RU2264381C1 - 2,3-dicarboxy-5,6,8-trimethylanthraquinone - Google Patents

Abstract

FIELD: organic chemistry.

SUBSTANCE: invention relates to 2,3-dicarboxy-5,6,8-trimethylanthraquinone of the formula (I):

. This compound can be used in synthesis of metal complexes of tetra-(tri-5,6,8-carboxy)-anthraquinonoporphyrazine used as dyes and catalysts. Compound of the formula (I) is characterized by melting point value (T_m) 207°C. Also, invention describes methods for synthesis and using compound of the formula (I).

EFFECT: valuable properties of compound.

4 cl, 6 ex

Description

The invention relates to the chemical industry, in particular to the preparation of a new derivative of 2,3-dicarboxyanthraquinone as a starting compound for the synthesis of tetra- (tri-5,6,8-carboxy) anthraquinonoporphyrazine metal complexes, which can be used as dyes, catalysts, and others branches of science and technology.

State of the art

The rich possibility of chemical modification of the compounds of the porphyrazine series allows you to use them as:

- light-resistant dyes and pigments [Stepanov B.I. Introduction to the chemistry and technology of organic dyes. Training for universities. 3rd ed. reslave. and add. M .: Chemistry, 1984. 592 p.];

- highly effective catalysts [Tarasevich M.S., Radyushkina K.A. Catalysis and electrolysis of metalloporphyrins. M .: Nauka, 1982.268 s .; Thomas A.L. The phthalocyanines. Research and Application. Boce Ration: CRC Press. 1990. 321 p.];

- organic semiconductor materials [Simon J., Andre J.-J. Molecular semiconductors. Photovoltaic properties and solar cells. M .: Mir, 1988. 342 p.];

- medicinal and analytical reagents [Mironov AF Photodynamic therapy of cancer // In the book: Advances in the chemistry of porphyrins / Ed. Golubchikova O.A. St. Petersburg: Publishing House of the Institute of Chemistry of St. Petersburg State University, 1997. T.1. S.357-374; Moser F.H :, Thomas A.L. Phthalocyanines compounds. N.-Y .: Reinhold Publ., 1963. 365 p.];

- gas sensors [Correlation between structure of copper phthalocyanine thin films and their general performance characteristics for gas sensors / Berger O. Fischer W.-J., Plotner M. et. al. // ICCP. Dijon, France, 25-30 June 2000. P.350];

- in some other fields of science and technology [The phthalocyanines: Properties and Applications / Eds. Leznoff C.C., Lever A.B.P. N.-Y .: VCH Publishers. 1989. Vol. 1. 436 p.; 1993. Vol. 2. 436 p.; 1993. Vol. 3. 303 p.; 1996. Vol. 4. 524 p.].

By varying the peripheral environment of the porphyrazine ligand, it is possible to significantly expand the assortment of compounds of this class with various useful application properties.

One of the areas of chemical modification is the use of various starting materials. Compounds that make it possible to synthesize various porphyrazines - aromatic ortho-dicarboxylic acids and their derivatives can be attributed to one of the groups of starting materials. Another group is made up of compounds already having a porphyrazine structure, which makes it possible to obtain porphyrazines with various substituents.

Known 2,3-dicarboxyanthraquinone, which is a structural analogue [K.Sakamoto, E.Ohno. Synthesis of Cobalt Phmalocyanine Derivatives and their Cyclic Voltammograms // Dyes and Pigments. 1997. Vol. 35. N 4. P.375-386].

However, when using this compound as the starting material, only tetraantraquinonoporphyrazines can be obtained which do not have coloring properties. Therefore, they can not be used either as a pigment or when dyed in solutions.

SUMMARY OF THE INVENTION

The inventive task was to find a new compound, which is a derivative of 2,3-dicarboxyanthraquinone, which, when used as a starting product, would make it possible to synthesize substituted tetraantraquinonoporphyrazines, which have the properties of dyes of cotton and viscose materials, as well as redox catalysts.

The problem is solved by 2,3-dicarboxy-5,6,8-trimethylanthraquinone of the formula:

The structure of this compound is proved by elemental analysis and IR spectroscopy.

So, in the IR spectrum of the claimed compounds (figure 1), a number of common absorption bands with anthraquinone can be distinguished [C. Pecile, B. Lunelli. Polarized Infrared Spectra of Single Crystals of 9,10 -Anthraquinone and 9,10-Anthraquinone-d s // J. Chem. Phys. 1967. Vol. 46. N6. P.2109-2118].

The invention allows to obtain the following advantages:

the use of 2,3-dicarboxy-5,6,8-trimethylanthraquinone makes it possible to synthesize metal complexes of tetra- (tri-5,6,8-carboxy) anthraquinonoporphyrazine, which are capable of dyeing cotton and viscose materials in aqueous alkaline media, as well as wool their use as an acid dye, which also exhibits catalytic activity in redox reactions.

Information confirming the possibility of carrying out the invention

The inventive compound can be obtained, for example, in the following way.

To implement the method using the following substances:

pyromellitic acid dianhydride - TU 6-14-786-72;

anhydrous aluminum chloride - OST 6-01-300-74;

concentrated sulfuric acid (monohydrate) - GOST 4204-77;

pseudocumene - TU 6-09-785-76.

The method is implemented in two stages:

1. Acylation of pseudocumene with pyromellitic acid dianhydride in the presence of anhydrous aluminum chloride according to the scheme:

10.0 g (0.046 mol) of pyromellitic acid dianhydride, 20 ml of pseudocumene are placed in a flask equipped with a stirrer, a thermometer and a reflux condenser, and 18.4 g (0.138 mol) of anhydrous aluminum chloride are added with vigorous stirring. The reaction mixture is slowly heated to 75-80 ° C and maintained at this temperature for 8 hours. After cooling, 50 ml of water was added to the reaction mass, and after holding for 30 minutes, a hot soda solution was added and the precipitated aluminum hydroxide was separated. Hydrochloric acid was added to the aqueous layer of the filtrate to a pH of 3-4 and the precipitate of the obtained product (5- (2,3,5-trimethyl) benzoyltrimellitic acid) was filtered off, which was washed with water to a neutral medium and dried at a temperature of 75-80 ° С.

Received 5- (2,3,5-trimethyl) benzoyltrimellitic acid.

2. Intramolecular cyclization by treating 5- (2,3,5-trimethyl) -benzoyltrimellitic acid with concentrated sulfuric acid (monohydrate) according to the scheme:

In a 200 ml flask equipped with a stirrer and a thermometer, 10 ml of monohydrate is placed and heated to 130 ° C. Then, over 15 minutes, with vigorous stirring, 5 g of 5- (2,3,5-trimethyl) benzoyltrimellitic acid obtained in the first stage are added, the temperature is raised to 150 ° C and held for 5 hours. After cooling, the mass is poured into 200 ml of water with stirring, filtered, washed with a large amount of ice water, dissolved in a soda solution and acidified with hydrochloric acid. The precipitate is filtered off and washed with water until the chloride ions disappear. This treatment is repeated twice. Dried at 100 ° C.

Found,%: C 68.2; H 4.3; C ₁₉ H ₁₄ O ₆ .

Calculated,%: C 67.5; H 4.2.

Yield: 6.7 g (43%). Melting point 207 ° C.

The obtained target product, 2,3-dicarboxy-5,6,8-trimethylanthraquinone, is a white solid, soluble in aqueous alkaline solutions, hot water, DMF.

Example 1. The use of 2,3-dicarboxy-5,6,8-dimethylanthraquinone as the starting compound for the synthesis of the copper complex of tetra- (tri-5,6,8-carboxy) anthraquinonoporphyrazine.

The method is carried out in two stages:

1st stage. A test mixture of quartz glass is filled with a triturated mixture of 0.2 g (0.6 mmol) of 2,3-dicarboxy-5,6,8-trimethylanthraquinone, 0.24 g (4.0 mmol) of urea, 0.036 g (0.18 mmol) of copper acetate, 0.02 g (0.4 mmol) ) ammonium chloride and 0.002 g (0.01 mmol) of ammonium molybdate. The mass is slowly heated to 180 ° C for an hour and incubated for 3 hours. Purification of the obtained product is carried out by sequential washing with 5% hydrochloric acid, acetone and reprecipitation from sulfuric acid.

The yield of copper tetra- (tri-5,6,8-methyl) anthraquinonoporphyrazine 0.06 g (32%).

Dark blue substance, has solubility in concentrated sulfuric acid.

Found,%: C 72.1; H 3.9; N 8.8. C ₇₆ H ₄₈ N ₈ O ₈ Cu.

Calculated,%: C 72.2; H 3.8; N 8.9.

2 stage. A solution of 0.2 g of tetra- (tri-5,6,8-methyl) anthraquinonoporphyrazine copper in 3 ml of concentrated sulfuric acid is added to a two-necked flask containing 10 ml of water, heated to 55-60 ° C and 0.3 g of potassium permanganate is added with stirring in portions of 0.05 g as the color disappears. Addition of lead to the appearance of a stable color of the solution. The hot suspension is filtered. The precipitate is washed with a hot solution of sodium hydroxide and after cooling, acidified with hydrochloric acid to pH 3-4. The precipitated tetra- (tri-5,6,8-carboxy) anthraquinonoporphyrazine copper precipitate is filtered off, washed with water until neutral. Then the product is dissolved in soda solution and acidified with hydrochloric acid. The precipitate is filtered off and washed with water until the chloride ions disappear. A similar treatment is repeated twice. Dried at 75-80 ° C.

Yield of copper tetra- (tri-5,6,8-carboxy) anthraquinonoporphyrazine: 0.13 g (49%).

Dark blue substance, has solubility in aqueous alkaline solutions, DMF, concentrated sulfuric acid.

ESP in an aqueous alkaline solution, λ _max , nm: 681 (figure 2).

Found,%: C 55.4; H 1.6; N, 7.0. C ₇₆ N ₈ H ₂₄ O ₃₂ Cu.

Calculated,%: C 56.2; H 1.5; N 6.9.

Example 2. The use of 2,3-dicarboxy-5,6,8-trimethylanthraquinone as the starting compound for the synthesis of the cobalt complex of tetra- (tri-5,6,8-carboxy) anthraquinonoporphyrazine.

The synthesis is carried out analogously to example 1. In the first stage, instead of copper acetate, 0.038 g (0.18 mmol) of cobalt acetate is used.

Yield of cobalt tetra- (tri-5,6,8-methyl) anthraquinonoporphyrazine: 0.10 g (52%).

Dark blue substance, has solubility in concentrated sulfuric acid.

Found,%: C 73.2; H 3.9; N 9.1. C ₇₆ N ₈ H ₄₈ O ₈ Co.

Calculated,%: C 72.4; H 3.8; N 8.9.

In the second stage, instead of copper tetra- (tri-5,6,8-methyl) anthraquinonoporphyrazine, 0.2 g of cobalt tetra- (tri-5,6,8-methyl) anthraquinonoporphyrazine is used.

Yield of cobalt tetra- (tri-5,6,8-carboxy) anthraquinonoporphyrazine: 0.11 g (45%).

Dark blue substance, has solubility in aqueous alkaline solutions, DMF, concentrated sulfuric acid.

ESP in an aqueous alkaline solution, λ _max , nm: 676 (Fig. 3).

Found,%: C 57.0; H 1.6; N, 7.1. C ₇₆ N ₈ H ₂₄ O ₃₂ Co.

Calculated,%: C 56.4; H 1.5; N 6.9.

Example 3. The use of tetra- (tri-5,6,8-carboxy) anthraquinonoporphyrazine copper as a dye of cotton fabrics. Dyeing was carried out according to the methodology [Laboratory workshop on the use of dyes. / Ed. Melnikova B.N. M .: Chemistry - 1972.342 s.].

A sample of cotton fabric weighing 1 g is wetted for 0.5 min, squeezed to 100% weight gain and placed in a dye bath composition (g / l):

Copper tetra- (tri-5,6,8-carboxy) anthraquinonoporphyrazine 2 Sulfoside - 31 0.5 Sodium chloride 5 Bath module  fifty.

Within 15-30 minutes, the bath is heated to a boil and incubated for 1 hour. Then the sample is squeezed, washed thoroughly with warm, then cold water, and dried.

Example 4. The use of tetra- (tri-5,6,8-carboxy) anthraquinonoporphyrazine copper as a dye of viscose fabrics. Dyeing was carried out according to the methodology [Laboratory workshop on the use of dyes. / Ed. Melnikova B.N. M .: Chemistry - 1972.342 s.].

A sample of viscose fabric weighing 1 g is moistened for 0.5 min at a temperature of 40 ° C, squeezed to 100% weight gain and placed in a dye bath composition (g / l):

Copper tetra- (tri-5,6,8-carboxy) anthraquinonoporphyrazine 2 Sulfoside - 31 0.5 Sodium chloride 10 Sodium carbonate 0.5 Bath module  fifty.

Within 15-30 minutes, the bath is heated to a boil and maintained for 40 minutes at this temperature and another 20 minutes in a bath cooling to 30 ° C. Then the sample is squeezed, washed thoroughly with warm, then cold water, and dried.

Example 5. The use of tetra- (tri-5,6,8-carboxy) anthraquinonoporphyrazine copper as an acid dye.

A sample of wool fiber weighing 1 g is placed in a dye bath composition (g / l):

Copper tetra- (tri-5,6,8-carboxy) anthraquinonoporphyrazine 6 Glauber's salt 40 Bath module  fifty.

For 15-30 minutes, the bath is heated to 60 ° C and maintained at this temperature for 40 minutes and 20 minutes in a bath cooling to 30 ° C.

Then the sample is squeezed, washed thoroughly with warm, then cold water and treated with a solution of sulfuric acid composition (ml):

sulfuric acid 1 water fifty

The sample is squeezed, washed thoroughly with warm, then cold water, and dried.

Samples of colorings according to examples 3, 4, 5 are shown in figure 4.

Example 6. The use of tetra- (di-6,7-carboxy) anthraquinonoporphyrazine cobalt as a catalyst in the reaction of liquid-phase oxidation of cysteine. Catalytic activity was determined according to the method [T. Shikova Investigation of the effect of chemical modification of ligand phthalocyanine on the catalytic properties of its metal complexes. Dis ... cand. Chem. sciences. - Ivanovo. 1999. 156 p.].

The experiments were carried out in the liquid phase in a reaction vessel mounted on a high-speed rocking chair (350 kach / min), thermostatically controlled with an accuracy of ± 0.2 ° С. The reaction rate was measured volumetric, measurement accuracy ± 0.05 ml. The processes were carried out at 298 K. In a reaction vessel connected to a gasometer, 10 ml of a substrate solution and an exact weighed catalyst were loaded into a boat. The experiments were carried out in the kinetic region, when a linear dependence on the number of swings was observed for the reaction rate.

The activity of tetra- (di-6,7-carboxy) anthraquinonoporphyrazine cobalt (A) in the reaction of liquid-phase oxidation of cysteine was

A = 126 g-mol O ₂ × (g-mol cat) ^-1 × min ^-1 .

Claims (1)

2,3-dicarboxy-5,6,8-dimethylanthraquinone of the formula

Images