RU2276145C1 - Method for preparing derivatives of 5,6-phthalylphenothiazine-s,s-dioxide - Google Patents

Abstract

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to a method for preparing derivatives of 5,6-phthalylphenothiazine-S,S-dioxide. Invention describes a method for preparing 5,6-phthalylphenothiazine-S,S-dioxide of the general formula:

wherein X means hydrogen, halogen atom or lower alkyl; Y means hydrogen atom or hydroxy-group. Method involves heating derivative of 2-phenylsulfonylanthraquinone in an organic solvent wherein 1-(triazene-N-sulfonate)-2-phenylsulfonylanthraquinone of the general formula:

wherein X and Y have above given values is used as derivative of 2-phenylsulfonylanthraquinone that is boiled in ethylene glycol medium in the presence of alkali or heated in glycerol medium at temperature 190-230°C. Invention provides simplifying technology of the process and expanding assortment of the end products. Prepared compounds can be used in plants of aniline-dyeing industry for preparing anthraquinone dyes.

EFFECT: improved preparing method.

2 tbl, 4 ex

Description

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

A known method for producing 5,6-phthalylphenothiazine-S, S-dioxides, which consists in the oxidation of the corresponding 5,6-phthalylphenothiazines 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, the duration of the oxidation process, and the fact that the 5,6-phthalylphenothiazines used for oxidation are themselves excellent dyes for polyester fibers (Ed. K. Venkataraman. Publishing house "Chemistry", 1974.3.205 )

The closest in technological essence and the achieved result is a method for producing 5,6-phalylphenothiazine-S, S-dioxides, 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 5,6-phthalylphenothiazine-S, S-dioxide.

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

The specified technical result is achieved by the method of obtaining compounds of General formula I,

which consists in the fact that 1- (triazene-N-sulfonate) -2-phenylsulfonylanthraquinone of the general formula II

where X and Y have the above meanings, are boiled in ethylene glycol or heated in glycerol in the presence of alkali at a temperature of 190-230 ° C. The resulting mass is cooled, neutralized with acetic acid, the precipitate is filtered off, washed on the filter with water and a pure product is obtained.

The inventive product: derivatives of 5,6-phthalylphenothiazine-S, S-dioxide of the formula I

where X is hydrogen, halogen or lower alkyl, Y is hydrogen or hydroxy.

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

Reaction conditions: boiling in ethylene glycol or heating in glycerol in the presence of alkali at temperatures up to 230 ° C.

The proposed method allows to obtain derivatives of 5,6-phthalylphenothiazine-S, S-dioxide in high yield from previously unused for this purpose 1- (triazene-N-sulfonate) -2-phenylsulfonylanthraquinones.

The composition and structure of the obtained 5,6-phthalylphenothiazine-S, S-dioxides were determined using elemental analysis and physicochemical methods.

Example 1. 5,6-Phthalylphenothiazine-S, S-dioxide

4.93 g (0.01 mol) of 1- (triazene-N-sulfonate) -2-phenylsulfonylanthraquinone, refluxed with stirring in 40 ml of ethylene glycol containing 0.4 g (0.01 mol) of sodium hydroxide , for 2.5 hours. The reaction mass is cooled to 10-15 ° C, neutralized with acetic acid, the precipitated crystals are filtered off, washed on the filter with 20-25 ml of hot water, dried at room temperature. The product yield was 2.96 g (82%) T _mp = 284-286 ° C. Found,%: N 4.18, 3.94; S 8.66, 9.01. C ₂₀ H ₁₁ NO ₄ S. Calculated,%: N 3.88; S 8.86.

Example 2. 5,6-Phthalyl-7-hydroxyphenothiazine-S, S-dioxide

In a flask equipped with a reflux condenser, 5.09 g (0.01 mol) of 1- (triazene-N-sulfonate) -2-phenylsulfonyl-4-hydroxylanthraquinone was charged with 50 ml of glycerol containing 0.4 g (0.01 mol ) potassium hydroxide and heated in an oil bath at a temperature of 230 ° C for 2.5 hours (heating in glycerin at a higher temperature is undesirable, since its decomposition begins). The reaction mass is cooled to 10-15 ° C, neutralized with acetic acid, the precipitated crystals are filtered off, washed on the filter with 20-25 ml of hot water, dried at room temperature. The product yield was 3.18 g (85%) T _mp = 304-306 ° C. Found,%: N 3.87, 4.20; S, 8.30, 8.52. C ₂₀ H ₁₁ NO ₅ S. Calculated,%: N 3.71; S 8.49.

Example 3. 5,6-Phthalylphenothiazine-S, S-dioxide

4.93 g (0.01 mol) of 1- (triazene-N-sulfonate) -2-phenylsulfonylanthraquinone is refluxed with stirring in 40 ml of glycerol containing 0.4 g (0.01 mol) of potassium hydroxide, within 2 hours. The reaction mass is cooled to 10-15 ° C, neutralized with acetic acid, the precipitated crystals are filtered off, washed on the filter with 20-25 ml of hot water, dried at room temperature. The product yield was 2.96 g (82%) T _mp = 284-286 ° C. Found,%: N 4.17, 3.95; S 8.67, 9.00. C ₂₀ H ₁₁ NO ₄ S. Calculated,%: N 3.88; S 8.86.

The synthesis of the remaining 5,6-phthalylphenothiazine-S, S-dioxides is carried out similarly when heated in glycerol, in the presence of alkali at temperatures up to 230 ° C, their characteristics are shown in table 1.

The synthesis of the starting 1- (triazene-N-sulfonate) -2-phenylsulfonylanthraquinones used to produce 5,6-phthalylphenothiazin-S, S-dioxides is carried out as follows.

Example 4. 1- (Triazene-N-sulfonate) -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. for 2 hours with a solution of nitrosyl sulfuric acid prepared from 0.83 g (0.012 mol) of nitrite sodium and 10 ml of 95% sulfuric acid. 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 sodium salt of sulfamic acid and 0.098 g (0.012 mol) of sodium acetate are added to the filtrate with stirring and cooling. They stand 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-phenylsulfonylanthraquinone are filtered off, washed on a filter with cold water, dried at room temperature. The product yield was 4.14 g (84%) T _mp = 141 ° C. Found,%: N 8.38, 8.65; S 12.81, 13.05. C ₂₀ H ₁₂ N ₃ O ₇ S ₂ Na. Calculated,%: N 8.52; S 12.98.

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

The starting 1-amino-2-phenylsulfonylanthraquinones were 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 resulting derivatives of 5,6 phthalylphenothiazine-S, S-dioxide can be used as dyes for polyester fibers.

Table 1
Characteristics of 5,6-phthalylphenothiazine-S, S-dioxides No. p / p Deputies T _pl , ° C Found Formula Calculated Exit, % X Y N% S% N% S% one. N H 284-286 3.94; 4.18 8.66; 9.01 C ₂₀ H ₁₁ NO ₄ S 3.88 8.86 82 2. N OH 304-306 3.88; 4.19 8.29; 8.56 C ₂₀ H ₁₁ NO ₅ S 3.71 8.49 84 3. CH ₃ H 327-329 3.90; 3.78 8.39; 8.58 C ₂₁ H ₁₃ NO ₄ S 3.73 8.56 85 four. CH ₃ OH 329-331 3.44; 3.61 8.42; 8.26; C ₂₁ H ₁₃ NO ₅ S 3,58 8.21 87 5. Cl H 343-345 3.62; 3.48 8.22; 8.07 C ₂₀ H ₁₀ ClNO ₄ S 3,54 8.09 85 6. Cl OH 314-316 3.28; 3.37 7.85; 7.97 C ₂₀ H ₁₀ ClNO ₅ S 3.40 7.78 84 7. Br OH 286-288 3.18; 3.00 7.20; 6.86 C ₂₀ H ₁₀ BrNO ₅ S 3.07 7.02 86

table 2
Characteristics of 1- (triazene-N-sulfonate) -2-phenylsulfonylanthraquinones No. p / p Deputies T _pl , ° C Found Formula Calculated Exit, % X Y N% S% N% S% one. H N 141 8.38; 8.65 12.81; 13.05 C ₂₀ H ₁₂ N ₃ O ₇ S ₂ Na 8.52 12.98 84 2. H IT 138 8.53; 8.21 12.79; 12.63 C ₂₀ H ₁₂ N ₃ O ₈ S ₂ Na 8.25 12.57 87 3. CH ₃ N 129 8.09; 7.99 12.93; 12.80 C ₂₁ H ₁₄ N ₃ O ₇ S ₂ Na 8.28 12.62 83 four. CH ₃ IT 127 7.79; 7.99 12.47; 12.56 C ₂₁ H ₁₄ N ₃ O ₈ S ₂ Na 8.03 12.24 86 5. Cl N 152 8.12; 7.87 11.86; 12.08 C ₂₀ H ₁₁ ClN ₃ O ₇ S ₂ Na 7.96 12,13 88 6. Cl IT 168 7.58; 7.84 11.63; 11.89 C ₂₀ H ₁₁ ClN ₃ O ₈ S ₂ Na 7.73 11.78 87 7. Br OH 175 6.99; 7.25 11.01; 10.75 C ₂₀ H ₁₁ BrN ₃ O ₈ S ₂ Na 7.14 10.88 84 * - the temperature at which decomposition of substances begins

Claims (1)

The method of obtaining derivatives of 5,6-phthalylphenothiazine-S, S-dioxide of the General formula

Where X is hydrogen, halogen or lower alkyl; Y is hydrogen or hydroxy; by heating a 2-phenylsulfonylanthraquinone derivative in an organic solvent, characterized in that 1- (triazene-N-sulfonate) -2-phenylsulfonylanthraquinone of the general formula

where X and Y have the indicated meanings, which in the presence of alkali is boiled in ethylene glycol or heated in glycerin at a temperature of 190-230 ° C.