Metal chelates of tetra-(6-bromo-7-hydroxy)-anthraquinone porphyrazine

FIELD: organic chemistry.

SUBSTANCE: invention relates to new derivatives of metalloporphyrazine of the formula (I): . These compounds can be used as dyes, catalysts in different processes and the material in sensitive members of gas transducers. Invention provides synthesis of compounds showing dyeing properties.

EFFECT: valuable properties of compounds.

5 dwg, 4 ex

 

Introduction

The invention relates to the chemical industry, namely, to obtain new derivatives metalloporphyrin - metal complexes of Tetra-(6-bromo-7-hydroxy) 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 C.; A.L. Thomas, 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.].

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.

It is known connection [Maizlish V.E., Shaposhnikov G.P., Snigireva FP, Molchanov D., Smirnov, R.P. - Ives. higher education institutions. Chem. and chem. the technologist. 1988. T, Iss.5. Pp.42-45.], which is a structural analogue of the claimed compounds - Oct-4,5-methylethanolamine formula:

where M=Cu, Co.

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. N4. 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. Therefore, they cannot be used as a pigment or dye in the solutions.

The invention

Inventive task was to search for new metalloporphyrins, who would possess the property p is yoga and acid dyes and catalyst for the oxidation of sulfur compounds.

The problem is solved by metal complexes of Tetra-(6-bromo-7-hydroxy)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. N4. P.375-386].

In the electronic absorption spectra of the Tetra-(6-bromo-7-hydroxy)-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-(6-bromo-7-hydroxy)-intrahemispheric cobalt in the form of associate with maximum absorption at 676 nm (figure 4).

Tetra-(6-bromo-7-hydroxy)intrahemispheric copper and cobalt are substances dark blue colour and has a solubility in aqueous-alkaline solutions and concentrated sulphuric acid.

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 eakly liquid-phase oxidation of cysteine.

Information confirming the possibility of carrying out the invention.

To implement the method uses the following substances:

urea - GOST 2081-92

acetate of copper - GOST 5852-70

cobalt acetate - GOST 5861-79

the ammonium molybdate - GOST 2677-78

ammonium chloride - GOST 2210-73

Since 2,3-dicarboxy-6-bromo-7-mitoxantrone is a new connection and not produced by the industry it was obtained in the following way: first, carry out the acylation of o-bromoanisole the dianhydride pyromellitic acid in the presence of anhydrous aluminum chloride, followed by intramolecular cyclization by treatment received at the first stage, 5-(3-bromo-4-methoxy)trimellitic acid concentrated sulfuric acid (monohydrate). In the intramolecular cyclization receive 2,3-dicarboxy-6-bromo-7-methoxyacridine.

Stage 1. The acylation of o-bromoanisole the dianhydride pyromellitic acid in the presence of anhydrous aluminum chloride.

In a flask equipped with stirrer, thermometer and reflux condenser, was placed 10.0 g (0.046 mole) of the dianhydride pyromellitic acid, 20 ml (0.16 mol) of o-bromoanisole. The mass is heated to 50°and under vigorous stirring was added 20.0 g (0.154 mol) of anhydrous aluminum chloride. The reaction mass is heated to 120-130°C and maintained for 6 hours. the donkey cooling to the reaction mass is added 50 ml of water and after soaking for 30 minutes, add hot soda solution and separating the precipitated precipitate aluminum hydroxide. To the aqueous layer of the filtrate add hydrochloric acid to pH 3-4. Precipitation 5-(3-bromo-4-methoxy)trimellitic acid. It is filtered off, washed with water until neutral environment and dried at a temperature of 75-80°C.

Obtained 5-(3-bromo-4-methoxy)trimellitate acid.

Stage 2. Intramolecular cyclization by treatment of 5-(3-bromo-4-methoxy)trimellitic acid concentrated sulfuric acid (monohydrate).

In a flask with a volume of 200 ml equipped with a stirrer and thermometer, was placed 10 ml monohydrate and heated to 130°C. and Then for 15 minutes with vigorous stirring, add 5 g of the obtained 5-(3-bromo-4-methoxy)trimellitic acid, the temperature was raised to 150°C and maintained for 5 hours. The mass after cooling with stirring, poured into 200 ml of water, filtered, washed with a large amount of ice-cold water, dissolve 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 100°C.

Found, %: C - 50.3; H - 2.3; Br - 19.6. With7H9Br7.

Calculated, %: 50.4; H - 2.2. Br - 19.7.

Yield: 4.0 g ( 86%). Melting point - 346°C.

The product obtained is 2,3-dicarboxy-6-bromo-7-methoxy-anthraquinone - solid pink color, soluble in aqueous-alkaline solutions, hot in the e, acetone, DMF.

Example 1. Synthesis of Tetra-(6-bromo-7-hydroxy)intrahemispheric copper.

The synthesis is carried out in two stages:

Stage 1. In a test tube made of quartz glass place the pounded mixture of 0.2 g (0.49 mmol) of 2,3-dicarboxy-6-bromo-7-methoxy-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 incubated for 3 hours. Purification of the reaction product is carried out by consecutive washing with 5%hydrochloric acid, acetone and presidenial of sulphuric acid.

The output of Tetra-(6-bromo-7-methoxy)intrahemispheric copper, 0.09 g (47%).

Stage 2. In a test tube made of quartz glass place the pounded mixture of 0.2 g (0.13 mmol) of Tetra-(6-bromo-7-methoxy)intrahemispheric copper and 10 ml of 1%sodium hydroxide solution and heated on a water bath 40-50 minutes Allocation received Tetra-(6-bromo-7-hydroxy)intrahemispheric copper produced by acidification of the reaction mixture with concentrated hydrochloric acid with subsequent filtering and washing the product of hydrolysis with water until neutral environment.

The output of Tetra-(6-bromo-7-hydroxy)intrahemispheric copper, 0.16 g (84%).

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

ESP in aqueous-alkaline the solution, λmaxnm: 681 (figure 2).

Found, %: 52.0; H 1.5; N, 7.3; Br 21.5. With64N8H20About12Br4Cu.

Calculated, %: 52.1; H 1.4; N, 7.6; Br 21.6.

Example 2. Synthesis of Tetra-(6-bromo-7-hydroxy)intrahemispheric cobalt.

Stage 1. Synthesis is carried out similarly to stage 1 of example 1, but instead of copper acetate is used 0.038 g (0.18 mmol) of cobalt acetate.

The output of Tetra-(6-bromo-7-methoxy)intrahemispheric cobalt: 0.08 g (42%).

In the second phase synthesis are similar to stage 2 of example 1, but instead of Tetra-(6-bromo-7-methoxy)intrahemispheric copper using 0.2 g (0.13 mmol) of Tetra-(6-bromo-7-hydroxy)intrahemispheric cobalt.

The output of Tetra-(6-bromo-7-hydroxy)intrahemispheric cobalt: 0.14 g (74%).

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

ESP in aqueous-alkaline solution, λmaxnm: 676 (figure 3).

Found, %: 52.2; H 1.5; N, 7.5; Br 21.4 C64N8H20O12Br4Co.

Calculated, %: 52.4; H 1.4; N, 7.6; Br 21.5.

Example 3. The use of Tetra-(6-bromo-7-hydroxy)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 was soaked in those is giving 0.5 min, press up to 100% of body weight and placed in a dye bath composition (g/l):

Tetra-(6-bromo-7-hydroxy)intrahemispheric copper2
Sulfacid-310.5
Sodium chloride5
Module baths50.

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.

The sample is attached (figure 5).

Example 4. The use of Tetra-(6-bromo-7-hydroxy)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 ±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 experiments were carried out in CIN the political field, when the reaction rate is observed linear dependence on the number of swings.

The activity of Tetra-(6-bromo-7-hydroxy)intrahemispheric cobalt (A) in the reaction liquid-phase oxidation of cysteine was

A=127 g-mol O2×(g-mol cat-RA)-1×min-1.

The metal complexes of Tetra-(6-bromo-7-hydroxy)intrahemispheric formula



 

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