Metal complexes of tetra-(tri-5,6,8-carboxy)- anthraquinonoporphyrazine

FIELD: organic chemistry of complex compounds.

SUBSTANCE: invention relates to new derivatives of metalloporphyrazines, namely to metal complexes of tetra-(tri-5,6,8-carboxy) -anthraquinonoporphyrazine of the general formula:

. These compounds can be sued as dyes, catalysts in different processes and materials for sensitive members of gas transducers.

EFFECT: valuable properties of compounds.

2 cl, 5 dwg, 6 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

The richest possibility of chemical modification of the compounds porphyrinogen series allows you to use them as:

- lightfastness of dyes and pigments [B. I. Stepanov introduction to the chemistry and technology of organic dyes. Educational. for schools, 3rd ed., Rev. and ext., M.: Chemistry, 1984. 592 S.];

- highly efficient catalysts [M. R. Tarasevich, Radyushkin K.A. Catalysis and electrolysis by metalloporphyrins. M.: Nauka, 1982. 168s.; Thomas A.L. The phthalocyanines. Research and Application. Boce Exploration: CRC Press, 1990. 321 p.];

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

- medicinal and analytical reagents [A.F. Mironov Photodynamic therapy of cancer // In the book. The success of the chemistry of porphyrins, Ed. Golubchikov O.A. SPb.: Publishing house of Institute of Chemistry, St. Petersburg state University, 1997. T.1. S-374; F.H. Moser, 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., M. Plotner et. al. // ICCP. Dijon, France, 25-30 June 2000. P.350];

in some other branches 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 R.; 1993. Vol.2. 436 R.; 1993. Vol.3. 303 R.; 1996. Vol.4. 524 R.].

One of the areas of chemical modification is used as a source of compounds that already have porphyrazines structure that allows you to get porphyrazines with different substituents.

By varying the peripheral environment porphyrinogen ligand, it is possible to significantly expand the range of compounds of this class with a variety of useful application properties.

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 - Oct-4,5-karboksimetilirovaniya formula

where M=Cu, Co, Ni, Fe, Al, etc.

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

where M=Co, Fe, Zn

They don't have coloring properties and therefore can not be used neither in quality is the firmness of the pigment, nor when dyeing in solutions.

The invention

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

The problem is solved by metal complexes of Tetra-(three-5,6,8-carboxy)intrahemispheric formula

where M=Cu, Co

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 the unsubstituted 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 absorption spectra of the Tetra-(three-5,6,8-carboxy)-intrahemispheric 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 predominantly in the form of a monomer, and Tetra-(three-5,6,8-carboxy)intrahemispheric cobalt in the form of associate with maximum absorption at 676 nm (figure 4).

Tetra-(three-5,6,8-carboxy)intrahemispheric copper and cobalt are substances dark blue colour and has a solubility in aqueous-alkaline solutions and concentrated sulfuric KIS is OTE.

The proposed new derivatives of metalloporphyrins have the properties of direct and acid dyes and can be used for dyeing of cotton, viscose fabrics and wool, and also show catalytic activity in the reaction of liquid-phase oxidation of cysteine.

Information confirming the possibility of carrying out the invention

The claimed compounds obtained by oxidation of Tetra-(three-5,6,8-methyl)intrahemispheric copper or cobalt potassium permanganate in acidic medium.

Because Tetra-(three-5,6,8-methyl)intrahemispheric copper and cobalt are new compounds and are not produced by the industry, they were obtained in the following way: first, carry out the acylation of pseudocumene the dianhydride pyromellitic acid in the presence of anhydrous aluminum chloride, followed by intramolecular cyclization by treatment received at the first stage, 5-(2,3,5-trimethyl)benzoyltartaric acid concentrated sulfuric acid (monohydrate). In the intramolecular cyclization receive 2,3-dicarboxy-5,6,8-trimethylxanthine. Spend the interaction of this compound with urea and copper acetate or cobalt in the presence of ammonium chloride and ammonium molybdate (catalyst). Get Tetra-(three-5,6,8-methyl)intrahemispheric, respectively, of copper or the of abalta.

Example 1. Synthesis of Tetra-(three-5,6,8-carboxy)intrahemispheric copper.

In dvuhhodovoy flask containing 10 ml of water, add a solution of 0.2 g of Tetra-(three-5,6,8-methyl)intrahemispheric copper in 3 ml of concentrated sulfuric acid. Heated to 55-60°and with stirring, add 0.3 g of potassium permanganate in units of 0.05 g as the disappearance of its color. Adding lead to the emergence of sustainable staining solution. The hot suspension is filtered. The precipitate is washed with hot sodium hydroxide solution and after cooling, acidified with hydrochloric acid to pH 3-4. The precipitation Tetra-(three-5,6,8-carboxy)intrahemispheric copper 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 disappearance of the chloride ions. Such processing is repeated twice. Dried at 75-80°C.

The output of Tetra-(three-5,6,8-carboxy)intrahemispheric copper: 0.13 g (49%).

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

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

Found, %: 55.4; H 1.6; N, 7.0. C76N8H24About32Cu.

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

Example 2. Synthesis of Tetra-(three-5,6,8-carboxy)intrahemispheric the cobalt.

Synthesis behave analogously to example 1. Instead of Tetra-(tri-5,b 8-methyl)-intrahemispheric copper using 0.2 g of Tetra-(three-5,6,8-methyl)-intrahemispheric cobalt.

The output of Tetra-(three-5,6,8-carboxy)intrahemispheric cobalt: 0.11 g (45%).

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

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

Found, %: C 57.0; H 1.6; N, 7.1. C76N8H24O32Co.

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

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

Example 3. The use of Tetra-(three-5,6,-carboxy)intrahemispheric copper as a dye cotton fabrics. Dyeing conducted according to the methodology [Laboratory workshop on the application of dyes, Ed. Melnikov B.N. M.: Chemistry 1972. 342 S.].

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):

Tetra-(three-5,6,8-carboxy)intrahemispheric copper2
Sulfacid - 310.5
Sodium chloride5
Module baths50.

In ECENA 15-30 min heat the bath to the boil and maintain for 1 hour. The sample was then drained, washed thoroughly with warm, then cold water, and dried.

Example 4. The use of Tetra-(three-5,6,8-carboxy)intrahemispheric copper as a dye viscose fabrics. Dyeing conducted according to the methodology [Laboratory workshop on the application of dyes, Ed. Melnikov B.N. M.: Chemistry 1972. 342 S.].

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-(three-5,6,8-carboxy)intrahemispheric copper2
Sulfacid - 310.5
Sodium chloride10
Sodium carbonate0.5
Module baths50.

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

Example 5. The use of Tetra-(three-5,6,8-carboxy)intrahemispheric copper as an acid dye.

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

Tetra-(three-5,6,8-carboxy)antrage noorbergen copper 6
Glauber's salt40
Module baths50.

Within 15-30 min heat the tub up to 60°C 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 treated with a solution of sulfuric acid composition (ml):

Sulfuric acid1
Water50

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

Samples of the color charts according to examples 3, 4, 5 are attached (see figure 5).

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

Example 6. The use of Tetra-(three-5,6,8-carboxy)intrahemispheric cobalt as a catalyst in the reaction liquid-phase oxidation of cysteine. Catalytic activity was determined by the method of [Shikova YEAR Study of the effect of chemical modification of the phthalocyanine ligand on the catalytic properties of metal complexes. Dis... Kida. chem. Sciences. Ivanov, 1999. 156 C.].

The experiments were carried out in the liquid phase in the reaction vessel, mounted on a high-speed shaker (350 qual/min), temperature-controlled with an accuracy of ±0.2°C. Speed reactionsoral volumetric, precision measurement ±0.05 ml. Processes were carried out at 298 K. the reaction vessel connected to a Gasometer, was loaded with 10 ml of substrate solution and an accurately weighed sample of the catalyst placed in the boat. The kinetic experiments were carried out in the field, when the reaction rate is observed linear dependence on the number of swings.

The activity of Tetra-(three-5,6,8-carboxy)intrahemispheric cobalt (A) in the reaction liquid-phase oxidation of cysteine was

A=126 g-mol O2·(g-mol cat-RA)-1·min-1.

1. The metal complexes of Tetra-(three-5,6,8-carboxy)intrahemispheric



 

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