The metal complexes of dihalogen-di(tert-butyl)-substituted phthalocyanines

 

(57) Abstract:

The present invention relates to new substituted metallophthalocyanines, which may find application as dyes, catalysts for various reactions, materials sensitive elements of sensors, gases, materials for thin-film microelectronics, etc. the Task of the technical solution is the development of new compounds that possess good solubility in organic solvents, ability to sublimation and can be used as dyes, catalysts, materials, sensors gas sensors, thin-film microelectronics, etc. the problem is solved by the synthesis of metal complexes dihalogen-di(tert-butyl)phthalocyanine. The metal complexes of dihalogen-di(tert-butyl)phthalocyanine obtained by the interaction between 6/7-halogen-1,3 .3m-trichloro - 6/7-tert-butyl-1-amino-3-iminoisoindolin in tetrahydrofuran in the presence of triethylamine, hydroquinone, sodium methylate and salts of the respective metals. 2 Il.

The present invention relates to new substituted metallophthalocyanines formula I which may find application as dyes, catalysts different is ectronic etc.

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The closest structural analogues of the claimed compounds are metal complexes of Tetra(tert-butyl)phthalocyanine of the formula II.

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Tetra(4-tert-butyl)phthalocyanine cobalt is 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. B. I. No. 45, 1990]

The task of the technical solution is the development of new compounds that possess good solubility in organic solvents, ability to thermal vacuum sublimation and can be used as dyes, catalysts, materials for sensors gas sensors, thin-film microelectronics, etc.

The problem is solved by the synthesis of metal complexes dihalogen-di(tert-butyl)phthalocyanine.

The metal complexes of dihalogen-di(tert-butyl)phthalocyanine are a dark blue powder, soluble in organic solvents (benzene, acetone, dimethylformamide, etc.) in concentrated sulfuric acid. They are sublimated without decomposition in vacuum (610-5mm RT.CT.) when 360-400oC.

We can assume that predlagaemye, materials for CHAD gases and thin-film microelectronics, etc.

In the IR spectra of the claimed compounds (Fig. 1) you can allocate a number of common absorption bands characteristic of phthalocyanines [Sidorov A. N. Kotlyar, I. P. Optics and spectroscopy, 1961, T. II, No. 2, S. 175-184] the metal complexes there is no absorption band characteristic of Bezmaternykh phthalocyanines. In the field 2870-2960 cm-1find bands that are characteristic of tert.-Budilnik groups. For dichlorsilane phthalocyanines band in the area 800-850 cm-1characteristic vibrations of C-Cl bond, and for dibromsalan 510 cm-1characteristic fluctuations due to C-Br [Dyer D. R. Application of absorption spectroscopy of organic compounds. M. Chemistry, 1970, S. 31-68]

In the electronic absorption spectra of the observed intense absorption in the region 668-677 nm, recorded in benzene (Fig. 2).

The claimed compounds obtained by the interaction of the respective 6/7-chloro - or 6/7-bromo-1,3 .3m-trichlorotoluene 6/7-tert-butyl-1-amino-3-iminoisoindolin in tetrahydrofuran in the presence of triethylamine, hydroquinone, sodium methylate and salts of the respective metals.

Example 1. Synthesis of 4,4"-dichloro-4',4"'-di(tert-butyl)copper phthalocyanineoC and added dropwise within 30 minutes, 20 ml of tetrahydrofuran containing 0,173 g (of 0.68 mmol) 6/7-chloro-1,3 .3m-trichlorotoluene. Stand under stirring for 1 hour, slowly heat the reaction mixture to room temperature and continue stirring under these conditions for six hours. Then filter the solution with the precipitate, the solution was added 0.08 g (0.81 mmol) of anhydrous copper chloride (I) and stirred in a stream of argon for 13 hours, after which the reaction mixture is make 0,092 g (1.7 mmol) of sodium methylate and 0.124 g (1.13 mmol) of hydroquinone and boil this mixture for 6 hours, then cooled and filtered. From the filtrate to remove the solvent, the resulting product is combined with the precipitate, washed with hydrochloric acid to colorless filtrates, then with water until neutral environment dried. Chromatographic aluminum oxide, using as eluent a mixture of benzene with ethanol in a ratio of 3:1. Output: 0,032 g (12.9 percent).

The resulting substance is highly soluble in benzene, acetone, dimethylformamide, Kon is insole:max677 nm.

IR spectra: 840 cm-1( C-CI); 2870 cm-1( nthe SIM.CH3); 2960 cm-1(MSS.CH3).

Found, C-64,1; H-4,1; N-14,7; CI-9,3; Cu-8,2. C40H30N8CI2Cu. Calculated C-and 63.4; H-4,0; N-14,8; CI-9,4; Cu-8,4.

Example 2. Synthesis of 4,4"-dichloro-4',4"'-di(tert-butyl) phthalocyanine cobalt

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In craptonne flask with a capacity of 100 ml, equipped with a magnetic stirrer, is placed 0,137 g (of 0.68 mmol) 6/7-tert-butyl-1-amino-3-iminoisoindolin and 0.5 ml of 3.56 mmol) of triethylamine.

With constant stirring in a stream of dry argon add 60 ml of dry tetrahydrofuran. After almost complete dissolution 6/7-tert-butyl-1-amino-3-iminoisoindolin the mixture is cooled to 0oC and added dropwise within 30 minutes, 20 ml of tetrahydrofuran containing 0,173 g (of 0.68 mmol) 6/7-chloro-1,3 .3m-trichlorotoluene, stand under stirring for 1 hour, slowly heat the reaction mixture to room temperature and continue stirring under these conditions for six hours. Then filter the solution, removing the precipitate, the solution was added 0.10 g (0.81 mmol) of anhydrous cobalt chloride and stirred in a stream of argon for 13 hours, after which the reaction mixture is make 0,092 g (1, altroot. From the filtrate to remove the solvent. The resulting product is combined with the precipitate, washed with hydrochloric acid to colorless filtrates, then with water until neutral environment dried. Chromatographic aluminum oxide, using as eluent a mixture of benzene with ethanol in a ratio of 3:1. Output: 0.035 g (14.1 per cent).

Dark blue substance, soluble in benzene, acetone, dimethylformamide, in concentrated sulfuric acid. Sublimated in vacuum (610, -5mm RT.CT.) at 390oC.

ESP in benzene:max668 nm.

IR spectra: 850 cm-1( C-CI); 2870 cm-1( nthe SIM.CH3); 2960 cm-1(MSS.CH3).

Found, C-64,4; H-4,2; N-14,8; CI-9,5; Co-7,9. C40H30N8CI2Co. Calculated C-63, 8mm; H-4,0; N-14,9; CI-9,4; Co-7,8.

Example 3. Synthesis of 4,4"-dibromo-4',4"'-di(tert-butyl) phthalocyanine cobalt.

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In a round bottom flask with a capacity of 100 ml, equipped with a magnetic stirrer, is placed 0,137 g (of 0.68 mmol) 6/7-tert-butyl-1-amino-3-iminoisoindolin and 0.5 ml of 3.56 mmol) of triethylamine. With constant stirring in a stream of dry argon add 60 ml of dry tetrahydrofuran. After almost complete dissolution 6/7-tert-butyl-1-amino-3-iminoisoindolin smrom-1,3 .3m-trichlorotoluene. Stand under stirring for 1 hour, slowly heated the reaction mass to room temperature and continue stirring under these conditions for six hours. The solution is filtered, removing the precipitate, the filtrate is added 0.10 g (0.81 mmol) of anhydrous cobalt chloride and stirred in a stream of argon for 13 hours, after which the reaction mixture is make 0,092 g (1.7 mmol) of sodium methylate and 0.124 g (1.13 mmol) of hydroquinone. Boil this mixture for six hours, then cooled and filtered. From the filtrate to remove the solvent. The resulting product is combined with the precipitate, washed with hydrochloric acid to colorless filtrates, then with water until neutral environment dried. Chromatographic aluminum oxide, using as eluent a mixture of benzene with ethanol in a ratio of 3:1. Output: 0,050 g (17.4 per cent).

Dark blue substance, soluble in benzene, acetone, dimethylformamide, in concentrated sulfuric acid. Sublimated in vacuum (610-5mm RT.CT.) if 400oC.

ESP in benzene:max673 nm.

IR spectra: 510 ( C-Br); 2870 cm-1( nthe SIM.CH3); 2960 cm-1(MSS.CH3)

Found, C-58,0; H To 3.8; N-13,2; Br-19,3; Co-7,1. C40H30N8Br2Co. The calc is butyl)phthalocyanine are organic compounds phthalocyaninato series identity structure and the presence in the molecule of the phthalocyanine simultaneously tert-Budilnik and halogensubstituted able to sublimate and well soluble in organic solvents. These properties allow the use of the claimed compounds as dyes, catalysts, materials sensitive elements of sensors, gases, materials for thin-film microelectronics, as well as in other branches of science and technology. In addition, dihalogen-di(tert-butyl)substituted metallophthalocyanine can be used for synthesis of other disubstituted - di(tert-butyl)phthalocyanine.

The metal complexes of dihalogen-di-(tert-butyl)-substituted phthalocyanines of General formula

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where M Cu (II), Hal is chlorine or M Co (II), Hal is chlorine, bromine.

 

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