KR101112574B1 - Phthalonitrile Derivatives - Google Patents

Abstract

The phthalonitrile derivative of the present invention is represented by the following Chemical Formula 1, and the synthesis and organic light-emitting device of the phthalocyanine derivative used in organic light emitter, IR sensing, organic semiconductor, nonlinear optical material, electrochromic material, photovoltaic material, liquid crystal, catalyst, etc. It can be usefully used as an intermediate for.

[Formula 1]

In the above, R is a cyano group and an integer of m = 2 to 5, except that when m = 3, compounds substituted with 2, 4 and 5 of benzene based on cyanomethyl are excluded.

Organic EL device, phthalocyanine, phthalonitrile, light emitting compound, cyanostilbene

Description

Phthalononitrile Derivatives             

1 shows an NMR spectrum of a phthalonitrile derivative of the present invention.

2 shows an NMR spectrum of a cyanostilbene-based light emitting compound synthesized using the phthalonitrile derivative of the present invention.

Figure 3 shows the UV-vis spectrum in the solution phase of the cyanostilbene-based light emitting compound.

Figure 4 shows the photoluminescence spectrum of the cyanostilbene-based light emitting compound in the solid film state.

Figure 5 shows the electroluminescence spectrum of the cyanostilbene-based light emitting compound in the solid film state.

Figure 6 shows the CIE color coordinates for the photoluminescence spectrum in the solid film state of the cyanostilbene-based light emitting compound.

7 is a view showing CIE color coordinates of an electroluminescence spectrum in the solid film state of the cyanostilbene-based light emitting compound.

FIG. 8 shows UV in a solution of 4-[(Z) -1-cyano-2- (4-diphenylamino-phenyl) -vinyl] -phthalonitrile synthesized using the phthalonitrile derivative of the present invention. -vis and photoluminescence spectra are shown.

Fig. 9 shows the photoluminescence spectra in the solid film state of 4-[(Z) -1-cyano-2- (4-diphenylamino-phenyl) -vinyl] -phthalonitrile.

10 shows CIE color coordinates for photoluminescence spectra in the solution and solid film states of 4-[(Z) -1-cyano-2- (4-diphenylamino-phenyl) -vinyl] -phthalonitrile will be.

 Field of invention

The present invention relates to phthalonitrile derivatives. More specifically, the present invention can be usefully used for the preparation of phthalocyanine derivatives and cyanostilbene-based light emitting compounds used as organic light emitters, IR sensing, organic semiconductors, nonlinear optical materials, electrochromic materials, photovoltaic materials, liquid crystals, catalysts, and the like. Phthalonitrile derivatives.

Background of the Invention

Liquid crystal display (LCD), which is widely used at present, is a non-light-emitting display device, which consumes little power and is light. However, the device driving system is complicated and the response time, contrast, etc. are not satisfactory. Therefore, researches on organic light emitting diodes, which are recently attracting attention as flat panel displays, are being actively conducted. The organic light emitting device is a self-luminous device and has various advantages such as excellent brightness, driving voltage, and response speed, and no viewing angle dependency, compared to the liquid crystal display.

The light emitting mechanism of the organic EL device is as follows. Holes injected from the anode into the valence band or highest occupied molecular orbital (HOMO) of the hole injection layer (HIL) proceed to the emitting layer through the hole transporting layer (HTL). At the same time, electrons move from the cathode to the emission layer through the electron injection layer to combine with holes to form excitons. The exciton falls to the ground and emits light.

Using the principle of the organic EL device described above, Eastman Kodak Co., Ltd. in 1987 used TPD (N-N'-DiphenyI-N-N'-bis (methylphenyl-1,1'-biphenyl-4) as a hole transporting layer. We developed an electroluminescent device using Alq ₃ (tris (8-hydroxy-quinoline) aluminum complex) as the light emitting layer ( Appl. Phys. Lett. , 51, 913, 1987). The research on the electroluminescent element used is becoming active.

To date, red light emitting materials have inherently low luminous efficiency, and also have a quenching effect due to intermolecular dipole-dipole interactions caused by expanded π electrons at high concentrations, and deterioration of color purity due to wide emission bands. Etc. There are problems. Therefore, a method using energy transfer from the host material to the red light emitting material which is less than 2% of the dopant is used ( Appl. Phys. Lett. 65, 3610, 1989). Among the dopants used in such a doping system are Eastman Kodak's DCM derivatives (US Pat. No. 5,853,81, US Pat. 5,357,020).

However, there is a difficulty in reproducibility in device fabrication compared to the actual undoped host light emitter. In order to solve this problem, Sony's 1,1'-dicyano-substituted bisstrylnaphthalene (BSN) has recently been used as red host light emitting materials for undoping systems (US Pat. No. 6,337167, US Pat. Patent No. 6765108, U.S. Patent 6,742,57, U.S. Pat.No.6790974), and many red light emitting materials are currently being developed.

However, among the three color light emitting materials known to be used for organic light emitting devices, green and blue materials have been developed with excellent brightness and efficiency. However, in the case of red color, the full color organic light emitting devices have a lower brightness and efficiency than green and blue colors. Not enough to produce.

In order to solve the above problems, the present inventors have developed a cyanostilbene-based light emitting compound which is excellent in light emission efficiency in a solid state and can be usefully used as an organic film of an organic light emitting device by controlling color from green to red. There is a bar. The cyanostilbene-based light emitting compound has a structure in which CN, etc. are substituted at the cyanostilbene terminal, for example, has the following structure.

In the above, 4-[(Z) -1-cyano-2- (4-dimethylamino-phenyl) -vinyl] -phthalonitrile is prepared by the following route.

The present inventors came to develop a phthalonitrile derivative useful for the preparation of the cyanostilbene-based light emitting compound. In addition, the phthalonitrile derivative of the present invention can be usefully used for the synthesis of phthalocyanine derivatives used in organic light emitting materials, IR sensing, organic semiconductors, nonlinear optical materials, electrochromic materials, photovoltaic materials, liquid crystals, catalysts and the like.

An object of the present invention is to provide a phthalonitrile derivative that can be used as an intermediate of a phthalocyanine derivative and a cyanostilbene-based light emitting compound used in an organic light emitting body.

Another object of the present invention is to provide a method for preparing the phthalonitrile derivative.

The above and other objects of the present invention can be achieved by the present invention described in detail below.

The phthalonitrile derivative of the present invention is represented by the following Chemical Formula 1, and may be usefully used as an intermediate of the phthalocyanine derivative and the cyanostilbene-based light emitting compound.

[Formula 1]

In the above, R is a cyano group and an integer of m = 2 to 5, except that when m = 3, compounds substituted with 2, 4 and 5 of benzene based on cyanomethyl are excluded.

Specific examples of the phthalonitrile derivative may be selected from the group consisting of the following formulas, but are not necessarily limited thereto.

The phthalonitrile derivative of the present invention is prepared by the following route.

First, halogenated benzyl bromide is prepared by reacting with halogenated toluene represented by the following Chemical Formula 2 with N-bromosuccinimide.

[Formula 2]

In the above, X is a halogen element and an integer of m = 2 to 5, except that when m = 3, the compound substituted at the 2, 4, 5 position of benzene.

Next, the halogenated benzyl bromide prepared above is reacted with potassium cyanide to prepare a halogenated benzyl cyanide, and then the copper cyanide is reacted with the halogenated benzyl cyanide to prepare the phthalonitrile derivative of the present invention.                     

The phthalonitrile derivatives of the present invention are phthalocyanine derivatives used in organic light emitters, IR sensing, organic semiconductors, nonlinear optical materials, electrochromic materials, photovoltaic materials, liquid crystals, catalysts, and cyanostilbene-based light emitting compounds used as organic light emitting devices. It can be usefully used for the preparation of.

The present invention will be further illustrated by the following examples, which are only specific examples of the present invention, and are not intended to limit or limit the protection scope of the present invention.

Example 1: Synthesis of 4-cyanomethyl-phthalonitrile

(1) first step: preparation of 3,4-dibromobenzyl bromide

50 g of 3,4-dibromotoluene, 35.6 g of N-bromosuccinimide, AIBN, 0.658 g, and 300 mL of carbon tetrachloride were added thereto, and the mixture was stirred while refluxing at 83 ° C. for 15 hours. Extracted with methylene chloride and water, dried over anhydrous magnesium sulfate and column purified with n-hexane. Yield 97%, ¹ H-NMR (CDCl ₃ , ppm): 7.10-7.80 (3H, Ar-H), 4.2 (2H, -CH ₂ Br).

(2) second step: preparation of 3,4-dibromobenzyl cyanide

25 g of 3,4-dibromobenzyl bromide prepared in the first step, 7 g of potassium cyanide, 72 mL of ethanol and 24 mL of water were added and reacted under reflux for 24 hours. Extraction with dichloromethane and water, water removal with anhydrous magnesium sulfate, and column purification with a developing solvent of nH: EA = 5: 1. Yield 50%, ¹ H-NMR (CDCl ₃ , ppm): 7.61 (2H, Ar-H), 7.13 (1H, Ar-H), 3.70 (2H, -CH ₂ CN).

(3) third step: preparation of 4-cyanomethyl-phthalonitrile

4 g of 3,4-dibromobenzyl cyanide prepared in step 2, 5.212 g of copper cyanide (I), and 50 mL of N, N-dimethylformamide were added thereto, followed by stirring for 4 hours under reflux cooling. Extraction with ethyl acetate and water was followed by column purification with nH: EA = 1: 1. Yield 40%, 7.75-7.86 (3H, Ar-H), 3.90 (2H, -CH ₂ CN).

The NMR spectrum of 4-cyanomethyl-phthalonitrile prepared above is shown in FIG. 1.

Example 2: Preparation of 4-[(Z) -1-Cyano-2- (4-dimethylamino-phenyl) -vinyl] -phthalonitrile

0.4 g (2.393 mmol) of 4- (cyanomethyl) phthalonitrile prepared in Example 1 and 0.356 g (2.393 mmol) of p-dimethylamino benzaldehyde were completely dissolved in benzene, and acetic acid and piperidine were added in catalytic amounts. After stirring at 80 ° C for 2 hours. After completion of the reaction, the solvent was evaporated under reduced pressure, recrystallized with dichloromethane and n-nucleic acid, and then filtered and dried under reduced pressure: 88% yield; ¹ H-NMR (CDCl ₃ , ppm): 7.79-8.01 (5H, Ar-H), 7.52 (1H, vinyl H), 6.75 (2H, Ar-H), 3.12 (6H, CH3), MS (EI) (calcd for C 19 H 14 N 4, 298.12; found, 299.3), Elem. Anal. (calcd .: C, 76.49; H, 4.73; N, 18.78, Estimated value: C, 76.11 H, 4.66 N, 18.08).

NMR of the prepared 4-[(Z) -1-cyano-2- (4-dimethylamino-phenyl) -vinyl] -phthalonitrile is shown in FIG. 2. The UV-vis spectrum in solution of 4-[(Z) -1-cyano-2- (4-dimethylamino-phenyl) -vinyl] -phthalonitrile is shown in FIG. 3. Photoluminescence spectra and electroluminescence spectra in the solid film state are shown in FIGS. 4 and 5, respectively. 6 and 7 show CIE color coordinates for the photoluminescence spectrum in the solid film state, CIE color coordinates for the electroluminescence spectrum in the solid film state, respectively.

Example 3: Preparation of 4-[(Z) -1-Cyano-2- (4-diphenylamino-phenyl) -vinyl] -phthalonitrile

Except for using p-diphenylamino benzaldehyde instead of p-dimethylamino benzaldehyde was carried out in the same manner as in Example 2, 4-[(Z) -1-cyano-2- ( 4-diphenylamino-phenyl) -vinyl] -phthalonitrile was prepared.

1 H-NMR (CDCl 3, ppm): 7.01-8.04 (17H, Ar-H), 7.53 (s, 1H vinyl H

UV-vis and photoluminescence spectra of the solution of 4-[(Z) -1-cyano-2- (4-diphenylamino-phenyl) -vinyl] -phthalonitrile are shown in FIG. The photoluminescence spectrum in the film state is shown in FIG. 9. FIG. 10 shows the photoluminescence spectra in the solution and solid film state of 4-[(Z) -1-cyano-2- (4-diphenylamino-phenyl) -vinyl] -phthalonitrile synthesized in Example 3. FIG. It shows the CIE color coordinates.

The present invention has the effect of providing an phthalonitrile derivative, which is an intermediate of a cyanostilbene-based light emitting compound having an AIEE characteristic having excellent luminous efficiency in a solid state, and a method for preparing the same.

Claims (3)

Phtharonitrile derivative represented by the following formula (1): [Formula 1]

Wherein R is a cyano group and m = 2. The phthalonitrile derivative according to claim 1, wherein the phthalonitrile derivative is selected from the group consisting of

Halogenated benzyl bromide is prepared by reacting halogenated toluene represented by Formula 2 with N-bromosuccinimide; Preparing halogenated benzyl cyanide by reacting potassium cyanide with the halogenated benzyl bromide; And Reacting copper cyanide with the halogenated benzyl cyanide; Method for producing a phthalonitrile derivative of claim 1 comprising the steps. [Formula 2]

In the above, X is a halogen element and m = 2.

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