1-acetyl-5,10-dioxy-5,10-dihydro-2h-anthra[2,3-d][1,2,3]triazole-7,8-dicarboxylic acid

FIELD: chemistry.

SUBSTANCE: described is a novel compound - 1-acetyl-5,10-dioxy-5,10-dihydro-2H-anthra[2,3-D][1,2,3]triazole-7,8-dicarboxylic acid of formula , which can be used as a starting compound in synthesis of metal complexes of tetra[4,5]([6,7]1-acetyl-2H-naphtho[2,3-D][1,2,3]triazole-5,8-dione)phthalocyanine.

EFFECT: possibility of use as dyes or catalysts.

1 cl, 3 ex, 4 dwg, 1 dwg

 

Introduction

The invention relates to the chemical industry, namely, to obtain a new derivative of 2,3-dicarboxaldehyde as starting compound for the synthesis of metal complexes of Tetra[4,5]([6,7]1-acetyl-2H-oil[2,3-D][1,2,3]triazole-5,8-dione)phthalocyanine, which can be used as dyes and catalysts.

The level of technology

Known 2,3-dicarboxaldehyde [K.Sakamoto, E.Ohno. Synthesis of Cobalt Phthalocyanine Derivatives and their Cyclic Voltammograms // Dyes and Pigments. 1997. Vol.35. # 4. P.380]

However, when using this compound as the source can be obtained only tetranitroaniline that do not have coloring properties and do not show catalytic activity.

The invention

Inventive task was to search for new compounds, which are derivatives of 2,3-dicarboxaldehyde that when using it as a source of product would give the opportunity to synthesize metal complexes of Tetra[4,5]([6,7]1-acetyl-2H-oil[2,3-D][1,2,3]triazole-5,8-dione)phthalocyanine having the properties of dyes for polymer materials and catalysts for various processes.

The problem is solved 1-acetyl-5,10-deoxy-5,10-dihydro-2H-anthra[2,3-D][1,2,3]triazole-7,8-dicarboxylic acid of the formula

The structure of this compound to the azan data of elemental analysis and IR spectroscopy.

Thus, in the IR spectrum of the inventive compound (1) it is possible to allocate a number of common absorption bands with anthraquinone [C.Pecile, B.Lunelli. Polarized Infrared Spectra of Single Crystals of 9,10-Anthraquinone and 9,10-Anthraquinone-ds// J. Chem. Phys. 1967. Vol.46. N 6. P.2109-2118].

The invention provides the following advantages: the use of 1-acetyl-5,10-deoxy-5,10-dihydro-2H-anthra[2,3-D][1,2,3]triazole-7,8-dicarboxylic acid gives the possibility to synthesize metal complexes of Tetra[4,5]([6,7]1-acetyl-2H-oil[2,3-D][1,2,3]triazole-5,8-dione)phthalocyanine having the ability to paint polymeric materials and exhibiting catalytic properties.

Information confirming the possibility of carrying out the invention

To implement the invention using the following ingredients:

benzotriazol - TU 6-09-1291-87;

acetic anhydride - GOST 21039-75;

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

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

concentrated sulphuric acid - GOST 4204-77.

The target product is obtained in three stages.

Stage 1. The acylation of benzotriazole acetic anhydride according to the scheme:

In a round-bottom three-neck flask with a capacity of 100 ml dissolve 11.9 g (0.1 mol) of benzotriazole in 20 ml of toluene. The flask connected with a reflux condenser and placed in the flask and the solution gently for 15 minutes, poured 11.3 ml (0.12 mol) of acetic any the reed. When this reaction mixture is heated to boiling. After adding the total amount of acetic anhydride mixture is allowed to cool. The precipitated crystals acicular forms is filtered on a Buechner funnel, washed with toluene in small portions until no odor of acetic acid and air-dried between sheets of filter paper.

Output 1-acetylbenzoate - 11,

Stage 2. Acylation of 1-acetylbenzoate the dianhydride pyromellitic acid in the presence of anhydrous aluminum chloride according to the scheme:

In triggerlevel flask with a capacity of 100 ml equipped with a stirrer, reflux condenser and thermometer, is placed 10.0 g (0.046 mole) of the dianhydride pyromellitic acid, 8.21 g (0.051 mol) of 1-acetylbenzoate and 20 ml of heptane. The mass is heated to 50°C. and with stirring add 16.12 g (0.119 mol) of anhydrous aluminum chloride. Stand 3 hours at boiling of the reaction mass (≈100°C), and after removal of the heptane another 6 hours at 120÷130°C. To the cooled mass consistently add 50 ml of water and 10 ml of concentrated hydrochloric acid and stirred for 12 hours. The precipitate is filtered off, washed with hot water and boil for 30÷40 minutes in a 10%solution of soda. The hot solution is filtered, the precipitate is treated in this way 3-4 times. The filtrate is acidified with hydrochloric acid to pH 4 and Oh adut to 10÷15°C. The precipitation is filtered off, washed with water until neutral. Dried at 80°C.

Output 5-[(1-acetyl-2H-1,2,3-benzotriazol-5-yl)carbonyl]-benzene-1,2,4-tricarboxylic acid - 7,

Stage 3. Intramolecular cyclization by treatment of 5-[(1-acetyl-2H-1,2,3-benzotriazol-5-yl)carbonyl]benzene-1,2,4-tricarboxylic acid, concentrated sulfuric acid (monohydrate) according to the scheme:

In a three-neck flask of 100 ml equipped with a stirrer, reflux condenser and thermometer, was placed 20 ml (0.18 mol) of monohydrate and heated to 130°C. and Then for 15 minutes with vigorous stirring, add 5 g (0.011 mol) of the obtained 5-[(1-acetyl-2H-1,2,3-benzotriazol-5-yl)carbonyl]benzene-1,2,4-tricarboxylic acid, the temperature was raised to 150°C and maintained for 5 hours. The mass after cooling with stirring, poured into 200 ml of water, filtered, the precipitate washed with a large amount of ice-cold water, dissolve in soda solution and acidified with hydrochloric acid. The precipitate is filtered off and washed with water until the disappearance of the chloride ions. Such processing is repeated twice. Dried at 100°C.

Found, %: C - 57.50; H - 2.32; N - 11.05. C18H9N3O7.

Calculated, %: C - 57.00; H - 2.39; N - 11.08.

Yield: 4.1 g (86%). Melting point - 346°C.

The obtained target product - 1-acetyl-5,10-deoxy-5,10-dihydro-2H-EN is RA[2,3-D][1,2,3]triazole-7,8-dicarboxylic acid solid white, has a solubility in aqueous-alkaline solutions, hot water, acetone, DMF.

Example 1. The use of 1-acetyl-5,10-deoxy-5,10-dihydro-2H-anthra[2,3-D][1,2,3]triazole-7,8-dicarboxylic acid as a starting compound for the synthesis of copper and cobalt complexes of Tetra[4,5]([6,7]1-acetyl-2H-oil[2,3-D][1,2,3]triazole-5,8-dione)-phthalocyanine

In a quartz ampoule put the pounded mixture of 0.23 g (0.60 mmol) of 1-acetyl-5,10-deoxy-5,10-dihydro-2H-anthra[2,3-D][1,2,3]triazole-7,8-dicarboxylic acid, 0.24 g (4.00 mmol) of urea, 0.036 g (0.18 mmol) of copper acetate or 0.036 g (0.18 mmol) of cobalt acetate, 0.02 g (0.40 mmol) of ammonium chloride and 0.002 g (0.01 mmol) of ammonium molybdate. The mass is slowly heated to 180°C for one hour and incubated for 3 hours. After cooling, the reaction mass is crushed, transferred to a filter Shota, washed with 5%hydrochloric acid and then with water until the wash liquid when applying the drops on a glass slide and evaporation remains solid residue. Dried at 100°C. Then periostat of concentrated sulfuric acid and washed to conventional Soxhlet extractions with acetone for 10 hours. Dried at 100°C.

The output of Tetra[4,5]([6,7] 1-acetyl-2H-oil[2,3-D][1,2,3]triazole-5,8-dione)of copper phthalocyanine - 0.13,

The output of Tetra[4,5]([6,7]1-acetyl-2H-oil[2,3-D][1,2,3]triazole-5,8-dione)phthalocyanine cobalt - 0.12,

These synthesized compounds is predstavlyaet a blue-green substance, soluble in concentrated sulfuric acid, dimethyl sulfoxide, dimethylformamide.

ESP Tetra[4,5]([6,7]1-acetyl-2H-oil[2,3-D][1,2,3]triazole-5,8-dione)of copper phthalocyanine in dimethyl sulfoxide. λmaxnm: 352, 644, 689 (figure 2).

ESP Tetra[4,5]([6,7]1-acetyl-2H-oil[2,3-D][1,2,3]triazole-5,8-dione)phthalocyanine cobalt in dimethyl sulfoxide. λmax; nm: 352, 646, 688 (figure 3).

Found, %: C 60.53; H 1.98; N 19.61. C54H28N11O9Cu;

With 60.73; H 1.98; N 19.67. C54H28N11O9Co.

Calculated, %: C 60.10; H, 1.80; N, 19.18. C54H28N11O9Cu;

C, 60.97; H, 1.75; N, 19.52. C54H28N11O9Co.

Example 2. The use of Tetra[4,5]([6,7]1-acetyl-2H-oil[2,3-D][1,2,3]triazole-5,8-dione)of copper phthalocyanine as a dye for dyeing polyethylene and polystyrene.

The dyeing of polyethylene. 2 g of polyethylene is placed in a porcelain Cup and heated to melt, then pour in 5 ml of dimethyl sulfoxide, which is dissolved 0.003 g of Tetra[4,5]([6,7]1-acetyl-2H-oil[2,3-D][1,2,3]triazole-5,8-dione)of copper phthalocyanine. Stand when heated to completely remove the dimethyl sulfoxide and the resulting mass is poured into the form.

The sample is attached (see figure 5).

Dyeing polystyrene. 2 g of the polystyrene is placed in a porcelain Cup and heated to melt, then pour in 5 ml of dimethyl sulfoxide, which is dissolved 0.003 g of Tetra[4,5]([6,7]1-acetyl-N-oil[2,3-D][1,2,3]triazole-5,8-dione)of copper phthalocyanine. Stand when heated to completely remove the dimethyl sulfoxide and the resulting mass is poured into the form.

The sample is attached (see figure 5).

Example 3. The use of Tetra[4,5]([6,7]1-acetyl-2H-oil[2,3-D][1,2,3]triazole-5,8-dione)phthalocyanine cobalt as catalyst for the oxidation of mercaptans.

Study of catalytic activity of the cobalt complex of Tetra[4,5]([6,7]1-acetyl-2H-oil[2,3-1)][1,2,3]triazole-5,8-dione)phthalocyanine was carried out on 0.02 M solution diethyldithiocarbamate sodium (DETC) on the setup depicted in figure 4. The installation contains: 1 thermometer, 2 - bubbler, 3 - glass, 4 - samples of a heterogeneous catalyst, 5 - pump, 6 - sampler 7 - reverse refrigerator.

For the preparation of heterogeneous catalyst in 50 ml of a solution of the cobalt complex of Tetra[4,5]([6,7]1-acetyl-2H-oil[2,3-D][1,2,3]triazole-5,8-dione)phthalocyanine in DMF to a concentration of 0.01 mol/l immersed and fully impregnate the sample of non-woven polypropylene weight 2, Then the sample is removed and immersed in water to remove the organic solvent. When this happens fast crystallization and precipitation of the cobalt complex on the surface of the polypropylene fibers. The concentration of the complex on the surface of the nonwoven material when such processing is 1.9·10-5mol per 1 g of polypropylene. Received this about the time the heterogeneous catalyst is placed in a glass DADD, equipped with a CIRCULATOR pump 650 capacity 600 l/h to supply air required for oxidation at a constant speed of 2 l/min. After the establishment in the reaction mixture in a glass of constant temperature selected a sample of 2 ml to determine the initial concentration DADD and breathable. The time of air supply is taken for the start of the reaction. During the reaction after a certain period of time take samples of 2 ml for spectrometric determination of current concentration DADD.

The effective rate constant for the oxidation DADD is 3.2±0.3 sec-1

1-Acetyl-5,10-deoxy-5,10-dihydro-2H-anthra[2,3-D][1,2,3]triazole-7,8-dicarboxylic acid of the formula



 

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