Copper tetra-(6-tertiary-butyl-2,3-quinolino)porphyrazine as dyeing substance of optical filter

FIELD: chemistry of chelated compounds.

SUBSTANCE: invention relates to copper porphyrazine chelates comprising linear anellated quinoline cycles, namely, to copper tetra-(6-tert.-butyl-2,3-quinolino)-porphyrazine of the formula (I): that can be used a dyeing substance of optical filters.

EFFECT: valuable properties of substance.

2 cl, 1 dwg, 1 ex

 

The invention relates to the chemical industry, namely the tetrapyrrole macroheterocycles - tetrabenzoporphyrin, i.e. the porphyrazine linearly fused aromatic or heteroaromatic cycles containing different substituents, specifically to new chemical compound is Tetra-(6-tert-butyl-2,3-chinoline)porphyrazine copper.

The level of technology

Tetrapyrrole the macroheterocycles play an important role in nature and technology, entering into the structure of the respiratory pigments, enzymes, vitamins, catalysts, sensors, etc. and having a narrow intense absorption band in the visible region, can be used as the coloring matter of optical filters.

Interest from tetrabenzoporphyrin having a maximum light absorption in the region above 700 nm in order to use them for photodynamic therapy and the creation of optical filters.

Optical filters are often painted plexiglass and can be obtained by surface staining of the last or dyeing in the mass. Dyeing in the mass, in turn, can be done in two ways:

the mixture of polymer solution in a suitable solvent with a solution of the coloring matter and the subsequent formation of the colored solution sheet is whether the film is dry or wet;

- the introduction of coloring matter into a monomer followed by polymerization of the colored monomer in forms.

Because the best of these methods of obtaining optical filters are methods of dyeing in the mass, an important property of the coloring matter is a good solubility in organic solvents, dissolving a polymer base of the filter, or in the monomers from which it is obtained.

Known Tetra-(2,3-chinoline)porphyrin copper (Korzhenevskaya A.B., Markova L.V., I. Koifman CHC, 1992, No. 8, s-1071)having a maximum absorption in organic solvents in the field 714-718 nm and a structural analogue of the claimed compounds.

The main disadvantage of this connection when using it as a dye stuff of the optical filter is a low solubility in different solvents not exceeding 10-5mol/l, which limits the choice of material of the optical filter and does not allow to derive optical filters with a high shielding ability.

The invention

The objective of the invention is the search for new compounds with higher solubility sufficient for use as a coloring substance of optical filters having a high shielding ability

This goal is achieved Tetra-(6-tert-butyl-2,3-chinoline)porphyrazine copper.

The identity and structure of the claimed compound installed according to elemental analysis, similar spectral characteristics in the visible region of the spectrum of its solution in DMF with those of his closest structural analogue and IR spectra (figure 2).

The data of elemental analysis, %:NNCu
for C60H52N12Cu calculated71,715,1816,736,38
found72,025,5416,586,11

Electronic absorption spectra (figure 1) solutions of the claimed compound and its structural analogues in DMSO were recorded on a spectrophotometer Perkin Elmer Lambda 20 in quartz rectangular cuvettes of 10 mm thickness, concentration of solutions ˜10-5M. the provisions of the long-wave absorption bands of these spectra is shown below.

Tetra-(6-tert-butyl-2,3-chinoline)porphyrin copper718 nm, 640 nm
Tetra-(2,3-chinoline)porphyrin copper714 nm, 637 nm

The data of elemental analysis in sovocool the analogy with high visible parts of the electronic absorption spectra strongly suggests that that the claimed compound belongs to the class of tetrabenzoporphyrins, and it is substituted Tetra-(2,3-chinoline)porphyrazine copper.

As peripheral substituents are four tert - butyne group. The number, location and nature of the substituents clearly derive from the structure used to produce Sinton - imida 6-tert-butylphenol-2,3-dicarboxylic acid and the presence of absorption bands in the IR spectra of the claimed compounds in the field 2923 cm-1related to the stretching vibrations of methyl radicals in the composition of tert-Budilnik groups, and in 1397 and 1437 cm-1related to the symmetric deformation vibrations (figure 2) tert-Budilnik groups.

Thus, the aggregate results of elemental analysis and spectral data uniquely identifies the structure of the claimed compounds as Tetra-(6-tert-butyl-2,3-chinoline)porphyrazine copper.

Tetra-(6-tert-butyl-2,3-chinoline)porphyrin copper is a blue-black crystalline substance with a metallic sheen, not fuse up to 400°S, soluble in methanol, chloroform, DMF and DMSO with the formation of intensely colored solutions.

To determine the solubility of the inventive compound and its structural analogue used spectrophotometric method (Berezin D. abstract of Prof. dis is ertale, Kiev, 1966, p.9). The method consists in the fact that experimentally received molar extinction coefficients (, l/mol·cm-1) substances in specified solvents. Then an accurately weighed sample of the substance was placed in a sealed vessel filled with an exact amount of the selected solvent, in a temperature-controlled (25° (C) a rocking chair. Dissolution of the sample was carried out before reaching the maximum value of the optical density of the resulting solution while maintaining the bottom phase and the nature of the spectrum obtained in the determination of the extinction coefficient.

The maximum values of optical density solubilitywas calculated by the formula

where- the equilibrium solubility of i-th substance in j-the solvent at 25°C, mol/l, and-maximum optical density of a solution of i-th substance in the j-th solvent at 25°C.

The values of solubility (mol/l), defined in the same way for the claimed compound and its structural analogue, below.

MethanolChloroformDMFDMSO
Tetra-(6-tert-butyl-2,3-chinoline)piperazin m is di ˜10-3˜5·10-3˜5·10-3˜5·10-3
Tetra-(2,3-chinoline)porphyrin copper00˜5·10-5˜5·10-5

Information confirming the possibility of carrying out the invention For carrying out the invention use imide 6-tert-butylphenol-2,3-dicarboxylic acid, which was obtained from 6-tert-butylphenol-2,3-dicarboxylic acid by heating in glacial acetic acid with ammonium carbonate. In turn, 6-tert-butylphenol-2,3-dicarboxylic acid is obtained from 4-tert-butylphenyl-1,2-diamine by the method (Maulding D.R. J. Heterocycl. Chem. 1988, Vol.25, 1777-1779). In addition, using the following ingredients: copper acetate (GOST 5852-79), hydrochloric acid "h" (GOST 857-78), ammonium molybdate (GOST 3765), urea (GOST 6691-77), sulfuric acid reactive (GOST 420477).

The inventive compound can be obtained, for example, as follows.

Carefully pounded mixture of 2.54 g (10 mmol) imide 6-tert-butylphenol-2,3-dicarboxylic acid, 0.55 g (3 mmol) of anhydrous copper acetate, 6 g (0.1 mol) of urea and 0.1 g of ammonium molybdate was heated for one hour to 220°C and kept at this temperature for 2 hours. Then, the melt was washed away with hot water, the solid phase was separated by filtration and about Yali on the filter successively with hot water and 5%hydrochloric acid until a colorless filtrate, and then perioadele from a solution in concentrated sulfuric acid on ice. Fallen blue-black crystals were separated by filtration, washed on the filter with water until neutral filtrate and dried at a temperature of 150°C.

Received 2 g (2 mmol) of Tetra-(6-tert-butyl-2,3-chinoline)porphyrazine copper. Output ˜80% of theory.

To determine the possibility of using Tetra-(6-tert.-butyl-2,3-chinoline)porphyrazine copper as the coloring matter of the optical filter 10 samples were prepared organic glass, painted the claimed compound. This prepared solution of this compound in methyl methacrylate concentration ˜10-5M, poured it into the folding glass shape and subjected thermopolymerization at 140°C for 24 hours. Then the samples dyed organic glass was removed from the forms and determine their optical density at the wavelength corresponding to maximum absorption coloring matter.

The obtained samples were subjected to light ageing by exposure under a lamp CES-375 375 watt at a distance of 20 cm at 25°C for 72 hours according to GOST 8979-85.

Subjected to aging samples dyed organic glass was photometrically at the wavelength corresponding to maximum absorption coloring matter.

Sitostanol the (R,%) was estimated as the percentage of preserving optical density organic glass after UV exposure by the formula

where A1and a2- the optical density of the glass before and after UV expozitii respectively.

Tests showed that the lightfastness of the claimed compounds is not inferior to any structural analogue.

Thus, having a maximum absorption in organic solvents in the field 715-720 nm, high light fastness and good solubility, the proposed Tetra-(6-tert-butyl-2,3-chinoline)porphyrin copper may be used as the coloring matter to create optical filters.

Tetra-(6-trebuil-2,3-chinoline)porphyrin copper formula

as the coloring matter of optical filters.



 

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