4-(1-benzotriazole)-5-(naphtaoxy)phtalodinitriles

FIELD: chemistry.

SUBSTANCE: invention refers to chemical industry, i.e. to the new chemical compounds 4-(1-benzotriazole)-5-(naphtaoxy)-phtalodinitriles of the general formula in which R stands for as the basic for synthesis of copper tetra-4-(1-benzotriazole) tetra-5(2-naphtaoxy)phthalocyanine and copper tetra-4-(1-benzotriazole) tetra-5(1-naphtaoxy)phthalocyanine which are the solvent dyes for waxes, synthetic fiber, polymers, hydrocarbons, fats, alcohols, plastic materials and resin elastic colouring.

EFFECT: end dyes are dissolved effectively in organic environments.

1 cl, 4 dwg, 5 ex

 

The invention relates to the chemical industry, namely, to obtain new derivatives benzothiazolinone of phthalodinitrile, specifically 4-(1-benzotriazolyl)-5-(naphthoxy)phthalodinitrile as starting compounds for the synthesis of copper complexes of Tetra-4-(1-benzotriazolyl)-Tetra-5-(naphthoxy)phthalocyanines, which can be used as soluble in organic media dyes suitable for dyeing waxes, synthetic fibers, polymers, hydrocarbons, fats, alcohols, plastics, rubber.

The level of technology

Known 4-(2-naphthoxy)phthalodinitrile [Bykova V.V., Usol'tseva N.V., Ananjeva GA, Maizlish V.E., Shaposhnikov G.P. Mesomorphism of Tetra-4-arylacetamides of copper phthalocyanine, " Izv. An. Series physical. 1998. T. No. 8. S] formula

,

which is a structural analogue of the claimed compounds - 4-(1-benzotriazolyl)-5-(2-naphthoxy)phthalodinitrile and 4-(1-benzotriazolyl)-5-(1-naphthoxy)phthalodinitrile.

However, when using this compound as the source can only be obtained Tetra-4-(2-naphthoxy)copper phthalocyanine, which is soluble in organic media dye, but does not allow to obtain a uniform and intense color when dyeing waxes, synthetic fibers, polymers, hydrocarbons, fats, alcohols, plastics,rubber, regardless of the number of dye.

Another close structural analogue of the claimed compound is 4-(1-benzotriazolyl)phthalodinitrile [Iguanaman, A.V. Smirnov, Voi. Aromatic nucleophilic substitution in the synthesis of heteroaromatic o-dicarbonitriles // Panorama of modern chemistry Russia. Advances in chemical synthesis of polyfunctional aromatic compounds. M.: Chemistry, 2005. S.89] formula

However, when using this compound as the source can only be obtained Tetra-4-(1-benzotriazolyl)copper phthalocyanine, which has a limited solubility in organic solvents, and, consequently, its use as soluble in organic media dye during dyeing waxes, synthetic fibers, polymers, hydrocarbons, fats, alcohols, plastics, rubber does not allow you to get rich colors and uniform color.

The invention

Inventive task was to search for new compounds which are derivatives of 4-(1-benzotriazolyl)phthalodinitrile that when using them as initial products would give an opportunity to synthesize naphthacenedione Tetra-4-(1-benzotriazolyl)copper phthalocyanines having solubility in organic media and is reshenii waxes, synthetic fibers, polymers, hydrocarbons, fats, alcohols, plastics, rubber would be getting saturated color and uniform color.

The problem is solved 4-(1-benzotriazolyl)-5-(2-naphthoxy)phthalodinitrile and 4-(1-benzotriazolyl)-5-(1-naphthoxy)phthalodinitrile General formula

,

where R=or

The structure of these compounds proved by data of elemental analysis and IR spectroscopy.

Thus, in the IR spectra of the inventive compounds (1, 2) we can distinguish a number of absorption bands, characteristic of phthalodinitrile [Rodionova G.N., Balaenkova GV, Mikhailenko, S.A., E.A. Lukyanets Vibrational spectra of dinitriles o-phthalic acids // Aniline-dye industry. M: niitekhim, 1974. Issue 1. Pp.5-7].

The invention allows to obtain the following advantage.

Using 4-(1-benzotriazolyl)-5-(naphthoxy)phthalodinitrile as a source of compounds provides an opportunity to synthesize copper complexes of Tetra-4-(1-benzotriazolyl)Tetra-5-(naphthoxy)phthalocyanines, which are soluble in organic media dyes, with the ability to paint waxes, synthetic fibers, polymers, hydrocarbons, fats, alcohols, plastics, rubber. The color get rich, and the color R is vnominal.

Information confirming the possibility of carrying out the invention

To implement the method using the following ingredients:

- DMF - GOST 20289-74

- 4-(1-benzotriazolyl)-5-nitrophthalonitrile - [Abramov I.G., Smirnov A.V., Plakhtinskii V.V., Krasovskaya G.G. 4-(1-Benzotriazolyl)-5-nitrophthalonitrile as a highly active substrate in aromatic nucleophilic substitution reactions // Mendeleev Commun. 2002. No. 2. P.72-74.]

- 2-naphthol - GOST 5835-79

- 2-propanol - TU 6-09-402-75

- 1-naphthol - GOST 5838-79

Example 1. Synthesis of 4-(1-benzotriazolyl)-5-(2-naphthoxy)phthalodinitrile.

In a flask equipped with stirrer, reflux condenser and thermometer, download 30 ml of DMF, 2.9 g (0.01 mol) of 4-(1-benzotriazolyl)-5-nitrophthalonitrile, 1.38 g (0.01 mol) of a solution To a2CO3in 10 ml of water and 1.39 g (0.01 mol) of 2-naphthol. After dissolution of the initial reagents under stirring the mixture was incubated for 0.5 h at room temperature (20°). The precipitation is filtered off, washed with 2-propanol (50 ml), water (3 portions of 50 ml) and dried at 70°C.

Output: 3.84 g (87%). TPL=210-211°

Found, %: C 70.49, H 3.84, N 17.14

Calculated, %: C 71.47, H 3.65, N 17.37

IR (KBr): 2234 (C≡N), 1198 (Ar-O-Ar) (1)

The obtained 4-(1-benzotriazolyl)-5-(2-naphthoxy)phthalodinitrile - light-yellow needles, soluble in acetone, chloroform, benzene, DMF and insoluble in water.

Example 2. Synthesis of 4-(1-benzotriazolyl)-5-(1-naphthoxy)phthalodinitrile.

img src="https://img.russianpatents.com/864/8641052-s.jpg" height="60" width="49" >

In a flask equipped with stirrer, reflux condenser and thermometer, download 30 ml of DMF, 2.9 g (0.01 mol) of 4-(1-benzotriazolyl)-5-nitrophthalonitrile, 1.38 g (0.01 mol) of a solution To a2CO3in 10 ml of water and 1.39 g (0.01 mol) of 1-naphthol. After dissolution of the initial reagents under stirring the mixture was incubated for 0.5 h at room temperature (20°). The precipitation is filtered off, washed with 2-propanol (50 ml), water (3 portions of 50 ml) and dried at 70°C.

Output: 3.84 g (84%). TPL=212-214°

Found, %: C 71.04, H 3.67, N 17.74

Calculated, %: C 71.47, H 3.65, N 17.37

IR (KBr): 2232 (C≡N), 1204 (Ar-O-Ar) (2)

The obtained 4-(1-benzotriazolyl)-5-(1-naphthoxy)phthalodinitrile - light-yellow powder, soluble in acetone, chloroform, benzene, DMF and insoluble in water.

Example 3. Using 4-(1-benzotriazolyl)-5-(2-naphthoxy)phthalodinitrile as a starting compound for the synthesis of copper complex of Tetra-4-(1-benzotriazolyl)Tetra-5-(2-naphthoxy)phthalocyanine.

In a test tube made of quartz glass is placed 0.050 g (0.13 mmol) of 4-(1-benzotriazolyl)-5-(2-naphthoxy)phthalodinitrile and 0.008 g (0.04 mmol) of copper acetate (II). The mixture is heated up to 215-220°C and maintained at this temperature for 2 hours. The target product is extracted with chloroform. Further cleaning is performed by the method of column chromatography on alumina with chloroform.

Output: 33.3 mg (63.9%)

Found, %: C 70.01, H 3.57, N 17.95

Calculated, %: C 71.49, H 3.28, N 17.38

ESP in chloroform, λmaxnm: 618; 688 (figure 3, curve 1)

ESP in DMF, λmaxnm: 613; 684 (figure 3, curve 2)

Received Tetra-4-(1-benzotriazolyl)Tetra-5-(2-naphthoxy)phthalocyanine copper - dark green substance has a solubility in organic solvents, such as chloroform, benzene, acetone, DMF.

Example 4. Using 4-(1-benzotriazolyl)-5-(1-naphthoxy)-phthalodinitrile as a starting compound for the synthesis of copper complex of Tetra-4-(1-benzotriazolyl)Tetra-5-(1-naphthoxy)phthalocyanine.

In a test tube made of quartz glass is placed 0.050 g (0.13 mmol) of 4-(1-benzotriazolyl)-5-(1-naphthoxy)phthalodinitrile and 0.008 g (0.04 mmol) of copper acetate (II). The mixture is heated up to 210-215°C and maintained at this temperature for 2 hours. The target product is extracted with chloroform. Further cleaning is performed by the method of column chromatography on alumina with chloroform.

Output: 39.1 mg (75.1%)

Found, %: C - 71.11, H 3.33, N - 17.52

Calculated, %: C - 71.49, H 3.28, N - 17.38

ESP in chloroform, λmaxnm: 618; 688 (figure 4, curve 1)

ESP in DMF, λmaxnm: 613; 684 (figure 4, curve 2)

Received Tetra-4-(1-benzotriazolyl)Tetra-5-(1-naphthoxy)phthalocyanine copper - dark green substance has a solubility in organic solvents, such as the chloroform, benzene, acetone, DMF.

Example 5. The use of Tetra-4-(1-benzotriazolyl)Tetra-5-(naphthoxy)copper phthalocyanines as dyes, soluble in organic solvents, for dyeing the wax and polystyrene.

Dyeing paraffin. 2.5 g of paraffin is placed in a porcelain Cup and heated to melt, then pour in a solution of 0.015 g of Tetra-4-(1-benzotriazolyl)Tetra-5-(naphthoxy)of copper phthalocyanine in 6 ml of benzene. Stand when heated to a complete removal of benzene and the resulting mass is poured into the form.

Dyeing polystyrene. The polystyrene in the amount of 0.5 g was dissolved by heating in 5 ml of benzene and added dropwise a solution of 0.01 g of Tetra-4-(1-benzotriazolyl)Tetra-5-(naphthoxy)of copper phthalocyanine in 1 ml of benzene. Boil the solution until complete removal of benzene, and then the resulting mass is poured into the form.

Dyeing the wax and polystyrene Tetra-4-(1-benzotriazol-Lil)phthalocyanine and copper Tetra-4-(2-naphthoxy)phthalocyanine copper (analogues) was similar to the dyeing of these objects of the claimed compounds.

4-(1-benzotriazolyl)-5-(naphthoxy) phthalodinitrile formula

,

where R=or



 

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