CN109970623B - Triarylamine derivative, preparation method, application and device thereof - Google Patents

Triarylamine derivative, preparation method, application and device thereof Download PDF

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CN109970623B
CN109970623B CN201711461177.1A CN201711461177A CN109970623B CN 109970623 B CN109970623 B CN 109970623B CN 201711461177 A CN201711461177 A CN 201711461177A CN 109970623 B CN109970623 B CN 109970623B
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tert
biphenyl
hole transport
filtering
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CN109970623A (en
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穆广园
徐鹏
庄少卿
任春婷
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Wuhan Shangsai Optoelectronics Technology Co ltd
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Abstract

The invention belongs to the technical field of photoelectric material application technologies, and particularly relates to triarylamine derivatives, and a preparation method and application thereof. The triarylamine derivative provided by the invention takes triarylamine and fluorenocarbazole as basic structural units, and an asymmetric structure is obtained after modification, so that a compound which is rich in holes and has high glass transition temperature is formed. When the compound is used as a hole transport material, compared with a hole transport material commonly used in the prior art, such as N, N '-diphenyl-N, N' -di (3-methylphenyl) -1,1 '-biphenyl-4, 4' -diamine (TPD), the hole transport capacity is obviously improved, and in an organic electroluminescent device, compared with a traditional hole transport material, the series of compounds are obviously improved in starting voltage and glass transition temperature, so that the compound is an ideal hole transport material. In addition, when the series of compounds are used as the light-emitting layer material, the efficiency of the organic electroluminescent device is greatly improved, and the series of compounds are ideal light-emitting layer materials.

Description

Triarylamine derivative, preparation method, application and device thereof
Technical Field
The invention belongs to the technical field of photoelectric material application technologies, and particularly relates to triarylamine derivatives, and a preparation method, application and devices thereof.
Background
An Organic Light-emitting Diode (OLED), also known as an Organic electroluminescent device or an Organic Light-emitting Display (OLED), is a Display device prepared by utilizing the phenomenon that carriers enter an Organic solid Light-emitting layer from the positive electrode and the negative electrode of the device to be compounded and emit Light under the action of an electric field (Tang, c.w.et al.appl.phys.lett.1987,52,913). The device mainly adopts organic micromolecule/high polymer semiconductor materials, and the organic micromolecule and the high polymer materials have the characteristics of easy preparation, processing and purification and high-selectivity modification, so that the device has great potential in the field of material application, and the device becomes a focus in both research and commerce.
As the most important 10 inventions in 30 years, the organic light emitting diode has undergone a rapid development process, and has achieved fruitful results from new material development, device structure preparation, mechanism exploration and marketization popularization, thus becoming a representative and innovative flag in the semiconductor field and having attractive market prospect.
The organic light emitting diode generally comprises an electron/hole injection layer, an electron/hole transport layer and a light emitting layer, and correspondingly comprises an electron/hole injection material, an electron/hole transport material, a light emitting material and the like, the performance of the hole transport material has an important influence on an OLED device, and the development of a new hole transport group for preparing an efficient OLED device is always a hotspot of research. In addition, how to reduce the dissipation of light in the device and improve the light extraction efficiency is a problem to be solved in the OLED field.
Disclosure of Invention
In order to solve the defects of the prior art, the invention provides a triarylamine derivative in a first aspect, which has the following structural general formula:
Figure BDA0001530170660000021
wherein R is1、R2Each independently selected from: a substituted or unsubstituted aromatic or heteroaromatic group; one of
R1And R2The same or different.
The triarylamine derivative has high hole mobility and good thermal stability, can effectively prevent the bad luminescence phenomenon caused by the agglutination and crystallization in the evaporation process and the reduction of the service life of devices, can obtain excellent effect when being applied to organic light-emitting diodes, and is a novel material with great commercial value.
As a preferable technical scheme of the invention, R is1、R2Each independently selected from: unsubstituted or substituted by C1-C10Alkyl-substituted C of6-C48Aryl of (a), unsubstituted or substituted by C1-C10Alkyl-substituted C of3-C48One of the aromatic heterocyclic groups of (1).
As a preferred embodiment of the present invention, the compound is unsubstituted or substituted by C1-C10Alkyl-substituted C of6-C48The aromatic group is selected from: unsubstituted or substituted by C1-C10Alkyl-substituted C of6-C48A condensed ring aromatic group of (A), unsubstituted or consisting of C1-C10Alkyl-substituted C of6-C48One of the non-condensed ring aromatic groups of (a);
said unsubstituted or substituted by C1-C10Alkyl-substituted C of3-C48The aromatic heterocyclic group of (a) is selected from: unsubstituted or substituted by C1-C10Alkyl-substituted C of3-C48Unsubstituted or substituted by C1-C10Alkyl-substituted C of5-C48Wherein the number of nitrogen atoms in the aromatic nitrogen heterocyclic group is 1 to 3.
As a preferred embodiment of the present invention, the compound is unsubstituted or substituted by C1-C10Alkyl-substituted C of3-C48The aromatic nitrogen heterocyclic group of (a) includes: unsubstituted or substituted by C1-C10Alkyl-substituted C of7-C48The aza-condensed ring aromatic radical of (A) being unsubstituted or consisting of C1-C10Alkyl-substituted C of7-C48The aza-acyclic aromatic group of (a);
the hetero element in the aromatic non-nitrogen heterocyclic group includes oxygen and/or sulfur.
As a preferable technical scheme of the invention, R is1、R2Each independently selected from: unsubstituted or substituted by C1-C10Alkyl-substituted phenyl, azaphenyl, unsubstituted or substituted by C1-C10Alkyl-substituted biphenyls, azabiphenyls, unsubstituted or substituted by C1-C10Alkyl-substituted terphenyl, azaterphenyl, unsubstituted or substituted by C1-C10Alkyl-substituted naphthyl, azanaphthyl, unsubstituted or substituted by C1-C10Alkyl-substituted fluorenyl, unsubstituted or substituted by C1-C10Alkyl-substituted 9, 9-spirobifluorenyl, unsubstituted or substituted by C1-C10Alkyl-substituted carbazolylphenyl, unsubstituted or substituted by C1-C10Alkyl-substituted 9-phenylcarbazolyl, unsubstituted or substituted by C1-C10Wherein the nitrogen in the azaphenyl group, the azabiphenyl group, the azaterphenyl group and the azanaphthyl group is respectively 1-3.
As a preferable technical means of the present invention, said C1-C10Each alkyl group of (a) is independently selected from: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl.
As shown in Table 1, is R1、R2Part structure and name of (a).
Table 1 general formula R1、R2Partial structure and name of substituent
Figure BDA0001530170660000031
Figure BDA0001530170660000041
Figure BDA0001530170660000051
As a preferred embodiment of the present invention, the derivatives are as follows:
Figure BDA0001530170660000052
Figure BDA0001530170660000061
Figure BDA0001530170660000071
Figure BDA0001530170660000081
Figure BDA0001530170660000091
Figure BDA0001530170660000101
Figure BDA0001530170660000111
Figure BDA0001530170660000121
Figure BDA0001530170660000131
Figure BDA0001530170660000141
Figure BDA0001530170660000151
Figure BDA0001530170660000161
Figure BDA0001530170660000171
Figure BDA0001530170660000181
Figure BDA0001530170660000191
Figure BDA0001530170660000201
Figure BDA0001530170660000211
Figure BDA0001530170660000221
Figure BDA0001530170660000231
Figure BDA0001530170660000241
Figure BDA0001530170660000251
Figure BDA0001530170660000261
Figure BDA0001530170660000271
Figure BDA0001530170660000281
Figure BDA0001530170660000291
the second aspect of the invention provides a preparation method of triarylamine derivatives, which comprises the following steps:
1) amine derivatives and bromine and iodine dihalides according to the molar ratio of 1: 1, adding toluene and sodium tert-butoxide, removing air by ultrasonic treatment, adding palladium acetate and tri-tert-butylphosphine under the protection of nitrogen, and heating and refluxing for 20-48 hours, wherein the amine derivative, the toluene, the sodium tert-butoxide, the palladium acetate and the tri-tert-butylphosphine are mixed according to a molar ratio of 1: 2: 3:3 ‰: feeding by 6 per mill;
2) cooling to room temperature, and treating to obtain an intermediate;
3)7, 7-dimethyl-7, 12-dihydroindeno [1,2-a ] carbazole and the intermediate in a molar ratio of 1: 1, adding DMAC (dimethylacetamide) and potassium carbonate, removing air by ultrasonic, adding cuprous iodide and crown ether under the protection of nitrogen, and carrying out heating reflux reaction for 48-64 hours, wherein the 7, 7-dimethyl-7, 12-dihydroindeno [1,2-a ] carbazole, DMAC, potassium carbonate, cuprous iodide and crown ether are mixed according to a molar ratio of 1: 2: 2: 1%: 1% of feeding;
4) cooling to room temperature, and processing to obtain a final product;
the synthetic route is as follows:
Figure BDA0001530170660000292
as a preferred technical solution of the present invention, the processing manner in step 2) is: washing with water twice, separating, drying oil phase with anhydrous magnesium sulfate, decolorizing with activated carbon, distilling under reduced pressure to remove solvent, and recrystallizing or separating with column chromatography;
the processing mode in the step 4) is as follows: washing with water twice, filtering, dissolving the filter cake in ethyl acetate, adding active carbon for decolorizing, distilling under reduced pressure, recrystallizing or separating with column chromatography.
The third aspect of the invention provides the application of the triarylamine derivative as a hole transport layer material, a luminescent layer material or a light-emitting layer material in an organic electroluminescent device or an organic solar cell device.
The invention provides an organic device, which is an organic electroluminescent device or an organic solar cell device and at least comprises a transmission layer and/or a luminescent layer and/or a light-emitting layer.
The device provided by the invention is an organic electroluminescent device prepared based on the arylamine derivative or the compound with similar functions in the prior art, such as a hole transport material applied to a light-emitting diode.
The compound provided by the invention is a compound which has an asymmetric rigid non-coplanar structure and is rich in holes, has higher glass transition temperature and wider energy level adaptability, has good thermal stability, effectively avoids the defect of no pinhole caused by accumulation during vacuum evaporation, effectively reduces the energy barrier in the carrier transmission process due to proper energy level adaptability, and further effectively improves the luminous efficiency and the service life of a device. When the material is used as a hole transport material, compared with the commonly used hole transport materials such as NPB (N-propyl-beta-butyl-beta) in the prior art, the material has high glass transition temperature and high hole transport efficiency, and the prepared device has lower starting voltage and higher luminous brightness and is an ideal hole transport material. In addition, when the series of compounds are used as the light-emitting layer material, the efficiency of the organic electroluminescent device is greatly improved, and the series of compounds are ideal light-emitting layer materials.
The arylamine derivative (250) is used as a hole transport material to prepare an OLED device, and when the OLED device emits sky-blue light, the starting voltage, the light-emitting brightness, the current efficiency, the lumen efficiency and the glass transition temperature of the OLED device respectively reach 2.8V and 30290cd/m258.6cd/A, 50.3lm/W and 177 ℃, show superior performance in OLED devices. The aromatic amine derivative (250) is used as a hole transport material and is simultaneously used as a light emitting layer material to prepare the OLED device, and the luminous brightness and the lumen efficiency are respectively improved to 36940cd/m261.4lm/W, the light extraction efficiency of the device is greatly improved.
Advantages of additional aspects of the invention will be set forth in part in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention.
Drawings
Fig. 1 is an energy level diagram of a device using the compound (250) provided by the present invention and N, N '-diphenyl-N, N' -bis (3-methylphenyl) -1,1 '-biphenyl-4, 4' -diamine (TPD) as a hole transport material;
FIG. 2 is a graph showing wavelength-light intensity characteristics of a device prepared by using the compound (250) provided by the present invention as a hole transporting material;
FIG. 3 is a graph showing voltage-current density-luminance characteristics of a device 18 made of the compound (250) provided in the present invention as a hole transporting material and a device 21 made of the hole transporting material and a light emitting layer material, respectively;
FIG. 4 is a graph of luminance vs. lumen efficiency characteristics of a device 18 made with the compound (250) provided in the present invention as a hole transport material and a device 21 made with the compound as a hole transport material and a light extraction layer material, respectively;
Detailed Description
The present invention will be further described with reference to the following examples. Any simple modifications, equivalent changes and the like to the following embodiments according to the technical spirit of the present invention still fall within the protection scope of the technical solution of the present invention. The present invention is not limited to the contents described in the following embodiments.
Example 1
The compound (3) of the present invention can be synthesized by the following method.
1) Adding N-phenylnaphthalene-2-amine (21.93g,100mmol) and 4' -bromo-4-iodobiphenyl (35.90g,100mmol), toluene (200mL) and sodium tert-butoxide (28.83g,300mmol) into a 500mL three-necked flask, ultrasonically removing air, adding palladium acetate (0.07g,0.3mmol) and tri-tert-butylphosphine (0.18g,0.6mmol) under nitrogen protection, heating at 115 ℃ and refluxing for 24 hours, and monitoring the reaction completion by TLC;
2) cooling to room temperature, washing twice with water, separating liquid, drying the organic phase with anhydrous magnesium sulfate, filtering, adding activated carbon into the filtrate, decoloring for 45 minutes at 115 ℃, filtering thermally, distilling and concentrating the filtrate under reduced pressure, and recrystallizing twice with ethyl acetate to obtain 35.13g of intermediate N- (4 '-bromo- [1,1' -biphenyl ] -4-yl) -N-phenylnaphthalene-2-amine with yield of 78%;
3) adding 7, 7-dimethyl-7, 12-dihydroindeno [1,2-a ] carbazole (14.17g,50mmol), N- (4 '-bromo- [1,1' -biphenyl ] -4-yl) -N-phenylnaphthalene-2-amine (22.52g,50mmol), DMAC (100mL) and potassium carbonate (13.82g,100mmol) into a 250mL three-neck flask, ultrasonically removing air, adding cuprous iodide (0.95g, 5mmol) and 18-C-6(1.32g, 5mmol) under the protection of nitrogen, heating and refluxing at 150 ℃ for 48 hours, and monitoring the completion of the reaction by TLC;
4) after cooling to room temperature, washing twice with water, filtering, dissolving the filter cake in ethyl acetate, decolorizing for 45 minutes at 75 ℃, hot filtering, recrystallizing the filtrate twice with ethyl acetate, drying under vacuum to obtain 27.09g of the compound (3) with 83% yield. Mass spectrum ms (apci) (m/z) 652.70 (theoretical value 652.84) for compound (3).
Example 2
The compound (12) of the present invention can be synthesized by the following method.
1) Adding N-phenylpyridin-4-amine (17.02g,100mmol) and 4' -bromo-4-iodobiphenyl (35.90g,100mmol), toluene (200mL) and sodium tert-butoxide (28.83g,300mmol) into a 500mL three-necked flask, ultrasonically removing air, adding palladium acetate (0.07g,0.3mmol) and tri-tert-butylphosphine (0.18g,0.6mmol) under nitrogen protection, heating at 115 ℃ and refluxing for 24 hours, and monitoring the reaction completion by TLC;
2) cooling to room temperature, washing twice with water, separating liquid, drying the organic phase with anhydrous magnesium sulfate, filtering, adding activated carbon into the filtrate, decoloring for 45 minutes at 115 ℃, filtering thermally, distilling and concentrating the filtrate under reduced pressure, and recrystallizing twice with ethyl acetate to finally obtain an intermediate N- (4 '-bromo- [1,1' -biphenyl ] -4-yl) -N-phenylpyridine-4-amine 30.89g with a yield of 77%;
3) adding 7, 7-dimethyl-7, 12-dihydroindeno [1,2-a ] carbazole (14.17g,50mmol), N- (4 '-bromo- [1,1' -biphenyl ] -4-yl) -N-phenylpyridin-4-amine (20.06g, 50mmol), DMAC (100mL) and potassium carbonate (13.82g,100mmol) into a 250mL three-neck flask, ultrasonically removing air, adding cuprous iodide (0.95g, 5mmol) and 18-C-6(1.32g, 5mmol) under nitrogen protection, heating and refluxing at 150 ℃ for 48 hours, and monitoring the completion of the reaction by TLC;
4) after cooling to room temperature, washing twice with water, filtering, dissolving the filter cake in ethyl acetate, decolorizing for 45 minutes at 75 ℃, hot filtering, recrystallizing the filtrate twice with ethyl acetate, drying under vacuum to obtain 25.35g of the compound (12) with 84% yield. Mass spectrum ms (apci) (m/z) 603.46 (theoretical value 603.77) for compound (12).
Example 3
The compound (22) of the present invention can be synthesized by the following method.
1) Adding 9-phenyl-N- (4-methylphenyl) -9H-carbazole-3-amine (34.84g,100mmol) and 4' -bromo-4-iodobiphenyl (35.90g,100mmol), toluene (200mL) and sodium tert-butoxide (28.83g,300mmol) into a 500mL three-necked flask, removing air by ultrasound, adding palladium acetate (0.07g,0.3mmol) and tri-tert-butylphosphine (0.18g,0.6mmol) under nitrogen protection, heating at 115 ℃ for reflux reaction for 24 hours, and monitoring the reaction completion by TLC;
2) cooling to room temperature, washing twice with water, separating, drying an organic phase with anhydrous magnesium sulfate, filtering, adding activated carbon into the filtrate, decoloring for 45 minutes at 115 ℃, carrying out heat filtration, carrying out reduced pressure distillation and concentration on the filtrate, and recrystallizing twice with ethyl acetate to finally obtain 43.47g of intermediate N- (4 '-bromo- [1,1' -biphenyl ] -4-yl) -9-phenyl-N- (4-methylphenyl) -9H-carbazole-3-amine with the yield of 75%;
3) adding 7, 7-dimethyl-7, 12-dihydroindeno [1,2-a ] carbazole (14.17g,50mmol), N- (4 '-bromo- [1,1' -biphenyl ] -4-yl) -9-phenyl-N- (4-methylphenyl) -9H-carbazol-3-amine (28.98g, 50mmol), DMAC (100mL) and potassium carbonate (13.82g,100mmol) into a 250mL three-neck flask, removing air by ultrasonic treatment, adding cuprous iodide (0.95g, 5mmol) and 18-C-6(1.32g, 5mmol) under the protection of nitrogen, heating at 150 ℃ for reflux reaction for 48 hours, and monitoring the reaction completion by TLC;
4) after cooling to room temperature, washing twice with water, filtering, dissolving the filter cake in ethyl acetate, decolorizing for 45 minutes at 75 ℃, hot filtering, recrystallizing the filtrate twice with ethyl acetate, drying under vacuum to obtain 31.67g of the compound (22) with 81% yield. Mass spectrum ms (apci) (m/z) 782.12 (theoretical value 782.00) for compound (22).
Example 4
The compound (44) of the present invention can be synthesized by the following method.
1) Adding N- (4-tert-butylphenyl) dibenzofuran-4-amine (31.54g,100mmol) and 4' -bromo-4-iodobiphenyl (35.90g,100mmol), toluene (200mL) and sodium tert-butoxide (28.83g,300mmol) in a 500mL three-necked flask, ultrasonically removing air, adding palladium acetate (0.07g,0.3mmol) and tri-tert-butylphosphine (0.18g,0.6mmol) under nitrogen, heating at 115 ℃ for reflux reaction for 24 hours, and monitoring the reaction completion by TLC;
2) cooling to room temperature, washing twice with water, separating, drying the organic phase with anhydrous magnesium sulfate, filtering, adding activated carbon into the filtrate, decoloring for 45 minutes at 115 ℃, filtering thermally, distilling and concentrating the filtrate under reduced pressure, and recrystallizing twice with ethyl acetate to obtain 40.98g of intermediate N- (4 '-bromo- [1,1' -biphenyl ] -4-yl) -N- (4-tert-butylphenyl) dibenzofuran-4-amine with a yield of 75%;
3) adding 7, 7-dimethyl-7, 12-dihydroindeno [1,2-a ] carbazole (14.17g,50mmol), N- (4 '-bromo- [1,1' -biphenyl ] -4-yl) -N- (4-tert-butylphenyl) dibenzofuran-4-amine (27.32g, 50mmol), DMAC (100mL) and potassium carbonate (13.82g,100mmol) into a 250mL three-necked flask, ultrasonically removing air, adding cuprous iodide (0.95g, 5mmol) and 18-C-6(1.32g, 5mmol) under nitrogen protection, heating at 150 ℃ for reflux reaction for 48 hours, and monitoring the reaction completion by TLC;
4) after cooling to room temperature, washing twice with water, filtering, dissolving the filter cake in ethyl acetate, decolorizing for 45 minutes at 75 ℃, hot filtering, recrystallizing the filtrate twice with ethyl acetate, drying under vacuum to obtain 30.71g of compound (44) with 82% yield. Mass spectrum ms (apci) (m/z) 748.62 (theoretical value 748.97) for compound (44).
Example 5
The compound (53) of the present invention can be synthesized by the following method.
1) Adding N- (4-tert-butylphenyl) - [1,1':3', 1' -terphenyl ] -5' -amine (37.75g,100mmol) and 4' -bromo-4-iodobiphenyl (35.90g,100mmol), toluene (200mL) and sodium tert-butoxide (28.83g,300mmol) in a 500mL three-necked flask, removing air with ultrasound, adding palladium acetate (0.07g,0.3mmol) and tri-tert-butylphosphine (0.18g,0.6mmol) under nitrogen, heating at 115 ℃ for reflux for 24 hours, and monitoring the completion of the reaction by TLC;
2) cooling to room temperature, washing twice with water, separating, drying the organic phase with anhydrous magnesium sulfate, filtering, adding activated carbon into the filtrate, decoloring for 45 minutes at 115 ℃, filtering thermally, distilling and concentrating the filtrate under reduced pressure, and recrystallizing twice with ethyl acetate to obtain an intermediate N- (4 '-bromo- [1,1' -biphenyl ] -4-yl) -N- (4-tert-butylphenyl) - [1,1':3',1 '-terphenyl ] -5' -amine 46.25g with a yield of 76%;
3) adding 7, 7-dimethyl-7, 12-dihydroindeno [1,2-a ] carbazole (14.17g,50mmol), N- (4 '-bromo- [1,1' -biphenyl ] -4-yl) -N- (4-tert-butylphenyl) - [1,1':3',1 '-terphenyl ] -5' -amine (30.43g, 50mmol), DMAC (100mL) and potassium carbonate (13.82g,100mmol) into a 250mL three-necked flask, ultrasonically removing air, adding cuprous iodide (0.95g, 5mmol) and 18-C-6(1.32g, 5mmol) under nitrogen protection, heating to reflux at 150 ℃ for 48 hours, and monitoring the reaction completion by TLC;
4) after cooling to room temperature, washing twice with water, filtering, dissolving the filter cake in ethyl acetate, decolorizing for 45 minutes at 75 ℃, hot filtering, recrystallizing the filtrate twice with ethyl acetate, drying under vacuum to obtain 32.44g of compound (53) with 80% yield. Mass spectrum ms (apci) (m/z) 811.42 (theoretical value 811.09) for compound (53).
Example 6
The compound (59) of the present invention can be synthesized by the following method.
1) In a 500mL three-necked flask, 3 '-isopropyl-N-phenyl- [1,1' -biphenyl ] -4-amine (28.74g,100mmol) and 4 '-bromo-3-iodo-1, 1' -biphenyl (35.90g,100mmol), toluene (200mL) and sodium tert-butoxide (28.83g,300mmol) were added, air was removed by sonication, palladium acetate (0.07g,0.3mmol) and tri-tert-butylphosphine (0.18g,0.6mmol) were added under nitrogen, the reaction was heated at 115 ℃ under reflux for 24 hours, and TLC monitored for completion;
2) cooling to room temperature, washing twice with water, separating, drying the organic phase with anhydrous magnesium sulfate, filtering, adding activated carbon into the filtrate, decoloring for 45 minutes at 115 ℃, filtering thermally, distilling and concentrating the filtrate under reduced pressure, and recrystallizing twice with ethyl acetate to obtain 39.92g of intermediate 4 '-bromo-N- (3' -isopropyl- [1,1 '-biphenyl ] -4-yl) -N-phenyl- [1,1' -biphenyl ] -3-amine with a yield of 77%;
3) adding 7, 7-dimethyl-7, 12-dihydroindeno [1,2-a ] carbazole (14.17g,50mmol), 4 '-bromo-N- (3' -isopropyl- [1,1 '-biphenyl ] -4-yl) -N-phenyl- [1,1' -biphenyl ] -3-amine (25.92g, 50mmol), DMAC (100mL) and potassium carbonate (13.82g,100mmol), removing air by ultrasonic, adding cuprous iodide (0.95g, 5mmol) and 18-C-6(1.32g, 5mmol) under nitrogen protection, heating at 150 ℃ for reflux reaction for 48 hours, and monitoring the reaction completion by TLC;
4) after cooling to room temperature, washing twice with water, filtering, dissolving the filter cake in ethyl acetate, decolorizing for 45 minutes at 75 ℃, hot filtering, recrystallizing the filtrate twice with ethyl acetate, drying under vacuum to obtain 29.92g of compound (59) with 83% yield. Mass spectrum ms (apci) (m/z) 720.62 (theoretical value 720.96) for compound (59).
Example 7
The compound (67) of the present invention can be synthesized by the following method.
1) Adding 3- (9H-carbazol-9-yl) -N-phenylaniline (33.44g,100mmol) and 4 '-bromo-3-iodo-1, 1' -biphenyl (35.90g,100mmol), toluene (200mL) and sodium tert-butoxide (28.83g,300mmol) into a 500mL three-necked flask, removing air by ultrasound, adding palladium acetate (0.07g,0.3mmol) and tri-tert-butylphosphine (0.18g,0.6mmol) under nitrogen protection, heating at 115 ℃ for reflux reaction for 24 hours, and monitoring the reaction completion by TLC;
2) cooling to room temperature, washing twice with water, separating liquid, drying an organic phase with anhydrous magnesium sulfate, filtering, adding activated carbon into the filtrate, decoloring for 45 minutes at 115 ℃, carrying out heat filtration, carrying out reduced pressure distillation and concentration on the filtrate, and recrystallizing twice with ethyl acetate to finally obtain an intermediate N- (3- (9H-carbazole-9-yl) phenyl) -4 '-bromo-N-phenyl- [1,1' -biphenyl ] -3-amine 42.40g with a yield of 75%;
3) adding 7, 7-dimethyl-7, 12-dihydroindeno [1,2-a ] carbazole (14.17g,50mmol), N- (3- (9H-carbazol-9-yl) phenyl) -4 '-bromo-N-phenyl- [1,1' -biphenyl ] -3-amine (28.27g, 50mmol), DMAC (100mL) and potassium carbonate (13.82g,100mmol) into a 250mL three-necked flask, removing air by ultrasonic treatment, adding cuprous iodide (0.95g, 5mmol) and 18-C-6(1.32g, 5mmol) under nitrogen protection, heating and refluxing at 150 ℃ for 48 hours, and monitoring the completion of the reaction by TLC;
4) after cooling to room temperature, washing twice with water, filtering, dissolving the filter cake in ethyl acetate, decolorizing for 45 minutes at 75 ℃, hot filtering, recrystallizing the filtrate twice with ethyl acetate, drying under vacuum to obtain 31.10g of the compound (67) with 81% yield. Mass spectrum ms (apci) (m/z) 767.81 (theoretical value 767.98) for compound (67).
Example 8
The compound (84) of the present invention can be synthesized by the following method.
1) Adding N- (4-methylphenyl) pyridin-4-amine (18.42g,100mmol) and 4 '-bromo-3-iodo-1, 1' -biphenyl (35.90g,100mmol), toluene (200mL) and sodium tert-butoxide (28.83g,300mmol) into a 500mL three-necked flask, removing air with ultrasound, adding palladium acetate (0.07g,0.3mmol) and tri-tert-butylphosphine (0.18g,0.6mmol) under nitrogen, heating at 115 deg.C for reflux for 24 hours, and monitoring the completion of the reaction by TLC;
2) cooling to room temperature, washing twice with water, separating liquid, drying the organic phase with anhydrous magnesium sulfate, filtering, adding activated carbon into the filtrate, decoloring for 45 minutes at 115 ℃, filtering thermally, distilling and concentrating the filtrate under reduced pressure, and recrystallizing twice with ethyl acetate to obtain 31.97g of intermediate N- (4 '-bromo- [1,1' -biphenyl ] -3-yl) -N- (4-methylphenyl) pyridin-4-amine with a yield of 77%;
3) adding 7, 7-dimethyl-7, 12-dihydroindeno [1,2-a ] carbazole (14.17g,50mmol), N- (4 '-bromo- [1,1' -biphenyl ] -3-yl) -N- (4-methylphenyl) pyridin-4-amine (20.76g, 50mmol), DMAC (100mL) and potassium carbonate (13.82g,100mmol) into a 250mL three-neck flask, ultrasonically removing air, adding cuprous iodide (0.95g, 5mmol) and 18-C-6(1.32g, 5mmol) under the protection of nitrogen, heating and refluxing at 150 ℃ for 48 hours, and monitoring the completion of the reaction by TLC;
4) after cooling to room temperature, washing twice with water, filtering, dissolving the filter cake in ethyl acetate, decolorizing for 45 minutes at 75 ℃, hot filtering, recrystallizing the filtrate twice with ethyl acetate, drying under vacuum to obtain 25.95g of the compound (84) with 84% yield. Mass spectrum ms (apci) (m/z) 617.65 (theoretical value 617.80) for compound (84).
Example 9
The compound (98) of the present invention can be synthesized by the following method.
1) Adding N- (4-tert-butylphenyl) dibenzofuran-4-amine (31.54g,100mmol) and 4 '-bromo-3-iodo-1, 1' -biphenyl (35.90g,100mmol), toluene (200mL) and sodium tert-butoxide (28.83g,300mmol) in a 500mL three-necked flask, removing air with ultrasound, adding palladium acetate (0.07g,0.3mmol) and tri-tert-butylphosphine (0.18g,0.6mmol) under nitrogen, heating at 115 ℃ for reflux for 24 hours, and monitoring the completion of the reaction by TLC;
2) cooling to room temperature, washing twice with water, separating, drying the organic phase with anhydrous magnesium sulfate, filtering, adding activated carbon into the filtrate, decoloring for 45 minutes at 115 ℃, filtering thermally, distilling and concentrating the filtrate under reduced pressure, and recrystallizing twice with ethyl acetate to obtain 40.98g of intermediate N- (4 '-bromo- [1,1' -biphenyl ] -3-yl) -N- (4-tert-butylphenyl) dibenzofuran-4-amine with a yield of 75%;
3) adding 7, 7-dimethyl-7, 12-dihydroindeno [1,2-a ] carbazole (14.17g,50mmol), N- (4 '-bromo- [1,1' -biphenyl ] -3-yl) -N- (4-tert-butylphenyl) dibenzofuran-4-amine (27.32g, 50mmol), DMAC (100mL) and potassium carbonate (13.82g,100mmol) into a 250mL three-necked flask, ultrasonically removing air, adding cuprous iodide (0.95g, 5mmol) and 18-C-6(1.32g, 5mmol) under nitrogen protection, heating at 150 ℃ for reflux reaction for 48 hours, and monitoring the reaction completion by TLC;
4) after cooling to room temperature, washing twice with water, filtering, dissolving the filter cake in ethyl acetate, decolorizing for 45 minutes at 75 ℃, hot filtering, recrystallizing the filtrate twice with ethyl acetate, drying under vacuum to obtain 30.33g of compound (98) with 81% yield. Compound (98) mass spectrum ms (apci) (m/z) ═ 748.66 (theoretical value 748.97).
Example 10
The compound (108) of the present invention can be synthesized by the following method.
1) In a 500mL three-necked flask, 4-tert-butyl-N- (4- (pyridin-4-yl) phenyl) aniline (30.24g,100mmol) and 4 '-bromo-3-iodo-1, 1' -biphenyl (35.90g,100mmol), toluene (200mL) and sodium tert-butoxide (28.83g,300mmol) were added, air was removed by sonication, palladium acetate (0.07g,0.3mmol) and tri-tert-butylphosphine (0.18g,0.6mmol) were added under nitrogen, the reaction was heated at 115 ℃ under reflux for 24 hours, and TLC monitored for completion;
2) cooling to room temperature, washing twice with water, separating, drying the organic phase with anhydrous magnesium sulfate, filtering, adding activated carbon into the filtrate, decoloring for 45 minutes at 115 ℃, carrying out heat filtration, carrying out reduced pressure distillation and concentration on the filtrate, and recrystallizing twice with ethyl acetate to finally obtain 40.00g of an intermediate 4 '-bromo-N- (4-tert-butylphenyl) -N- (4- (pyridin-4-yl) phenyl) - [1,1' -biphenyl ] -3-amine with a yield of 75%;
3) adding 7, 7-dimethyl-7, 12-dihydroindeno [1,2-a ] carbazole (14.17g,50mmol), 4 '-bromo-N- (4-tert-butylphenyl) -N- (4- (pyridin-4-yl) phenyl) - [1,1' -biphenyl ] -3-amine (26.67g, 50mmol), DMAC (100mL) and potassium carbonate (13.82g,100mmol) into a 250mL three-necked flask, removing air by ultrasonic treatment, adding cuprous iodide (0.95g, 5mmol) and 18-C-6(1.32g, 5mmol) under nitrogen protection, heating to reflux at 150 ℃ for 48 hours, and monitoring by TLC that the reaction is complete;
4) after cooling to room temperature, washing twice with water, filtering, dissolving the filter cake in ethyl acetate, decolorizing for 45 minutes at 75 ℃, hot filtering, recrystallizing the filtrate twice with ethyl acetate, drying under vacuum to obtain 30.54g of compound (108) with 83% yield. Mass spectrum ms (apci) (m/z) 735.71 (theoretical value 735.98) for compound (108).
Example 11
The compound (131) of the present invention can be synthesized by the following method.
1) Adding 4-methyl-N- (4- (pyrimidin-5-yl) phenyl) aniline (26.13g,100mmol), 3-bromo-4 '-iodo-1, 1' -biphenyl (35.90g,100mmol), toluene (200mL) and sodium tert-butoxide (28.83g,300mmol) into a 500mL three-necked flask, removing air by sonication, adding palladium acetate (0.07g,0.3mmol) and tri-tert-butylphosphine (0.18g,0.6mmol) under nitrogen, heating at 115 ℃ for reflux for 24 hours, and monitoring the reaction completion by TLC;
2) cooling to room temperature, washing twice with water, separating liquid, drying an organic phase with anhydrous magnesium sulfate, filtering, adding activated carbon into the filtrate, decoloring for 45 minutes at 115 ℃, carrying out heat filtration, carrying out reduced pressure distillation and concentration on the filtrate, and recrystallizing twice with ethyl acetate to finally obtain 36.93g of an intermediate 3 '-bromo-N- (4- (pyrimidin-5-yl) phenyl) -N- (4-methylphenyl) - [1,1' -biphenyl ] -4-amine with the yield of 75%;
3) adding 7, 7-dimethyl-7, 12-dihydroindeno [1,2-a ] carbazole (14.17g,50mmol), 3 '-bromo-N- (4- (pyrimidin-5-yl) phenyl) -N- (4-methylphenyl) - [1,1' -biphenyl ] -4-amine (24.62g, 50mmol), DMAC (100mL) and potassium carbonate (13.82g,100mmol) into a 250mL three-necked flask, removing air by ultrasonic treatment, adding cuprous iodide (0.95g, 5mmol) and 18-C-6(1.32g, 5mmol) under nitrogen protection, heating and refluxing at 150 ℃ for 48 hours, and monitoring the completion of the reaction by TLC;
4) after cooling to room temperature, washing twice with water, filtering, dissolving the filter cake in ethyl acetate, decolorizing for 45 minutes at 75 ℃, hot filtering, recrystallizing the filtrate twice with ethyl acetate, drying under vacuum to obtain 28.49g of compound (131) with 82% yield. Mass spectrum ms (apci) (m/z) 694.67 (theoretical value 694.88) for compound (131).
Example 12
The compound (147) of the present invention can be synthesized by the following method.
1) Adding N- (4-tert-butylphenyl) isoquinolin-6-amine (27.64,100mmol) and 3-bromo-4 '-iodo-1, 1' -biphenyl (35.90g,100mmol), toluene (200mL) and sodium tert-butoxide (28.83g,300mmol) in a 500mL three-necked flask, ultrasonically removing air, adding palladium acetate (0.07g,0.3mmol) and tri-tert-butylphosphine (0.18g,0.6mmol) under nitrogen, heating at 115 ℃ under reflux for 24 hours, and monitoring by TLC for reaction completion;
2) cooling to room temperature, washing twice with water, separating, drying the organic phase with anhydrous magnesium sulfate, filtering, adding activated carbon into the filtrate, decoloring for 45 minutes at 115 ℃, carrying out hot filtration, carrying out reduced pressure distillation and concentration on the filtrate, and recrystallizing twice with ethyl acetate to finally obtain 38.56g of intermediate N- (3 '-bromo- [1,1' -biphenyl ] -4-yl) -N- (4-tert-butylphenyl) isoquinoline-6-amine with the yield of 76%;
3) adding 7, 7-dimethyl-7, 12-dihydroindeno [1,2-a ] carbazole (14.17g,50mmol), N- (3 '-bromo- [1,1' -biphenyl ] -4-yl) -N- (4-tert-butylphenyl) isoquinolin-6-amine (25.37g, 50mmol), DMAC (100mL) and potassium carbonate (13.82g,100mmol) into a 250mL three-necked flask, ultrasonically removing air, adding cuprous iodide (0.95g, 5mmol) and 18-C-6(1.32g, 5mmol) under nitrogen protection, heating at 150 ℃ for reflux reaction for 48 hours, and monitoring the reaction completion by TLC;
4) after cooling to room temperature, washing twice with water, filtering, dissolving the filter cake in ethyl acetate, decolorizing for 45 minutes at 75 ℃, hot filtering, recrystallizing the filtrate twice with ethyl acetate, drying under vacuum to obtain 28.40g of compound (147) with 80% yield. Compound (147) mass spectrum ms (apci) (m/z) ═ 709.65 (theoretical value 709.94).
Example 13
The compound (157) of the present invention can be synthesized by the following method.
1) Adding N- (4-tert-butylphenyl) -3- (9H-carbazol-9-yl) aniline (39.05,100mmol) and 3-bromo-4 '-iodo-1, 1' -biphenyl (35.90g,100mmol), toluene (200mL) and sodium tert-butoxide (28.83g,300mmol) in a 500mL three-necked flask, removing air with ultrasound, adding palladium acetate (0.07g,0.3mmol) and tri-tert-butylphosphine (0.18g,0.6mmol) under nitrogen protection, heating at 115 ℃ for reflux for 24 hours, and monitoring the completion of the reaction by TLC;
2) cooling to room temperature, washing twice with water, separating, drying the organic phase with anhydrous magnesium sulfate, filtering, adding activated carbon into the filtrate, decoloring for 45 minutes at 115 ℃, carrying out heat filtration, carrying out reduced pressure distillation and concentration on the filtrate, and recrystallizing twice with ethyl acetate to finally obtain 47.24g of intermediate N- (3- (9H-carbazole-9-yl) phenyl) -3 '-bromo-N- (4-tert-butylphenyl) - [1,1' -biphenyl ] -4-amine with the yield of 76%;
3) adding 7, 7-dimethyl-7, 12-dihydroindeno [1,2-a ] carbazole (14.17g,50mmol), N- (3- (9H-carbazol-9-yl) phenyl) -3 '-bromo-N- (4-tert-butylphenyl) - [1,1' -biphenyl ] -4-amine (31.08g, 50mmol), DMAC (100mL) and potassium carbonate (13.82g,100mmol) in a 250mL three-necked flask, ultrasonically removing air, adding cuprous iodide (0.95g, 5mmol) and 18-C-6(1.32g, 5mmol) under nitrogen protection, heating at 150 ℃ for reflux reaction for 48 hours, and monitoring the completion of the reaction by TLC;
4) after cooling to room temperature, washing twice with water, filtering, dissolving the filter cake in ethyl acetate, decolorizing for 45 minutes at 75 ℃, hot filtering, recrystallizing the filtrate twice with ethyl acetate, drying under vacuum to obtain 28.40g of compound (157) with 81% yield. Mass spectrum ms (apci) (m/z) 824.39 (theoretical value 824.08) for compound (157).
Example 14
The compound (178) of the present invention can be synthesized by the following method.
1) Adding N-phenyl dibenzofuran-3-amine (25.93,100mmol) and 3-bromo-3 '-iodo-1, 1' -biphenyl (35.90g,100mmol), toluene (200mL) and sodium tert-butoxide (28.83g,300mmol) into a 500mL three-necked flask, removing air with ultrasound, adding palladium acetate (0.07g,0.3mmol) and tri-tert-butylphosphine (0.18g,0.6mmol) under nitrogen, heating at 115 deg.C under reflux for 24 hr, and monitoring by TLC for reaction completion;
2) cooling to room temperature, washing twice with water, separating, drying the organic phase with anhydrous magnesium sulfate, filtering, adding activated carbon into the filtrate, decoloring for 45 minutes at 115 ℃, filtering thermally, distilling and concentrating the filtrate under reduced pressure, and recrystallizing twice with ethyl acetate to obtain 36.78g of intermediate N- (3 '-bromo- [1,1' -biphenyl ] -3-yl) -N-phenyl dibenzofuran-3-amine with the yield of 75%;
3) adding 7, 7-dimethyl-7, 12-dihydroindeno [1,2-a ] carbazole (14.17g,50mmol), N- (3 '-bromo- [1,1' -biphenyl ] -3-yl) -N-phenyldibenzofuran-3-amine (24.52g, 50mmol), DMAC (100mL) and potassium carbonate (13.82g,100mmol) into a 250mL three-neck flask, ultrasonically removing air, adding cuprous iodide (0.95g, 5mmol) and 18-C-6(1.32g, 5mmol) under the protection of nitrogen, heating and refluxing at 150 ℃ for 48 hours, and monitoring the completion of the reaction by TLC;
4) after cooling to room temperature, washing twice with water, filtering, dissolving the filter cake in ethyl acetate, decolorizing for 45 minutes at 75 ℃, hot filtering, recrystallizing the filtrate twice with ethyl acetate, drying under vacuum to obtain 28.41g of compound (178), 82% yield. Compound (178) mass ms (apci) (m/z) ═ 692.71 (theoretical value 692.86).
Example 15
The compound (191) of the present invention can be synthesized by the following method.
1) In a 500mL three-necked flask, 4-tert-butyl-N- (4-methylphenyl) aniline (23.94,100mmol) and 3-bromo-3 '-iodo-1, 1' -biphenyl (35.90g,100mmol), toluene (200mL) and sodium tert-butoxide (28.83g,300mmol) were added, air was removed by sonication, palladium acetate (0.07g,0.3mmol) and tri-tert-butylphosphine (0.18g,0.6mmol) were added under nitrogen, the reaction was heated under reflux at 115 ℃ for 24 hours, and the completion of the reaction was monitored by TLC;
2) cooling to room temperature, washing twice with water, separating, drying the organic phase with anhydrous magnesium sulfate, filtering, adding activated carbon into the filtrate, decoloring for 45 minutes at 115 ℃, carrying out heat filtration, distilling and concentrating the filtrate under reduced pressure, and recrystallizing twice with ethyl acetate to finally obtain 36.69g of intermediate 3 '-bromo-N- (4-tert-butylphenyl) -N- (4-methylphenyl) - [1,1' -biphenyl ] -3-amine with yield of 78%;
3) adding 7, 7-dimethyl-7, 12-dihydroindeno [1,2-a ] carbazole (14.17g,50mmol), 3 '-bromo-N- (4-tert-butylphenyl) -N- (4-methylphenyl) - [1,1' -biphenyl ] -3-amine (23.52g, 50mmol), DMAC (100mL) and potassium carbonate (13.82g,100mmol) into a 250mL three-necked flask, ultrasonically removing air, adding cuprous iodide (0.95g, 5mmol) and 18-C-6(1.32g, 5mmol) under the protection of nitrogen, heating and refluxing at 150 ℃ for 48 hours, and monitoring the completion of the reaction by TLC;
4) after cooling to room temperature, washing twice with water, filtering, dissolving the filter cake in ethyl acetate, decolorizing for 45 minutes at 75 ℃, hot filtering, recrystallizing the filtrate twice with ethyl acetate, drying under vacuum to obtain 28.26g of compound (191) with 84% yield. Mass spectrum ms (apci) (m/z) 672.35 (theoretical value 672.92) for compound (191).
Example 16
The compound (211) of the present invention can be synthesized by the following method.
1) Adding N- (4-tert-butylphenyl) -3- (9H-carbazol-9-yl) aniline (23.94,100mmol) and 3-bromo-3 '-iodo-1, 1' -biphenyl (39.05g,100mmol), toluene (200mL) and sodium tert-butoxide (28.83g,300mmol) in a 500mL three-necked flask, removing air with ultrasound, adding palladium acetate (0.07g,0.3mmol) and tri-tert-butylphosphine (0.18g,0.6mmol) under nitrogen protection, heating at 115 ℃ for reflux for 24 hours, and monitoring the completion of the reaction by TLC;
2) cooling to room temperature, washing twice with water, separating liquid, drying an organic phase with anhydrous magnesium sulfate, filtering, adding activated carbon into the filtrate, decoloring for 45 minutes at 115 ℃, carrying out heat filtration, carrying out reduced pressure distillation and concentration on the filtrate, and recrystallizing twice with ethyl acetate to finally obtain 46.62g of intermediate N- (3- (9H-carbazole-9-yl) phenyl) -3 '-bromo-N- (4-tert-butylphenyl) - [1,1' -biphenyl ] -3-amine with the yield of 75%;
3) adding 7, 7-dimethyl-7, 12-dihydroindeno [1,2-a ] carbazole (14.17g,50mmol), N- (3- (9H-carbazol-9-yl) phenyl) -3 '-bromo-N- (4-tert-butylphenyl) - [1,1' -biphenyl ] -3-amine (31.08g, 50mmol), DMAC (100mL) and potassium carbonate (13.82g,100mmol) in a 250mL three-necked flask, ultrasonically removing air, adding cuprous iodide (0.95g, 5mmol) and 18-C-6(1.32g, 5mmol) under nitrogen protection, heating at 150 ℃ for reflux reaction for 48 hours, and monitoring the completion of the reaction by TLC;
4) after cooling to room temperature, washing twice with water, filtering, dissolving the filter cake in ethyl acetate, decolorizing for 45 minutes at 75 ℃, hot filtering, recrystallizing the filtrate twice with ethyl acetate, drying under vacuum to obtain 33.37g of compound (211) with 81% yield. Mass spectrum ms (apci) (m/z) 824.17 (theoretical value 824.08) for compound (211).
Example 17
The compound (221) of the present invention can be synthesized by the following method.
1) In a 500mL three-necked flask, bis ([1,1' -biphenyl ] -4-yl) amine (32.14g,100mmol) and 4-bromo-4 ' -iodo-1, 1' -biphenyl (39.05g,100mmol), toluene (200mL) and sodium tert-butoxide (28.83g,300mmol) were added, air was removed by sonication, palladium acetate (0.07g,0.3mmol) and tri-tert-butylphosphine (0.18g,0.6mmol) were added under nitrogen, the reaction was heated at 115 ℃ under reflux for 24 hours, and the completion of the reaction was monitored by TLC;
2) cooling to room temperature, washing twice with water, separating liquid, drying the organic phase with anhydrous magnesium sulfate, filtering, adding activated carbon into the filtrate, decoloring for 45 minutes at 115 ℃, filtering thermally, distilling and concentrating the filtrate under reduced pressure, and recrystallizing twice with ethyl acetate to obtain an intermediate N, N-bis ([1,1' -biphenyl ] -4-yl) -4' -bromo- [1,1' -biphenyl ] -4-amine 41.99g with a yield of 76%;
3) adding 7, 7-dimethyl-7, 12-dihydroindeno [1,2-a ] carbazole (14.17g,50mmol), N, N-bis ([1,1' -biphenyl ] -4-yl) -4' -bromo- [1,1' -biphenyl ] -4-amine (27.63g, 50mmol), DMAC (100mL) and potassium carbonate (13.82g,100mmol) into a 250mL three-neck flask, ultrasonically removing air, adding cuprous iodide (0.95g, 5mmol) and 18-C-6(1.32g, 5mmol) under nitrogen protection, heating to reflux for 48 hours at 150 ℃, and monitoring by TLC that the reaction is completed;
4) after cooling to room temperature, washing twice with water, filtering, dissolving the filter cake in ethyl acetate, decolorizing for 45 minutes at 75 ℃, hot filtering, recrystallizing the filtrate twice with ethyl acetate, drying under vacuum to obtain 31.33g of compound (221), 83% yield. Mass spectrum ms (apci) (m/z) 754.77 (theoretical value 754.98) for compound (221).
Example 18
The compound (227) of the present invention can be synthesized by the following method.
1) Adding N- ([1,1' -biphenyl ] -4-yl) -9, 9-dimethyl-9H-fluorene-2-amine (36.15g,100mmol) and 4-bromo-4 ' -iodo-1, 1' -biphenyl (39.05g,100mmol), toluene (200mL) and sodium tert-butoxide (28.83g,300mmol) in a 500mL three-necked flask, removing air by sonication, adding palladium acetate (0.07g,0.3mmol) and tri-tert-butylphosphine (0.18g,0.6mmol) under nitrogen, heating to reflux at 115 deg.C for 24 hours, and monitoring by TLC for completion of the reaction;
2) cooling to room temperature, washing twice with water, separating, drying the organic phase with anhydrous magnesium sulfate, filtering, adding activated carbon into the filtrate, decoloring for 45 minutes at 115 ℃, filtering thermally, distilling and concentrating the filtrate under reduced pressure, and recrystallizing twice with ethyl acetate to obtain 45.63g of intermediate N- ([1,1' -biphenyl ] -4-yl) -N- (4' -bromo- [1,1' -biphenyl ] -4-yl) -9, 9-dimethyl-9H-fluorene-2-amine with 77% yield;
3) adding 7, 7-dimethyl-7, 12-dihydroindeno [1,2-a ] carbazole (14.17g,50mmol), N- ([1,1' -biphenyl ] -4-yl) -N- (4' -bromo- [1,1' -biphenyl ] -4-yl) -9, 9-dimethyl-9H-fluoren-2-amine (29.63g, 50mmol), DMAC (100mL) and potassium carbonate (13.82g,100mmol) into a 250mL three-necked flask, ultrasonically removing air, adding cuprous iodide (0.95g, 5mmol) and 18-C-6(1.32g, 5mmol) under nitrogen protection, heating to reflux for 48 hours at 150 ℃, and monitoring by TLC that the reaction is complete;
4) after cooling to room temperature, washing twice with water, filtering, dissolving the filter cake in ethyl acetate, decolorizing for 45 minutes at 75 ℃, hot filtering, recrystallizing the filtrate twice with ethyl acetate, drying under vacuum to obtain 32.20g of compound (227) with 81% yield. Compound (227) mass spectrum ms (apci) (m/z) ═ 795.22 (theoretical value 795.04).
Example 19
The compound (248) of the present invention can be synthesized by the following method.
1) Adding N- (2- (9H-carbazol-9-yl) phenyl) isoquinoline-6-amine (38.54g,100mmol) and 4-bromo-4 '-iodo-1, 1' -biphenyl (39.05g,100mmol), toluene (200mL) and sodium tert-butoxide (28.83g,300mmol) in a 500mL three-necked flask, removing air by sonication, adding palladium acetate (0.07g,0.3mmol) and tri-tert-butylphosphine (0.18g,0.6mmol) under nitrogen, heating at 115 ℃ for reflux for 24 hours, and monitoring the completion of the reaction by TLC;
2) cooling to room temperature, washing twice with water, separating liquid, drying an organic phase with anhydrous magnesium sulfate, filtering, adding activated carbon into the filtrate, decoloring for 45 minutes at 115 ℃, carrying out heat filtration, carrying out reduced pressure distillation and concentration on the filtrate, and recrystallizing twice with ethyl acetate to finally obtain 45.62g of intermediate N- (2- (9H-carbazole-9-yl) phenyl) -N- (4 '-bromo- [1,1' -biphenyl ] -4-yl) isoquinoline-6-amine with the yield of 74%;
3) adding 7, 7-dimethyl-7, 12-dihydroindeno [1,2-a ] carbazole (14.17g,50mmol), N- (2- (9H-carbazol-9-yl) phenyl) -N- (4 '-bromo- [1,1' -biphenyl ] -4-yl) isoquinoline-6-amine (30.83g, 50mmol), DMAC (100mL) and potassium carbonate (13.82g,100mmol) into a 250mL three-necked flask, ultrasonically removing air, adding cuprous iodide (0.95g, 5mmol) and 18-C-6(1.32g, 5mmol) under the protection of nitrogen, heating to reflux for 48 hours at 150 ℃, and monitoring the completion of the reaction by TLC;
4) after cooling to room temperature, washing twice with water, filtering, dissolving the filter cake in ethyl acetate, decolorizing for 45 minutes at 75 ℃, hot filtering, recrystallizing the filtrate twice with ethyl acetate, drying under vacuum to obtain 33.99g of compound (248) with 83% yield. Mass spectrum ms (apci) (m/z) 819.28 (theoretical value 819.02) for compound (248).
Example 20
The compound (277) of the present invention can be synthesized by the following method.
1) Adding N- (naphthalene-2-yl) -9,9' -spirobifluorene-2-amine (45.76g,100mmol), 4' -bromo-3-iodo-1, 1' -biphenyl (39.05g,100mmol), toluene (200mL) and sodium tert-butoxide (28.83g,300mmol) into a 500mL three-necked flask, removing air with ultrasound, adding palladium acetate (0.07g,0.3mmol) and tri-tert-butylphosphine (0.18g,0.6mmol) under nitrogen protection, heating at 115 ℃ for reflux for 24 hours, and monitoring the completion of the reaction by TLC;
2) cooling to room temperature, washing twice with water, separating, drying the organic phase with anhydrous magnesium sulfate, filtering, adding activated carbon into the filtrate, decoloring for 45 minutes at 115 ℃, carrying out heat filtration, carrying out reduced pressure distillation and concentration on the filtrate, and recrystallizing twice with ethyl acetate to finally obtain 48.20g of intermediate N- (4' -bromo- [1,1' -biphenyl ] -3-yl) -N- (naphthalene-2-yl) -9,9' -spirobifluorene-2-amine with the yield of 70%;
3) adding 7, 7-dimethyl-7, 12-dihydroindeno [1,2-a ] carbazole (14.17g,50mmol), N- (4' -bromo- [1,1' -biphenyl ] -3-yl) -N- (naphthalen-2-yl) -9,9' -spirobifluoren-2-amine (34.43g, 50mmol), DMAC (100mL) and potassium carbonate (13.82g,100mmol), removing air by ultrasonic, adding cuprous iodide (0.95g, 5mmol) and 18-C-6(1.32g, 5mmol) under nitrogen protection, heating at 150 ℃ for reflux reaction for 48 hours, and monitoring the reaction completion by TLC;
4) after cooling to room temperature, washing twice with water, filtering, dissolving the filter cake in ethyl acetate, decolorizing for 45 minutes at 75 ℃, hot filtering, recrystallizing the filtrate twice with ethyl acetate, drying under vacuum to obtain 35.64g of compound (277) with 80% yield. Mass spectrum ms (apci) (m/z) 891.02 (theoretical 891.13) for compound (277).
The following device examples relate to the use of the triarylamine derivatives of the present invention as hole transport materials and/or light extraction layer materials for organic electroluminescent devices and their properties, and the structure of the triarylamine derivatives of the present invention as hole transport materials for multilayer organic electroluminescent devices is shown in fig. 1.
Device example 1
The compound (1) is used as a hole transport material to prepare a device 1.
This example demonstrates the performance validation of an electroluminescent device prepared with compound (1) as the hole transport material. The ITO (indium tin oxide) glass was successively cleaned with ultrasound in a cleaning agent and deionized water for 30 minutes. Then vacuum drying for 2 hours (105 ℃), putting ITO (indium tin oxide) glass into a plasma reactor for oxygen plasma treatment for 5 minutes, transferring the ITO glass into a vacuum chamber to prepare an organic film and a metal electrode, preparing a layer of molybdenum trioxide as a hole injection material with the thickness of 5nm by a vacuum evaporation method, evaporating a compound (1) with the thickness of 45nm as a hole transmission material, and continuously evaporating a luminescent layer material with the thickness of 20nm on the hole transmission layer by vacuum evaporation, wherein the luminescent layer material is 3 percent of bis (4, 6-difluorophenylpyridine-N, C) doped with2) 4,4' -bis (9-Carbazole) Biphenyl (CBP) of iridium (Firpic) is benzoylated, and finally a layer of 15nm azole compound 1,3, 5-tris (1-phenyl-1H-benzimidazole-2-yl) benzene (TPBi), 1nm LiF and 100nm Al are evaporated to form the device structure of ITO (indium tin oxide)/MoO3(5 nm)/chemical conversionCompound (1) (45nm)/CBP wt 3% Firpic (20nm)/TPBi (15nm)/LiF (1nm)/Al (100 nm).
Device example 2
The compound (21) is used as a hole transport material to prepare the device 2.
This example demonstrates the performance validation of an electroluminescent device prepared with compound (21) as the hole transport material. The ITO (indium tin oxide) glass was successively cleaned with ultrasound in a cleaning agent and deionized water for 30 minutes. Then vacuum drying for 2 hours (105 ℃), putting ITO (indium tin oxide) glass into a plasma reactor for oxygen plasma treatment for 5 minutes, transferring the ITO glass into a vacuum chamber to prepare an organic film and a metal electrode, preparing a layer of molybdenum trioxide as a hole injection material with the thickness of 5nm by a vacuum evaporation method, evaporating a compound (21) with the thickness of 45nm as a hole transmission material, and continuously evaporating a luminescent layer material with the thickness of 20nm on the hole transmission layer by vacuum evaporation, wherein the luminescent layer material is 3 percent of bis (4, 6-difluorophenylpyridine-N, C) doped with2) 4,4' -bis (9-Carbazole) Biphenyl (CBP) of iridium (Firpic) is benzoylated, and finally a layer of 15nm azole compound 1,3, 5-tris (1-phenyl-1H-benzimidazole-2-yl) benzene (TPBi), 1nm LiF and 100nm Al are evaporated to form the device structure of ITO (indium tin oxide)/MoO3(5 nm)/Compound (21) (45nm)/CBP wt 3% Firpic (20nm)/TPBi (15nm)/LiF (1nm)/Al (100 nm).
Device example 3
The compound (35) is used as a hole transport material to prepare the device 3.
This example demonstrates the performance validation of an electroluminescent device prepared with compound (35) as the hole transport material. The ITO (indium tin oxide) glass was successively cleaned with ultrasound in a cleaning agent and deionized water for 30 minutes. Then vacuum drying for 2 hours (105 deg.C), placing ITO (indium tin oxide) glass into a plasma reactor for 5 minutes of oxygen plasma treatment, transferring into a vacuum chamber to prepare an organic film and a metal electrode, preparing a layer of 5nm hole injection material molybdenum trioxide by a vacuum evaporation method, then evaporating a 45nm thick compound (35) as a hole transport material, and then continuously evaporating a 20nm light-emitting layer material on the hole transport layer by vacuum evaporationThe material of the luminescent layer is 3 percent of bis (4, 6-difluorophenylpyridine-N, C)2) 4,4' -bis (9-Carbazole) Biphenyl (CBP) of iridium (Firpic) is benzoylated, and finally a layer of 15nm azole compound 1,3, 5-tris (1-phenyl-1H-benzimidazole-2-yl) benzene (TPBi), 1nm LiF and 100nm Al are evaporated to form the device structure of ITO (indium tin oxide)/MoO3(5 nm)/Compound (35) (45nm)/CBP wt 3% Firpic (20nm)/TPBi (15nm)/LiF (1nm)/Al (100 nm).
According to the production method of the device in the above-mentioned example, compound (45) as a hole transporting material produces device 4, compound (51) as a hole transporting material produces device 5, compound (66) as a hole transporting material produces device 6, compound (71) as a hole transporting material produces device 7, compound (85) as a hole transporting material produces device 8, compound (98) as a hole transporting material produces device 9, compound (112) as a hole transporting material produces device 10, compound (131) as a hole transporting material produces device 11, compound (147) as a hole transporting material produces device 12, compound (221) as a hole transporting material produces device 13, compound (224) as a hole transporting material produces device 14, compound (227) as a hole transporting material produces device 15, compound (238) as the hole transporting material produced device 16, compound (244) as the hole transporting material produced device 17, compound (250) as the hole transporting material produced device 18, and compound (277) as the hole transporting material produced device 19.
Device example 20
The device 20 is prepared by using N, N '-diphenyl-N, N' -bis (3-methylphenyl) -1,1 '-biphenyl-4, 4' -diamine (TPD) as a hole transport material and using a compound (250) as a light-emitting layer material.
This example demonstrates performance validation of an electroluminescent device prepared with compound (250) as the light extraction layer material. The ITO (indium tin oxide) glass was successively cleaned with ultrasound in a cleaning agent and deionized water for 30 minutes. Then vacuum drying for 2 hours (105 deg.C), placing ITO (indium tin oxide) glass into a plasma reactor for 5 minutes oxygen plasma treatment, transferring into a vacuum chamber to prepare an organic film and a metal electrode, and then preparing the film by a vacuum evaporation methodPreparing a layer of molybdenum trioxide with the thickness of 5nm as a hole injection material, evaporating TPD with the thickness of 45nm as a hole transport material, continuously evaporating a layer of light-emitting layer material with the thickness of 20nm on the hole transport layer by vacuum evaporation, wherein the light-emitting layer material is 4,4' -bis (9-Carbazole) Biphenyl (CBP) doped with 3% bis (4, 6-difluorophenylpyridine-N, C2) pyridine formyl iridium (Firpic), finally evaporating a layer of azole compound 1,3, 5-tris (1-phenyl-1H-benzimidazole-2-yl) benzene (TPBi) with the thickness of 15nm, continuously evaporating a layer of compound (250) with the thickness of 10nm as a light-emitting layer material after evaporating a layer of LiF with the thickness of 1nm, and taking Al with the thickness of 100nm as a cathode, wherein the formed device structure is ITO (oxide)/MoO indium tin oxide3(5nm)/TPD (45nm)/CBP wt 3% Firpic (20nm)/TPBi (15nm)/LiF (1 nm)/Compound (250) (10nm)/Al (100 nm). Device example 21
The compound (250) is used as a hole transport material and further as a light extraction layer material to prepare the device 21.
This example demonstrates performance verification of an electroluminescent device prepared with compound (250) as a hole transport material and further as a light extraction layer material. The ITO (indium tin oxide) glass was successively cleaned with ultrasound in a cleaning agent and deionized water for 30 minutes. Then vacuum drying for 2 hours (105 ℃), putting ITO (indium tin oxide) glass into a plasma reactor for oxygen plasma treatment for 5 minutes, transferring the ITO glass into a vacuum chamber to prepare an organic film and a metal electrode, preparing a layer of molybdenum trioxide as a hole injection material with the thickness of 5nm by a vacuum evaporation method, evaporating a compound (250) with the thickness of 45nm as a hole transmission material, continuing to evaporate a luminescent layer material with the thickness of 20nm on the hole transmission layer by vacuum evaporation, wherein the luminescent layer material is 4,4' -bis (9-Carbazole) Biphenyl (CBP) doped with 3 percent of bis (4, 6-difluorophenylpyridine-N, C2) pyridine formyl iridium (Firpic), evaporating a layer of 1,3, 5-tris (1-phenyl-1H-benzimidazole-2-yl) benzene (TPBi) with the thickness of 15nm, after a layer of 1nm LiF is evaporated, a layer of 10nm compound (250) is continuously evaporated to be used as a light-emitting layer material, 100nm Al is used as a cathode, and the formed device structure is ITO (indium tin oxide)/MoO3(5 nm)/Compound (250) (45nm)/CBP wt 3% Firpic (20nm)/TPBi (15nm)/LiF (1 nm)/Compound (250) (10nm)/Al (100 nm).
Comparative examples
Device 22 is fabricated using N, N '-diphenyl-N, N' -bis (3-methylphenyl) -1,1 '-biphenyl-4, 4' -diamine (TPD) as the hole transport material.
This example demonstrates the performance verification of electroluminescent devices made with a conventional hole transport material TPD. The ITO (indium tin oxide) glass was successively cleaned with ultrasound in a cleaning agent and deionized water for 30 minutes. Then vacuum drying for 2 hours (105 ℃), putting ITO (indium tin oxide) glass into a plasma reactor for oxygen plasma treatment for 5 minutes, transferring the ITO glass into a vacuum chamber to prepare an organic film and a metal electrode, preparing a layer of 5nm hole injection material molybdenum trioxide by a vacuum evaporation method, evaporating TPD with the thickness of 45nm as a hole transport material, and continuously evaporating a layer of 20nm luminous layer material on the hole transport layer by vacuum evaporation, wherein the luminous layer material is 3% doped bis (4, 6-difluorophenylpyridine-N, C2) 4,4' -bis (9-Carbazole) Biphenyl (CBP) of iridium (Firpic) is benzoylated, and finally a layer of 15nm azole compound 1,3, 5-tris (1-phenyl-1H-benzimidazole-2-yl) benzene (TPBi), 1nm LiF and 100nm Al are evaporated to form the device structure of ITO (indium tin oxide)/MoO3(5nm)/TPD(45nm)/CBP:wt 3％Firpic(20nm)/TPBi(15nm) /LiF(1nm)/Al(100nm)。
The positive electrode of the direct current was applied to the ITO (indium tin oxide) layer, the negative electrode was applied to the metal layer where aluminum was present, and the device performance was evaluated as shown in Table 2
TABLE 2 characterization of organic electroluminescent device Properties
Figure BDA0001530170660000481
Figure BDA0001530170660000491
As can be seen from Table 1, the arylamine derivatives provided by the invention have good service performance in the aspects of starting voltage, luminous brightness, current efficiency, lumen efficiency, glass transition temperature and the like when being used as hole transport materials and/or devices prepared from the hole transport materials, and are ideal hole transport materials and light-emitting layer materials.
As shown in FIG. 1, ITO (indium tin oxide)/MoO is used3The energy level diagram of a device prepared by taking (5nm)/TPD (45nm) or a compound (250)/CBP (wt 3% Firpic (20nm)/TPBi (15nm)/LiF (1nm)/Al (100nm) as a structure shows that compared with TPD, the triarylamine derivative provided by the invention has wider energy band, better energy level matching degree with a hole injection layer and a luminescent layer material, effectively reduces the driving voltage and energy consumption of the device and improves the performance of the device. As shown in FIG. 2, the voltage-wavelength characteristic curve of the device prepared by using the compound (250) as the hole transport material shows that compared with the prior art, the triarylamine derivative provided by the invention has good thermal stability as the hole transport material, can effectively improve the deterioration of the luminescence phenomenon caused by the aggregation and crystallization, so that the device emits 470nm pure blue light, and can better realize the physical blending of the three primary colors of red, green and blue of the color light device. As shown in FIG. 3, the voltage-current density-luminance characteristic curve of the device using the compound (250) as the hole transport material and further as the light emitting layer material, compared with the prior art, the triarylamine derivative provided by the invention has good hole transport rate as the hole transport material, is beneficial to realizing recombination of hole-electron in the light emitting layer to a greater extent, and can make the device luminance reach 30290cd/m2And when the light-emitting layer is further used as a light-emitting layer material to be applied to a device, the light-emitting brightness is improved to 36940cd/m2The amplification reaches 22 percent. As shown in fig. 4, a luminance-external quantum efficiency characteristic curve of a device prepared by using a compound (250) as a hole transport material and further as a light-emitting layer material, compared with the prior art, the triarylamine derivative provided by the invention has good carrier transport rate and energy gap width as the hole transport material, effectively improves the lumen efficiency, enables the lumen efficiency of the device to reach 50.3lm/W, and when the triarylamine derivative is further applied to the device as the light-emitting layer material, the lumen efficiency reaches 61.3lm/W, and the increase reaches 22%.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.

Claims (5)

1. The triarylamine derivative is characterized in that the structural general formula is as follows:
Figure FDA0002723550290000011
wherein R is1、R2Each independently selected from: unsubstituted or substituted by C1-C10The alkyl substituted phenyl, azaphenyl, biphenyl, azabiphenyl, terphenyl, naphthyl, azanaphthyl, fluorenyl, 9-spirobifluorenyl, carbazolyl phenyl, 9-phenylcarbazolyl or dibenzofuranyl, wherein the nitrogen in the azaphenyl, the azabiphenyl, the azaterphenyl and the azanaphthyl is 1-3 respectively, and the C is1-C10Each alkyl group of (a) is independently selected from: one of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl and tert-butyl; r1And R2The same or different.
2. A process for the preparation of triarylamine derivatives as claimed in claim 1, comprising the steps of:
1) amine derivatives and bromine and iodine dihalides according to the molar ratio of 1: 1, adding toluene and sodium tert-butoxide, removing air by ultrasonic treatment, adding palladium acetate and tri-tert-butylphosphine under the protection of nitrogen, and heating and refluxing for 20-48 hours, wherein the amine derivative, the toluene, the sodium tert-butoxide, the palladium acetate and the tri-tert-butylphosphine are mixed according to a molar ratio of 1: 2: 3:3 ‰: feeding by 6 per mill;
2) cooling to room temperature, and treating to obtain an intermediate;
3)7, 7-dimethyl-7, 12-dihydroindeno [1,2-a ] carbazole and the intermediate in a molar ratio of 1: 1, adding DMAC (dimethylacetamide) and potassium carbonate, removing air by ultrasonic, adding cuprous iodide and crown ether under the protection of nitrogen, and carrying out heating reflux reaction for 48-64 hours, wherein the 7, 7-dimethyl-7, 12-dihydroindeno [1,2-a ] carbazole, DMAC, potassium carbonate, cuprous iodide and crown ether are mixed according to a molar ratio of 1: 2: 2: 1%: 1% of feeding;
4) cooling to room temperature, and processing to obtain a final product;
the synthetic route is as follows:
Figure FDA0002723550290000021
3. a process for the preparation of triarylamine derivatives according to claim 2, wherein the treatment in step 2) is: washing with water twice, separating, drying oil phase with anhydrous magnesium sulfate, decolorizing with activated carbon, distilling under reduced pressure to remove solvent, and recrystallizing or separating with column chromatography;
the processing mode in the step 4) is as follows: washing with water twice, filtering, dissolving the filter cake in ethyl acetate, adding active carbon for decolorizing, distilling under reduced pressure, recrystallizing or separating with column chromatography.
4. Use of a triarylamine derivative according to claim 1 in a hole transport layer material, a light emitting layer material or a light emitting layer material in an organic electroluminescent device or an organic solar cell device.
5. An organic device, which is an organic electroluminescent device or an organic solar cell device and at least comprises a transmission layer and/or a luminescent layer and/or a light emergent layer, and is characterized in that the transmission layer and/or the luminescent layer and/or the light emergent layer are made of at least one triarylamine derivative as claimed in claim 1.
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