CN109970623A - Derivative of tri-arylamine group and preparation method thereof, application and device - Google Patents

Derivative of tri-arylamine group and preparation method thereof, application and device Download PDF

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CN109970623A
CN109970623A CN201711461177.1A CN201711461177A CN109970623A CN 109970623 A CN109970623 A CN 109970623A CN 201711461177 A CN201711461177 A CN 201711461177A CN 109970623 A CN109970623 A CN 109970623A
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alkyl
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substituted
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derivative
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CN109970623B (en
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穆广园
徐鹏
庄少卿
任春婷
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WUHAN SHANGSAI PHOTOELECTRIC TECHNOLOGY Co Ltd
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Abstract

The invention belongs to photoelectric material applicating technology technical fields, and in particular to derivative of tri-arylamine group and its preparation method and application.Derivative of tri-arylamine group provided by the present invention, using triaryl amine and fluorenes and carbazole is basic structural unit, and dissymmetrical structure is obtained after being modified, and constitutes a kind of rich in hole and with the compound of high glass transition temperature.When it is used as hole mobile material, with hole mobile material commonly used in the prior art such as N, N'- diphenyl-N, N'- bis- (3- aminomethyl phenyl) -1,1'- biphenyl -4,4'- diamines (TPD) compares, cavity transmission ability is significantly improved, in organic electroluminescence device, it is ideal hole mobile material which all increases significantly in terms of starting voltage and glass transition temperature compared with traditional hole mobile material.In addition, the efficiency of organic electroluminescence device increases substantially when the series compound is as photosphere materials'use is gone out, it is preferably to go out photosphere material.

Description

Derivative of tri-arylamine group and preparation method thereof, application and device
Technical field
The invention belongs to photoelectric material applicating technology technical fields, and in particular to derivative of tri-arylamine group and its preparation side Method, application and device.
Background technique
Organic light emitting diode (Organic Light-emitting Diode) be also known as organic electroluminescence device or Organic light emitting display (Organic Light-emitting Display, OLED), principle be it is a kind of using carrier in electricity Under field action by device positive and negative electrode enter organic solid luminescent layer it is compound and luminous phenomenon preparation display device (Tang, C.W.et al.Appl.Phys.Lett.1987,52,913).Device mainly uses small organic molecule/semiconducting polymer's material Material, since small organic molecule and high molecular material have the characteristics that easily to prepare processing purification and high selectivity modification, in material Application field has great potential, no matter studies or commercially, they all become a focus.
As 10 inventions most important over 30 years, Organic Light Emitting Diode experienced one section of course comparatively fast developed, from New material exploitation, device architecture preparation, mechanism probe into and the marketization promote all achieve great successes, become semiconductor The representative and innovative flag of the one side in field, its fine market prospects are especially noticeable.
Organic Light Emitting Diode is usually to be made of electrons implanted layer, electrons transport layer and luminescent layer, phase Corresponding includes electrons injection material, electrons transmission material and luminescent material etc., hole mobile material performance it is good Bad to have critically important influence to OLED device, developing new cavity transmission group to prepare efficient OLED device is us always The hot spot of research.It dissipates in addition, how to reduce light in device inside, it is also that the field OLED is to be solved that it is low, which to improve light extraction efficiency, Problem.
Summary of the invention
To solve the deficiencies in the prior art, first aspect of the present invention provides derivative of tri-arylamine group, and general structure is such as Under:
Wherein, R1、R2It is independently selected from: substitution or unsubstituted aromatic radical or fragrant heterocyclic radical；One of
R1And R2It is identical or different.
Derivative of tri-arylamine group of the present invention has very high hole mobility and good thermal stability, can be effective It prevents agglutination during vapor deposition from crystallizing the reduction for causing the severe and device lifetime of luminescence phenomenon, is applied to organic light emitting diode It is middle to obtain excellent effect, it is a kind of new material with very big commercial value.
As a preferred technical solution of the present invention, the R1、R2It is independently selected from: unsubstituted or by C1- C10Alkyl-substituted C6-C48Aromatic radical, unsubstituted or by C1-C10Alkyl-substituted C3-C48Fragrant heterocyclic radical One of.
It is described unsubstituted or by C as a preferred technical solution of the present invention1-C10Alkyl-substituted C6-C48 Aromatic radical be selected from: it is unsubstituted or by C1-C10Alkyl-substituted C6-C48Polycyclic aromatic base, it is unsubstituted or by C1-C10Alkyl-substituted C6-C48One of non-polycyclic aromatic base；
It is described unsubstituted or by C1-C10Alkyl-substituted C3-C48Fragrant heterocyclic radical be selected from: it is unsubstituted or By C1-C10Alkyl-substituted C3-C48Aromatic aza ring group, unsubstituted or by C1-C10Alkyl-substituted C5-C48 One of the non-Azacyclyl of fragrance, wherein the nitrogen in the aromatic aza ring group has 1-3.
It is described unsubstituted or by C as a preferred technical solution of the present invention1-C10Alkyl-substituted C3-C48 Aromatic aza ring group include: unsubstituted or by C1-C10Alkyl-substituted C7-C48Azepine condensed ring aromatic radical, not by Replace or by C1-C10Alkyl-substituted C7-C48The non-polycyclic aromatic base of azepine；
Miscellaneous element in the non-Azacyclyl of fragrance includes oxygen and/or sulphur.
As a preferred technical solution of the present invention, the R1、R2It is independently selected from: unsubstituted or by C1- C10Alkyl-substituted phenyl, azepine phenyl, unsubstituted or by C1-C10Alkyl-substituted xenyl, azepine xenyl, It is unsubstituted or by C1-C10Alkyl-substituted terphenyl, azepine terphenyl, unsubstituted or by C1-C10Alkane It is naphthalene that base replaces, azepine naphthalene, unsubstituted or by C1-C10Alkyl-substituted fluorenyl, unsubstituted or by C1-C10 Alkyl-substituted two fluorenyl of 9,9- spiral shell, unsubstituted or by C1-C10Alkyl-substituted carbazyl phenyl, unsubstituted Or by C1-C10Alkyl-substituted 9- phenyl carbazole base, unsubstituted or by C1-C10Alkyl-substituted dibenzofuran group One of, wherein the nitrogen in the azepine phenyl, azepine xenyl, azepine terphenyl and azepine naphthalene has 1-3 respectively It is a.
As a preferred technical solution of the present invention, the C1-C10Alkyl be independently selected from: methyl, ethyl, One of n-propyl, isopropyl, normal-butyl, isobutyl group, tert-butyl.
It as shown in table 1, is R1、R2Part-structure and title.
R in 1 general formula of table1、R2The part-structure and title of substituent group
As a preferred technical solution of the invention, derivative is as follows:
The second aspect of the present invention provides the preparation method of derivative of tri-arylamine group, includes the following steps:
1) amine derivant and bromine, iodine dihalo object feed intake according to molar ratio 1:1, and toluene and sodium tert-butoxide is added, and surpass Sound removes air, under nitrogen protection addition palladium acetate and tri-tert-butylphosphine, and heating reflux reaction 20~48 hours, wherein institute Amine derivant, toluene, sodium tert-butoxide, palladium acetate and tri-tert-butylphosphine is stated to feed intake according to molar ratio 1:2:3:3 ‰: 6 ‰；
2) after being cooled to room temperature, processing obtains intermediate；
3) 7,7- dimethyl -7,12- dihydro indeno [1,2-a] carbazole and the intermediate are thrown according to molar ratio 1:1 DMAC and potassium carbonate is added in material, and ultrasound removes air, and cuprous iodide and crown ether, heating reflux reaction are added under nitrogen protection 48~64 hours, wherein 7,7- dimethyl -7,12- dihydro indeno [1,2-a] carbazole, DMAC, potassium carbonate, cuprous iodide It feeds intake with crown ether according to molar ratio 1:2:2:1%:1%；
4) after being cooled to room temperature, processing obtains final products；
Synthetic route is as follows:
Processing mode as a preferred technical solution of the present invention, in step 2) are as follows: it is washed with water twice, liquid separation, It is oily mutually dry with anhydrous magnesium sulfate, active carbon is added and carries out decolorization, after then vacuum distillation removes solvent, recrystallization or Use pillar layer separation；
Processing mode in step 4) are as follows: be washed with water twice, filter, filter cake is dissolved in ethyl acetate and active carbon progress is added Decolorization, vacuum distillation, recrystallizes or uses pillar layer separation.
Third aspect of the present invention provides the application of derivative of tri-arylamine group, as organic electroluminescence device or organic Hole transport layer material, emitting layer material in solar cell device or out photosphere material.
The 4th aspect of the present invention provides a kind of organic assembly, and the organic assembly is organic electroluminescence device or has Machine solar cell device includes at least transport layer and/or luminescent layer and/or out photosphere, which is characterized in that the transport layer And/or luminescent layer and/or out photosphere using at least one derivative of tri-arylamine group provided by the present invention as material production and At.
Device of the present invention refers to based on aromatic amino-derivative of the invention or in the prior art has similar function The organic electroluminescence device of the compound preparation of energy, is such as applied to the hole mobile material for having in Light-Emitting Diode.
Compound provided by the invention is a kind of compound for having the non-co-planar structure of asymmetric rigidity and being rich in hole, Glass transition temperature with higher and wider energy rank adaptability, when good thermal stability effectively prevents vacuum evaporation It hoards to form no pin-hole defect, energy rank applicability appropriate effectively reduces the energy barrier obstacle during carrier transport, in turn Effectively improve the luminous efficiency and service life of device.When its as hole mobile material in use, in the prior art often The hole mobile materials such as NPB compare, and glass transition temperature is high, and hole transport efficiency is high, be prepared into device have compared with Low starting voltage and higher light emission luminance, is ideal hole mobile material.In addition, the series compound is as photosphere out When materials'use, the efficiency of organic electroluminescence device is increased substantially, and is preferably to go out photosphere material.
The OLED device that a kind of aromatic amino-derivative (250) is prepared as hole mobile material, issues sky blue coloured light Meanwhile start voltage, light emission luminance, current efficiency, luminous efficiency and glass transition temperature have respectively reached 2.8V, 30290cd/m2, 58.6cd/A, 50.3lm/W and 177 DEG C, superior performance is shown in OLED device.By a kind of arylamine Analog derivative (250) is used as hole mobile material, while the OLED device as the preparation of photosphere material out, by light emission luminance, stream Obvious results rate is respectively increased to 36940cd/m2, 61.4lm/W, significantly improve device light extraction efficiency.
The advantages of additional aspect of the invention, will be set forth in part in the description, and will partially become from the following description It obtains obviously, or practice is recognized through the invention.
Detailed description of the invention
Fig. 1 is with compound provided by the present invention (250) and to use N, bis- (3- methylbenzene of N'- diphenyl-N, N'- Base) the energy diagram of -1,1'- biphenyl -4,4'- diamines (TPD) as the device of hole mobile material；
Fig. 2 is wavelength-luminous intensity spy that compound provided by the present invention (250) prepare device as hole mobile material Linearity curve figure；
Fig. 3 be compound provided by the present invention (250) as hole mobile material prepare device 18 and respectively as Hole mobile material and photosphere material prepares the voltage-current density-luminosity response figure of device 21 out；
Fig. 4 be compound provided by the present invention (250) as hole mobile material prepare device 18 and respectively as Hole mobile material and out photosphere material prepare brightness-luminous efficiency performance diagram of device 21；
Specific embodiment
Below with reference to embodiment, the present invention will be further described.According to the technical essence of the invention to following embodiment institute Any simple modification, equivalent variations for making etc., still fall within the protection scope of technical solution of the present invention.The present invention is not limited to following realities Apply content described in example.
Embodiment 1
Compound (3) of the present invention can be synthesized by following method.
1) in 500ml there-necked flask, N- phenylnaphthalene -2- amine (21.93g, 100mmol) and the bromo- 4- iodine biphenyl of 4'- is added (35.90g, 100mmol), toluene (200mL) and sodium tert-butoxide (28.83g, 300 mmol), ultrasound remove air, protect in nitrogen Under shield, palladium acetate (0.07g, 0.3mmol) and tri-tert-butylphosphine (0.18g, 0.6mmol) is added, in 115 DEG C of heating reflux reactions 24 hours, TLC monitoring reaction was completed；
2) it after being cooled to room temperature, is washed with water twice, liquid separation, organic phase is dried with anhydrous magnesium sulfate, and filtering, filtrate adds Enter active carbon to carry out decolourizing 45 minutes at 115 DEG C, heat filtering, be used twice of re-crystallizing in ethyl acetate after filtrate decompression distillation and concentration, Finally obtain intermediate N (bromo- [1,1'- the biphenyl] -4- base of 4'-)-N- phenylnaphthalene -2- amine 35.13g, 78% yield；
3) in 250ml there-necked flask, addition 7,7- dimethyl -7,12- dihydro indeno [1,2-a] carbazole (14.17g, 50mmol), N- (bromo- [1,1'- the biphenyl] -4- base of 4'-)-N- phenylnaphthalene -2- amine (22.52g, 50mmol), DMAC (100mL) and Potassium carbonate (13.82g, 100mmol), ultrasound remove air, under nitrogen protection be added cuprous iodide (0.95g, 5mmol) and 18-C-6 (1.32g, 5mmol), in 150 DEG C heating reflux reaction 48 hours, TLC monitoring reaction complete；
4) it after being cooled to room temperature, is washed with water twice, filters, filter cake carries out 45 points of decoloration at 75 DEG C after being dissolved in ethyl acetate Clock, heat filtering, filtrate is with twice of re-crystallizing in ethyl acetate, dry final compound (3) 27.09g, 83% receipts under vacuum Rate.Compound (3) mass spectrum MS (APCI) (m/z)=652.70 (theoretical value 652.84).
Embodiment 2
Compound (12) of the present invention can be synthesized by following method.
1) in 500ml there-necked flask, N- phenylpyridine -4- amine (17.02g, 100mmol) and the bromo- 4- iodine connection of 4'- is added Benzene (35.90g, 100mmol), toluene (200mL) and sodium tert-butoxide (28.83g, 300 mmol), ultrasound removes air, in nitrogen Under protection, palladium acetate (0.07g, 0.3mmol) and tri-tert-butylphosphine (0.18g, 0.6mmol) is added, is heated to reflux at 115 DEG C anti- It answers 24 hours, TLC monitoring reaction is completed；
2) it after being cooled to room temperature, is washed with water twice, liquid separation, organic phase is dried with anhydrous magnesium sulfate, and filtering, filtrate adds Enter active carbon to carry out decolourizing 45 minutes at 115 DEG C, heat filtering, be used twice of re-crystallizing in ethyl acetate after filtrate decompression distillation and concentration, Finally obtain intermediate N (bromo- [1,1'- the biphenyl] -4- base of 4'-)-N- phenylpyridine -4- amine 30.89g, 77% yield；
3) in 250ml there-necked flask, addition 7,7- dimethyl -7,12- dihydro indeno [1,2-a] carbazole (14.17g, 50mmol), N- (bromo- [1,1'- the biphenyl] -4- base of 4'-)-N- phenylpyridine -4- amine (20.06g, 50mmol), DMAC (100mL) and potassium carbonate (13.82g, 100mmol), ultrasound remove air, under nitrogen protection be added cuprous iodide (0.95g, 5mmol) and 18-C-6 (1.32g, 5mmol), in 150 DEG C heating reflux reaction 48 hours, TLC monitoring reaction is completed；
4) it after being cooled to room temperature, is washed with water twice, filters, filter cake carries out 45 points of decoloration at 75 DEG C after being dissolved in ethyl acetate Clock, heat filtering, filtrate is with twice of re-crystallizing in ethyl acetate, dry final compound (12) 25.35g, 84% receipts under vacuum Rate.Compound (12) mass spectrum MS (APCI) (m/z)=603.46 (theoretical value 603.77).
Embodiment 3
Compound (22) of the present invention can be synthesized by following method.
1) in 500ml there-necked flask, addition 9- phenyl-N- (4- aminomethyl phenyl) -9H- carbazole -3- amine (34.84g, 100mmol) and the bromo- 4- iodine biphenyl (35.90g, 100mmol) of 4'-, toluene (200mL) and sodium tert-butoxide (28.83g, 300mmol), ultrasound removes air, under nitrogen protection, palladium acetate (0.07g, 0.3mmol) and tri-tert-butylphosphine is added (0.18g, 0.6mmol), 115 DEG C heating reflux reaction 24 hours, TLC monitoring reaction complete；
2) it after being cooled to room temperature, is washed with water twice, liquid separation, organic phase is dried with anhydrous magnesium sulfate, and filtering, filtrate adds Enter active carbon to carry out decolourizing 45 minutes at 115 DEG C, heat filtering, be used twice of re-crystallizing in ethyl acetate after filtrate decompression distillation and concentration, Finally obtain intermediate N (bromo- [1,1'- the biphenyl] -4- base of 4'-) -9- phenyl-N- (4- aminomethyl phenyl) -9H- carbazole -3- amine 43.47g, 75% yield；
3) in 250ml there-necked flask, addition 7,7- dimethyl -7,12- dihydro indeno [1,2-a] carbazole (14.17g, 50mmol), N- (bromo- [1,1'- the biphenyl] -4- base of 4'-) -9- phenyl-N- (4- aminomethyl phenyl) -9H- carbazole -3- amine (28.98g, 50mmol), DMAC (100mL) and potassium carbonate (13.82g, 100mmol), ultrasound remove air, under nitrogen protection Cuprous iodide (0.95g, 5mmol) and 18-C-6 (1.32g, 5mmol) is added, in 150 DEG C heating reflux reaction 48 hours, TLC Monitoring reaction is completed；
4) it after being cooled to room temperature, is washed with water twice, filters, filter cake carries out 45 points of decoloration at 75 DEG C after being dissolved in ethyl acetate Clock, heat filtering, filtrate is with twice of re-crystallizing in ethyl acetate, dry final compound (22) 31.67g, 81% receipts under vacuum Rate.Compound (22) mass spectrum MS (APCI) (m/z)=782.12 (theoretical value 782.00).
Embodiment 4
Compound (44) of the present invention can be synthesized by following method.
1) in 500ml there-necked flask, addition N- (4- tert-butyl-phenyl) dibenzofurans -4- amine (31.54g, 100mmol) and the bromo- 4- iodine biphenyl (35.90g, 100mmol) of 4'-, toluene (200mL) and sodium tert-butoxide (28.83g, 300mmol), ultrasound removes air, under nitrogen protection, palladium acetate (0.07g, 0.3mmol) and tri-tert-butylphosphine is added (0.18g, 0.6mmol), 115 DEG C heating reflux reaction 24 hours, TLC monitoring reaction complete；
2) it after being cooled to room temperature, is washed with water twice, liquid separation, organic phase is dried with anhydrous magnesium sulfate, and filtering, filtrate adds Enter active carbon to carry out decolourizing 45 minutes at 115 DEG C, heat filtering, be used twice of re-crystallizing in ethyl acetate after filtrate decompression distillation and concentration, Finally obtain intermediate N (bromo- [1,1'- the biphenyl] -4- base of 4'-)-N- (4- tert-butyl-phenyl) dibenzofurans -4- amine 40.98g, 75% yield；
3) in 250ml there-necked flask, addition 7,7- dimethyl -7,12- dihydro indeno [1,2-a] carbazole (14.17g, 50mmol), N- (bromo- [1,1'- the biphenyl] -4- base of 4'-)-N- (4- tert-butyl-phenyl) dibenzofurans -4- amine (27.32g, 50mmol), DMAC (100mL) and potassium carbonate (13.82g, 100mmol), ultrasound remove air, iodate are added under nitrogen protection Cuprous (0.95g, 5mmol) and 18-C-6 (1.32g, 5mmol), in 150 DEG C heating reflux reaction 48 hours, TLC monitoring reaction It completes；
4) it after being cooled to room temperature, is washed with water twice, filters, filter cake carries out 45 points of decoloration at 75 DEG C after being dissolved in ethyl acetate Clock, heat filtering, filtrate is with twice of re-crystallizing in ethyl acetate, dry final compound (44) 30.71g, 82% receipts under vacuum Rate.Compound (44) mass spectrum MS (APCI) (m/z)=748.62 (theoretical value 748.97).
Embodiment 5
Compound (53) of the present invention can be synthesized by following method.
1) in 500ml there-necked flask, N- (4- tert-butyl-phenyl)-[1,1':3', 1 "-terphenyl] -5'- amine is added The bromo- 4- iodine biphenyl (35.90g, 100mmol) of (37.75g, 100mmol) and 4'-, toluene (200mL) and sodium tert-butoxide (28.83g, 300mmol), ultrasound remove air, under nitrogen protection, palladium acetate (0.07g, 0.3mmol) and three tertiary fourths are added Base phosphine (0.18g, 0.6mmol), 115 DEG C heating reflux reaction 24 hours, TLC monitoring reaction complete；
2) it after being cooled to room temperature, is washed with water twice, liquid separation, organic phase is dried with anhydrous magnesium sulfate, and filtering, filtrate adds Enter active carbon to carry out decolourizing 45 minutes at 115 DEG C, heat filtering, be used twice of re-crystallizing in ethyl acetate after filtrate decompression distillation and concentration, Finally obtain intermediate N (bromo- [1,1'- the biphenyl] -4- base of 4'-)-N- (4- tert-butyl-phenyl)-[1,1':3', 1 "-three connection Benzene] -5'- amine 46.25g, 76% yield；
3) in 250ml there-necked flask, addition 7,7- dimethyl -7,12- dihydro indeno [1,2-a] carbazole (14.17g, 50mmol), N- (bromo- [1,1'- the biphenyl] -4- base of 4'-)-N- (4- tert-butyl-phenyl)-[1,1':3', 1 "-terphenyl] -5'- Amine (30.43g, 50mmol), DMAC (100mL) and potassium carbonate (13.82g, 100mmol), ultrasound remove air, protect in nitrogen Lower addition cuprous iodide (0.95g, 5mmol) of shield and 18-C-6 (1.32g, 5mmol) are small in 150 DEG C of heating reflux reactions 48 When, TLC monitoring reaction is completed；
4) it after being cooled to room temperature, is washed with water twice, filters, filter cake carries out 45 points of decoloration at 75 DEG C after being dissolved in ethyl acetate Clock, heat filtering, filtrate is with twice of re-crystallizing in ethyl acetate, dry final compound (53) 32.44g, 80% receipts under vacuum Rate.Compound (53) mass spectrum MS (APCI) (m/z)=811.42 (theoretical value 811.09).
Embodiment 6
Compound (59) of the present invention can be synthesized by following method.
1) in 500ml there-necked flask, addition 3'- isopropyl-N- phenyl-[1,1'- biphenyl] -4- amine (28.74g, 100mmol) and iodo- 1, the 1'- biphenyl (35.90g, 100mmol) of the bromo- 3- of 4'-, toluene (200mL) and sodium tert-butoxide (28.83g, 300mmol), ultrasound removes air, under nitrogen protection, palladium acetate (0.07g, 0.3mmol) and tri-tert-butylphosphine is added (0.18g, 0.6mmol), 115 DEG C heating reflux reaction 24 hours, TLC monitoring reaction complete；
2) it after being cooled to room temperature, is washed with water twice, liquid separation, organic phase is dried with anhydrous magnesium sulfate, and filtering, filtrate adds Enter active carbon to carry out decolourizing 45 minutes at 115 DEG C, heat filtering, be used twice of re-crystallizing in ethyl acetate after filtrate decompression distillation and concentration, Finally obtain the bromo- N- of intermediate 4'- (3'- isopropyl-[1,1'- biphenyl] -4- base)-N- phenyl-[1,1'- biphenyl] -3- amine 39.92g, 77% yield；
3) in 250ml there-necked flask, addition 7,7- dimethyl -7,12- dihydro indeno [1,2-a] carbazole (14.17g, 50mmol), the bromo- N- of 4'- (3'- isopropyl-[1,1'- biphenyl] -4- base)-N- phenyl-[1,1'- biphenyl] -3- amine (25.92g, 50mmol), DMAC (100mL) and potassium carbonate (13.82g, 100mmol), ultrasound remove air, iodate are added under nitrogen protection Cuprous (0.95g, 5mmol) and 18-C-6 (1.32g, 5mmol), in 150 DEG C heating reflux reaction 48 hours, TLC monitoring reaction It completes；
4) it after being cooled to room temperature, is washed with water twice, filters, filter cake carries out 45 points of decoloration at 75 DEG C after being dissolved in ethyl acetate Clock, heat filtering, filtrate is with twice of re-crystallizing in ethyl acetate, dry final compound (59) 29.92g, 83% receipts under vacuum Rate.Compound (59) mass spectrum MS (APCI) (m/z)=720.62 (theoretical value 720.96).
Embodiment 7
Compound (67) of the present invention can be synthesized by following method.
1) in 500ml there-necked flask, be added 3- (9H- carbazole -9- base)-N- phenylaniline (33.44g, 100mmol) and Iodo- 1, the 1'- biphenyl (35.90g, 100mmol) of the bromo- 3- of 4'-, toluene (200mL) and sodium tert-butoxide (28.83g, 300mmol), Ultrasound removes air, under nitrogen protection, be added palladium acetate (0.07g, 0.3mmol) and tri-tert-butylphosphine (0.18g, 0.6mmol), 115 DEG C heating reflux reaction 24 hours, TLC monitoring reaction complete；
2) it after being cooled to room temperature, is washed with water twice, liquid separation, organic phase is dried with anhydrous magnesium sulfate, and filtering, filtrate adds Enter active carbon to carry out decolourizing 45 minutes at 115 DEG C, heat filtering, be used twice of re-crystallizing in ethyl acetate after filtrate decompression distillation and concentration, Intermediate N (3- (9H- carbazole -9- base) phenyl) the bromo- N- phenyl-of -4'- [1,1'- biphenyl] -3- amine 42.40g is finally obtained, 75% yield；
3) in 250ml there-necked flask, addition 7,7- dimethyl -7,12- dihydro indeno [1,2-a] carbazole (14.17g, 50mmol), N- (3- (9H- carbazole -9- base) phenyl) the bromo- N- phenyl-of -4'- [1,1'- biphenyl] -3- amine (28.27g, 50mmol), DMAC (100mL) and potassium carbonate (13.82g, 100mmol), ultrasound remove air, iodate are added under nitrogen protection Cuprous (0.95g, 5mmol) and 18-C-6 (1.32g, 5mmol), in 150 DEG C heating reflux reaction 48 hours, TLC monitoring reaction It completes；
4) it after being cooled to room temperature, is washed with water twice, filters, filter cake carries out 45 points of decoloration at 75 DEG C after being dissolved in ethyl acetate Clock, heat filtering, filtrate is with twice of re-crystallizing in ethyl acetate, dry final compound (67) 31.10g, 81% receipts under vacuum Rate.Compound (67) mass spectrum MS (APCI) (m/z)=767.81 (theoretical value 767.98).
Embodiment 8
Compound (84) of the present invention can be synthesized by following method.
1) in 500ml there-necked flask, N- (4- aminomethyl phenyl) pyridine -4- amine (18.42g, 100mmol) and 4'- is added Bromo- iodo- 1, the 1'- biphenyl (35.90g, 100mmol) of 3-, toluene (200mL) and sodium tert-butoxide (28.83 g, 300mmol), ultrasound Air is removed, under nitrogen protection, palladium acetate (0.07g, 0.3mmol) and tri-tert-butylphosphine (0.18g, 0.6mmol) is added, 115 DEG C heating reflux reaction 24 hours, TLC monitoring reaction complete；
2) it after being cooled to room temperature, is washed with water twice, liquid separation, organic phase is dried with anhydrous magnesium sulfate, and filtering, filtrate adds Enter active carbon to carry out decolourizing 45 minutes at 115 DEG C, heat filtering, be used twice of re-crystallizing in ethyl acetate after filtrate decompression distillation and concentration, Finally obtain intermediate N (bromo- [1,1'- the biphenyl] -3- base of 4'-)-N- (4- aminomethyl phenyl) pyridine -4- amine 31.97g, 77% Yield；
3) in 250ml there-necked flask, addition 7,7- dimethyl -7,12- dihydro indeno [1,2-a] carbazole (14.17g, 50mmol), N- (bromo- [1,1'- the biphenyl] -3- base of 4'-)-N- (4- aminomethyl phenyl) pyridine -4- amine (20.76g, 50mmol), DMAC (100mL) and potassium carbonate (13.82g, 100mmol), ultrasound remove air, cuprous iodide are added under nitrogen protection (0.95g, 5mmol) and 18-C-6 (1.32g, 5mmol), in 150 DEG C heating reflux reaction 48 hours, TLC monitoring has reacted At；
4) it after being cooled to room temperature, is washed with water twice, filters, filter cake carries out 45 points of decoloration at 75 DEG C after being dissolved in ethyl acetate Clock, heat filtering, filtrate is with twice of re-crystallizing in ethyl acetate, dry final compound (84) 25.95g, 84% receipts under vacuum Rate.Compound (84) mass spectrum MS (APCI) (m/z)=617.65 (theoretical value 617.80).
Embodiment 9
Compound (98) of the present invention can be synthesized by following method.
1) in 500ml there-necked flask, addition N- (4- tert-butyl-phenyl) dibenzofurans -4- amine (31.54g, 100mmol) and iodo- 1, the 1'- biphenyl (35.90g, 100mmol) of the bromo- 3- of 4'-, toluene (200mL) and sodium tert-butoxide (28.83g, 300mmol), ultrasound removes air, under nitrogen protection, palladium acetate (0.07g, 0.3mmol) and tri-tert-butylphosphine is added (0.18g, 0.6mmol), 115 DEG C heating reflux reaction 24 hours, TLC monitoring reaction complete；
2) it after being cooled to room temperature, is washed with water twice, liquid separation, organic phase is dried with anhydrous magnesium sulfate, and filtering, filtrate adds Enter active carbon to carry out decolourizing 45 minutes at 115 DEG C, heat filtering, be used twice of re-crystallizing in ethyl acetate after filtrate decompression distillation and concentration, Finally obtain intermediate N (bromo- [1,1'- the biphenyl] -3- base of 4'-)-N- (4- tert-butyl-phenyl) dibenzofurans -4- amine 40.98g, 75% yield；
3) in 250ml there-necked flask, addition 7,7- dimethyl -7,12- dihydro indeno [1,2-a] carbazole (14.17g, 50mmol), N- (bromo- [1,1'- the biphenyl] -3- base of 4'-)-N- (4- tert-butyl-phenyl) dibenzofurans -4- amine (27.32g, 50mmol), DMAC (100mL) and potassium carbonate (13.82g, 100mmol), ultrasound remove air, iodate are added under nitrogen protection Cuprous (0.95g, 5mmol) and 18-C-6 (1.32g, 5mmol), in 150 DEG C heating reflux reaction 48 hours, TLC monitoring reaction It completes；
4) it after being cooled to room temperature, is washed with water twice, filters, filter cake carries out 45 points of decoloration at 75 DEG C after being dissolved in ethyl acetate Clock, heat filtering, filtrate is with twice of re-crystallizing in ethyl acetate, dry final compound (98) 30.33g, 81% receipts under vacuum Rate.Compound (98) mass spectrum MS (APCI) (m/z)=748.66 (theoretical value 748.97).
Embodiment 10
Compound (108) of the present invention can be synthesized by following method.
1) in 500ml there-necked flask, addition 4- tert-butyl-n-(4- (pyridin-4-yl) phenyl) aniline (30.24g, 100mmol) and iodo- 1, the 1'- biphenyl (35.90g, 100mmol) of the bromo- 3- of 4'-, toluene (200mL) and sodium tert-butoxide (28.83g, 300mmol), ultrasound removes air, under nitrogen protection, palladium acetate (0.07g, 0.3mmol) and tri-tert-butylphosphine is added (0.18g, 0.6mmol), 115 DEG C heating reflux reaction 24 hours, TLC monitoring reaction complete；
2) it after being cooled to room temperature, is washed with water twice, liquid separation, organic phase is dried with anhydrous magnesium sulfate, and filtering, filtrate adds Enter active carbon to carry out decolourizing 45 minutes at 115 DEG C, heat filtering, be used twice of re-crystallizing in ethyl acetate after filtrate decompression distillation and concentration, Finally obtain the bromo- N- of intermediate 4'- (4- tert-butyl-phenyl)-N- (4- (pyridin-4-yl) phenyl)-[1,1'- biphenyl] -3- amine 40.00g, 75% yield；
3) in 250ml there-necked flask, addition 7,7- dimethyl -7,12- dihydro indeno [1,2-a] carbazole (14.17g, 50mmol), the bromo- N- of 4'- (4- tert-butyl-phenyl)-N- (4- (pyridin-4-yl) phenyl)-[1,1'- biphenyl] -3- amine (26.67g, 50mmol), DMAC (100mL) and potassium carbonate (13.82g, 100mmol), ultrasound remove air, under nitrogen protection Cuprous iodide (0.95g, 5mmol) and 18-C-6 (1.32g, 5mmol) is added, in 150 DEG C heating reflux reaction 48 hours, TLC Monitoring reaction is completed；
4) it after being cooled to room temperature, is washed with water twice, filters, filter cake carries out 45 points of decoloration at 75 DEG C after being dissolved in ethyl acetate Clock, heat filtering, filtrate is with twice of re-crystallizing in ethyl acetate, dry final compound (108) 30.54g, 83% receipts under vacuum Rate.Compound (108) mass spectrum MS (APCI) (m/z)=735.71 (theoretical value 735.98).
Embodiment 11
Compound (131) of the present invention can be synthesized by following method.
1) in 500ml there-necked flask, addition 4- methyl-N- (4- (pyrimidine -5- base) phenyl) aniline (26.13g, 100mmol) and iodo- 1, the 1'- biphenyl (35.90g, 100mmol) of the bromo- 4'- of 3-, toluene (200mL) and sodium tert-butoxide (28.83g, 300mmol), ultrasound removes air, under nitrogen protection, palladium acetate (0.07g, 0.3mmol) and tri-tert-butylphosphine is added (0.18g, 0.6mmol), 115 DEG C heating reflux reaction 24 hours, TLC monitoring reaction complete；
2) it after being cooled to room temperature, is washed with water twice, liquid separation, organic phase is dried with anhydrous magnesium sulfate, and filtering, filtrate adds Enter active carbon to carry out decolourizing 45 minutes at 115 DEG C, heat filtering, be used twice of re-crystallizing in ethyl acetate after filtrate decompression distillation and concentration, Finally obtain the bromo- N- of intermediate 3'- (4- (pyrimidine -5- base) phenyl)-N- (4- aminomethyl phenyl)-[1,1'- biphenyl] -4- amine 36.93g, 75% yield；
3) in 250ml there-necked flask, addition 7,7- dimethyl -7,12- dihydro indeno [1,2-a] carbazole (14.17g, 50mmol), the bromo- N- of 3'- (4- (pyrimidine -5- base) phenyl)-N- (4- aminomethyl phenyl)-[1,1'- biphenyl] -4- amine (24.62g, 50mmol), DMAC (100mL) and potassium carbonate (13.82g, 100mmol), ultrasound remove air, iodate are added under nitrogen protection Cuprous (0.95g, 5mmol) and 18-C-6 (1.32g, 5mmol), in 150 DEG C heating reflux reaction 48 hours, TLC monitoring reaction It completes；
4) it after being cooled to room temperature, is washed with water twice, filters, filter cake carries out 45 points of decoloration at 75 DEG C after being dissolved in ethyl acetate Clock, heat filtering, filtrate is with twice of re-crystallizing in ethyl acetate, dry final compound (131) 28.49g, 82% receipts under vacuum Rate.Compound (131) mass spectrum MS (APCI) (m/z)=694.67 (theoretical value 694.88).
Embodiment 12
Compound (147) of the present invention can be synthesized by following method.
1) in 500ml there-necked flask, N- (4- tert-butyl-phenyl) isoquinolin -6- amine (27.64,100mmol) and 3- is added Bromo- iodo- 1, the 1'- biphenyl (35.90g, 100mmol) of 4'-, toluene (200mL) and sodium tert-butoxide (28.83g, 300mmol) surpass Sound removes air, under nitrogen protection, palladium acetate (0.07g, 0.3mmol) and tri-tert-butylphosphine (0.18g, 0.6mmol) is added, 115 DEG C heating reflux reaction 24 hours, TLC monitoring reaction complete；
2) it after being cooled to room temperature, is washed with water twice, liquid separation, organic phase is dried with anhydrous magnesium sulfate, and filtering, filtrate adds Enter active carbon to carry out decolourizing 45 minutes at 115 DEG C, heat filtering, be used twice of re-crystallizing in ethyl acetate after filtrate decompression distillation and concentration, Intermediate N (bromo- [1,1'- the biphenyl] -4- base of 3'-)-N- (4- tert-butyl-phenyl) isoquinolin -6- amine 38.56g is finally obtained, 76% yield；
3) in 250ml there-necked flask, addition 7,7- dimethyl -7,12- dihydro indeno [1,2-a] carbazole (14.17g, 50mmol), N- (bromo- [1,1'- the biphenyl] -4- base of 3'-)-N- (4- tert-butyl-phenyl) isoquinolin -6- amine (25.37g, 50mmol), DMAC (100mL) and potassium carbonate (13.82g, 100mmol), ultrasound remove air, iodate are added under nitrogen protection Cuprous (0.95g, 5mmol) and 18-C-6 (1.32g, 5mmol), in 150 DEG C heating reflux reaction 48 hours, TLC monitoring reaction It completes；
4) it after being cooled to room temperature, is washed with water twice, filters, filter cake carries out 45 points of decoloration at 75 DEG C after being dissolved in ethyl acetate Clock, heat filtering, filtrate is with twice of re-crystallizing in ethyl acetate, dry final compound (147) 28.40g, 80% receipts under vacuum Rate.Compound (147) mass spectrum MS (APCI) (m/z)=709.65 (theoretical value 709.94).
Embodiment 13
Compound (157) of the present invention can be synthesized by following method.
1) in 500ml there-necked flask, addition N- (4- tert-butyl-phenyl) -3- (9H- carbazole -9- base) aniline (39.05, 100mmol) and iodo- 1, the 1'- biphenyl (35.90g, 100mmol) of the bromo- 4'- of 3-, toluene (200mL) and sodium tert-butoxide (28.83g, 300mmol), ultrasound removes air, under nitrogen protection, palladium acetate (0.07g, 0.3mmol) and tri-tert-butylphosphine is added (0.18g, 0.6mmol), 115 DEG C heating reflux reaction 24 hours, TLC monitoring reaction complete；
2) it after being cooled to room temperature, is washed with water twice, liquid separation, organic phase is dried with anhydrous magnesium sulfate, and filtering, filtrate adds Enter active carbon to carry out decolourizing 45 minutes at 115 DEG C, heat filtering, be used twice of re-crystallizing in ethyl acetate after filtrate decompression distillation and concentration, Finally obtain intermediate N (3- (9H- carbazole -9- base) phenyl) bromo- N- of -3'- (4- tert-butyl-phenyl)-[1,1'- biphenyl] -4- Amine 47.24g, 76% yield；
3) in 250ml there-necked flask, addition 7,7- dimethyl -7,12- dihydro indeno [1,2-a] carbazole (14.17g, 50mmol), N- (3- (9H- carbazole -9- base) phenyl) the bromo- N- of -3'- (4- tert-butyl-phenyl)-[1,1'- biphenyl] -4- amine (31.08g, 50mmol), DMAC (100mL) and potassium carbonate (13.82g, 100mmol), ultrasound remove air, under nitrogen protection Cuprous iodide (0.95g, 5mmol) and 18-C-6 (1.32g, 5mmol) is added, in 150 DEG C heating reflux reaction 48 hours, TLC Monitoring reaction is completed；
4) it after being cooled to room temperature, is washed with water twice, filters, filter cake carries out 45 points of decoloration at 75 DEG C after being dissolved in ethyl acetate Clock, heat filtering, filtrate is with twice of re-crystallizing in ethyl acetate, dry final compound (157) 28.40g, 81% receipts under vacuum Rate.Compound (157) mass spectrum MS (APCI) (m/z)=824.39 (theoretical value 824.08).
Embodiment 14
Compound (178) of the present invention can be synthesized by following method.
1) in 500ml there-necked flask, N- phenyl dibenzofurans -3- amine (25.93,100mmol) and the bromo- 3'- of 3- is added Iodo- 1,1'- biphenyl (35.90g, 100mmol), toluene (200mL) and sodium tert-butoxide (28.83 g, 300mmol), ultrasound remove Under nitrogen protection palladium acetate (0.07g, 0.3mmol) and tri-tert-butylphosphine (0.18g, 0.6mmol) is added, 115 in air DEG C heating reflux reaction 24 hours, TLC monitoring reaction was completed；
2) it after being cooled to room temperature, is washed with water twice, liquid separation, organic phase is dried with anhydrous magnesium sulfate, and filtering, filtrate adds Enter active carbon to carry out decolourizing 45 minutes at 115 DEG C, heat filtering, be used twice of re-crystallizing in ethyl acetate after filtrate decompression distillation and concentration, Finally obtain intermediate N (bromo- [1,1'- the biphenyl] -3- base of 3'-)-N- phenyl dibenzofurans -3- amine 36.78g, 75% Yield；
3) in 250ml there-necked flask, addition 7,7- dimethyl -7,12- dihydro indeno [1,2-a] carbazole (14.17g, 50mmol), N- (bromo- [1,1'- the biphenyl] -3- base of 3'-)-N- phenyl dibenzofurans -3- amine (24.52g, 50mmol), DMAC (100mL) and potassium carbonate (13.82g, 100mmol), ultrasound remove air, under nitrogen protection be added cuprous iodide (0.95g, 5mmol) and 18-C-6 (1.32g, 5mmol), in 150 DEG C heating reflux reaction 48 hours, TLC monitoring reaction is completed；
4) it after being cooled to room temperature, is washed with water twice, filters, filter cake carries out 45 points of decoloration at 75 DEG C after being dissolved in ethyl acetate Clock, heat filtering, filtrate is with twice of re-crystallizing in ethyl acetate, dry final compound (178) 28.41g, 82% receipts under vacuum Rate.Compound (178) mass spectrum MS (APCI) (m/z)=692.71 (theoretical value 692.86).
Embodiment 15
Compound (191) of the present invention can be synthesized by following method.
1) in 500ml there-necked flask, 4- tert-butyl-n-(4- aminomethyl phenyl) aniline (23.94,100mmol) and 3- is added Bromo- iodo- 1, the 1'- biphenyl (35.90g, 100mmol) of 3'-, toluene (200mL) and sodium tert-butoxide (28.83g, 300mmol) surpass Sound removes air, under nitrogen protection, palladium acetate (0.07g, 0.3mmol) and tri-tert-butylphosphine (0.18g, 0.6mmol) is added, 115 DEG C heating reflux reaction 24 hours, TLC monitoring reaction complete；
2) it after being cooled to room temperature, is washed with water twice, liquid separation, organic phase is dried with anhydrous magnesium sulfate, and filtering, filtrate adds Enter active carbon to carry out decolourizing 45 minutes at 115 DEG C, heat filtering, be used twice of re-crystallizing in ethyl acetate after filtrate decompression distillation and concentration, The bromo- N- of intermediate 3'- (4- tert-butyl-phenyl)-N- (4- aminomethyl phenyl)-[1,1'- biphenyl] -3- amine 36.69g is finally obtained, 78% yield；
3) in 250ml there-necked flask, addition 7,7- dimethyl -7,12- dihydro indeno [1,2-a] carbazole (14.17g, 50mmol), the bromo- N- of 3'- (4- tert-butyl-phenyl)-N- (4- aminomethyl phenyl)-[1,1'- biphenyl] -3- amine (23.52g, 50mmol), DMAC (100mL) and potassium carbonate (13.82g, 100mmol), ultrasound remove air, iodate are added under nitrogen protection Cuprous (0.95g, 5mmol) and 18-C-6 (1.32g, 5mmol), in 150 DEG C heating reflux reaction 48 hours, TLC monitoring reaction It completes；
4) it after being cooled to room temperature, is washed with water twice, filters, filter cake carries out 45 points of decoloration at 75 DEG C after being dissolved in ethyl acetate Clock, heat filtering, filtrate is with twice of re-crystallizing in ethyl acetate, dry final compound (191) 28.26g, 84% receipts under vacuum Rate.Compound (191) mass spectrum MS (APCI) (m/z)=672.35 (theoretical value 672.92).
Embodiment 16
Compound (211) of the present invention can be synthesized by following method.
1) in 500ml there-necked flask, addition N- (4- tert-butyl-phenyl) -3- (9H- carbazole -9- base) aniline (23.94, 100mmol) and iodo- 1, the 1'- biphenyl (39.05g, 100mmol) of the bromo- 3'- of 3-, toluene (200mL) and sodium tert-butoxide (28.83g, 300mmol), ultrasound removes air, under nitrogen protection, palladium acetate (0.07g, 0.3mmol) and tri-tert-butylphosphine is added (0.18g, 0.6mmol), 115 DEG C heating reflux reaction 24 hours, TLC monitoring reaction complete；
2) it after being cooled to room temperature, is washed with water twice, liquid separation, organic phase is dried with anhydrous magnesium sulfate, and filtering, filtrate adds Enter active carbon to carry out decolourizing 45 minutes at 115 DEG C, heat filtering, be used twice of re-crystallizing in ethyl acetate after filtrate decompression distillation and concentration, Finally obtain intermediate N (3- (9H- carbazole -9- base) phenyl) bromo- N- of -3'- (4- tert-butyl-phenyl)-[1,1'- biphenyl] -3- Amine 46.62g, 75% yield；
3) in 250ml there-necked flask, addition 7,7- dimethyl -7,12- dihydro indeno [1,2-a] carbazole (14.17g, 50mmol), N- (3- (9H- carbazole -9- base) phenyl) the bromo- N- of -3'- (4- tert-butyl-phenyl)-[1,1'- biphenyl] -3- amine (31.08g, 50mmol), DMAC (100mL) and potassium carbonate (13.82g, 100mmol), ultrasound remove air, under nitrogen protection Cuprous iodide (0.95g, 5mmol) and 18-C-6 (1.32g, 5mmol) is added, in 150 DEG C heating reflux reaction 48 hours, TLC Monitoring reaction is completed；
4) it after being cooled to room temperature, is washed with water twice, filters, filter cake carries out 45 points of decoloration at 75 DEG C after being dissolved in ethyl acetate Clock, heat filtering, filtrate is with twice of re-crystallizing in ethyl acetate, dry final compound (211) 33.37g, 81% receipts under vacuum Rate.Compound (211) mass spectrum MS (APCI) (m/z)=824.17 (theoretical value 824.08).
Embodiment 17
Compound (221) of the present invention can be synthesized by following method.
1) in 500ml there-necked flask, two ([1,1'- biphenyl] -4- base) amine (32.14g, 100mmol) is added and 4- is bromo- Iodo- 1, the 1'- biphenyl (39.05g, 100mmol) of 4'-, toluene (200mL) and sodium tert-butoxide (28.83 g, 300mmol), ultrasound is removed Air is removed, under nitrogen protection, palladium acetate (0.07g, 0.3mmol) and tri-tert-butylphosphine (0.18g, 0.6mmol) is added, 115 DEG C heating reflux reaction 24 hours, TLC monitoring reaction complete；
2) it after being cooled to room temperature, is washed with water twice, liquid separation, organic phase is dried with anhydrous magnesium sulfate, and filtering, filtrate adds Enter active carbon to carry out decolourizing 45 minutes at 115 DEG C, heat filtering, be used twice of re-crystallizing in ethyl acetate after filtrate decompression distillation and concentration, Finally obtain intermediate N, N- bis- ([1,1'- biphenyl] -4- base) bromo- [1,1'- biphenyl] -4- amine 41.99g of -4'-, 76% receipts Rate；
3) in 250ml there-necked flask, addition 7,7- dimethyl -7,12- dihydro indeno [1,2-a] carbazole (14.17g, 50mmol), bromo- [1,1'- the biphenyl] -4- amine (27.63g, 50mmol) of N, N- bis- ([1,1'- biphenyl] -4- base) -4'-, DMAC (100mL) and potassium carbonate (13.82g, 100mmol), ultrasound remove air, under nitrogen protection be added cuprous iodide (0.95g, 5mmol) and 18-C-6 (1.32g, 5mmol), in 150 DEG C heating reflux reaction 48 hours, TLC monitoring reaction is completed；
4) it after being cooled to room temperature, is washed with water twice, filters, filter cake carries out 45 points of decoloration at 75 DEG C after being dissolved in ethyl acetate Clock, heat filtering, filtrate is with twice of re-crystallizing in ethyl acetate, dry final compound (221) 31.33g, 83% receipts under vacuum Rate.Compound (221) mass spectrum MS (APCI) (m/z)=754.77 (theoretical value 754.98).
Embodiment 18
Compound (227) of the present invention can be synthesized by following method.
1) in 500ml there-necked flask, N- ([1,1'- biphenyl] -4- base) -9,9- dimethyl -9H- fluorenes -2- amine is added Iodo- 1, the 1'- biphenyl (39.05g, 100mmol) of (36.15g, 100mmol) and the bromo- 4'- of 4-, toluene (200mL) and sodium tert-butoxide (28.83g, 300mmol), ultrasound remove air, under nitrogen protection, palladium acetate (0.07g, 0.3mmol) and three tertiary fourths are added Base phosphine (0.18g, 0.6mmol), 115 DEG C heating reflux reaction 24 hours, TLC monitoring reaction complete；
2) it after being cooled to room temperature, is washed with water twice, liquid separation, organic phase is dried with anhydrous magnesium sulfate, and filtering, filtrate adds Enter active carbon to carry out decolourizing 45 minutes at 115 DEG C, heat filtering, be used twice of re-crystallizing in ethyl acetate after filtrate decompression distillation and concentration, Finally obtain intermediate N ([1,1'- biphenyl] -4- base)-N- (bromo- [1,1'- the biphenyl] -4- base of 4'-) -9,9- dimethyl -9H- Fluorenes -2- amine 45.63g, 77% yield；
3) in 250ml there-necked flask, addition 7,7- dimethyl -7,12- dihydro indeno [1,2-a] carbazole (14.17g, 50mmol), N- ([1,1'- biphenyl] -4- base)-N- (bromo- [1,1'- the biphenyl] -4- base of 4'-) -9,9- dimethyl -9H- fluorenes -2- amine (29.63g, 50mmol), DMAC (100mL) and potassium carbonate (13.82g, 100mmol), ultrasound removes air, in nitrogen protection Lower addition cuprous iodide (0.95g, 5mmol) and 18-C-6 (1.32g, 5mmol), in 150 DEG C heating reflux reaction 48 hours, TLC monitoring reaction is completed；
4) it after being cooled to room temperature, is washed with water twice, filters, filter cake carries out 45 points of decoloration at 75 DEG C after being dissolved in ethyl acetate Clock, heat filtering, filtrate is with twice of re-crystallizing in ethyl acetate, dry final compound (227) 32.20g, 81% receipts under vacuum Rate.Compound (227) mass spectrum MS (APCI) (m/z)=795.22 (theoretical value 795.04).
Embodiment 19
Compound (248) of the present invention can be synthesized by following method.
1) in 500ml there-necked flask, addition N- (2- (9H- carbazole -9- base) phenyl) isoquinolin -6- amine (38.54g, 100mmol) and iodo- 1, the 1'- biphenyl (39.05g, 100mmol) of the bromo- 4'- of 4-, toluene (200mL) and sodium tert-butoxide (28.83g, 300mmol), ultrasound removes air, under nitrogen protection, palladium acetate (0.07g, 0.3mmol) and tri-tert-butylphosphine is added (0.18g, 0.6mmol), 115 DEG C heating reflux reaction 24 hours, TLC monitoring reaction complete；
2) it after being cooled to room temperature, is washed with water twice, liquid separation, organic phase is dried with anhydrous magnesium sulfate, and filtering, filtrate adds Enter active carbon to carry out decolourizing 45 minutes at 115 DEG C, heat filtering, be used twice of re-crystallizing in ethyl acetate after filtrate decompression distillation and concentration, Finally obtain intermediate N (2- (9H- carbazole -9- base) phenyl)-N- (bromo- [1,1'- the biphenyl] -4- base of 4'-) isoquinolin -6- amine 45.62g, 74% yield；
3) in 250ml there-necked flask, addition 7,7- dimethyl -7,12- dihydro indeno [1,2-a] carbazole (14.17g, 50mmol), N- (2- (9H- carbazole -9- base) phenyl)-N- (bromo- [1,1'- the biphenyl] -4- base of 4'-) isoquinolin -6- amine (30.83g, 50mmol), DMAC (100mL) and potassium carbonate (13.82g, 100mmol), ultrasound remove air, under nitrogen protection Cuprous iodide (0.95g, 5mmol) and 18-C-6 (1.32g, 5mmol) is added, in 150 DEG C heating reflux reaction 48 hours, TLC Monitoring reaction is completed；
4) it after being cooled to room temperature, is washed with water twice, filters, filter cake carries out 45 points of decoloration at 75 DEG C after being dissolved in ethyl acetate Clock, heat filtering, filtrate is with twice of re-crystallizing in ethyl acetate, dry final compound (248) 33.99g, 83% receipts under vacuum Rate.Compound (248) mass spectrum MS (APCI) (m/z)=819.28 (theoretical value 819.02).
Embodiment 20
Compound (277) of the present invention can be synthesized by following method.
1) in 500ml there-necked flask, two fluorenes -2- amine (45.76g, 100mmol) of N- (naphthalene -2- base) -9,9'- spiral shell is added, Iodo- 1, the 1'- biphenyl (39.05g, 100mmol) of the bromo- 3- of 4'-, toluene (200mL) and sodium tert-butoxide (28.83g, 300mmol), Ultrasound removes air, under nitrogen protection, be added palladium acetate (0.07g, 0.3mmol) and tri-tert-butylphosphine (0.18g, 0.6mmol), 115 DEG C heating reflux reaction 24 hours, TLC monitoring reaction complete；
2) it after being cooled to room temperature, is washed with water twice, liquid separation, organic phase is dried with anhydrous magnesium sulfate, and filtering, filtrate adds Enter active carbon to carry out decolourizing 45 minutes at 115 DEG C, heat filtering, be used twice of re-crystallizing in ethyl acetate after filtrate decompression distillation and concentration, Two fluorenes -2- amine 48.20g of intermediate N (bromo- [1,1'- the biphenyl] -3- base of 4'-)-N- (naphthalene -2- base) -9,9'- spiral shell is finally obtained, 70% yield；
3) in 250ml there-necked flask, addition 7,7- dimethyl -7,12- dihydro indeno [1,2-a] carbazole (14.17g, 50mmol), two fluorenes -2- amine of N- (bromo- [1,1'- the biphenyl] -3- base of 4'-)-N- (naphthalene -2- base) -9,9'- spiral shell (34.43g, 50mmol), DMAC (100mL) and potassium carbonate (13.82g, 100mmol), ultrasound remove air, iodate are added under nitrogen protection Cuprous (0.95g, 5mmol) and 18-C-6 (1.32g, 5mmol), in 150 DEG C heating reflux reaction 48 hours, TLC monitoring reaction It completes；
4) it after being cooled to room temperature, is washed with water twice, filters, filter cake carries out 45 points of decoloration at 75 DEG C after being dissolved in ethyl acetate Clock, heat filtering, filtrate is with twice of re-crystallizing in ethyl acetate, dry final compound (277) 35.64g, 80% receipts under vacuum Rate.Compound (277) mass spectrum MS (APCI) (m/z)=891.02 (theoretical value 891.13).
Following device embodiments are related to using derivative of tri-arylamine group of the invention as the hole of organic electroluminescence device Transmission material and/or out photosphere material and its performance, derivative of tri-arylamine group of the invention is as multilayer organic electroluminescence The structure of part hole mobile material is as shown in Figure 1.
Device embodiments 1
Compound (1) prepares device 1 as hole mobile material.
This example illustrates the performance verification for the electroluminescent device that compound (1) is prepared as hole mobile material. By ITO (tin indium oxide) glass phase after in cleaning agent and deionized water with ultrasonic cleaning 30 minutes.Then vacuum drying 2 is small When (105 DEG C), then ITO (tin indium oxide) glass is put into the oxygen plasma treatment carried out in plasma reactor 5 minutes, transmitted Organic film and metal electrode are prepared in vacuum chamber, and material is then injected by the hole that the method being evaporated in vacuo prepares one layer of 5nm Expect molybdenum trioxide, the compound (1) that 45nm thickness is then deposited is used as hole mobile material, then continues on this hole transmission layer By the emitting layer material of one layer of 20nm in vacuum evaporation, emitting layer material is bis- (4,6- difluorophenyl pyrroles doped with 3% Pyridine-N, C2) pyridinecarboxylic close iridium (Firpic) 4,4 '-two (9- carbazole) biphenyl (CBP), be finally deposited one layer of 15nm's again Azole compounds 1,3,5- tri- (1- phenyl -1H- benzimidazolyl-2 radicals-yl) benzene (TPBi), the Al of the LiF and 100nm of 1nm, institute's shape At device architecture be ITO (tin indium oxide)/MoO3(5nm)/compound (1) (45nm)/CBP:wt 3%Firpic (20nm)/TPBi(15nm)/LiF(1nm)/Al(100nm)。
Device embodiments 2
Compound (21) prepares device 2 as hole mobile material.
This example illustrates the performance verification for the electroluminescent device that compound (21) is prepared as hole mobile material. By ITO (tin indium oxide) glass phase after in cleaning agent and deionized water with ultrasonic cleaning 30 minutes.Then vacuum drying 2 is small When (105 DEG C), then ITO (tin indium oxide) glass is put into the oxygen plasma treatment carried out in plasma reactor 5 minutes, transmitted Organic film and metal electrode are prepared in vacuum chamber, and material is then injected by the hole that the method being evaporated in vacuo prepares one layer of 5nm Expect molybdenum trioxide, the compound (21) of 45nm thickness be then deposited as hole mobile material, then on this hole transmission layer after The continuous emitting layer material by one layer of 20nm in vacuum evaporation, emitting layer material are bis- (4,6- difluorophenyl pyrroles doped with 3% Pyridine-N, C2) pyridinecarboxylic close iridium (Firpic) 4,4 '-two (9- carbazole) biphenyl (CBP), be finally deposited one layer of 15nm's again Azole compounds 1,3,5- tri- (1- phenyl -1H- benzimidazolyl-2 radicals-yl) benzene (TPBi), the Al of the LiF and 100nm of 1nm, institute's shape At device architecture be ITO (tin indium oxide)/MoO3(5nm)/compound (21) (45nm)/CBP:wt 3%Firpic (20nm)/TPBi(15nm)/LiF(1nm)/Al(100nm)。
Device embodiments 3
Compound (35) prepares device 3 as hole mobile material.
This example illustrates the performance verification for the electroluminescent device that compound (35) is prepared as hole mobile material. By ITO (tin indium oxide) glass phase after in cleaning agent and deionized water with ultrasonic cleaning 30 minutes.Then vacuum drying 2 is small When (105 DEG C), then ITO (tin indium oxide) glass is put into the oxygen plasma treatment carried out in plasma reactor 5 minutes, transmitted Organic film and metal electrode are prepared in vacuum chamber, and material is then injected by the hole that the method being evaporated in vacuo prepares one layer of 5nm Expect molybdenum trioxide, the compound (35) of 45nm thickness be then deposited as hole mobile material, then on this hole transmission layer after The continuous emitting layer material by one layer of 20nm in vacuum evaporation, emitting layer material are bis- (4,6- difluorophenyl pyrroles doped with 3% Pyridine-N, C2) pyridinecarboxylic close iridium (Firpic) 4,4 '-two (9- carbazole) biphenyl (CBP), be finally deposited one layer of 15nm's again Azole compounds 1,3,5- tri- (1- phenyl -1H- benzimidazolyl-2 radicals-yl) benzene (TPBi), the Al of the LiF and 100nm of 1nm, institute's shape At device architecture be ITO (tin indium oxide)/MoO3(5nm)/compound (35) (45nm)/CBP:wt 3%Firpic (20nm)/TPBi(15nm)/LiF(1nm)/Al(100nm)。
According to the preparation method of device in above-described embodiment, compound (45) prepares device 4 as hole mobile material, changes Object (51) are closed as hole mobile material and prepare device 5, compound (66) prepares device 6, compound as hole mobile material (71) device 7 is prepared as hole mobile material, compound (85) prepares device 8, compound (98) as hole mobile material Device 9 is prepared as hole mobile material, compound (112) prepares device 10, compound (131) as hole mobile material Device 11 is prepared as hole mobile material, compound (147) prepares device 12, compound (221) as hole mobile material Device 13 is prepared as hole mobile material, compound (224) prepares device 14, compound (227) as hole mobile material Device 15 is prepared as hole mobile material, compound (238) prepares device 16, compound (244) as hole mobile material Device 17 is prepared as hole mobile material, compound (250) prepares device 18, compound (277) as hole mobile material Device 19 is prepared as hole mobile material.
Device embodiments 20
(3- the aminomethyl phenyl) -1,1'- biphenyl -4,4'- diamines of N, N'- diphenyl-N, N'- bis- (TPD) is used as hole transport Material, compound (250) prepare device 20 as photosphere material is gone out.
This example illustrates performance verification of the compound (250) as the electroluminescent device for going out the preparation of photosphere material. By ITO (tin indium oxide) glass phase after in cleaning agent and deionized water with ultrasonic cleaning 30 minutes.Then 2 are dried in vacuo Hour (105 DEG C), then ITO (tin indium oxide) glass is put into the oxygen plasma treatment carried out in plasma reactor 5 minutes, it passes It is sent in vacuum chamber and prepares organic film and metal electrode, the hole injection of one layer of 5nm is then prepared by the method being evaporated in vacuo Then material molybdenum trioxide is deposited the TPD of 45nm thickness as hole mobile material, then continues through on this hole transmission layer The emitting layer material of one layer of 20nm in vacuum evaporation, emitting layer material be doped with 3% it is bis- (4,6- difluorophenyl pyridinato-N, C2) pyridinecarboxylic closes 4,4 '-two (9- carbazole) biphenyl (CBP) of iridium (Firpic), and the azole of one layer of 15nm is finally deposited again Object 1,3,5- tri- (1- phenyl -1H- benzimidazolyl-2 radicals-yl) benzene (TPBi) is closed, after the LiF that one layer of 1nm is deposited, continues vapor deposition one The compound (250) of layer 10nm makees cathode as photosphere material, the Al of 100nm is gone out, and being formed by device architecture is ITO (oxidation Indium tin)/MoO3(5nm)/TPD (45nm)/CBP:wt 3%Firpic (20nm)/TPBi (15nm)/LiF (1nm)/compound (250)(10nm)/Al(100nm).Device embodiments 21
Compound (250) prepares device 21 as hole mobile material and further as photosphere material out.
This example illustrates compound (250) as hole mobile material and further as photosphere material preparation out Electroluminescent device performance verification.By ITO (tin indium oxide) glass phase after in cleaning agent and deionized water with ultrasonic wave Cleaning 30 minutes.Then be dried in vacuo 2 hours (105 DEG C), then by ITO (tin indium oxide) glass be put into plasma reactor into 5 minutes oxygen plasma treatments of row, are transmitted in vacuum chamber and prepare organic film and metal electrode, then the side by being evaporated in vacuo Method prepares the hole-injecting material molybdenum trioxide of one layer of 5nm, and the compound (250) that 45nm thickness is then deposited is used as hole transport Material, then continues through the emitting layer material of one layer of 20nm in vacuum evaporation on this hole transmission layer, and emitting layer material is 4,4 '-two (9- carbazole) biphenyl of iridium (Firpic) are closed doped with 3% bis- (4,6- difluorophenyl pyridinato-N, C2) pyridinecarboxylics (CBP), azole compounds 1,3,5- tri- (1- phenyl -1H- benzimidazolyl-2 radicals-yl) benzene of one layer of 15nm is finally deposited again (TPBi), after the LiF that one layer of 1nm is deposited, the compound (250) for continuing to be deposited one layer of 10nm is used as photosphere material, The Al of 100nm makees cathode, and being formed by device architecture is ITO (tin indium oxide)/MoO3(5nm)/compound (250) (45nm)/CBP:wt 3%Firpic (20nm)/TPBi (15nm)/LiF (1nm)/compound (250) (10nm)/Al (100nm)。
Comparative example
(3- the aminomethyl phenyl) -1,1'- biphenyl -4,4'- diamines of N, N'- diphenyl-N, N'- bis- (TPD) is used as hole transport Material prepares device 22.
This example illustrates the performance verification of the electroluminescent device of common hole mobile material TPD preparation.By ITO (tin indium oxide) glass phase after in cleaning agent and deionized water with ultrasonic cleaning 30 minutes.Then it is dried in vacuo 2 hours (105 DEG C), then ITO (tin indium oxide) glass is put into the oxygen plasma treatment carried out in plasma reactor 5 minutes, it is transmitted to Organic film and metal electrode are prepared in vacuum chamber, and the hole-injecting material of one layer of 5nm is then prepared by the method being evaporated in vacuo Then molybdenum trioxide is deposited the TPD of 45nm thickness as hole mobile material, then continues through vacuum on this hole transmission layer The emitting layer material of one layer of 20nm is deposited, emitting layer material is bis- (4,6- difluorophenyl pyridinato-N, C doped with 3%2) Pyridinecarboxylic closes 4,4 '-two (9- carbazole) biphenyl (CBP) of iridium (Firpic), and the azole compounds of one layer of 15nm are finally deposited again 1,3,5- tri- (1- phenyl -1H- benzimidazolyl-2 radicals-yl) benzene (TPBi), the Al of the LiF and 100nm of 1nm are formed by device junction Structure is ITO (tin indium oxide)/MoO3(5nm)/TPD (45nm)/CBP:wt 3%Firpic (20nm)/TPBi (15nm)/LiF (1nm)/Al(100nm)。
The anode of direct current is added on ITO (tin indium oxide) layer, metal layer cathode being added on where aluminium carries out device Performance evaluation, such as table 2
2 organic electroluminescence device performance characterization of table
As can be seen from Table 1, aromatic amino-derivative provided by the present invention is as hole mobile material and/or preparation Device start voltage, light emission luminance, current efficiency, luminous efficiency and in terms of have good make It is ideal hole mobile material and photosphere material out with performance.
It should be noted that as shown in Figure 1, with ITO (tin indium oxide)/MoO3(5nm)/TPD (45nm) or compound (250)/CBP:wt 3%Firpic (20nm)/TPBi (15nm)/LiF (1nm)/Al (100nm) is the device of structure preparation Energy diagram, it can be seen that, compared with TPD, the energy band of derivative of tri-arylamine group provided by the invention is wider, with hole injection layer and The level-density parameter degree of emitting layer material is more preferable, and the driving voltage and energy consumption of device is effectively reduced, and improves device performance.Such as Fig. 2 It is shown, voltage-wavelength characteristic curve figure of the device prepared using compound (250) as hole mobile material, with the prior art It compares, derivative of tri-arylamine group provided by the invention has good thermal stability as hole mobile material, can effectively improve Agglutination crystallization caused by luminescence phenomenon deterioration make device sending 470nm pure blue light, be better achieved glory device it is red, Green, primary colors physical modulateds are matched.As shown in figure 3, using compound (250) as hole mobile material and being further used as out light The voltage-current density-luminosity response figure of the device of layer material, compared with prior art, triaryl amine provided by the invention Analog derivative has good hole transport rate as hole mobile material, is conducive to hole-electron and is shining to a greater extent Layer realization is compound, and device brightness can be made up to 30290cd/m2, and device, luminance are applied to when being further used as out photosphere material Degree is promoted to 36940cd/m2, amplification reaches 22%.As shown in figure 4, going forward side by side one using compound (250) as hole mobile material Brightness-external quantum efficiency characteristic curve graph as the device for going out the preparation of photosphere material is walked, compared with prior art, the present invention mentions The derivative of tri-arylamine group of confession has good carrier transport rate and energy gap width as hole mobile material, effectively improves Luminous efficiency makes device luminous efficiency up to 50.3lm/W, and further ought be applied to device, lumen effect as photosphere material out Rate reaches 61.3lm/W, and amplification is up to 22%.
The foregoing is merely presently preferred embodiments of the present invention, is not intended to limit the invention, it is all in spirit of the invention and Within principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.

Claims (10)

1. derivative of tri-arylamine group, which is characterized in that general structure such as following structural:
Wherein, R1、R2It is independently selected from: substitution or one of unsubstituted aromatic radical or fragrant heterocyclic radical；
R1And R2It is identical or different.
2. derivative of tri-arylamine group according to claim 1, which is characterized in that the R1、R2It is independently selected from: not It is substituted or by C1-C10Alkyl-substituted C6-C48Aromatic radical, unsubstituted or by C1-C10Alkyl-substituted C3- C48One of fragrant heterocyclic radical.
3. derivative of tri-arylamine group according to claim 2, which is characterized in that described unsubstituted or by C1-C10's Alkyl-substituted C6-C48Aromatic radical be selected from: it is unsubstituted or by C1-C10Alkyl-substituted C6-C48Polycyclic aromatic base, It is unsubstituted or by C1-C10Alkyl-substituted C6-C48Non- polycyclic aromatic base；
It is described unsubstituted or by C1-C10Alkyl-substituted C3-C48Fragrant heterocyclic radical be selected from it is unsubstituted or by C1- C10Alkyl-substituted C3-C48Aromatic aza ring group, unsubstituted or by C1-C10Alkyl-substituted C5-C48Fragrance One of non-Azacyclyl, wherein the nitrogen in the aromatic aza ring group has 1-3.
4. derivative of tri-arylamine group according to claim 3, which is characterized in that described unsubstituted or by C1-C10's Alkyl-substituted C3-C48Aromatic aza ring group be selected from: it is unsubstituted or by C1-C10Alkyl-substituted C7-C48Azepine It is polycyclic aromatic base, unsubstituted or by C1-C10Alkyl-substituted C7-C48The non-polycyclic aromatic base of azepine；
Miscellaneous element in the non-Azacyclyl of fragrance includes oxygen and/or sulphur.
5. derivative of tri-arylamine group according to any one of claims 1 to 4, which is characterized in that the R1、R2Independently Be selected from: it is unsubstituted or by C1-C10Alkyl-substituted phenyl, azepine phenyl, unsubstituted or by C1-C10Alkyl It is substituted xenyl, azepine xenyl, unsubstituted or by C1-C10Alkyl-substituted terphenyl, azepine terphenyl, It is unsubstituted or by C1-C10Alkyl-substituted naphthalene, azepine naphthalene, unsubstituted or by C1-C10It is alkyl-substituted It is fluorenyl, unsubstituted or by C1-C10Alkyl-substituted two fluorenyl of 9,9- spiral shell, unsubstituted or by C1-C10Alkyl take It is the carbazyl phenyl in generation, unsubstituted or by C1-C10Alkyl-substituted 9- phenyl carbazole base, unsubstituted or by C1- C10One of alkyl-substituted dibenzofuran group, wherein the azepine phenyl, azepine xenyl, azepine terphenyl There are 1-3 respectively with the nitrogen in azepine naphthalene.
6. derivative of tri-arylamine group according to claim 5, which is characterized in that the C1-C10Alkyl independently It is selected from: one of methyl, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, tert-butyl.
7. a kind of preparation method of such as derivative of tri-arylamine group as claimed in any one of claims 1 to 6, which is characterized in that including Following steps:
1) amine derivant and bromine, iodine dihalo object feed intake according to molar ratio 1:1, and toluene is added and sodium tert-butoxide, ultrasound are removed Air is removed, under nitrogen protection addition palladium acetate and tri-tert-butylphosphine, heating reflux reaction 20~48 hours, wherein the amine Analog derivative, toluene, sodium tert-butoxide, palladium acetate and tri-tert-butylphosphine feed intake according to molar ratio 1:2:3:3 ‰: 6 ‰；
2) after being cooled to room temperature, processing obtains intermediate；
3) 7,7- dimethyl -7,12- dihydro indeno [1,2-a] carbazole feeds intake with the intermediate according to molar ratio 1:1, is added DMAC and potassium carbonate, ultrasound remove air, and cuprous iodide is added under nitrogen protection and crown ether, heating reflux reaction 48~64 are small When, wherein 7,7- dimethyl -7,12- dihydro indeno [1,2-a] carbazole, DMAC, potassium carbonate, cuprous iodide and crown ether are pressed It feeds intake according to molar ratio 1:2:2:1%:1%；
4) after being cooled to room temperature, processing obtains final products；
Synthetic route is as follows:
8. the preparation method of derivative of tri-arylamine group according to claim 7, which is characterized in that the processing side in step 2) Formula are as follows: be washed with water twice, liquid separation, oil is mutually dry with anhydrous magnesium sulfate, and active carbon is added and carries out decolorization, then decompression is steamed After solvent is removed in distillation, pillar layer separation is recrystallized or used；
Processing mode in step 4) are as follows: be washed with water twice, filter, filter cake is dissolved in ethyl acetate addition active carbon and decolourizes Processing, vacuum distillation, recrystallizes or uses pillar layer separation.
9. a kind of application of the derivative of tri-arylamine group as described in claim 1 to 6 is any, which is characterized in that be used for Organic Electricity Electroluminescence device or hole transport layer material in organic solar batteries device, emitting layer material or photosphere material out.
10. a kind of organic assembly, the organic assembly is organic electroluminescence device or organic solar batteries device, is at least wrapped Include transport layer and/or luminescent layer and/or out photosphere, which is characterized in that the transport layer and/or luminescent layer and/or photosphere is adopted out Any derivative of tri-arylamine group of at least one claim 1 to 6 is used to be made as material.
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