Metal complexes of tetra-(tri-5,6,8-methyl)-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-methyl)-anthraquinonoporphyrazine of the general formula:

. These compounds can be used as parent substances for synthesis, respectively, copper and cobalt complexes of tetra-(tri-5,6,8-carboxy)-anthraquinonoporphyrazine used as dyes, catalysts in different processes, materials in sensitive members of gas transducers.

EFFECT: valuable properties of complexes.

2 cl, 7 dwg, 8 ex

 

Introduction

The invention relates to the chemical industry, namely, to obtain new derivatives metalloporphyrins as starting compound for the synthesis of metal complexes of Tetra-(three-5,6,8-carboxy)-intrahemispheric that can be used as dyes, catalysts, and other fields of science and technology.

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 universities. 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, 168 S.; A.L. Thomas, The phthalocyanines. Research and Application. Boce Exploration: CRC Press, 1990, 321 R.];

organic semiconductor materials [SIM 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 R.];

- gas sensors [Correlation between structure of copper phthalocyanine thin films and their general perfrmance characteristics for gas sensors / O. Berger 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.].

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.

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.

Known compounds [Kovshov H., E.A. Lukyanets // Sat. "Aniline dye industry. M.: NETAFIM. 1972. 4. P.9-12], which is a structural analogue of the claimed compounds - Oct-4,5-methylethanolamine 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.

However, when using this compound as the source can be obtained only tetranitroaniline that do not have coloring properties. The poet is mu they cannot be used as a pigment, nor when dyeing in solutions.

The invention

Inventive task was to search for new metalloporphyrins that when using them as a source of connection would give the opportunity to synthesize metal complexes of Tetra-(three-5,6,8-carboxy)intrahemispheric with the properties of direct and acid dyes, as well as catalyst for the oxidation of sulfur compounds.

The problem is solved by metal complexes of Tetra-(three-5,6,8-methyl)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 disulfiramum analogue [K.Sakamoto, E.Ohno Synthesis of Cobalt Phthalocyanine Derivatives and their Cyclic Voltammograms // Dyes and Pigments. 1997. Vol.35. No. 4. P.375-386].

Tetra-(three-5,6,8-methyl)intrahemispheric copper and cobalt are substances dark blue color, having a solubility in concentrated sulfuric acid.

The use of metal complexes of Tetra-(three-5,6,8-methyl)intrahemispheric gives you the ability to synthesize metal complexes of Tetra-(three-5,6,8-carboxy)intrahemispheric with the properties of direct and acid dyes that can be used is s for dyeing cotton and viscose fabrics, as well as wool and exhibit catalytic activity in the reaction of liquid-phase oxidation of sulfur compounds.

Information confirming the possibility of carrying out the invention.

The claimed compounds obtained by the interaction of 2,3-dicarboxy-5,6,8-trimethylhydroquinone with urea and acetates of the respective metals in the presence of ammonium chloride and ammonium molybdate (catalyst).

Since 2,3-dicarboxy-5,6,8-trimethylxanthine is the new connection is not released by the industry, it was obtained in the following way: in the first stage, carry out the acylation of pseudocumene the dianhydride pyromellitic acid in the presence of anhydrous aluminum chloride, and the second stage is conducted intramolecular cyclization by treatment received at the first stage, 5-(2,3,5-trimethyl)benzoyltartaric acid concentrated sulfuric acid (monohydrate).

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

In a test tube made of quartz glass place the pounded mixture of 0.2 g (0.6 mmol) of 2,3-dicarboxy-5,6,8-trimethylxanthine, 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 incubated for 3 hours. Purification of the target product consistently promivka is 5%hydrochloric acid, acetone and presidenial of sulphuric acid.

The output of Tetra-(three-5,6,8-methyl)intrahemispheric copper 0.06 g (32%).

Dark blue substance has a solubility in concentrated sulfuric acid.

ESP in concentrated sulphuric acid, λmaxnm: 746 (Fig 3).

Found, %: C 72,1; H 3,9; N 8,8. C76H48N8O8Cu.

Calculated, %: C 72,2; N 3,8; N 8,9.

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

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

The output of Tetra-(three-5,6,8-methyl)intrahemispheric cobalt: 0.10 g (52%).

Dark blue substance has a solubility in concentrated sulfuric acid.

ESP in concentrated sulphuric acid, λmaxnm: 745 (figure 4).

Found, %: C 73,2; H 3,9; N 9,1. C76N8H48O8Co.

Calculated, %: Decreased From 72.4; H 3,8; N 8,9.

Example 3. The use of Tetra-(three-5,6,8-methyl)intrahemispheric copper for the 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 portions 0.05 g as the disappearance of its color. Adding to the DUT until a steady coloration of the 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 5).

Found %: With A 55.4; H 1,6; N 7,0. C76N8H24O32Cu.

Calculated, %: From 56.2; H 1,5; N 6,9.

Example 4. The use of Tetra-(three-5,6,8-methyl)intrahemispheric cobalt for the synthesis of Tetra-(three-5,6,8-carboxy)intrahemispheric cobalt.

Synthesis behave analogously to example 3. Instead of Tetra-(three-5,6,8-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 the but-alkaline solutions, DMF, concentrated sulfuric acid.

ESP in aqueous-alkaline solution, λmaxnm: 676 (Fig.6).

Found, %: C To 57.0; H 1,6; N 7,1. C76N8H24O32Co.

Calculated, %: From 56.4; H 1,5; N 6,9.

Example 5. 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 weight of 1 g ml for 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 baths - 50.

Within 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 6. 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 weight of 1 g ml for 0.5 min at tempo is the atur 40° With a squeeze 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 chloride10
Sodium carbonate0,5

Module baths - 50.

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 7. 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)intrahemispheric copper6
Glauber's salt40

Module baths - 50.

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):

with the NSS acid 1
water50

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

Samples of the color charts according to examples 5, 6, 7 depicted in Fig.7.

Example 8. 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. Ivanovo, 1999, 156 S.].

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. the reaction Rate was measured volumetric, accuracy of measurement ±of 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.

The metal complexes tet is a-(three-5,6,8-methyl)intrahemispheric formula



 

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