RU2246495C1 - Tetra-6-(para-sulfophenylene)-anthraquinone porphyrazine metal chelates - Google Patents

Abstract

FIELD: organic chemistry.

SUBSTANCE: invention relates to new derivatives of metalloporphyrazine of the general formula (I):

wherein M means Cu, Co. These compounds can be used as dyes, catalysts in different processes and materials of sensitive members of gas sensor.

EFFECT: valuable properties of compounds.

2 cl, 6 sch, 1 dwg, 5 ex

Description

Introduction

The invention relates to the chemical industry, namely to the production of new derivatives of metalloporphyrazines, which can be used as dyes, catalysts of various processes, materials of sensitive elements (CHED) of gases, etc.

State of the art

Known compounds [Bykova V.V., Usoltseva N.V., Zharova M.A., Lutsenko O.G., Kulinich V.P., Shaposhnikov G.P. Synthesis and study of the mesomorphic properties of sulfonic acids of substituted metallophthalocyanines // Liquid crystals and their practical use. 2003. No1. C.7-13], which are a structural analogue of the claimed compounds, tetra-4- (para-sulfophenylene) metallophthalocyanines of the formula

Tetra-4- (para-sulfophenylene) phthalocyanine of copper in water and in aqueous solutions of sodium or ammonium hydroxides exhibits a lyotropic mesophase [Bykova VV, Usoltseva NV, Zharova MA, Lutsenko OG, Kulinich V.P., Shaposhnikov G.P. Synthesis and study of the mesomorphic properties of sulfonic acids of substituted metallophthalocyanines // Liquid crystals and their practical use. 2003. No1. S.7-13].

The closest structural analogue of the claimed compounds [K.Sakamoto, E.Ohno Synthesis of Cobalt Phthalocyanine Derivatives and their Cyclic Voltammograms // Dyes and Pigments. 1997. Vol. 35. N 4. P.375-386] are metal complexes of tetraantraquinonoporphyrazine of the formula

They do not have coloring properties and therefore can not be used either as a pigment or when dyed in solutions.

SUMMARY OF THE INVENTION

The inventive task was to search for new metalloporphyrazines that possessed the properties of a direct dye and an oxidation catalyst for sulfur compounds.

The problem is solved by tetra-6- (para-sulfophenylene) anthraquinonoporphyrazine metal complexes of the formula

The structure of this compound is proved by the data of elemental analysis, IR and electron spectroscopy.

So, in the IR spectra of the claimed compounds (FIGS. 1, 2), a number of common absorption bands with a non-sulfonated analogue can be distinguished [K.Sakamoto, E.Ohno Synthesis of Cobalt Phthalocyanine Derivatives and their Cyclic Voltammograms // Dyes and Pigments. 1997. Vol. 35. N 4. P.375-386].

In the electronic spectra of tetra-6- (para-sulfophenylene) anthraquinonoporphyrazine of copper absorption, intense absorption is observed at 684 nm, recorded in dimethylformamide (Fig. 3) and at 682 nm, recorded in an aqueous alkaline solution (Fig. 4), and for tetra -6- (para-sulfophenylene) cobalt anthraquinonoporphyrazine intense absorption at 684 nm, recorded in an aqueous alkaline solution (Fig. 5), and an associated state with a maximum at 696 nm, recorded in dimethylformamide (Fig. 6).

Tetra-6- (para-sulfophenylene) anthraquinonoporphyrazines of copper and cobalt are dark blue substances with solubility in dimethylformamide, aqueous alkaline solutions, and concentrated sulfuric acid.

The proposed new derivatives of metalloporphyrazines have the properties of direct dyes and can be used for dyeing cotton and viscose fabrics; exhibit catalytic activity in the reaction of liquid-phase oxidation of hydrogen sulfide.

Information confirming the possibility of carrying out the invention.

The claimed compounds are obtained by the interaction of 2,3-dicarboxy-6- (para-sulfophenylene) anthraquinone with urea and acetates of the corresponding metals in the presence of ammonium chloride and ammonium molybdate (catalyst).

Example 1. Synthesis of tetra-6- (para-sulfophenylene) anthraquinonoporphyrazine copper.

In a test tube made of quartz glass, we put in a ground mixture of 0.27 g (0.6 mmol) 2,3-dicarboxy-6- (para-sulfophenylene) anthraquinone, 0.24 g (4.0 mmol) urea, 0.036 g (0.18 mmol) of copper acetate, 0.02 g (0.4 mmol) of ammonium chloride and 0.002 g (0.01 mmol) of ammonium molybdate. The mass is slowly heated to 180 ° C for an hour and maintained for 3 hours. Purification of the target product is carried out by sequential washing with 5% hydrochloric acid, acetone and reprecipitation from sulfuric acid.

The yield of tetra-6- (para-sulfophenylene) anthraquinonoporphyrazine copper 0.06 g (22%).

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

ESP, λ _max , nm: in DMF - 684 (figure 3); in aqueous alkaline solution: 682 nm (figure 4).

Found,%: C 62.1; H 2.4; N, 6.4; S 7.3. C ₈₈ H ₄₀ N ₈ S ₄ O ₂₀ Cu.

Calculated,%: C 61.4; H 2.3; N 6.5; S 7.5.

Example 2. Synthesis of tetra-6- (para-sulfophenylene) anthraquinonoporphyrazine cobalt.

The synthesis is carried out analogously to example 1. Instead of copper acetate, we use 0.038 g (0.18 mmol) of cobalt acetate.

Yield of cobalt tetra-6- (para-sulfophenylene) anthraquinonoporphyrazine: 0.1 g (38%).

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

ESP, λ _max , nm: in DMF - 696 nm (Fig. 5); in aqueous alkaline solution: 684 nm (Fig.6).

Found,%: C 62.3; H 2.5; N, 6.4; S 7.4. C ₈₈ H ₄₀ N ₈ S ₄ O ₂₀ Co.

Calculated,%: C 61.6; H 2.4; N 6.5; S 7.5.

The claimed compounds can be used for dyeing cotton and viscose materials.

Dyeing was carried out according to the methods [Laboratory workshop on the use of dyes / Ed. Melnikova B.N. M .: Chemistry - 1972.342 s.].

Example 3

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

Tetra-6- (para-sulfophenylene) anthraquinonoporphyrazine copper 2

Sulfosite - 31 0.5

Sodium Chloride 5

Bath Module - 50

Within 15-30 minutes, the solution 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

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):

Tetra-6- (para-sulfophenylene) anthraquinonoporphyrazine copper 2

Sulfosite - 31 0.5

Sodium Chloride 10

Sodium carbonate 0.5

Bath Module - 50

Within 15-30 minutes, the solution is heated to a boil 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 dried.

Samples attached.

The claimed compounds can be used as catalysts for the oxidation of sulfur compounds.

Example 5 using tetra-6- (para-sulfophenylene) anthraquinonoporphyrazine cobalt as a catalyst in the reaction of liquid-phase oxidation of hydrogen sulfide.

The catalytic activity in the reaction of liquid-phase oxidation of hydrogen sulfide in aqueous solutions was measured on a laboratory static setup [Maizlish V.E., Kudrik E.V., Shaposhnikov G.P., Stuchinskaya T.L., Kundo N.N. Synthesis and study of new homogeneous catalysts for desulfurization processes // Zh. adj. chemistry. 1999.V. 72. Issue 11. S.1827-1832]. The installation consists of a sealed thermostatic reactor mounted on a rocking chair and connected to a thermostated measuring burette filled with oxygen. Accuracy of gas readings on a burette taken from a gas meter 0.05 ml; thermostating accuracy is 0.5 ° C. The pressure in the reactor is atmospheric. A solution containing cobalt tetra-6-sulfoanthraquinonoporphyrazine and ammonium sulfide (pH 7.7; 25 ° С) was loaded into the reactor, and purged with oxygen, the reactor was connected to a measuring burette, the gas pressure in the reactor – gas burette system was quickly reduced to atmospheric using pressure flask. We measured the initial and, at certain intervals, the volumes of oxygen in the gas burette, bringing the pressure in the reactor – burette system to atmospheric. At the end of the reaction, the rocking chair was stopped, the oxidized solution was analyzed for the residual content of sulfur compounds by the method of reverse iodometric titration.

The activity of tetra-6- (para-sulfophenylene) anthraquinonoporphyrazine cobalt (A) in the reaction of liquid-phase oxidation of hydrogen sulfide was

A = 358 g-mol O ₂ × (g-mol cat) ^-1 × min ^-1 .

Claims (1)

Tetra-6- (para-sulfophenylene) anthraquinonoporphyrazine metal complexes of the formula

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