Tetra (3-bromo-4-carboxy-5-sulfo)phthalocyanine cobalt


The invention relates to new substituted the phthalocyanine, which may find application as a dye, catalyst different redox processes. Describes Tetra(3-bromo-4-carboxy-5-sulfo)cobalt phthalocyanine of the formula I

The technical result is the ability to synthesize phthalocyaninato connection, is able to dissolve in a wider pH range and have the ability to dye cotton fibers and fabrics made from them. 2 Il.

The technical field,

The present invention relates to new substituted metallophthalocyanines interest as dyes, catalysts of oxidation-reduction processes, biologically active drugs, etc.

The level of technology

Known for a number of substituted metallophthalocyanines, in particular halogen-substituted [Maizlish C. E., N. Fedosov.L., Shaposhnikov, P., Smirnov, R. P., Anoshkin, I. Y. Poslednie metalphthalocyanine // Izv. higher education institutions. Chemistry and chem. technology. - 1990. - So-33 - Vol.8 - S. 43-46], carboxy - and sulfadimidine [Maizlish C. E., Shaposhnikov, P., Snegireva F. P., Kolesnikov chemistry and chem. technology. - 1990. - So-33 - Vol.1 - S. 70-74], [Maizlish C. E., Mochalova N. L., Snegireva F. P., Borodkin C. F. Synthesis and spectral properties of sulfonic acids of macroheterocyclic compounds and their complexes, " Izv. higher education institutions. Chemistry and chem. technology. - 1986. - So 29. - Vol.1. - N-10] with different numbers and locations of these substituents, and zmechanizowane derivatives, combining two different substituent (a halogen and alphagroup (VI, VII), carboxy - and alphagroup (V)).

M=Co; C M=Co; C




R=Hal R1=N (IV)

The presence of certain substituents in the benzene rings phthalocyaninato ligand provides these complexes a number of useful properties: carboxy - and sulfopropyl - solubility in aqueous media, which allows the use of such compounds as water-soluble dyes [Stepankov B. I. introduction to the chemistry and technology of organic dyes. M.: Chemistry. - 1984. - S. 520-539], catalysts for various processes in homogeneous environments [Porphyrins: spectroscopy, electrochemistry, application / Ed. N.With.Enikolopyan autodynamica cancer therapy: second and third generation photosensitizers. WPI. An. A series of chemical, 1998, No. 5, S. 836-845] and in other areas of science and technology; halogen improve the color fastness of the colored surfaces [Chemistry of synthetic dyes // Under the editorship of K. venkataramana. Volume V. L.: Chemistry, 1977, S. 221-225].

Compounds I-IV are monofunctionalized metalphthalocyanine and compounds V-VII-biofunctionalization.

The presence of different substituents in the phthalocyanine molecule gives the complex a variety of useful properties.

The closest structural analogue of the claimed compound is a cobalt complex of Tetra(4-bromo-5-sulfo)phthalocyanine (VII). However, although the structure of this complex contains two different Deputy, imparting solubility in neutral and water-alkaline environments and lightfastness, but this compound is not soluble in acidic solutions, which limits its use for dyeing in acidic media.

Individual phthalocyanine compounds containing in the molecule at the same time three different substituent (bromine, carboxy - and sulfopropyl), is unknown.

The invention

Inventive task was to find compounds that are substituted by metalphthalocyanine capable of simultaneously dissolving in boleta ability to dye cotton fibers and fabrics made from them.

The problem is solved by the synthesis of Tetra(3-bromo-4-carboxy-5-sulfo)phthalocyanine cobalt

The invention provides the following advantages:

- Tetra(3-bromo-4-carboxy-5-sulfo)phthalocyanine cobalt has a solubility in alkaline and neutral and weakly acidic aqueous media that can be used for dyeing of cotton fibers and fabrics from them in the blue-green color, extending the color gamut of water-soluble phtalocyanine dyes;

connection provides obtaining permanent colors cotton fibers and fabrics from them.

The structure of the claimed compounds was confirmed by elemental analysis data, vibrational and electronic spectroscopy.

IR spectrum in KBR Tetra(3-bromo-4-carboxy-5-sulfo)phthalocyanine cobalt (Fig.1) has a band, corresponding to stretching vibrations of relations: S=O (1100 cm-1), C=O (1700 cm-1) and C-Br (600 cm-1) [Gordon A., Ford, R. Satellite chemist. M.: Mir, 1976, S. 200-234]. Unlike the IR spectra of unsubstituted metallophthalocyanines [Sidorov, A. N., Kotlyar, I. P. / Optics and spectroscopy, 1961, T. 11, No. 2, S. 175] the spectrum of the inventive compound has a weak resolution that indicates possible MIM COOH), and bromine atoms.

Electronic absorption spectra of the Tetra(3-bromo-4-carboxy-5-sulfo)phthalocyanine cobalt in dimethylformamide, water and aqueous ammonia (Fig.2) are characteristic for metalphthalocyanine Q-band in the area 684-688 nm [Lever A. C. R. // Inorg. Chem. and Radiochem., 1965, v.7, R. 68].

Information regarding the playback of the invention

The inventive compound is obtained in a known manner urea fusion [Chemistry of synthetic dyes // Under the editorship of K. venkataramana, volume V, L.: Chemistry, 1977, S. 212-214] from Pikalevo salts of 3-bromo-4-carboxy-5-sulfophthalic acid in the presence of anhydrous cobalt acetate and ammonium molybdate scheme

This used the following reagents:

- urea GOST 6691-77;

anhydrous cobalt acetate GOST 5861-79;

- molybdate of ammonium GOST 3765-78;

- dikalova salt of 3-bromo-4-carboxy-5-sulfophthalic acid. This reagent industry currently not available, therefore, was synthesized according to the following scheme:

of 8.4 g (0.03 mol) of 3-bromo-5-sulfamidate suspended in 200 ml of water, podslushivaet CON with a slightly alkaline reaction and add 100 ml of pyridine. Heated to 70

Yield: 4 g (30%).


Found, %: VG 17,3, S 7,8.

Calculated, % Br 18,0, S 7,2.

IR spectrum in KBR,cm-1: 1720 (C=O of COOH); 1624, 1384 (C=O in soo-), 1100 (S=O); 600 (C-Br). The m-4-carboxy-5-sulfophthalic acid is mixed with 2.2 g (36 mmol) of urea, 0,37 g (0.3 mmol) of anhydrous cobalt acetate and 0.03 g (0.15 mmol) of ammonium molybdate. Thoroughly mixed reagents placed in the tube, located vertically in an electric resistance furnace and incubated with stirring in the following temperature-time mode:

140-150C - 90 min; 170-180C - 35 min; 190C - 15 min; 200S - 60 minutes

After cooling, the reaction mass is crushed, washed first with 17%, then 5% solution of hydrochloric acid to colorless filtrates. The filter residue is dissolved in aqueous ammonia, filtered and evaporated on a water bath. Then the obtained residue again treated with 17% hydrochloric acid and the final cleaning is performed by extraction of the impurities in methanol to conventional Soxhlet extractions.

The product is a powdery substance dark purple color with metallic luster, soluble in water, water-alkaline water and acidic environments, limited soluble in DMF and other polar organic solvents.

Yield 0.36 g (23%).

IR spectrum in KBR, cm-1: 1700 (C=O of COOH); 1100 (S=O); 600 (hydroxy-5-sulfo)phthalocyanine cobalt is an organic substance class of substituted metallophthalocyanines, identity structure, the presence in the molecules of three different substituents fixed their position in the benzene nuclei, the ability to dissolve in alkaline and neutral and weakly acidic aqueous media. These properties of Tetra(3-bromo-4-carboxy-5-sulfo)phthalocyanine cobalt allow it to be used for dyeing cotton fibers and fabrics made from them; in different environments, as a catalyst in various processes in a homogeneous environment, as well as in other areas of science and technology.


Tetra (3-bromo-4-carboxy-5-sulfo)phthalocyanine cobalt formulas


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