RU2276143C1 - METHOD FOR PREPARING DERIVATIVES OF 3-PHENYLSULFONYLANTHRA-[1,9-cd]-ISOXAZOLE-6-ONE - Google Patents

Abstract

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to a method for preparing derivatives of 3-phenylsulfonylanthra-[1,9-cd]-isoxazole-6-one of the general formula:

wherein X means hydrogen, halogen atom or lower alkyl; Y means hydrogen atom or hydroxy-group. Method involves heating 1-substituted derivative of 2-phenylsulfonylanthraquinone in organic solvent wherein 1-hydroxytriazeno-2-phenylsulfonylanthraquinone of the general formula:

wherein X and Y have above given values is used as 1-substituted derivative of 2-phenylsulfonylanthraquinone, and acetic anhydride is used as an organic solvent. Invention provides simplifying technology of the process and expanding assortment of the end products.

EFFECT: improved preparing method.

2 tbl, 5 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.

The known starting material for producing 5,6-phthalylphenothiazin-S, S-dioxides is the corresponding 5,6-phthalylphenothiazines, which are oxidized with hydrogen peroxide in acetic acid (Patent 3519623. 1970. USA. S.A. V.73. 121548a).

The disadvantage of this method is the use of explosive hydrogen peroxide, as well as the duration of the oxidation process.

The closest in technological essence and the achieved result is a method for producing 3-phenylsulfonylantra [1,9-cd] isoxazol-6-ones, based on heating the corresponding 1-azido-2-phenylsulfonylanthraquinones in organic solvents (Gornostaev L.M., Levdansky V .A. // ZhORKh. 1984. T.XX. Issue 11. S.2452-2458).

The disadvantage of producing 1-azido-2-phenylsulfonylanthraquinones 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-phenylsulfonylanthra [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 technical result is achieved in the development of a new method for producing derivatives of 3-phenylsulfonylanthra [1,9cd] isoxazol-6-one of the general formula I

where X is hydrogen, halogen or lower alkyl;

Y is hydrogen or hydroxy;

by heating a 1-substituted 2-phenylsulfonylanthraquinone derivative in an organic solvent in which 1-hydroxytriazeno-2-phenylsulfonylanthraquinone of the general formula II is used as the 1-substituted derivative

where X and Y have the indicated meanings, and acetic anhydride is used as the organic solvent.

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

where X is hydrogen, halogen or lower alkyl, Y is a hydrogen or hydroxy-group, consists in heating in acetic anhydride for 2-2.5 hours derivatives of 1-hydroxytriazeno-2-phenylsulfonylanthraquinone of the formula II

The resulting mass is cooled, the precipitate is filtered off and a pure product is obtained.

The proposed method allows to obtain derivatives of 3-phenylsulfonylanthra [1,9-cd] isoxazol-6-one with a high yield of previously unused 1-hydroxytriazeno-2-phenylsulfonylanthraquinones.

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

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

4.07 g (0.01 mol) of 1-hydroxytriazeno-2-phenylsulfonylanthraquinone in 30 ml of acetic anhydride are refluxed in 30 ml of flask for 2 hours. The progress of the reaction is monitored by TLC on Silufol plates. From the reaction mixture cooled to room temperature, 3-phenylsulfonylanthra [1.9-cd] isoxazol-6-one is isolated by filtration. Yield 3.03 g (84%) T _mp = 183 ° C. Found,%: N 4.07, 3.96; S 8.79, 9.01. C ₂₀ H ₁₁ NO ₄ S. Calculated,%: N 3.88. S 8.86.

Example 2. 3-Phenylsulfonyl-5-hydroxyantra [1,9-cd] isoxazol-6-one

4.23 g (0.01 mol) of 1-hydroxytriazeno-2-phenylsulfonyl-4-hydroxyanthraquinone is refluxed in 35 ml of acetic anhydride for 2.5 hours. Then the reflux condenser is changed to direct and 10 ml of acetic anhydride is distilled off from the reaction mass. The resulting solution was cooled to room temperature and the precipitated yellow crystals of 3-phenylsulfonyl-5-hydroxyantra [1,9-cd] isoxazol-6-one was filtered off, washed with 15-20 ml of water from the residue of acetic anhydride and dried at room temperature. The product yield was 3.24 g (86%) T _mp = 167 ° C. Found,%: N 3.92, 3.61; S 8.56, 8.27. C ₂₀ H ₁₁ NO ₅ S. Calculated,%: N 3.71; S 8.49.

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

4.07 g (0.01 mol) of 1-hydroxytriazeno-2-phenylsulfonylanthraquinone in 30 ml of acetic anhydride are refluxed in a flask under reflux for 2.5 hours. The progress of the reaction is monitored by TLC on Silufol plates. 3-phenylsulfonylantra [1,9-cd] isoxazol-6-one is isolated from the reaction mixture cooled to room temperature. Yield 3.05 g (85%) T _mp = 183 ° C. Found,%: N 4.08, 3.95; S 8.80 9.00. C ₂₀ H ₁₁ NO ₄ S. Calculated,%: N 3.88; S 8.86.

Example 4. 3-Phenylsulfonyl-5-hydroxyantra [1,9-cd] isoxazol-6-one

4.23 g (0.01 mol) of 1-hydroxytriazeno-2-phenylsulfonyl-4-hydroxyanthraquinone is refluxed in 35 ml of acetic anhydride for 2 hours. Then the reflux condenser is changed to direct and 10 ml of acetic anhydride is distilled off from the reaction mass. The resulting solution was cooled to room temperature and the precipitated yellow crystals of 3-phenylsulfonyl-5-hydroxyantra [1,9-cd] isoxazol-6-one was filtered off, washed with 15-20 ml of water from the residue of acetic anhydride and dried at room temperature. The product yield was 3.23 g (86%) T _mp = 167 ° C. Found,%: N 3.91, 3.62; S 8.57, 8.26. C ₂₀ H ₁₁ NO ₅ S. Calculated,%: N 3.71; S 8.49.

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

The synthesis of the starting 1-hydroxytriazeno-2-phenylsulfonylanthraquinones used to produce 3-phenylsulfonylanthra [1,9-cd] isoxazol-6-ones is carried out as follows.

Example 5. 1-Hydroxytriazeno-2-phenylsulfonylanthraquinone

A solution of 3.63 g (0.01 mol) of 1-amino-2-phenylsulfonylanthraquinone 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 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. The filtrate is slowly poured with stirring a mixture of 200 ml of ice-water, in which 0.83 g (0.012 mol) of hydroxylamine hydrochloride and 0.098 g (0.012 mol) of sodium acetate are dissolved, after 20-25 minutes yellow crystals precipitate. The mixture was kept for another 10-15 minutes, then the precipitated 1-hydroxytriazeno-2-phenylsulfonylanthraquinone was filtered off, washed on a filter with cold water, and dried at room temperature. The product yield was 3.50 g (86%) T _mp = 132 ° C. Found,%: N 10.51, 10.23; S 8.07, 7.73. C ₂₀ H ₁₃ N ₃ O ₅ S. Calculated,%: N 10.32; S 7.86.

The synthesis of the remaining 1-hydroxytriazeno-2-phenylsulfonylanthraquinones is carried out under similar conditions. Characteristics of the obtained compounds are shown in table 2.

The starting 1-amino-2-phenylsulfonylanthraquinones are prepared in a known manner by reacting 1-amino-2-chloroanthraquinone and 1-amino-2-chloro-4-hydroxyanthraquinone with the sodium salts of phenylsulfinic acids (Patent 1266902. 1968. Germany. S.A. V.69. 28600 i).

The obtained derivatives of 3-phenylsulfonylanthra [1.9cd] isoxazol-6-one can be used in basic organic synthesis to obtain derivatives of 5,6-phthalylphenothiazine-S, S-dioxides, used as dyes for polyester fibers.

Table 1 Characteristics of 3-phenylsulfonylantra [1.9cd] isoxazol-6-ones No. p / p Deputies * T _pl , ° C Found Formula Calculated Exit, % X Y N% S% N% S% one. N H 183 4.07; 3.96 8.79; 9.01 C ₂₀ H ₁₁ NO ₄ S 3.88 8.86 84 2. N OH 167 3.92; 3.61 8.27; 8.56 C ₂₀ H ₁₁ NO ₅ S 3.71 8.49 86 3. CH ₃ H 220 3.58; 3.84 8.73; 8.50 C ₂₁ H ₁₃ NO ₄ S 3.73 8.56 82 four. CH ₃ OH 187 3.77; 3.42 8.42; 8.56; C ₂₁ H ₁₃ NO ₅ S 3,58 8.21 83 5. Cl H 213 3.72; 3,50 7.91; 8.17 C ₂₀ H ₁₀ CINO ₄ S 3,54 8.09 87 6. Cl OH 177 3.63; 3.57 7.98; 8.01 C ₂₀ H ₁₀ CINO ₅ S 3.40 7.78 88 7. Br OH 197 3.21: 2.97 7.11; 7.28 C ₂₀ H ₁₀ BrNO ₅ S 3.07 7.02 81 * - the temperature at which decomposition of substances begins

table 2 Characteristics of 1-hydroxytriazeno-2-phenylsulfonylanthraquinones No. p / p Deputies * T _pl , ° C Found Formula Calculated Exit, % X Y N% S% N% S% one. N H 132 10.51; 10.23 8.07; 7.73 C ₂₀ H ₁₃ N ₃ O ₅ S 10.32 7.86 86 2. N OH 127 10.12; 9.87 7.80; 7.49 C ₂₀ H ₁₃ N ₃ O ₆ S 9.93 7.56 86 3. CH ₃ H 121 10.16; 9.81 7.79; 7.85 C ₂₁ H ₁₅ N ₃ O ₅ S 9.98 7.60 82 four. CH ₃ OH 118 9.78; 9.57 7.56; 7.69 C ₂₁ H ₁₅ N ₃ O ₆ S 9.61 7.32 83 5. Cl H 146 9.72; 9.50 7.12; 7.37 C ₂₀ H ₁₂ CIN ₃ O ₅ S 9.51 7.25 87 6. Cl OH 156 9.01; 9.25 7.17; 7.29 C ₂₀ H ₁₂ CIN ₃ O ₆ S 9.18 6.99 88 7. Br OH 166 8.51; 8.30 6.54; 6.23 C ₂₀ H ₁₂ BrN ₃ O ₆ S 8.37 6.37 81 * - the temperature at which decomposition of substances begins

Claims (1)

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

where X is hydrogen, halogen or lower alkyl; Y is hydrogen or hydroxy; by heating a 1-substituted 2-phenylsulfonylanthraquinone derivative in an organic solvent, characterized in that 1-hydroxytriazeno-2-phenylsulfonylanthraquinone of the general formula is taken as a 1-substituted derivative

where X and Y have the indicated meanings, and as an organic solvent, acetic anhydride is used.