Calculated Exit % N% S% N% S,% one N 118 9.29; 9.08 6.79; 7.05 C ₂₁ H ₁₂ N ₃ O ₆ SNa 9.19 7.00 89 2 CH ₃ 126 8.81; 9.07 6.58; 6.70 C ₂₂ H ₁₄ N ₃ O ₆ SNa 8.92 6.79 87 3 Cl 137 8.72; 8.63 6.37; 6.61 C ₂₁ H ₁₁ ClN ₃ O ₆ SNa 8.54 6.51 90 four Br 130 7.98; 8.01 6.13; 5.89 C ₂₁ H ₁₁ BrN ₃ O ₆ SNa 7.84 5.97 88 * - the temperature at which decomposition of substances begins

Claims (1)

The method of obtaining derivatives of 3-aroylanthra [1,9-cd] isoxazol-6-one of the General formula

where X is hydrogen, halogen or lower alkyl, heating the 2-aroylanthraquinone derivative in an organic solvent, characterized in that 1- (triazene-N-sulfonate) -2-aroylanthraquinone of the general formula is used as the 2-aroylanthraquinone derivative

where X has the indicated meanings, which is boiled in an alcohol solution of alkali, followed by neutralization with acetic acid.