CN1789252A - Novel blue light material-thiotrzinone-containing anthracene derivatives - Google Patents
Novel blue light material-thiotrzinone-containing anthracene derivatives Download PDFInfo
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Abstract
The invention relates to an anthracene deviant containing triazine ring, its preparing method and application, which is prepared through trilooping reaction under strong protonic acid catalysis with cyano anthracene derivant. The molecular structure of this material employs triazine ring as parent body and employs anthracene derivant as extending arm. The product can be used as luminescent layer for organic light-emitting diode, and the produced device emits blue light. The invention is characterized by the simple synthetic process, easy for purification, high heat stability, easy to dissolve into normal organic dissolvent and high fluorescent light intensity.
Description
Technical field
The present invention relates to the novel anthracene derivative that contains triazine ring of a class, is that starting raw material makes by commercial 2-methylanthraquinone and fragrance group halohydrocarbon.Compound provided by the present invention is the blue organic electroluminescent material that a class has electronic transmission performance.
Background technology
Organic electroluminescent LED (OLED) has been subjected to the close attention of scientific and technological circle and industrial community because of its huge applications prospect in various indicating meters.Through the effort of two more than ten years, the part commercialization of present green device, and blue and red device or because of efficient or because of reasons such as life-spans still have distance from industrialization.Because the end-use of organic electroluminescence, be large-size ultra-thin colorful display screen of new generation (Science, 1996,273,884; Journal of the American Chemical Society, 2002,124,11576), therefore, study novel redness and blue emitting material and device, significant.
With regard to blue emitting material, that generally uses at present has an ADN, TBADN, and BCzVBi, DPVBi etc., these materials can adopt doping, also can directly use as the main body luminescent layer.Because evaporation thickness and doping is different, the device of acquisition can be launched light from dark blue to sapphire (Liao, C.-H.; Lee, M.-T.; Tsai, C.-H.; Chen, C.H, Applied Physics Letters, 2005,86 (20), 203507/1-203507/3).In addition, ADN, TBADN and BCzVBi have hole-transfer ability preferably, in making the device process, if film thickness monitoring is improper, light device after, the hole is delivered among the electron transfer layer AlQ easily, thereby obtains launching the device of bluish-green coloured light.So,, need control evaporation thickness and doping carefully, be unfavorable for mass-produced devices like this, particularly the occasion of having relatively high expectations in yield rate in order to guarantee to obtain pure blue-light-emitting.
Compound in triazine class has thermostability and electron transport ability preferably, in recent years, studies confirm that also it has hole barrier ability (C.J.Tonzola, M.M.Alam, W.Kaminsky, S.A.Jenekhe, J.Am.Chem.Soc.2003,125,13548).If triazine ring is introduced in the existing blue light material, by the effect of triazine ring, can adjust the bandwidth of existing blue light material, make its emission wavelength blue shift; Simultaneously, utilize the hole barrier ability of triazine ring, can prevent effectively that the hole from entering and cause the emission wavelength red shift among the AlQ; In addition, the electronic transmission performance of triazine ring can improve the transmission speed from the current carrier of negative electrode, thus the transmission speed in opposite directions of hole in the balancing device and electronics, and then the luminous efficiency of raising device.Based on this, it is starting raw material that the present invention adopts the cyano group anthracene, and by the cyclization of cyano group, a synthetic class contains the anthracene derivative of triazine ring, thereby obtains novel efficient blue light material with electron transport ability.
Summary of the invention
Purport of the present invention provides a class the new anthracene derivative that contains triazine ring;
Purpose of the present invention also provides the above-mentioned preparation that contains the anthracene derivative of triazine ring;
Another object of the present invention provides the above-mentioned application that contains the anthracene derivative of triazine ring.And be applied in the organic electroluminescent LED, to obtain efficient blue light material.
Novel electroluminescent material provided by the present invention has following general structure:
Wherein, Ar is
Or
The building-up reactions formula that a class proposed by the invention contains the anthracene derivative of triazine ring can be exemplified below:
In the formula, ArLi is an aryl lithiumation thing; ArMgBr is the aryl magnesium bromide; THF is a tetrahydrofuran (THF); BPO is a benzoyl peroxide; NBS is a bromo-succinimide.
The invention provides the route of a convenient-to-running synthetic triazine-anthracene derivant.Concrete implementation step is expressed as follows:
(1), in tetrahydrofuran (THF), glycol dimethyl ether, benzene, toluene or their mixture, the reaction product of aromatic bromide and magnesium is reacted with 2-methylanthraquinone again, or directly with the reaction of aryl lithiumation thing ArLi and 2-methylanthraquinone.Hydrolysis obtains the dihydroxy-anthracene quinone derivative then.The reaction mass proportioning is, the mol ratio of magnesium and aromatic bromide is 1: 1～1.5, and the mol ratio of 2-methylanthraquinone and aromatic bromide is 1: 2～4; Temperature of reaction is-78～50 ℃, and the reaction times is 24～50 hours.
(2), containing NaH
2PO
2In the acetum of KI, heating dihydroxy-anthracene quinone derivative gets 2-methyl-9, the 10-diaryl anthracene.The reaction mass proportioning is NaH
2PO
2With the mol ratio of dihydroxy-anthracene quinone derivative be 1: 1～2, the consumption of KI is with respect to NaH
2PO
2Be 20～50mol%, temperature of reaction is 50～150 ℃, and the reaction times is 24～50 hours.
(3), 2-methyl-9, the 10-diaryl anthracene obtains 2-monochloromethyl-9,10-diaryl anthracene with bromo-succinimide or chlorosuccinimide or iodo for the succimide reaction in the presence of benzoyl peroxide or Diisopropyl azodicarboxylate.In the reaction; bromo-succinimide or chlorosuccinimide or iodo succimide and 2-methyl-9; the mol ratio of 10-diaryl anthracene is 1: 1～1.5, and the consumption of benzoyl peroxide or Diisopropyl azodicarboxylate is 1～10% with respect to the weight of bromo-succinimide or chlorosuccinimide or iodo succimide.
(4), 2-monochloromethyl-9, the 10-diaryl anthracene is coughed up tropine reaction with crow in halogenated alkane or halogenated aryl hydrocarbon solvent, obtain 2-monochloromethyl-9, the quaternary ammonium salt of 10-diaryl anthracene.Response feature is a 2-monochloromethyl-9, and the 10-diaryl anthracene is 1: 1～4 with the mol ratio that crow is coughed up tropine, and temperature of reaction is 50～150 ℃, and the reaction times is 24～50 hours.
(5), 2-monochloromethyl-9, the hydrolysis in formalin of the quaternary ammonium salt of 10-diaryl anthracene obtains 2-aldehyde radical-9, the 10-diaryl anthracene, the reaction times is 24～36 hours.Described 2-monochloromethyl-9, the quaternary ammonium of 10-diaryl anthracene and the mol ratio of formaldehyde are 1: 1～5; Described formalin is the formaldehyde that contains 5～40% weight.
(6), 2-aldehyde radical-9, the 10-diaryl anthracene generates 2-cyano group-9,10-diaryl anthracene with the azanol effect in acetum.Reacting material ratio is, 2-aldehyde radical-9, and the mol ratio of 10-diaryl anthracene and azanol is 1: 1～3, and temperature of reaction is 40～150 ℃, and the reaction times is 5～20 hours.
(7), 2-cyano group-9,10-diaryl anthracene trimerization Cheng Huan under the trifluoromethanesulfonic acid effect obtains the compound of target molecular structure.Described 2-cyano group-9, the mol ratio of 10-diaryl anthracene and trifluoromethanesulfonic acid are 100: 1～10, and temperature of reaction is 0～50 ℃, and the reaction times is 24～100 hours.
Described aryl is identical with preceding described Ar.
The anthracene derivative that contains triazine ring of the present invention has excellent chemical property, high thermostability and good electron transmitted performance.When it used as the main body luminescent layer, the current efficiency that can obtain to launch blue light reached the efficient device of 5cd/A.
Embodiment
Following examples help and understand the present invention, but are not limited to content of the present invention.
Embodiment 1 2-methyl-9,10-phenylbenzene-anthracene synthetic
Under argon shield and the violent stirring, in 60 ℃ with bromobenzene (7.9g, THF (tetrahydrofuran (THF) 50mmol); 40mL) solution dropwise join contain magnesium (1.44g, 60mmol), in the mixed solution of the iodine of catalytic amount and THF (40mL); drip and finish, continue stirring and refluxing after 3 hours, be cooled to room temperature.Gained solution under agitation dropwise is added under the argon shield 2-methylanthraquinone (5.4g that is cooled to-78 ℃; in THF 24mmol) (80mL) solution, finish, reaction solution be warming up to room temperature naturally and stir spend the night after; in the impouring 100mL distilled water, with methylene dichloride (200mL) extracting twice.Merge organic phase, behind washing, saturated common salt washing and anhydrous sodium sulfate drying, filter, filtrate decompression is flung to solvent, obtains khaki color solid 15g.With all solids of gained join potassiumiodide (34.03g, 205mmol), NaH
2PO
2(40.5g, 382.1mmol) and in the mixed liquid of Glacial acetic acid (100mL), night is flow through in argon shield next time.After the reaction mixture cooling, pour in the 200mL water, obtain showing slightly red precipitation.Filter, washing, ethanol is washed, and vacuum-drying gets 10g light yellow solid product, yield 58%.
1H NMR (300MHz, CDCl
3): δ 7.16-8.05 (aromatic ring hydrogen, multiplet, 17H), 2.4 (methyl hydrogen, unimodal, 3H).
Embodiment 2 2-methyl-9,10-two (2-naphthyl)-anthracene synthetic
In the argon atmospher, under 60 ℃, in violent stirring contain magnesium (1.4g, 60mmol), the iodine of catalytic amount and THF (40mL) mixture in, dropwise add 2-bromonaphthalene (10.4g, THF 50mmol) (40mL) solution.Drip and finish, reaction solution continued stirring and refluxing after 3 hours, was cooled to room temperature.Gained solution is under stirring and argon shield; dropwise be added to the 2-methylanthraquinone (5.4g that is cooled to-78 ℃; in THF 24mmol) (80mL) solution, finish, reaction solution be warming up to room temperature naturally and stir spend the night after; pour in the 100mL distilled water; with methylene dichloride (200mL) extracting twice, merge organic phase, after washing, saturated common salt washing, anhydrous sodium sulfate drying and filtration; filtrate decompression boils off solvent, obtains khaki color solid 11.3g.With all solids of gained join potassiumiodide (34.03g, 205mmol), NaH
2PO
2(40.5g 382.1mmol) and in the mixed liquid of Glacial acetic acid (100mL), flows through night next time in argon shield.After being chilled to room temperature, reaction mixture is poured in the 200mL water, obtains the light red precipitation.Filter, filter cake is after water and ethanol are washed respectively, and vacuum-drying gets yellow solid product, 7.2g.Yield 32%.
1H NMR (300MHz, CDCl
3): δ 7.14-8.11 (aromatic ring hydrogen, multiplet, 21H), 2.35 (methyl hydrogen, unimodal, 3H).
Embodiment 3 2-methyl-9,10-two (pentafluorophenyl group)-anthracene synthetic
In the argon atmospher, under-78 ℃, in 1-bromo-2,3,4,5, (12.4g in THF 50mmol) (40mL) solution, slowly drips the hexane solution (1.6 mol, 35 milliliters) of n-Butyl Lithium to the 6-tetra fluoro benzene.After stirring 1 hour under this temperature, remove cryostat, reaction mixture is warming up to room temperature naturally.The material that is obtained slowly adds under the argon shield 2-methylanthraquinone that is cooled to-78 ℃, and (5.4g is in THF 24mmol) (80mL) solution.Finish, reaction solution is heated to backflow after being warming up to room temperature naturally, and stirs under this temperature and spend the night.After mixture is chilled to room temperature, in the impouring 100mL distilled water, with methylene dichloride (200mL) extracting twice.Merge organic phase, behind washing, saturated common salt washing and anhydrous sodium sulfate drying, filter.Filtrate decompression boils off solvent, obtains white solid 25g.With all solids of gained join potassiumiodide (34g, 205mmol), NaH
2PO
2(40.51g, 382.1mmol) and in the mixed liquid of Glacial acetic acid (100mL), night is flow through in argon shield next time.Reaction mixture is poured in the 200mL water after being chilled to room temperature, obtains the xanchromatic precipitation.Filter, washing, ethanol is washed, and vacuum-drying gets shallow white solid product, 18g.Yield 70%.
1H NMR (300MHz, CDCl
3): δ 7.22-8.41 (aromatic ring hydrogen, multiplet, 7H), 2.48 (methyl hydrogen, unimodal, 3H).MALDI-MS：524(M+)。
Embodiment 4 2-brooethyls-9,10-phenylbenzene-anthracene synthetic
Under the argon shield, in the 250mL reaction flask, add the 2-methyl-9 that embodiment 1 is obtained, 10-phenylbenzene-anthracene (5.5g; 16.1mmol), NBS (2.9g, 16.1mmol) and tetracol phenixin (150mL); after the mixture heating up to 60 ℃, add benzoyl peroxide (30mg).The mixed solution that obtains is heated to backflow and after stirring under this temperature is spent the night, naturally cools to room temperature.Organic phase is filtered behind washing, saturated common salt washing and anhydrous sodium sulfate drying.After filtrate concentrated, residue used column chromatography.Eluent is the mixture of sherwood oil and methylene dichloride.Product behind the purifying is a yellow solid, 4g, yield 59%.
1H NMR (300MHz, CDCl
3): δ 7.25-8.03 (aromatic ring hydrogen, 17H), 4.43 (methyl hydrogen, unimodal, 2H).
Embodiment 5 2-brooethyls-9,10-two (2-naphthyl)-anthracene synthetic
Under the argon shield, add the 2-methyl-9 that embodiment 2 is obtained in the 250mL reaction flask, and 10-two (2-naphthyl)-anthracene (7.2g, 16.1mmol), NBS (2.9g, 16.10mmol) and tetracol phenixin (150mL).After mixture is stirred and heated to 60 ℃, add benzoyl peroxide (30mg).After the reaction mass reflux is spent the night, be cooled to room temperature.Organic phase washes with water, saturated common salt is washed and anhydrous sodium sulfate drying after, column chromatography for separation, eluent is the mixture of sherwood oil and methylene dichloride.The heavy 4.12g of purified product, yellow solid, productive rate 49%.
1H NMR (300MHz, CDCl
3): δ 7.27-8.13 (aromatic ring hydrogen, multiplet, 21H), 4.50 (unimodal, 2H).
Embodiment 6 2-brooethyls-9,10-two (pentafluorophenyl group)-anthracene synthetic
Under the argon shield, in the 250mL reaction flask, add the 2-methyl-9 that embodiment 3 is obtained, 10-two (pentafluorophenyl group)-anthracene (8.4g; 16.10mmol), NBS (2.87g, 16.10mmol) and tetracol phenixin (150mL); be stirred and heated to 60 ℃, add benzoyl peroxide (30mg).Reflux is spent the night, naturally cool to room temperature after, organic phase with saturated common salt washing, washing and anhydrous sodium sulfate drying after, filter.After filtrate was flung to organic solvent, residue used column chromatography, and eluent is the mixture of sherwood oil and methylene dichloride.The heavy 2.9g of purified product, yellow solid, productive rate 30%.
1H NMR (300MHz, CDCl
3): δ 7.3-8.4 (aromatic ring hydrogen, multiplet, 7H), 4.61 (unimodal, brooethyl, 2H).
Embodiment 7 2-aldehyde radicals-9,10-phenylbenzene-anthracene synthetic
Under the nitrogen protection, add 2-brooethyl-9 successively in the 250mL reaction flask, (4g, 9.5mmol), crow is coughed up tropine, and (16g is 114mmol) with 200 milliliters of chloroforms for the 10-diphenylanthrancene.Mixture heating up is to refluxing, and under this temperature stir about 8 hours, obtain yellow turbid solution.Decompression volatilization dechlorination is imitative, and residue obtained mixed and be heated to 50 ℃ with 100 milliliters of formalins, after keeping 15 hours under this temperature, cool to room temperature also adds dichloromethane extraction 3 times.Combining extraction liquid behind anhydrous sodium sulfate drying, filters.After filtrate was flung to organic solvent, residue used column chromatography, and eluent is the mixture of sherwood oil and ethyl acetate.Purified product is the yellow solid of transmitting green fluorescence, 3.4g, yield 60%.
1H?NMR(CDCl
3)：δ8.82(s，1H)，7.32-8.4(m，17H)。
Embodiment 8 2-aldehyde radicals-9,10-two (2-naphthyl) anthracene synthetic
Under the nitrogen protection, add 2-brooethyl-9 successively in the 250mL reaction flask, (4.97g, 9.5mmol), crow is coughed up tropine, and (16g is 114mmol) with 200 milliliters of chloroforms for 10-two (2-naphthyl) anthracene.Mixture heating up is to refluxing, and under this temperature stir about 8 hours, obtain yellow turbid solution.Decompression volatilization dechlorination is imitative, and residue obtained mixed and be heated to 50 ℃ with 100 milliliters of formalins, after keeping 15 hours under this temperature, cool to room temperature also adds dichloromethane extraction 3 times.Combining extraction liquid behind anhydrous sodium sulfate drying, filters.After filtrate concentrated, residue used column chromatography, and eluent is the mixture of sherwood oil and ethyl acetate.Purified product 1.7g is the yellow solid of transmitting green fluorescence, yield 40%.
1H?NMR(CDCl
3)：δ8.79(s，1H)，7.25-8.37(m，21H)。
Embodiment 9 2-aldehyde radicals-9,10-two (pentafluorophenyl group)-anthracene synthetic
After the 100mL reaction flask usefulness purging with nitrogen gas 3 times, add 2-brooethyl-9 successively, (5.73g, 9.5mmol), crow is coughed up tropine, and (16g is 114mmol) with 200 milliliters of chloroforms for 10-two (pentafluorophenyl group)-anthracene.Mixture heating up is to refluxing, and under this temperature stir about 8 hours, obtain grey turbid solution.Decompression volatilization dechlorination is imitative, and residue obtained mixed and be heated to 50 ℃ with 100 milliliters of formalins, after keeping 15 hours under this temperature, cool to room temperature also adds dichloromethane extraction 3 times.Combining extraction liquid behind anhydrous sodium sulfate drying, filters.After filtrate concentrated, residue used column chromatography.Eluent is the mixture of sherwood oil and ethyl acetate.Product after the column chromatography for separation gets the light yellow solid that 2.3g launches strong green fluorescence with the toluene recrystallization, yield 45%.
1H NMR (CDCl
3): δ 8.92 (aldehyde radical hydrogen, unimodal, 1H), 7.33-8.50 (aromatic ring hydrogen, multiplet, 7H).
Embodiment 10 2-cyano group-9,10-phenylbenzene-anthracene synthetic
The 2-aldehyde radical-9 of mixed 0.5 mmole, 10-diphenylanthrancene, the oxammonium hydrochloride of 2 mmoles and 100 milliliters of Glacial acetic acid be in 100 ml flasks, and be heated to 80 degree.After 10 hours, the orange-yellow turbid solution that obtains is cooled to room temperature at stir about under this temperature.In 500 milliliters of frozen water of mixture impouring, add dichloromethane extraction 3 times.Combining extraction liquid behind anhydrous sodium sulfate drying, filters.Boil off solvent under the filtrate decompression, residue with column chromatography (silica gel, sherwood oil/chloroform wash-out) separate the 2-cyano group-9 of 0.4 mmole, 10-diphenylanthrancene, yield 80%.FTIR, 2224cm
-1(-CN),
1H NMR (CDCl
3): δ 7.28-8.07 (aromatic ring hydrogen, multiplet, 17H).
Embodiment 11 2-cyano group-9,10-two (2-naphthyl)-anthracene synthetic
The 2-aldehyde radical-9 that in the 100mL there-necked flask, adds 0.5 mmole successively, 10-two (2-naphthyl) anthracene, the oxammonium hydrochloride of 2 mmoles and 100 milliliters of Glacial acetic acid.Mixture heating up to 80 degree, and under this temperature stir about 10 hours, obtain orange-yellow turbid solution.Mixture is poured in 500 milliliters of frozen water after being cooled to room temperature, adds dichloromethane extraction 3 times.Combining extraction liquid is used anhydrous sodium sulfate drying.Filter.After filtrate decompression is flung to organic solvent, residue with column chromatography (silica gel, sherwood oil/chloroform wash-out) separate the 2-cyano group-9 of 0.4 mmole, 10-two (2-naphthyl) anthracene, yield 80%.FTIR, 2230cm
-1(-CN),
1H NMR (CDCl
3): δ 7.32-8.16 (aromatic ring hydrogen, multiplet, 21H).
Embodiment 12 2-cyano group-9,10-two (pentafluorophenyl group)-anthracene synthetic
0.5 the 2-aldehyde radical-9 of mmole, 10-two (pentafluorophenyl group)-anthracene add in the miscellany of the oxammonium hydrochloride of 2 mmoles and 100 milliliters of Glacial acetic acid, stir half an hour under the room temperature after, be heated to 80 degree, and under this temperature stir about 10 hours, obtain the grey turbid solution.Mixture is poured in 500 milliliters of frozen water after being cooled to room temperature, adds dichloromethane extraction 3 times.Combining extraction liquid, with anhydrous sodium sulfate drying with after concentrating, column chromatography (silica gel, sherwood oil/chloroform wash-out) separate the 2-cyano group-9 of 0.4 mmole, 10-two (pentafluorophenyl group)-anthracene, yield 80%.FTIR, 2244cm
-1(-CN),
1H NMR (CDCl
3): δ 7.32-8.16 (aromatic ring hydrogen, multiplet, 7H).
Embodiment 13 2, and 4,6-three [2-(9, the 10-phenylbenzene) anthryl]-1,3,5-s-triazine synthetic
Under the nitrogen protection, in the 50mL reaction flask, add the 2-cyano group-9 of 0.2 mmole successively, 10-phenylbenzene-anthracene and 20 milliliters of chloroforms.Stir after 0.5 hour, under the ice bath cooling, Dropwise 5 milliliter trifluoromethanesulfonic acid.The mazarine mixture that is obtained is after stirring 24 hours under the room temperature, in the impouring frozen water.Tell organic layer, water layer chloroform extraction 3 times.Merge organic layer.Use anhydrous sodium sulfate drying, filter.After filtrate concentrates, residue with column chromatography (silica gel, sherwood oil/chloroform wash-out) separate 0.1 mmole 2,4,6-three [2-(9, the 10-phenylbenzene) anthryl]-1,3,5-s-triazine, yield 50%.FTIR, 1585,1544cm
-1(triazine ring).
1H NMR (CDCl
3): δ 7.32-8.16 (aromatic ring hydrogen, multiplet, 51H).MALDI-MS：1066(M
+)。
Embodiment 14 2, and 4,6-three [2-(9,10-two (2-naphthyl) anthryl]-1,3,5-s-triazine synthetic
0.2 the 2-cyano group-9 of mmole, 10-two (2-naphthyl) anthracene is dissolved in 25 milliliters of chloroforms, and under nitrogen protection and ice bath cooling, splashes in the mixed solution of 5 milliliters of trifluoromethanesulfonic acids and 5 milliliters of chloroforms.The mazarine mixture that is obtained is after stirring 24 hours under the room temperature, in the impouring frozen water.Tell organic layer, water layer chloroform extraction 3 times.Merge organic layer.With anhydrous sodium sulfate drying with after concentrating, column chromatography (silica gel, sherwood oil/chloroform wash-out) separate 0.15 mmole 2,4,6-three (9,10-two (2-naphthyl) anthracene-2)-1,3,5-s-triazine, yield 75%.FTIR, 1574,1535cm
-1(triazine ring).
1H NMR (CDCl
3): δ 7.41-8.22 (aromatic ring hydrogen, multiplet, 63H).MALDI-MS：1366(M
+)。
Embodiment 15 2, and 4,6-three [2-(9,10-two (pentafluorophenyl group) anthryl]-1,3,5-s-triazine synthetic
Under the nitrogen protection, in the 50mL reaction flask, add the 2-cyano group-9 of 0.1 mmole successively, 10-two (2-naphthyl) anthracene and 50 milliliters of chloroforms.Stir after 0.5 hour, under the ice bath cooling, Dropwise 5 milliliter trifluoromethanesulfonic acid.The scarlet mixture that is obtained is after stirring 3 days under the room temperature, in the impouring frozen water.Tell organic layer, water layer chloroform extraction 3 times.Merge organic layer.With anhydrous sodium sulfate drying with after concentrating, column chromatography (silica gel, sherwood oil/chloroform wash-out) separate 0.03 mmole 2,4,6-three (9,10-two (2-naphthyl) anthracene-2)-1,3,5-s-triazine, yield 30%.FTIR, 1580,1347cm
-1(triazine ring);
1H NMR (CDCl
3): δ 7.51-8.47 (aromatic ring hydrogen, multiplet, 621H).MALDI-MS：1606(M
+)。
Embodiment 16 2, and 4,6-three [2-(9,10-two (2-naphthyl) anthryl]-1,3, the making and the performance of the luminescent device that the 5-s-triazine constitutes
With NPB is hole transport layer, 2,4, and 6-three (9,10-two (2-naphthyl) anthracene-2)-1,3,5-s-triazine be as luminescent layer, Alq
3Being electron transfer layer, is anode with the ito glass, and lithium fluoride is an electron injecting layer, and aluminium is negative electrode, prepares luminescent device by the vacuum evaporation mode.The thickness of each material layer is in the device: NPB, 30nm; 2,4,6-three (9,10-two (2-naphthyl) anthracene-2)-1,3,5-s-triazine, 30nm; Alq
3, 30nm; LiF, 0.5nm.Under the operating voltage of 10V, the blue light of emission 470nm, brightness is 3000cd/m
2In the element manufacturing, used hole transport layer NPB and electron transfer layer Alq
3Chemical structure be:
Embodiment 17 is [2-(9,10-two (pentafluorophenyl group) anthryl]-1,3 by three, the making and the performance of the luminescent device that the 5-s-triazine constitutes
The manufacture craft of device is with embodiment 16.Device performance is, under the operating voltage of 6V, and the blue light of emission 480nm, brightness is 5000cd/m
2
Claims (4)
1. a class contains the anthracene compounds of triazine ring, it is characterized in that having following chemical structure:
Wherein Ar is
Or
2. a class as claimed in claim 1 contains the preparation method of the anthracene compounds of triazine ring, it is characterized in that being made by following method:
(1), in organic solvent, the reaction product of aromatic bromide and magnesium is reacted with 2-methylanthraquinone again, or directly with the reaction of aryl lithiumation thing ArLi and 2-methylanthraquinone, hydrolysis obtains the dihydroxy-anthracene quinone derivative then; Described organic solvent is tetrahydrofuran (THF), glycol dimethyl ether, benzene, toluene or their mixture; The mol ratio of described magnesium and aromatic bromide is 1: 1～1.5, and the mol ratio of 2-methylanthraquinone and aromatic bromide is 1: 2～4, and temperature of reaction is-78～50 ℃, and the reaction times is 24～50 hours;
(2), containing NaH
2PO
2In the acetum of KI, heating dihydroxy-anthracene quinone derivative gets 2-methyl-9, the 10-diaryl anthracene; Described NaH
2PO
2With the mol ratio of dihydroxy-anthracene quinone derivative be 1: 1～2, the consumption of KI is with respect to NaH
2PO
2Be 20～50mol%, temperature of reaction is 50～150 ℃, and the reaction times is 24～50 hours;
(3), 2-methyl-9, the 10-diaryl anthracene obtains 2-monochloromethyl-9,10-diaryl anthracene with bromo-succinimide or chlorosuccinimide or iodo for the succimide reaction in the presence of benzoyl peroxide or Diisopropyl azodicarboxylate; Described bromo-succinimide or chlorosuccinimide or iodo succimide and 2-methyl-9, the mol ratio of 10-diaryl anthracene is 1: 1～1.5, and the consumption of benzoyl peroxide or Diisopropyl azodicarboxylate is 1～10% with respect to the weight of bromo-succinimide or chlorosuccinimide or iodo succimide;
(4), 2-monochloromethyl-9, the 10-diaryl anthracene is coughed up tropine reaction with crow in halogenated alkane or halogenated aryl hydrocarbon solvent, obtain 2-monochloromethyl-9, the quaternary ammonium salt of 10-diaryl anthracene; Described 2-monochloromethyl-9, the 10-diaryl anthracene is 1: 1～4 with the mol ratio that crow is coughed up tropine, and temperature of reaction is 50～150 ℃, and the reaction times is 24～50 hours;
(5), 2-monochloromethyl-9, the quaternary ammonium salt of 10-diaryl anthracene obtained 2-aldehyde radical-9,10-diaryl anthracene in hydrolysis 24-36 hour in formalin; Described 2-monochloromethyl-9, the quaternary ammonium salt of 10-diaryl anthracene and the mol ratio of formaldehyde are 1: 1～5; Described formalin is the formaldehyde that contains 5～40% weight.
(6), 2-aldehyde radical-9, the 10-diaryl anthracene generates 2-cyano group-9,10-diaryl anthracene with the azanol effect in acetum, described 2-aldehyde radical-9, the mol ratio of 10-diaryl anthracene and azanol is 1: 1～3, and temperature of reaction is 40～150 ℃, and the reaction times is 5～20 hours;
(7), 2-cyano group-9,10-diaryl anthracene trimerization Cheng Huan under the trifluoromethanesulfonic acid effect obtains the described structural compounds of claim 1; Described 2-cyano group-9, the mol ratio of 10-diaryl anthracene and trifluoromethanesulfonic acid are 100: 1～10, and temperature of reaction is 0～50 ℃, and the reaction times is 24～100 hours;
Above-mentioned aryl is described with Ar in the claim 1.
3. a class as claimed in claim 1 contains the purposes of the anthracene derivative of triazine ring, it is characterized in that as electroluminescent organic material.
4. purposes as claimed in claim 3 is characterized in that described electroluminescent organic material is the Organic Light Emitting Diode of emission blue light.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101910359A (en) * | 2007-10-24 | 2010-12-08 | 巴斯夫欧洲公司 | Use of substituted tris(diphenylamino)-triazine compounds in oleds |
| CN103159689A (en) * | 2013-03-13 | 2013-06-19 | 唐山师范学院 | Blue light conversion agent s-triazine derivatives for agricultural film and their preparation method and use method |
| CN104693836A (en) * | 2014-12-08 | 2015-06-10 | 大连理工大学 | Anthraquinone azo-type active dye |
| CN105153130A (en) * | 2015-08-03 | 2015-12-16 | 上海道亦化工科技有限公司 | Electron transport compound adopting triazine derivative and OLED (organic light-emitting device) applying electron transport compound |
| CN108893105A (en) * | 2018-05-08 | 2018-11-27 | 上海大学 | Small molecular blue light material and preparation method thereof |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6465115B2 (en) * | 1998-12-09 | 2002-10-15 | Eastman Kodak Company | Electroluminescent device with anthracene derivatives hole transport layer |
| US6656608B1 (en) * | 1998-12-25 | 2003-12-02 | Konica Corporation | Electroluminescent material, electroluminescent element and color conversion filter |
| US6225467B1 (en) * | 2000-01-21 | 2001-05-01 | Xerox Corporation | Electroluminescent (EL) devices |
| EP1182183B1 (en) * | 2000-03-29 | 2009-12-09 | Idemitsu Kosan Co., Ltd. | Anthracene derivatives and organic electroluminescent devices made by using the same |
| US6638644B2 (en) * | 2001-08-28 | 2003-10-28 | Eastman Kodak Company | Electroluminescent devices having diarylanthracene polymers |
| CN1239447C (en) * | 2002-01-15 | 2006-02-01 | 清华大学 | Organic electroluminescent material |
| US7169482B2 (en) * | 2002-07-26 | 2007-01-30 | Lg.Philips Lcd Co., Ltd. | Display device with anthracene and triazine derivatives |
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- 2005-12-29 CN CNB2005101122435A patent/CN100361980C/en not_active Expired - Fee Related
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101910359A (en) * | 2007-10-24 | 2010-12-08 | 巴斯夫欧洲公司 | Use of substituted tris(diphenylamino)-triazine compounds in oleds |
| CN103159689A (en) * | 2013-03-13 | 2013-06-19 | 唐山师范学院 | Blue light conversion agent s-triazine derivatives for agricultural film and their preparation method and use method |
| CN104693836A (en) * | 2014-12-08 | 2015-06-10 | 大连理工大学 | Anthraquinone azo-type active dye |
| CN105153130A (en) * | 2015-08-03 | 2015-12-16 | 上海道亦化工科技有限公司 | Electron transport compound adopting triazine derivative and OLED (organic light-emitting device) applying electron transport compound |
| CN105153130B (en) * | 2015-08-03 | 2019-01-15 | 上海道亦化工科技有限公司 | Triazine derivative electron transport compound and its organic electroluminescence device |
| CN108893105A (en) * | 2018-05-08 | 2018-11-27 | 上海大学 | Small molecular blue light material and preparation method thereof |
| CN108893105B (en) * | 2018-05-08 | 2021-05-07 | 上海大学 | Micromolecular blue light material and preparation method thereof |
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