Di(1,4-directlogic)-di(tert.-butylbenzo)porphyrin and its metal complexes

 

(57) Abstract:

The present invention relates to new sulfur-containing derivative of piperazine and its metal complexes, which can be used as dyes, catalysts of oxidation-reduction processes, semiconductor materials for thin-film microelectronics, biologically active substances, etc. the Task of the technical solution is the development of new sulfur-containing derivatives of piperazine, which have good solubility in organic solvents, ability to thermal vacuum sublimation and can be used as dyes, catalysts of oxidation-reduction processes, semiconductor materials for thin-film microelectronics, biologically active substances. Di(1,4-DirectLOGIC)-di(tert. -butylbenzo)porphyrin and its metal complexes obtained by the interaction between 6/7-tert.-butyl-1,3 .3m-trichlorotoluene and 1-amino-3-imino-4,5,6,7-tetrahydroisoquinoline in acetone in the presence of triethylamine, hydroquinone, sodium methylate, and in the case of metal complexes in the presence of salts of the respective metals. 2 Il.

The present invention rela what about the tubes of condensed with 1,4-detalladamente and tert.-butylsilane benzene rings

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M = HH, Co, Cu

The claimed compounds can be used as dyes, catalysts of oxidation-reduction processes, semiconductor materials for thin-film microelectronics, biologically active substances, etc.

Known relatives on their link structure - Tetra(tert. -butyl)phthalocyanine of the formula II [Mikhalenko, S. A., S. Barkanova Century, Lebedev O. L., Lukyanets E. A. Journal of General chemistry, 1971, No. 12, S. 2735-2739].

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M = HH, Co, Cu

Tetra(4-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 161410 the USSR. B. I. No. 45, 1990].

Also known structural analogues of the claimed compounds - Tetra(1,4-DirectLOGIC)porphyrazines formula III [Shaposhnikov, P., Kulinich B. N., Smirnov, R. P. Chemistry of heterocyclic compounds. 1986, N 5, c. 603-606].

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M = HH, Co, Cu

These compounds can be used as dyes [Chemistry of synthetic dyes. Under the editorship of K. Venkataraman, T. 5, L.: Chemistry, 1977, S. 269-270] , and exhibit semiconducting properties [Shaposhnikov, P., Kulinich B. N., V. Y. M., Smirnov, R. P. Istvan is a metal complex di(1,4-DirectLOGIC)-di(alfabeto)porphyrazine (dissolvability of tetrathiotetracene) formula IV [Maizlish C. E., Snegireva F. P. , Mochalova N. L., Borodkin C. F. Izv. higher education institutions. Chemistry and chemical technology, 1986, T. 29, N 1, c. 3-20].

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M = Fe, Co

These complexes can be used as catalysts for the oxidation of sulfur compounds [Borodkin C. F., Maizlish C. E. Fomin, C. A., Mazgarov A. M. Izv. higher education institutions. Chemistry and chemical technology, 1979, T. 22, N 4, S. 413-416] and dye [Maizlish C. E., Mosquitoes, R. D., Borodkin C. F. Izv. higher education institutions. Chemistry and chemical technology, 1980, T. 23, S. 646-647].

However, the low solubility of known sulfur-containing derivatives of piperazine 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 sulfur-containing derivatives of piperazine, which have good solubility in organic solvents, ability to thermal vacuum sublimation and can be used as dyes, catalysts of oxidation-reduction processes, semiconductor materials for thin-film microelectronics, biologically active substances, etc.

The problem is solved by the synthesis of di(1,4-DirectLOGIC)-di(tert.-butylbenzo)porphyrazine and IU cobalt are powders dark purple color, well soluble in organic solvents (benzene, acetone, -chloronaphthalene and others ) and in concentrated sulfuric acid. Di(1,4-DirectLOGIC)-di(tert. -butylbenzo)porphyrin has the ability to sublimate without decomposition in vacuum (610-5mm RT.CT.) at a temperature of 350-360oC.

Thus, the proposed new sulfur-containing derivatives of piperazine and its metal complexes can be used as dyes, catalysts, semiconductor materials for thin-film microelectronics, biologically active substances, 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) in the field of 1000-1100 cm-1detected absorption characteristic of thioester linkages. The absorption band at 2840 and 2870 cm-1refer to symmetric and asymmetric stretching vibrations of relations CH3-tert groups. -Budilnik deputies [Gordon A., Ford, R. Satellite chemist. M.: Mir, 1976, S. 223]. In the field of 400-2000 cm-1absorption bands in the IR spectra of the claimed compounds is less resolved than the phthalocyanines, due to intermolecular ot the arts absorption Wu di(1,4-DirectLOGIC)-di(tert.-butylbenzo)porphyrazine observed.tsya two intense bands at 610 and 728 nm, and its metal complexes - wide band at 651-653 nm (Fig.2). In addition, in the field of 500-530 nm there are additional low intensity bands corresponding to n - n' transition due to the excitation of the n - electrons of the sulfur atoms peripheral 1,4-ditzikloverina rings [Shaposhnikov, P., Kulinich B. N., V. Y. M., Smirnov, R. P. Chemistry of heterocyclic compounds. 1986, No. 9, S. 1276-1279].

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

Example 1. Synthesis of di(1,4-DirectLOGIC)-di(tert.-butylbenzo)-porphyrazine/

Mix 0.124 g (of 0.68 mmol) 1-amino-3-imino-4,7-dithia-4,5,6,7-tetrahydroisoquinoline and 0,353 g (3.5 mmol) of triethylamine. With constant stirring in a stream of dry argon add 60 ml of dry acetone. After the complete dissolution of 1-amino-3-imino-4,7-dithia-4,5,6,7-tetrahydroisoquinoline the mixture is cooled to 0oC for 30 minutes add 0,188 g (of 0.68 mmol) 6/7-tert.-butyl-1,3 .3m-trichlorotoluene dissolved in 20 ml of acetone. The mixture was kept for the dry 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 0,074 g (0.67 mmol) of hydroquinone and to 0.108 g (2 mmol) of sodium methylate. The mixture is boiled for 6 hours with constant transmittance over the reaction mass of argon, then cooled and filtered. The precipitate is washed with a 15% solution of hydrochloric acid to colorless filtrates, then with water until no chloride ions. Chromatographic aluminum oxide, using as eluent a mixture of benzene with ethanol in a ratio of 3:1. Yield 0.025 g (10,6%).

Dark purple substance, soluble in benzene, acetone, naphthalene chloride, concentrated sulfuric acid. Sublimated in vacuum (610-5mm RT.CT.) at 350-360oC. ESP in benzene,maxnm: 728; 610.

The infrared spectrum, cm-1: 1080 (C-S); 2870 (asCH3); 2950 (SCH3).

Found,%: C To 59.9; H 4,4; N 15,1; S 18,0.

C36H34N8S4< / BR>
Calculated, %: C 61,2; H 4,8; N 15,9; S 18,1.

Example 2. Synthesis of di(1,4-DirectLOGIC)-di(tert.-butylbenzo)porphyrazine cobalt.

Mix 0.124 g (of 0.68 mmol) 1-amino-3-imino-4,7-dithia-4,5,6,7-tetrahydroisoquinoline and 0,353 Cetona. After the complete dissolution of 1-amino-3-imino-4,7-dithia-4,5,6,7-tetrahydroisoquinoline the mixture is cooled to 0oC for 30 minutes add 0,188 g (of 0.68 mmol) 6/7-tert.-butyl-1,3 .3m-trichlorotoluene dissolved in 20 ml of acetone. The mixture was incubated for 1 hour at 0oC, then slowly raised to room temperature and continue stirring 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 in a stream of argon for 13 hours. After that, the reaction flask make 0.124 g (1,75 mmol) of sodium methylate and 0,092 g (1.13 mmol) of hydroquinone. The reaction mixture is boiled for 6 hours, then cooled and filtered. The precipitate is washed successively with a 15% solution of hydrochloric acid until a colorless filtrate and water until no chloride ions. Final cleaning is performed by presidenial from solution in sulfuric acid. The output was 0.026 g (10.0%).

Dark purple substance, soluble in benzene, acetone, naphthalene chloride, concentrated sulfuric acid. ESP in benzenemax, what about the, %: C Of 56.4; H 4.2; N 14,3; S 16,2; Co7,7.

C36H32N8S4Co

Calculated, %: C 56,6; H 4.2; N 14,7; S 16,7; Co 7,7.

Example 3. Synthesis of di(1,4-DirectLOGIC)-di(tert.-butylbenzo)porphyrazine copper.

Mix 0.124 g (of 0.68 mmol) 1-amino-3-imino-4,7-dithia-4,5,6,7-tetrahydroisoquinoline and 0,353 g (3.5 mmol) of triethylamine. With constant stirring in a stream of dry argon add 60 ml of dry acetone. After the complete dissolution of 1-amino-3-imino-4,7-dithia-4,5,6,7-tetrahydroisoquinoline the mixture is cooled to 0oC for 30 minutes add 0,188 g (of 0.68 mmol) 6/7-tert.-butyl-1,3 .3m-trichlorotoluene dissolved in 20 ml of acetone. The mixture was incubated for 1 hour at 0oC, then slowly raised to room temperature and continue stirring 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 0,076 g (0,56 mmol) of anhydrous copper chloride (I) and stirred at room temperature in a stream of argon for 13 hours. After that, the reaction flask make 0.124 g (1,75 mmol) of sodium methylate and 0,092 g (1.13 mmol) of hydroquinone. The reaction mixture is boiled in the tech what about the colorless filtrate and water until no chloride ions. Final cleaning is performed by presidenial from solution in sulfuric acid. Output 0,054 g (20.5 percent). ESP in benzene,maxnm: 653.

The infrared spectrum, cm-1: 1040-1060 (C-S); 12870 (asCH3); 2950 (SCH3).

Found, %: C 55,9; H 4,1; N 14,3; S 16,5; C 8,9.

C36H32N8S4Cu Calculated, %: C 56,2; H 4.2; N 14,6; S 16,7; C 8,3.

Thus, the claimed di(1,4-DirectLOGIC)-di(tert.-butylbenzo)porphyrin and its metal complexes are new sulfur-containing derivatives of piperazine, identity construction, in particular the presence on the periphery of the molecule 1,4-ditzikloverina and tert.-butylsilane benzene rings. They have the ability to dissolve in a wide variety of organic solvents, and bezmetallny di(1,4-DirectLOGIC-di(tert. -butylbenzo)piperazin sublimates without decomposition in a vacuum. These properties allow the use of these compounds as dyes, catalysts of oxidation-reduction processes, semiconductor materials for thin-film microelectronics, biologically active substances, as well as in other branches of science and technology.

Di(1,4-DirectLOGIC)-di(tert. -butylbenzo)p is

 

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