The metal complexes of tetra (2,3-pyridone-6)porphyrazine
The invention relates to new derivatives of metalloporphyrins that can primeneniia as pigments, catalysts, materials sensitive elements gases. Describes complexes of Tetra(2,3-pyridone-6)porphyrazine General formula I, where M = Cu, Co, Ni
The technical result is the expansion of the color gamut pigment blue with low solubility in dimethylformamide, diluted mineral acids, insoluble in water and aqueous solutions of alkalis. 1 Il.
The invention relates to new derivatives of metalloporphyrins, which may find application as pigments, catalysts for various processes, materials sensitive elements (CHAD) gases, etc.
The level of technology
Known compounds (al'yanov, M. I., Borodkin C. F., Bender C. A. absorption Spectra oxiclean of meditationen and their vysokomehanizirovannyh salts, Izv. higher education institutions. Ser. Chemistry and chemical. the technologist. 1970. So 13. Vol.6. C. 855-860; Maizlish C. E., Shaposhnikov, P., Snegireva F. P., Mochalova N. L., Smirnov, R. P. Electronic absorption spectra of I structural analogues of the claimed compounds the metal complexes of Tetra-4-hydroxypteridine formula
They are used as a starting compound to obtain effective catalysts of oxidation-reduction reactions (Maizlish C. E., Borodkin C. F. Catalytic properties of soluble metallomatrichnoi compounds, Izv. higher education institutions. Ser. Chemistry and chemical. the technologist. 1984. So 27. Vol.9.With.1003-1016).
The closest structural analogue of the claimed compounds are metal complexes of Tetra-2,3-pyridinethione (Halpern M,, Lukyanets E. A. Phthalocyanines and related compounds. III. Synthesis and electronic absorption spectra of some nitrogen-containing heterocyclic analogues phthalocyanine //Ukr. General chemistry). 1969. So 69. Vol. 11. C. 2536-2541) formula
Inventive task was to find compounds Tetra(2,3-pyridone-6)porphyrazines series expansion of the color gamut pigment blue color.
The problem is solved by the synthesis of metal complexes of Tetra(2,3-pyridone-6)porphyrazine formula
The structure of these compounds proved by data of elemental analysis, IR,1-1), C=O (1699 - 1709 cm-1),- N (2926 - 2922 cm-1), and C=N (1394 - 1358 cm-1) (Dyer D. R. Application of absorption spectroscopy of organic compounds. M.: Chemistry, 1970, S. 31-68).
In1H NMR spectrum of the complex with Nickel marked the signals of three protons. The singlet at 7.52 memorial plaques corresponds to the resonance of the proton in position 4 Spiridonovka cycle, a singlet at 7.26 memorial plaques - in position 5, and a singlet at 7.01 M. D. characterizes the resonance of the proton on the nitrogen atom in position 1.
In the mass spectrum of the cobalt complex was marked signal of the molecular ion with m/z 639.
Electronic absorption spectra of the claimed compounds, measured in dilute mineral acids, very similar in nature and are characterized by absorption in the range of 622 - 645 nm (Q - band) and in the field 329 - 334 nm (In - band). In Fig.1 shows the electronic spectrum of the cobalt complex.
The metal complexes of Tetra(2,3-pyridone-6)porphyrazine are blue substance with low solubility in dimethylformamide, good solubility in dilute mineral acid is not soluble in water and aqueous solutions of alkalis.
These new derivatives porphyrazine can knight is Chikov (CHAD) gases, etc.
Information confirming the possibility of carrying out the invention
The claimed compounds obtained by the interaction of 2,3-dicarboxy-pyridone-6 with urea in the presence of chlorides of the corresponding metals and catalytic amounts of ammonium molybdate.
2,3-dicarboximido-6. In a three-neck flask with a capacity of 2 liters was placed 1000 ml of water, 21 g (0.375 mole) of potassium hydroxide, 57 grams (0.4 mole) of 2-hydroxyquinoline solution and loaded 384 g (2,43 mole) of potassium permanganate in portions of 10 g for 3 hours After loading oxidizer mass was stirred for 2 hours, heated to 80 °C for 1 h and kept at this temperature for another 3 hours At the end of the reaction the precipitate of manganese dioxide was filtered and washed on the filter with 500 ml of hot water. The filtrate and the washing water was evaporated to a volume of 500 ml and treated with hydrochloric acid to stop the release of carbon dioxide, then add the sodium hydroxide to pH = 9 and was added a solution of 84 g (0.34 mole) of barium chloride in 400 ml of water.
Precipitated precipitated barium salt of 2-hydroxy-5,6-dicarboximide was filtered, washed with water until neutral, suspended in 400 ml of water was added 6 ml monohydrate sulfuric acid. The mass was stirred for 30 min, the precipitate of BaSO4was filtered and polyvalente 60°C. Yield 28 g (38%) as a crystalline white powder. IR spectrum, v, cm-1: 3457 (O-H), 3098 (N-H), 2924 (C-H), 1720 (C=O), 1604,1554, 1311, 1246 (C=N), 1128, 841, 753, 672, 429. Range1H NMR,, M. D.: (CF3D) 9.39-9.35 (D., 1H), 9.21-9.19 (D., 1H), 8.54 - 8.47 (t, 1H). Range13With NMR,, M. D.: (CF3COOD) 152.17, 146.95, 132.93, 125.09, 113.84, 108.20, 87.54. The compound is well soluble in water, aqueous solutions of acids and alkalis, sparingly soluble in alcohol, DMF, DMSO. Found,%: C 45.25; N, 3.10; N, 7.52. C7H5NO5. Calculated,%: 45.91; H 2.75; N7.65.
Example 1. The metal complexes of Tetra(2,3-pyridone-6)porphyrazine. The quartz tube was placed 0.9 g (0.05 mole) of 2,3-dicarboximido-6, 6 g (0.1 mole) of urea, 0.02 g of ammonium molybdate and 0.02 mole of anhydrous chloride of the corresponding metal. The mixture was heated at 200 °C for 30 min, cooled to 20 °C, the reaction mass was extracted, crushed, washed with 10% solution of ammonia, water, perioadele of concentrated Hydrobromic acid, was filtered, washed successively DMF, hot water, acetone and dried at a temperature of 100 °C.
Tetra(2,3-pyridone-6)porphyrin copper. Yield 0.40 g (51%). The electronic absorption spectrum,the, 506, 1394 (C=N), 1138, 758, 739. Found, %: C 52.84; H 2.21; N 26.90. C28H12N12About4Cu. Calculated, %: C 52.22; H 1.88; N 26.10.
Tetra(2,3-pyridone-6)porphyrin cobalt. Yield 0.37 g (47%). The electronic absorption spectrum,max, (D): (DMF) 629 (1.07), 574 (0.24), 406PL(0.27), 329 (0.51); (27% model HC1) 622 (0.79), 548 (0.23), 334 (0.45). IR spectrum, v, cm-1: 3116 (N-H), 2926 (C-H), 1709 (C=O), 1510, 1391 (C=N), 1131, 754, 743. Mass spectrum, m/z: 639 [M]+. Found,%: C 52.25; H 1.94; N 25.66. C28H12CoN12O4. Calculated,%: C 52.58; H 1.89; N 26.30.
Tetra(6-hydroxy-2,3-pyridine)porphyrin Nickel. Yield 0.42 g (58%). The electronic absorption spectrum,max, (D): (DMF) 641 (1.10), 577 (0.21), 410PL(0.30), 330 (0.52); (27% model HC1) 645 (0.72), 578 (0.24), 331 (0.37). IR spectrum, v, cm-1: 3106 (N-H), 2923 (C-H), 1699 (C=O), 1358 (C=N), 1085, 773, 611. An NMR spectrum1H,, M. D.: ([D6]DMSO) 7.52 (S., 1H), 7.26 (S., 1H), 7.01 (S., 1H). Found,%: C 51.15; H 2.01; N 27.00. C28H12N12NiO4. Calculated,%: C 52.62; H 1.89; N 26.30.
Example 2. The use of the claimed compounds as pigments.
A mixture of 3 g of zinc oxide and 0.75 g of the metal complex of Tetra(2,3-pyridone-6)porphyrazine carefully rubbed kuranta until a homogeneous powder was added 0.5 ml of varnish and continued to RUB up on the obtained according to example 2, attached.
The metal complexes of Tetra(2,3-pyridone-6)porphyrazine General formula
where M = si, Co, Ni.