Metal-complexes of tetra-6-carboxy-antthraquinone porphyrazine

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 [Maizlish V.E., Snegireva FP, Shaposhnikov G.P., Kolesnikova E.E., Smirnov R.P. Synthesis and physico-chemical properties carboxyamides of metallophthalocyanines // Izv. higher education institutions. Ser. Chemistry and chemical. the technologist. 1990. V.33. Issue 1. P.70-74], which is a structural analogue of the claimed compounds, - Tetra-4-karboksimetilirovaniya formula

Karboksimetilirovaniya are used as dyes [Maizlish V.E., Shaposhnikov G.P., Zhukov Z. Tetra-4-carboxylation copper is a chemical additive and dye for composite materials and polycaproamide // Ukr. go active. chemistry. 2002. T. VIP. S-2045], effective catalysts for a variety of redox reactions [Velichko AV, Maizlish V.E., Shaposhnikov G.P., Smirnov, R.P. Metallophthalocyanine - heterogeneous catalysts for the reduction of nitrogen oxides, " Izv. higher education institutions. Ser. Chemistry and chemical. the technologist. 1993. T.36. V.2. P.47-52; Faddeeva GA, Another NA, Maizlish V.E., Shaposhnikov G.P., Condo NN. Carboxyaldehyde cobalt phthalocyanines breaktek liquid-phase oxidation of hydrogen sulfide with oxygen in the presence of cyanide ions // J. go active. chemistry 2000. T. Vol.5. S-777].

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. N4. 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-carbox-sintramienergetica formula

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

So 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. N4. P.375-386].

In the electronic absorption spectra of Tetra-6-carboxyltransferase copper intensive absorption at 681 nm, recorded in aqueous-alkaline solution (figure 3). The character of the spectrum indicates that the compound exists in solution advantages the government in the form of a monomer, and Tetra-6-carboxyltransferase cobalt in the form of associate with maximum absorption at 676 nm (figure 4).

Tetra-6-carboxyltransferase copper and cobalt are substances dark blue colour and has a solubility in 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 2,3,6-tricarbocyanine with urea and acetates of the respective metals in the presence of ammonium chloride and ammonium molybdate (catalyst).

Example 1. Synthesis of Tetra-6-carboxyltransferase copper.

In a test tube made of quartz glass place the pounded mixture of 0.2 g (0.6 mmol) of 2,3,6-tricarbocyanine, 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 issarny acid.

The output of Tetra-6-carboxyltransferase copper 0.1 g (85%).

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

ESP in aqueous-alkaline solution, λ_maxnm: 681 (figure 3).

Found,%: 63.3; H 2.0; N, 9.0. C₆₈N₈H₂₄O₁₆Cu.

Calculated,%: 64.2; H 1.9; N 8,8.

Example 2. Synthesis of Tetra-6-carboxyltransferase 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-carboxyltransferase cobalt: 0.09 g (40%).

Dark blue substance has a solubility in aqueous-alkaline solutions and concentrated sulphuric acid.

ESP in aqueous-alkaline solution, λ_maxnm: 676 (figure 4).

Found,%: 64.0; H 2.0; N, 8.6. C₆₈N₈H₂₄O₁₆Co.

Calculated,%: C 64.4; H 1.9; N, 8.8.

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 min, squeezed to 100% gain and is placed in a dye bath composition (g/l):

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):

Within 15-30 min heat the solution to boiling and maintained at this temperature for 40 min and 20 min 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. The use of Tetra-6-carboxyltransferase cobalt as a catalyst in the reaction liquid-phase oxidation Serov is Dorota.

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

A=185 g-mole O₂×(g-mol cat-RA)^-1×min^-1.

The metal complexes of Tetra-6-carboxyltransferase formula