The metal complexes of piperidin-di(tert.-butylbenzo)porphyrazine

 

(57) Abstract:

The invention relates to new complexes of pyridine containing derived porphyrazine, which may find application as dyes, catalysts for various processes, semiconductor materials for thin-film microelectronics, biologically active substances, photoactivation and so on Objective technical solution is the development of new metal complexes of pyridine containing derivatives of piperazine, which have good solubility in organic solvents and can be more widely used, in particular, as dyes, catalysts for various processes, semiconductor materials for thin-film microelectronics, biologically active substances, photoactivation, etc. the problem is solved by the synthesis of metal complexes of piperidin-di(tert. -butylbenzo)porphyrazine formula I where M = Cu, Co. The metal complexes of piperidin-di(tert. -butylbenzo)porphyrazine obtained by the interaction between 5/6-tert. -butyl-1,3 .3m-trichlorotoluene and 1-amino-3-imino-4/7-asiatinnen in acetone in the presence of triethylamine, hydroquinone, sodium methylate and salts of the respective metals. 3 Il.

the tion of the macrocycle condensed with a pyridine and tert.-butylsilane benzene rings:

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The inventive compounds may find application as catalysts, dyes, semiconductor materials, biologically active substances, photoactivation etc.

Known relatives on their link structure - Tetra(tert.-butylphthalocyanine formula II [Mikhailenko, S. A., S. Barkanova C., Lebedev, O. A., Lukyanets E. A. Journal of General chemistry, 1971, No. 12, S. 2735-2739]

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Tetra(tert.-butyl)phthalocyanine cobalt can be used as a catalyst for cleaning exhaust gases from nitrogen oxides [Maizlish C. E. and other Method of cleaning exhaust gases from nitrogen oxides. A. S. N 1611410 the USSR, BI N 45, 1990].

The disadvantage of this compound is its relatively low catalytic activity.

The closest analogue to the structure and properties are the metal complexes of tetraphenylporphyrin formula III [Galperin M,, Lukyanets E. A. Phthalocyanines and related compounds. III. Synthesis and electronic absorption spectra of some nitrogen-containing heterocyclic analogues phthalocyanine. Journal of General chemistry, 1969, T. 39, No. 11, C. 2536-2541].

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These complexes can be used as catalysts [Radyushkin K. A. and other Aza-analogues of the phthalocyanine in the elect is their dyes, so 5. Under the editorship of K. Venkataraman, L. : Chemistry, 1977, S. 263], semiconductors [Danzig M. J., C. Y. Liang, E. Passaglia J. Amer. Chem. Soc., 1963, vol. 86, N 6, p. 668-621].

However, the low solubility of the known derivatives of pyridine containing porphyrazine in organic solvents limits the technological possibilities of their treatment and of practical use.

The task of the technical solution is the development of new derivatives of pyridine containing piperazine, which have good solubility in organic solvents and can be more widely used, in particular, as dyes, catalysts for various processes, semiconductor materials for thin-film microelectronics, biologically active substances, photoactivation etc.

The problem is solved by the synthesis of metal complexes of piperidin-di(tert. -butylbenzo)porphyrazine.

Complexes of piperidin-di(tert.-butylbenzo)porphyrazine with copper and cobalt are powders dark blue color, having solubility in organic solvents (benzene, dimethylformamide, dimethylsulfoxide - chloronaphthalene, and so on), and concentrated sulfuric acid.

Thus, Pritula, catalysts, semiconductor materials for thin-film microelectronics, biologically active substances, photoactivation etc.

The individuality of the claimed compounds was confirmed by elemental analysis data, vibrational and electronic spectroscopy. In the IR spectra of the claimed compounds (Fig. 1, where 1 piperidin-di(tert.-butylbenzo)porphyrazine cobalt, 2 - piperidin-di(tert.-butylbenzo)porphyrazine copper) observed a number of common bands with phthalocyanines and tetraphenylporphyrinate. In addition, in the field 2850-2970 cm-1observed absorption bands, which belong to the symmetric and asymmetric stretching vibrations of relations CH3groups, tert.-Budilnik deputies [Gordon A., Ford, R. Satellite chemist. M.: Mir, 1976, S. 223]. Absorption bands in the region of 700-800 cm-1typical out-of-plane deformation vibrations of CH-bonds pyridine nuclei (low frequency component) and the fluctuations of the rings (high frequency band) and band in the range of 1550-1600 cm-1can be attributed to the stretching vibrations of C=C and C=N-bonds pyridine residues [Bykov centuries the Study of the impact of atatamete in the benzene rings on the properties of phthalocyanine and its complexes. The dissertation on says the Oia has one intense band at 649-655 nm, that is a convincing confirmation of the structure, as it was in this region of the spectrum absorb metal complexes derived porphyrazine [Porphyrins: structure, synthesis, properties. Ed. by N. With. Enikolopov, M. : Nauka, 1985, S. 83-113] (Fig. 2 - ESP piperidin-di(tert.butylbenzo)-porphyrazine cobalt in benzene, Fig. 3 - ESP piperidin-di(tert.-butylbenzo)porphyrazine copper in benzene).

The claimed compounds obtained by the interaction between 5/6-tert.-butyl-1,3 .3m-trichlorotoluene with 1-amino-3-imino-4/7-assasonation in acetone in the presence of triethylamine, hydroquinone, sodium methylate and chlorides of the respective metals.

Example 1. Synthesis of piperidin-di(tert.-butylbenzo)porphyrazine copper. In 60 ml of dry acetone with constant stirring in a stream of dry argon add 0,099 g (of 0.68 mmol) 1-amino-3-imino-4/7-asiatinnen and 0,353 g (3.5 mmol) of triethylamine. After the complete dissolution of 1-amino-3-imino-4/7-asiatinnen the mixture is cooled to 0oC and for 30 min add 0,188 g (of 0.68 mmol) 5/6-tert.-butyl-1,3 .3m-trichlorotoluene dissolved in 20 ml of dry acetone. The mixture was incubated for 1 h at 0oC, then slowly raise the temperature to room and continue premesis amemait in the reaction flask, equipped with stirrer and reflux condenser. Add 0,058 g (0,056 mmol) of anhydrous copper chloride (1) and stirred at room temperature in a stream of argon for 13 hours then the reaction flask make 0,095 g (1,75 mmol) of sodium methylate and 0.124 g (1.13 mmol) of hydroquinone. The reaction mixture is boiled for 6 h, then cooled and filtered. The precipitate is washed successively with 1% solution of ammonium hydroxide until a colorless filtrate and water until neutral environment. Final cleaning is performed by presidenial from solution in sulfuric acid.

Output: 0,026 g (11.2 per cent).

ESP in benzene,maxnm: 655.

Found, %: C 65,3; H 4,6; N 19,7; Cu 9,0

C38H30N10Cu

Calculated, %: C 66,1; H 4,4; N 20,3; Cu 9,2

Example 2. Synthesis of piperidin-di(tert.-butylbenzo)porphyrazine cobalt.

In 60 ml of dry acetone with constant stirring in a stream of dry argon add 0,099 g (of 0.68 mmol) 1-amino-3-imino-4/7-asiatinnen and 0,353 g (3.5 mmol) of triethylamine. After the complete dissolution of 1-amino-3-imino-4/7-asiatinnen the mixture is cooled to 0oC and for 30 min add 0,188 g (of 0.68 mmol) 5/6-tert.-butyl-1,3 .3m-trichlorotoluene dissolved in 20 ml of fresh acetone. Semeshin in a stream of argon for 6 hours The precipitate (triethylamine hydrochloride) is filtered off, the filtrate is placed in a reaction flask equipped with stirrer and reflux condenser. Add 0,073 g (0,56 mmol) of anhydrous cobalt chloride and stirred at room temperature for 13 hours then the reaction flask make 0,095 g (1,75 mmol) of sodium methylate and 0.124 g (1.13 mmol) of hydroquinone. The reaction mixture is boiled for 6 h, then cooled and filtered. The precipitate was washed with 1% aqueous solution of ammonium hydroxide until a colorless filtrate and water until neutral environment. Final cleaning is performed by presidenial from solution in sulfuric acid.

Yield: 0.025 g (10.7 per cent).

ESP in benzene,maxnm: 649.

Found, %: C 65,9; H 4,6; N 19,9; Co 8,4

C38H30N10Co

Calculated, %: C 66,6; H 4,4; N 20,4; Co 8,6

Thus, the inventive metal complexes of piperidin-di(tert.-butylbenzo)porphyrazine are new derivatives of pyridine containing porphyrazine, identity construction, in particular, by the presence on the periphery of the macrocycle pyridine and tert.-butylsilane benzene rings. They have the ability to dissolve in organic solvents. This allows more sesow, semiconductor materials for thin-film microelectronics, biologically active substances, photoactivation, as well as in other areas of science and technology.

1. The metal complexes of piperidin-di(tert-butylbenzo) porphyrazine formula

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where M = Cu, Co.

 

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