Method for preparing metal complex of tetra-(5,8-dihydroxy-6-sulfo)-anthraquinone porphyrazine

FIELD: chemistry of metalloorganic compounds, chemical technology.

SUBSTANCE: invention relates to the improved method for preparing metal complexes of tetra-(5,8-dihydroxy-6-sulfo)-anthraquinone porphyrazine. Method is carried out by interaction of 2,3-dicarboxy-5,8-dimethoxy-6-sulfoanthraquinone with urea and the corresponding metal salt in the presence of chloride and ammonium molybdate and the following hydrolysis of the synthesized metal complex - tetra-(5,8-dimethoxy-6-sulfo)-anthraquinone porphyrazine by its treatment with sodium hydroxide. Proposed metal complexes can be used as catalysts, dyes and in other fields of science and technique.

EFFECT: improved preparing method.

2 cl, 3 dwg, 4 ex

 

The invention relates to the chemical industry, namely to a process for the preparation of metal complexes of Tetra-(5,8-dihydroxy-6-sulfo)intrahemispheric, which can be used as catalysts, dyes and other areas of science and technology.

The level of technology

A method of obtaining metal complexes of Tetra-(5,8-dihydroxy-6-sulfo)intrahemispheric [Borisov A.V., Pobedinskaya I.A., Maizlish V.E., Shaposhnikov Gpoints and properties tetranitroaniline proc. Dokl. IX international conference on the chemistry of porphyrins and their analogues 8-12 September 2003, Suzdal. Proceedings of the conference Ivanovo 2003. S. 95-96], including the interaction of 2,3-dicarboxy-5,8-dihydroxy-6-sulfentrazone with urea and copper acetate or cobalt in the presence of ammonium chloride and ammonium molybdate.

The method is implemented in one stage:

The disadvantage of this method is the small yield of the target product is not more than 10%.

The invention

Inventive task consisted of finding ways to obtain complexes of Tetra-(5,8-dihydroxy-6-sulfo)intrahemispheric, including the interaction of substituted 2,3-dicarboxaldehyde with urea, salt of the corresponding metal in the presence of chloride and ammonium molybdate, which would boost the output of the spruce product.

This goal is achieved by a method of producing metal complexes of Tetra-(5,8-dihydroxy-6-sulfo)intrahemispheric the interaction of substituted 2,3-dicarboxaldehyde with urea, salt of the corresponding metal in the presence of chloride and ammonium molybdate, in which the substituted 2,3-dicarboxaldehyde use 2,3-dicarboxy-5,8-dimethoxy-6-solventrefined obtained metal complex of Tetra-(5,8-dimethoxy-6-sulfo)intrahemispheric subjected to hydrolysis by treating it with sodium hydroxide.

The proposed method allows to obtain the target product with a yield not less than at 37.59%.

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-5,8-dimethoxy-6-solventrefined is a new connection and not produced by the industry, it was obtained in the following way: first, carry out the acylation dimethyl ether of hydroquinone by dianhydride pyromellitic acid in the presence of anhydrous aluminum chloride, followed by intramolecular cyclization by treatment received at the first stage, 5-(2,5-dimethoxy)benzyltri litovoi acid concentrated sulfuric acid (monohydrate). In the intramolecular cyclization receive 2,3-dicarboxy-5,8-diethoxyanthracene, which is subjected to sulfonation 20%oleum, receiving 2,3-dicarboxy-5,8-dimethoxy-6-solventrefined.

Stage 1. In a flask equipped with stirrer, thermometer and reflux condenser, was placed 10.0 g (0.046 mole) of the dianhydride pyromellitic acid, 12.66 g (0.091 mol) of dimethyl ether of hydroquinone and 20 ml of heptane. The mass is heated to 50°and under vigorous stirring was added 20.0 g (0.154 mol) of anhydrous aluminum chloride. Stand 3 hours at the boiling temperature of the reaction mixture and distilled heptane under vacuum. Then 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 10 ml of concentrated hydrochloric acid and stirred for further 12 hours. The residue after filtration is washed with hot water, then placed in a 10%solution of soda and boil for 30-40 minutes. The hot solution is filtered, the precipitate is treated in the same way 3 times. The filtrates are combined acidified with hydrochloric acid to pH 4 and cooled to 10-15°C. the precipitation is filtered off, washed with water until neutral environment and absence of chloride ions and dried at 80°C.

Obtained 5-((2,5-dimethoxy)benzoyl)trimellitate acid.

Stage 2. In a flask with a volume of 200 ml equipped with what esilkoy and thermometer, put 10 ml of concentrated sulfuric acid (monohydrate) and heated to 130°C. and Then for 15 minutes with vigorous stirring, add 5 g of the obtained 5-((2,5-dimethoxy)benzoyl)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-60.1; H-3.5. C18H12O8.

Calculated, %: C-60.7; H-3.4.

Yield: 4.0 g ( 86%). The melting point of 354°C.

The obtained target product - 2,3-dicarboxy-5,8-dimethoxy-anthraquinone-solid pink color, soluble in aqueous-alkaline solutions, hot water, acetone, DMF.

Stage 3. Sulfonation 2,3-dicarboxy-5,8-diethoxyanthracene 20%oleum.

In a flask with a capacity of 50 ml equipped with a stirrer, reflux condenser and thermometer, placed 16 ml of 20%oleum and heated the reaction mass to 120-140°With, then load 2.2 g (0.005 mol) of 2,3-dicarboxy-5,8-diethoxyanthracene and maintained at this temperature for 6 hours. Cooled and poured on ice. Filtered, washed with a mixture of water with Sol is Oh acid (5:1), then ice-cold water. The mass is dissolved in the 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 80°C.

Got 2,3-dicarboxy-5,8-dimethoxy-6-solventrefined.

Yield: 2 g (74.4%). The melting point of 213°C.

Found: 49.5; H 2.9; S 7.5. C18H12O11S.

Calculated: 49.6; H 2.8; S 7.4.

The product is a pink substance, soluble in aqueous-alkaline solution, DMF, acetone.

The claimed method is implemented in two stages.

The interaction of 2,3-dicarboxy-5,8-dimethoxy-6-sulfentrazone with urea, salt of the corresponding metal in the presence of chloride and ammonium molybdate get the metal complex of Tetra-(5,8-dimethoxy-6-sulfo)intrahemispheric, which is subjected to hydrolysis to obtain the target product.

Example 1. Synthesis of Tetra-(5,8-dihydroxy-6-sulfo)intrahemispheric copper.

Stage 1. In a test tube made of quartz glass place the pounded mixture of 0.2 g (0.46 mmol) of 2,3-dicarboxy-5,8-dimethoxy-6-sulfentrazone, 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 washing with 5%hydrochloric acid, acetone and presidenial of sulphuric acid.

The output of Tetra-(5,8-dimethoxy-6-sulfo)intrahemispheric copper, 0.08 g (42%).

Stage 2. In a test tube made of quartz glass place the pounded mixture of 0.2 g (0.12 mmol) of Tetra-(5,8-dimethoxy-6-sulfo)intrahemispheric copper 10 ml of 1%sodium hydroxide solution and heated on a water bath 40-50 minutes Allocation received Tetra-(5,8-dihydroxy-6-sulfo)intrahemispheric copper produced by acidification of the reaction mixture with concentrated hydrochloric acid with subsequent filtration and washing of the target product with water until neutral environment. Dried at 75-80°C.

The output of Tetra-(5,8-dihydroxy-6-sulfo)intrahemispheric copper, 0.17 g (89.5%).

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

ESP in aqueous-alkaline solution, λmaxnm: 681 (figure 1).

Found, %: C 49.7; H 1.7; N, 7.2; S 8.2. C64N8H24O28S4Cu.

Calculated, %: 49.8; H 1.6; N, 7.3; S 8.3.

The overall yield of the Tetra-(5,8-dihydroxy-6-sulfo)intrahemispheric of copper is (0.42×0.895)×100=at 37.59%.

Example 2. Synthesis of Tetra-(5,8-dihydroxy-6-sulfo)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-(5,8-dim the toxi-6-sulfo)intrahemispheric cobalt: 0.09 g (47.4%).

Stage 2. The synthesis are similar to stage 2 of example 1, but instead of Tetra-(5,8-dimethoxy-6-sulfo)intrahemispheric copper using 0.2 g (0.12 mmol) of Tetra-(5,8-dimethoxy-6-sulfo)intrahemispheric cobalt.

The output of Tetra-(5,8-dihydroxy-6-sulfo)intrahemispheric cobalt: 0.16 g (84.2%).

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

ESP in aqueous-alkaline solution, λmax,nwo nm: 676 (figure 2).

Found, %: 49.8; H 1.7; N, 7.4; S 8.4. C64N8H24O28S4Co.

Calculated, %: 49.9; H 1.6; N, 7.3; S 8.3.

The overall yield of the Tetra-(5,8-dihydroxy-6-sulfo)intrahemispheric cobalt is (0.474×0.842)×100=39.91%.

The claimed compounds can be used for dyeing cotton and viscose materials [Laboratory workshop on the application of dyes, Ed. Melnikov B.N. M.:Chemistry-1972. 3420.].

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-(5,8-dihydroxy-6-sulfo)intrahemispheric copper - 2

Sulfacid - 31-0 .5

Sodium chloride - 5

Module baths - 50.

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 the ode, dry.

The sample is attached (see figure 3).

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

Example 4. The use of Tetra-(5,8-dihydroxy-6-sulfo)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 C.].

Experiments are performed 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 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-(5,8-dihydroxy-6-sulfo)intrahemispheric cobalt (A) in the reaction liquid-phase oxidation of cysteine is

A=154 g-mol O2×(g-mol cat-RA)-1×min-1.

The method of producing metal complexes of Tetra-(5,8-dihydroxy-6-su is tho)intrahemispheric, including the interaction of substituted 2,3-dicarboxaldehyde with urea, salt of the corresponding metal in the presence of chloride and ammonium molybdate, characterized in that the substituted 2,3-dicarboxaldehyde use 2,3-dicarboxy-5,8-dimethoxy-6-solventrefined, and the resulting metal complex of Tetra-(5,8-dimethoxy-6-sulfo) intrahemispheric subjected to hydrolysis by treating it with sodium hydroxide.



 

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