6/7-tert-butyl-1,3 .3m-trichlorethane as an intermediate product for the synthesis of tert-butylsilane phthalocyanines or their complexes

 

(57) Abstract:

Usage: as intermediates in the synthesis of tert-butylsilane phthalocyanines or their complexes used as colorants. The inventive product 6/7-tert-butyl-1,3 .3m-trichlorethane f-ly 1. B. F.12H12N Cl3the output of 35.4%., viscous mass. Reagent 1: compound f-crystals 2. Reagent 2: P 15. Reaction conditions: in a medium of an organic solvent at 105 deg. With over 170 hours. The structure of compounds 1 and 2, 1 Il.

The invention relates to a new derivative of formula 1, which can be used as an intermediate product in the synthesis of novel di-tert-butylsilane phthalocyanines and their complexes used as dyes, organic semiconductor materials, etc.

The closest structural analogue of the claimed compounds is 6/7-nitro-1,3 .3m-trichlorethane 11 used for the synthesis of dinitrotoluene phthalocyanines and their complexes [Kulinich Century. P. and others]. higher education institutions. Chemistry and chem. technology, 1993, T. 36, N 3, S. 37-41]

< / BR>
However, in this case are only dinitrotoluene phthalocyanines. Obtaining individual compounds containing two tert-butylene group in molecu, which may find application as an intermediate product in the synthesis of novel di-tert-butylsilane phthalocyanines. The problem is solved by the synthesis 6/7-tert-butyl-1,3 .3m-trichlorotoluene.

6/7-Tert-butyl-1,3 .3m-trichlorethane is a light yellow viscous mass. During long-term storage crystallizes. Soluble in organic solvents (tetrahydrofuran, acetone and others). Distilled at a temperature of 170-180oC at a pressure of 12 mm RT. Art.

The IR spectrum of the claimed compounds (Fig.1) you can select the number of bands shared with 1-amino-3-iminoisoindolin and substituted 1,3 .3m-trichlorotoluene. So, in the field 1580-1620 cm-1there are bands that are characteristic of isoindoline fragments. The bands at 800-850 cm-1belong to the stretching vibrations of the C-C1. In addition, the inventive compounds in the field 2870-2960 cm-1observed absorption bands characteristic of tert-Budilnik groups [Dyer D. R. Application of absorption spectroscopy of organic compounds. M. Chemistry, 1970, S. 31-68]

The claimed compound obtained by the interaction of 4-tert-butylphthalide with with phosphorus pentachloride when heated in dry 1,2-dichlorobenzene with subsequent fractional bakounine.

In a 250 ml flask equipped with a stirrer with trap, reflux condenser and potassium chloride tube, placed 21,52 g (0,106 mol) of 4-tert-butylphthalide, 46,7 (0,224 mol) petaluridae phosphorus and stirred in 80 ml of dry 1,2-dichlorobenzene. The reaction mass is heated to 105oC and maintained at this temperature for 170 hours. The reaction mixture is cooled to room temperature and remove volatile impurities at low vacuum, then slowly heated and vacuum distillation at 110-125oC remove phosphorus oxychloride and the solvent is 1,2-dichlorobenzene. After that, when 170-180oC (12 mm RT.CT.) distilled target product. The compound obtained light yellow viscous mass. If prolonged storage is crystallized is dissolved in tetrahydrofuran and acetone. Yield: 10.3 g (35.4 per cent).

Found, C-53,0; H-4,5; N-4,9; Cl-38,0.

C12H12NCl3< / BR>
Calculated C-52,1; H-4,4; N-5,1; Cl-38,5

Example 2. Synthesis of 4,4"di-tert-butylphthalocyanine.

In a round bottom flask with a capacity of 100 ml, equipped with a magnetic stirrer, is placed 0,100 g (of 0.68 mmol) 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 svezhevykachanuyu within 30 minutes 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 at 0oC for 1 hour, and then slowly raised to room temperature and stirred at this mode for 6 hours. Then the precipitate is filtered off, the solution is returned to the reaction flask, equipped with stirrer and reflux condenser. Add 0,074 g (0.67 mmol) of hydroquinone and to 0.108 g (2.0 mmol) of sodium methylate. The mixture is boiled in a stream of argon for 6 hours, then cooled and filtered. The precipitate is washed with water, hydrochloric acid, again with water and dried. Chromatographic aluminum oxide, using as eluent a mixture of benzene with ethanol in a ratio of 3:1.

4,4"-di-tert-butylphthalocyanine dark blue powder, soluble in benzene, acetone and other organic solvents, concentrated sulfuric acid. Output: 0,032 g (15,0%). The individuality of the obtained compounds was confirmed by the data of elemental analysis, electronic, and vibrational spectroscopy.

Found, C-To 76.4; H-5,6; N-17,7.

C40H34N8< / BR>
Calculated C-To 76.6; H-5,5; N-17,9.

ESP in benzene,maxnm: 696; 660.

Example 3. Synthesis of 4,4"di-tert-butylphthalocyanine copper.

In a round bottom flask with a capacity of 100 ml, snapzpro constant stirring in a stream of dry argon add 60 ml of dry acetone. After almost complete dissolution of 1-amino-3-iminoisoindolin the mixture is cooled to 0oC and added dropwise within 30 minutes 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 at 0oC for 1 hour, and then slowly raised to room temperature and stirred at this mode for 6 hours. Then the precipitate is filtered off, the solution is returned to the reaction flask, equipped with stirrer and reflux condenser. Add 0,076 g (0,76 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 another 6 hours. The reaction mass is then cooled, filtered. The precipitate is washed with water, hydrochloric acid, again with water and dried. Chromatographic aluminum oxide, using as eluent a mixture of benzene with ethanol in a ratio of 3:1.

4,4"-Di-tert-butylphthalocyanine copper dark blue powder, soluble in acetone, benzene and other organic solvents, concentrated sulfuric acid. Output: 0,048 g (20.5 percent). The individuality of the complex is confirmed by the data of elemental analysis, electronic, and is/BR> Calculated C-69,8; H-4,7; N-16,3; Cu-9,3

ESP in benzene,maxnm: 674.

Example 4. Synthesis of 4,4"-di-tert-butyl-4',4"-Dichlorotoluene copper.

Synthesis behave analogously to example 3. Instead of 1-amino-3-iminoisoindolin use 0,122 g (of 0.68 mmol) 6/7-chloro-1-amino-3-iminoisoindolin.

4,4"-Di-tert-butyl-4', 4"-dichlorofluorene copper dark blue powder, soluble in acetone, benzene and other organic solvents, concentrated sulfuric acid. Output 0,047 g (18.3 percent).

The individuality of the complex is confirmed by the data of elemental analysis, electronic, and vibrational spectroscopy.

Found, C-63,6; H-3,9; N-14,9; Cl-9,5; Cu-8,2.

C40H30N8CuCl2< / BR>
Calculated C-And 63.4; H-4,0; N-14,8; Cl-9,4; Cu-8,4.

ESP in benzene, maxnm: 677.

Thus, the claimed 6/7-tert-butyl-1,3 .3m-trichlorethane is an organic substance class derived from 1-amino-3-iminoisoindolin that makes it possible to obtain new di-tert-butylsilane phthalocyanines and their complexes with personality structure, the presence of tert-Budilnik groups with a fixed position in the molecule of the phthalocyanine, and the ability to dissolve in organic races of the tion as organic semiconductors, catalysts, dyes, as well as in other areas of science and technology.

6/7-tert-Butyl-1,3 .3m-trichlorethane formula

< / BR>
as an intermediate product for the synthesis of tert-butylsilane phthalocyanines or their complexes.

 

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