Tetra-6-(para-sulfophenylene)-anthraquinone porphyrazine metal chelates

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

 

Introduction

The invention relates to the chemical industry, namely, to obtain new derivatives metalloporphyrins, which may find application as dyes, catalysts for various processes, materials sensitive elements (CHAD) gases, etc.

The level of technology

Known compounds [Bykova V.V., Usol'tseva N.V., Zharova M.A., Lutsenko OG, Kulinich VP, Shaposhnikov Gpoints and study of mesomorphic properties of sulfonic acids substituted metallophthalocyanines // Liquid crystals and their practical use. 2003. No. 1. P.7-13], which is a structural analogue of the claimed compounds, - Tetra-4-(para-sulfophenyl)metallophthalocyanine formula

Tetra-4-(para-sulfophenyl)phthalocyanine copper in water and in aqueous solutions of hydroxides of sodium or ammonium shows the lyotropic mesophase [Bykova V.V., Usol'tseva N.V., Zharova M.A., Lutsenko OG, Kulinich VP, Shaposhnikov Gpoints and study of mesomorphic properties of sulfonic acids substituted metallophthalocyanines // Liquid crystals and their practical use. 2003. No. 1. P.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. # 4. P.375-386] are the metal complexes of tetranitroaniline formula

They don't have coloring properties and therefore cannot be used as a pigment or dye in the solutions.

The invention

Inventive task was to search for new metalloporphyrins who possessed the properties of a direct dye and catalyst for the oxidation of sulfur compounds.

The problem is solved by metal complexes of Tetra-6-(para-sulfophenyl)intrahemispheric formula

The structure of this compound proved by data of elemental analysis, IR and electronic spectroscopy.

Thus, in the IR spectra of the inventive compounds (1, 2) it is possible to allocate a number of common absorption bands with disulfiramum analogue [K.Sakamoto, E.Ohno Synthesis of Cobalt Phthalocyanine Derivatives and their Cyclic Voltammograms // Dyes and Pigments. 1997. Vol.35. # 4. P.375-386].

In the electronic spectra of Tetra-6-(para-sulfophenyl)intrahemispheric copper absorption is observed intense absorption at 684 nm, recorded in dimethylformamide (3) and at 682 nm, recorded in aqueous-alkaline solution (figure 4), and Tetra-6-(para-sulfophenyl)intrahemispheric cobalt intense absorption at 684 nm, recorded in aqueous-alkaline solution (figure 5), and assotsiirovannoi state with a maximum at 696 nm, recorded in dimethylformamide (6).

Tetra-6-(para-sulfophenyl)intra ironporphyrin copper and cobalt are substances dark blue, having a solubility in dimethylformamide, aqueous-alkaline solutions, concentrated sulfuric acid.

The proposed new derivatives of metalloporphyrins 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 obtained by the interaction of 2,3-dicarboxy-6-(para-sulfophenyl)anthraquinone with urea and acetates of the respective metals in the presence of ammonium chloride and ammonium molybdate (catalyst).

Example 1. Synthesis of Tetra-6-(para-sulfophenyl)intrahemispheric copper.

In a test tube made of quartz glass place the pounded mixture of 0.27 g (0.6 mmol) of 2,3-dicarboxy-6-(para-sulfophenyl)anthraquinone, 0.24 g (4.0 mmol) of 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 one hour and maintained for 3 hours. Purification of the target product have sequential washing with 5%hydrochloric acid, acetone and presidenial of sulphuric acid.

The output of Tetra-6-(para-sulfophenyl)intrahemispheric copper 0.06 g (22%).

Dark blue substance has a solubility in dim is telharmonic, aqueous-alkaline solutions, concentrated sulfuric acid.

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

Found, %: 62.1; N, 2.4; N, 6.4; S 7.3. C88H40N8S4O20Cu.

Calculated, %: 61.4; H 2.3; N 6,5; S 7,5.

Example 2. Synthesis of Tetra-6-(para-sulfophenyl)intrahemispheric cobalt.

Synthesis behave analogously to example 1. Instead of copper acetate use 0.038 g (0.18 mmol) of cobalt acetate.

The output of Tetra-6-(para-sulfophenyl)intrahemispheric cobalt: 0.1 g (38%).

Dark blue substance has a solubility in dimethylformamide, aqueous-alkaline solutions, kontsentrirovannoy sulfuric acid.

ESP, λmaxnm: DMF - 696 nm (figure 5); in aqueous-alkaline solution: 684 nm (6).

Found, %: 62.3; N, 2.5; N, 6.4; S 7.4. C88H40N8S4O20Co.

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

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

Dyeing conducted according to the methods [Laboratory workshop on the application of dyes, Ed. Melnikov B.N. M.: Chemistry - 1972. 342 S.].

Example 3.

A sample of cotton fabric weighing 1 g moisten within 0.5 minutes, wring out up to 100% of body weight and placed in a dye bath composition (g/l):

Tetra-6-(para-sulfophenyl)intrahemispheric copper 2

Sul is osit - 31 0.5

Sodium chloride 5

Module baths - 50

Within 15-30 min heat the solution to boiling and allowed to stand for 1 hour. The sample was then drained, washed thoroughly with warm, then cold water, and dried.

Example 4.

Sample viscose fabric weighing 1 g was soaked in a period of 0.5 minutes at a temperature of 40° C, press up to 100% of body weight and placed in a dye bath composition (g/l):

Tetra-6-(para-sulfophenyl)intrahemispheric copper 2

Sulfacet - 31 0.5

Sodium chloride 10

Sodium carbonate 0.5

Module baths - 50

Within 15-30 min heat the solution to boiling and maintained at this temperature for 40 minutes and 20 minutes in the cooling up to 30° With tub. The sample was then drained, washed thoroughly with warm, then cold water, and dried.

Samples are attached.

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

Example 5 use of Tetra-6-(para-sulfophenyl)intrahemispheric cobalt as a catalyst in the reaction liquid-phase oxidation of hydrogen sulfide.

The measurement of catalytic activity in the reaction of liquid-phase oxidation of hydrogen sulfide in aqueous solutions were conducted in a laboratory static setting [Maizlish V.E., Kudrik E.V., Shaposhnikov G.P., Stuzhinskaya TL, Condo NN. Synthesis and study of new homogeneous catalysts for the process is economical desulfurization //Ukr. go active. chemistry. 1999. T. VIP. S-1832]. The unit consists of a sealed temperature-controlled reactor, installed on the rocking chair and connected to the temperature-controlled measuring burette filled with oxygen. The accuracy of the reference gas in the burette, taken from the Gasometer 0.05 ml; precision thermostat 0.5° C. the reactor Pressure is atmospheric. The reactor was loaded solution containing Tetra-6-soloandriarahery cobalt and ammonium sulfide (pH 7.7; 25° (C), and was purged with oxygen, were connected to the reactor with the measuring burette, the gas pressure in the reactor gas burette” quickly led to a naturally-aspirated using a pressure flask. Measured initial and after a certain period of time, the amount of oxygen in the gas burette, causing the pressure in the reactor burette” to atmospheric. Upon completion of the reaction, the rocking stopped, the oxidized solution was analyzed for the residual content of sulfur compounds by the method iodometric back titration.

The activity of Tetra-6-(para-sulfophenyl)intrahemispheric cobalt (A) in the reaction liquid-phase oxidation of hydrogen sulfide was

A=358 g-mol O2×(g-mol cat-RA)-1×min-1.

The metal complexes of Tetra-6-(para-sulfophenyl)intrahemispheric formula



 

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