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=N R1=COOH (I) R=SO3N R1=COOH (V)

R=COOH R1=N(II) R=SO3N R1=CL(VI)

R=SO3N R1=N(III) R=SO3N R1=Br(VII)

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%).

With9H3WMC2About9S.

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.

Claims

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



 

Same patents:
The invention relates to methods for producing socialization for the polymerization of butadiene, occurring in the presence of cobalt containing catalysts, and may find application in the IC industry in the production of CIS-1,4-polybutadiene

The invention relates to storage-based catalysts on the media that are used in the polymerization of olefins

The invention relates to an improved dual metallocyanide (DMC) catalysts and methods for their preparation

The invention relates to an improved dual metallocyanide (DMC) catalysts and methods for their preparation

The invention relates to the preparation of catalyst components on the carrier, including a carrier and alumoxane, the catalysts on the media containing the metallocene compound and the ways polyaddition using these catalysts
The invention relates to the synthesis of alternating copolymers of carbon monoxide and olefins under the action of catalysts containing phosphine palladium salt and an organic boron salt

The invention relates to ORGANOMETALLIC compounds, to compositions containing them and their use

The invention relates to petrochemistry, specifically to the production dialkyldithiocarbamate accelerators of vulcanization of rubbers

The invention relates to a method for the polymerization of 1-olefins which can be used in catalytic systems and which include nitrogen-containing compounds of transition metals, including structural unit represented by the formula (V), where M represents Fe (II), Fe (III), Ru (II), Ru (III) or Ru (IV), X represents an atom of Cl or Br, T denotes the oxidation state of the transition metal M and b is the valency of the group X, the values of each of R1, R2, R3, R4and R6independently from each other selected from hydrogen, methyl, ethyl, n-propyl, n-butyl, n-hexyl, n-octyle, and values of each of R5and R7independently from each other selected from phenyl, 1-naphthyl, 2-naphthyl, 2-methylphenyl, 2-ethylphenyl, 2,6-diisopropylphenyl, 2,3-diisopropylphenyl, 2,4-diisopropylphenyl, 2,6-di-n-butylphenyl, 2,6-dimetilfenil, 2,3-dimetilfenil, 2,4-dimetilfenil, 2-tert-butylphenyl, 2,6-diphenylphenol, 2,4,6-trimetilfenil, 2,6-triptoreline, 4-bromo-2,6-dimetilfenil, 3,5-dichloro-2,6-diethylphenyl and 2,6-bis(2,6-dimetilfenil)phenyl, the cyclohexyl and pyridinyl

The invention relates to a new method of obtaining metallizovannyh derived bacteriochlorophyll for use in the methods of photodynamic therapy (PDT) and in vivo diagnostics and photodynamic destruction of viruses and microorganisms in vitro, as well as some new metallosalen derived bacteriochlorophyll

The invention relates to a new stable complex compound containing macrocyclic tetradentate ligand having the structure of formula I, where R1and R2have the same or different values are related or unrelated, and each is selected from the group consisting of hydrogen, halogen, methyl, CF3and, if they are connected, cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl, are spatial and confirmation difficult, so that the oxidative degradation of complex metal compound is limited, when the complex is in the presence of an oxidizing environment, Z represents a stable to oxidation atom, which metallocomplexes selected from nitrogen and oxygen, X represents an oxidation resistant functional group selected from O or NRswhere Rsrepresents a methyl, phenyl, hydroxyl, auxillou group, CF3or CH2CF3, R3, R4, R5represent fragments of connecting adjacent Z atoms containing structure described in the claims

- cyclodextrin and method of suppressing tumor growth" target="_blank">

The invention relates to organic chemistry, and medicine, and it applies to substances used in combination with ascorbic acid for the treatment of malignant neoplasms (binary catalytic "dark" therapy of malignant tumors) and method of suppressing tumor growth

The invention relates to a phthalocyanine of the formula (I) used as a means for marking liquids, such as mineral oils
Up!