Metal complexes of tetra-(5-bromo-6-carboxy)-anthraquinone porphyrazine

FIELD: organic chemistry of complex compounds.

SUBSTANCE: invention relates to novel derivatives of metalloporphyrazine of the formula (I) that can be used as dyes, catalysts in different processes. Invention provides preparing compounds possessing with coloring properties.

EFFECT: valuable properties of complexes.

5 dwg, 4 ex

 

Introduction

The invention relates to the chemical industry, namely, to obtain new derivatives metalloporphyrins, which may find application as dyes, catalysts of various process 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 chem. 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 reactions in liquid-phase oxidation serviceregistered in the presence cianidanol //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. # 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 derivatives, metal complexes of tetranitroaniline, which would have the properties of a direct dye and catalyst for the oxidation of sulfur compounds.

The problem is solved by metal complexes of Tetra-(5-bromo-6-carboxy)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 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-(5-bromo-6-carboxy)intrahemispheric copper intensive absorption at 681 nm, recorded in aqueous-alkaline solution (figure 3). The nature of the spectrum, what it shows, if the connection exists in solution predominantly in the form of a monomer, and Tetra-(5-bromo-6-carboxy)intrahemispheric cobalt in the form of associate with maximum absorption at 676 nm (figure 4).

Tetra-(5-bromo-6-carboxy)intrahemispheric copper and cobalt are substances dark blue color, having a solubility of water-alkaline solutions, concentrated sulfuric acid.

The proposed compounds have the properties of direct dyes and can be used for dyeing cotton and viscose fabrics, and also show catalytic activity in the reaction of liquid-phase oxidation of hydrogen sulfide.

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

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

As 2,3,6-tricarbonic-5-bromoanthracene is a new connection and not produced by the industry, it was obtained in the following way: first, carry out the acylation of o-bromthymol the dianhydride pyro is elfovoy acid in the presence of anhydrous aluminum chloride, this is followed by intramolecular cyclization by treatment received at the first stage, 5-(3-bromo-4-methyl-benzoyl)trimellitic acid concentrated sulfuric acid (monohydrate). In the intramolecular cyclization receive 2,3-dicarboxy-5-bromo-6-methylanthracene, which are oxidized by potassium permanganate, getting 2,3,6-tricarbonic-5-bromoanthracene.

Stage 1. The acylation of o-bromthymol the dianhydride pyromellitic acid in the presence of anhydrous aluminum chloride, according to the scheme:

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-bromthymol. 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. After 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-methylbenzoyl)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-methylbenzoyl)Tr is malletova acid.

Stage 2. Intramolecular cyclization by treatment of 5-(3-bromo-4-methylbenzoyl)trimellitic acid concentrated sulfuric acid (monohydrate), according to the scheme:

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-methylbenzoyl)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 - 52.3; H - 2.4; Br - 20.317H9BrO7.

Calculated, %: C - 52.5; H - 2.3; Br - 20.5.

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

The obtained target product - 2,3-dicarboxy-5-bromo-6-methylanthracene - solid pink color, soluble in aqueous-alkaline solutions, hot water, acetone, DMF.

Stage 3. Oxidation of 2,3-dicarboxy-5-bromo-6-methylanthraquinone in the presence of potassium permanganate, according to the scheme:

In a flask equipped with stirrer, thermometer is, place 2 g (to 0.007 mol) of 2,3-dicarboxy-5-bromo-6-methylanthraquinone, in the form of its suspension in 80 ml of water, add potassium hydroxide until alkaline reaction. Heated to 90-95°and with stirring, add 3 g of potassium permanganate in portions of 0.5 g as the disappearance of its color (30-40 minutes). Adding lead to the emergence of sustainable staining solution. The hot suspension is filtered. The precipitated manganese dioxide is washed with hot water. The filtrates are combined evaporated to half the original volume, and after cooling, acidified with hydrochloric acid to pH 3-4. The precipitation 2,3,6-tricarbonic-5-bromoanthraquinone filtered off, washed with ice 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.

Found, %: C - 48.3; H - 1.8; Br - 18.9 C17H9BrO8.

Calculated, %: C - 48.7; H - 1.7; Br - 19.1.

Yield: 1.4 g (62%). Melting point - 341°C.

The product is solid white in color, soluble in soda solution, acetone, chloroform, hot water, DMF.

Example 1. Synthesis of Tetra-(5-bromo-6-carboxy)intrahemispheric copper.

In a test tube made of quartz glass place the pounded mixture of 0.2 g (0.49 mmol) of 2,3,6-tricarbonic-5-br is santraginean, 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-(5-bromo-6-carboxy)intrahemispheric copper, 0.09 g (47%).

Dark blue substance has a solubility in aqueous-alkaline solutions, DMF, concentrated sulfuric acid. ESP in aqueous-alkaline solution, λmaxnm: 681 (figure 3).

Found, %: 52.0; H 1.5; N, 7.3; Br 21.5. C64N8H20O12Br4Cu.

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

Example 2. Synthesis of Tetra-(5-bromo-6-carboxy)intrahemispheric cobalt.

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

The output of Tetra-(5-bromo-6-carboxy)intrahemispheric cobalt: 0.08 g (42%).

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

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

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.

The claimed compounds can be used for coloring chlapci Toumani and viscose materials.

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

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):

Tetra-(5-bromo-6-carboxy)intrahemispheric copper2
Sulfacet-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 shown in figure 5.

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

Example 4. The use of Tetra-(5-bromo-6-carboxy)intrahemispheric cobalt as a catalyst in the reaction liquid-phase oxidation of cysteine. Catalytic activity 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.]

Experiments are performed in the liquid phase in the reaction vessel, strengthened by speed is achaleke (350 qual/min), temperature-controlled with an accuracy of ±0.2°C. the reaction Rate is measured volumetric, accuracy of measurement ±0.05 ml of the Processes carried out at 298 K. the reaction vessel connected to a Gasometer, load 10 ml of the substrate solution and an accurately weighed sample of the catalyst placed in the boat. Experiments are performed in the kinetic region, when the reaction rate is observed linear dependence on the number of swings.

The activity of Tetra-(5-bromo-6-carboxy)intrahemispheric cobalt (A) in the reaction liquid-phase oxidation of cysteine is

A=234 g-mol O2×(g-mol cat-RA)-1×min-1.

Metalcomplex Tetra-(5-bromo-6-carboxy)intrahemispheric formula



 

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