CN1314656C - 9,9-bis(triphenyl amino) fluorine derivatives and preparation and use thereof - Google Patents
9,9-bis(triphenyl amino) fluorine derivatives and preparation and use thereof Download PDFInfo
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- CN1314656C CN1314656C CNB2004100681413A CN200410068141A CN1314656C CN 1314656 C CN1314656 C CN 1314656C CN B2004100681413 A CNB2004100681413 A CN B2004100681413A CN 200410068141 A CN200410068141 A CN 200410068141A CN 1314656 C CN1314656 C CN 1314656C
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Abstract
The present invention relates to a preparation method for a 9, 9-bi (triphenylamine group) fluorene derivative and application thereof. The material is characterized in that the material has a structure which is in a 9, 9-bi (triphenylamine group) fluorene shape. The material can be obtained by the Suzuki coupling reaction of aromatic ring or heterocyclic ring boric acid or boric acid ester and dihalogenated 9, 9-bi (triphenylamine group) fluorene. The material is used as the cavity aid transfer material of an Organic light emitting diode, and can greatly reduce the initial light voltage of a device. The material is easy to synthesize and purify, is easy to dissolve in ordinary organic solvents, and has high thermal stability and fluorescence intensity.
Description
Technical field
It is novel 9 to the present invention relates to a class, and two (triphen amido) fluorene derivativess of 9-are that starting raw material makes by commercial triphenylamine and Fluorenone.Compound provided by the present invention be a class excellent performance help the hole-transfer material, itself and hole-transfer materials such as traditional TPD and NPB are united use, can reduce the bright voltage that rises of photodiode greatly, and brightness and current efficiency do not made significant difference.
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.Multinomial deep research has been carried out in aspects such as in the recent two decades in the past, many in the world famous research institutions such as Ma Pu institute, Princeton University and Cambridge University etc. are synthetic at material, device manufacturing; How tame transnational company in the whole world such as DOW Chemical, Du Pont, the Philips, IBM, Motorola, big Japanese ink etc. also drops into a large amount of financial resources and manpower, concentrate research Organic Light Emitting Diode capable of being industrialized and develop its potential purposes, particularly Development of New Generation large-size ultra-thin display screen (Science, 1996,273,884; Journal of the American Chemical Society, 2002,124,11576).
Common Organic Light Emitting Diode is made up of anodal (ito glass), hole transport layer, luminescent layer, electron transfer layer and metal negative pole (Ca, Mg, Al etc.).Wherein, the purity of hole-transfer layer material, stability etc. are to the big (Angew.Chem.Int.Ed. of performance impact of entire device, 1998,37,402-428), and present employed triphenylamine class hole-transfer material is difficult to purify, stability is not high, simultaneously, its complex synthetic route, material cost is higher.Therefore, seeking suitable hole-transfer material, is a focus in the OLED investigation of materials in recent years.Particularly importantly, for the luminescent device of obtained performance excellence, having hanged down bright voltage OLED is one of target of present industrial community pursuit, adopts usually at ito glass and hole-transfer interlayer increase hole injection layer and realizes.Hole injection layer commonly used is doping Polythiophene (PEDOT) and CuPc (CuPc).Although these two kinds of materials can reach the effect that has reduced bright voltage, PEDOT costs an arm and a leg, and CuPc then can absorptive red light, remains the hole of development of new to inject and transmit material.
Fluorene derivatives has been widely used as the luminescent layer of electroluminescent material, but the hole transport layer that contains fluorenes does not appear in the newspapers.Because fluorene derivatives has high thermo-oxidative stability, the electron conjugated system of big pi-can be by modification, the material of obtained performance excellence.On the other hand, the fluorene derivatives wide material sources are easy to synthesize, and are expected to obtain lower cost materials.Based on this, the present invention adopts 9, and two (triphen amido) fluorenes of 9-are parent, and a synthetic class contains the novel fluorene derivatives of triphenylamine functional group, obtains novel hole-transfer material.
Summary of the invention
The present invention aims to provide new class 9, two (triphen amido) fluorene derivativess of 9-and preparation method thereof.
The present invention also will deal with problems and be and will provide this new class 9, and two (triphen amido) fluorene derivativess of 9-are applied to electroluminescent organic material, to obtain to have hanged down the purposes that bright voltage is widened this compounds.
Novel electroluminescent material provided by the present invention has following general structure:
Wherein, Ar is
In the following formula, R is H, C
1～C
6Alkyl, phenyl, benzyl.
Of the present invention 9, two (triphen amido) fluorene derivativess of 9-can prepare by following method:
The organic boronic of Ar or its ester and dihalo 9, (halogen is Cl or Br to two (triphen amido) fluorenes of 9-, further be recommended as Br) be dissolved in organic solvent, the mixture that adds mineral alkali and You Ji Palladium catalyzer or organic palladium and organophosphorus ligand is as catalyzer, and mixture reaction makes.Be preferable under 60-150 ℃ (preferably 80-100 ℃) reaction 10-48 hour and make.In synthetic, organic boronic or its ester and dihalo 9, preferred 3: 1～4: 1 of the mol ratio of two (triphen amido) fluorenes of 9-, the organic palladium catalyst levels is preferably 5-10mol% (with respect to dihalo 9, two (triphen amido) fluorenes of 9-), the mineral alkali consumption is preferably the twice (mol ratio) of organic boronic or its ester.Wherein Ar as previously mentioned.
Further be recommended in the organic solvent that contains mineral alkali, in the presence of the mixture of organic palladium catalyzer or organic palladium catalyzer and organophosphorus ligand, 2,7-two bromo-9, organic boronic or its ester mol ratio of two (triphen amido) fluorenes of 9-and aromatic ring or heterocycle Ar are 1: 4, back flow reaction 36 hours.
Organic solvent of the present invention is preferably tetrahydrofuran (THF), glycol dimethyl ether, benzene, toluene etc.; The mixture of 1: 1 of toluene and glycol dimethyl ether (volume ratio) preferably.
Organic palladium catalyzer of the present invention is the title complex of palladium metal and organic phosphine, and further recommending described organic palladium catalyzer can be Pd (PPh
3)
4, Pd (PPh
3)
2Cl
2Or Pd
2(dba)
3/ P (t-Bu)
3, be preferably Pd (PPh
3)
4The mixture of described organic palladium and organophosphorus ligand can be Pd
2(dba)
3With P (t-Bu)
3Mixture.PPh wherein
3For triphenylphosphinyl, dba are to benzyl acetone, t-Bu is a normal-butyl.
Mineral alkali of the present invention is preferably the aqueous solution of alkali metal hydroxide or alkaline carbonate, preferably the aqueous sodium carbonate of 2M.
Described 2,7-dihalo-9, two (triphen amido) fluorenes of 9-can be by following method preparations: under methanesulfonic catalysis, and triphenylamine and 2,7-dihalo-9-Fluorenone prepared in reaction 2,7-dihalo-9, two (triphen amido) fluorenes of 9-.Its preferred reaction conditions is under protection of inert gas; 2, the mol ratio of 7-dihalo-9-Fluorenone, triphenylamine is recommended as 1: 1～and 20, the consumption of methanesulfonic is recommended as and 2; the mol ratio of 7-dihalo-9-Fluorenone is 1: 0.5～2, and reaction was preferably carried out 6-12 hour at 120 ℃～160 ℃.Its further preferred reaction conditions is under protection of inert gas; 2, the mol ratio of 7-dihalo-9-Fluorenone, triphenylamine is recommended as 1: 14, and the consumption of methanesulfonic is recommended as and 2; the mol ratio of 7-dihalo-9-Fluorenone is 1: 1, and reaction was preferably carried out 8-10 hour at 140 ℃.
The organic boronic of described aromatic ring or heterocycle Ar or its ester can be prepared by following method: in organic solvent, ArBr reacts with the boron alkoxide acid esters under n-Butyl Lithium or magnesium effect, obtains the product of organic boronic or its ester; Ar such as preceding in the formula.The alkoxyl group of described boron alkoxide acid esters is recommended C
1～C
12Alkoxyl group.Its preferred reaction conditions be the mol ratio of ArBr and boron alkoxide acid esters be recommended as 1: 1～2.-78 ℃～room temperature reaction 1～5 hour, product returned and heats up in a steamer through concentrating back adding organic solvent.The mol ratio that its further preferred reaction conditions is ArBr and boron alkoxide acid esters is recommended as 1: 1.5.After carrying out 2 hours under-78 ℃, rose to room temperature reaction 1 hour, product adds the mixture of ethylene glycol/toluene after concentrating, return and heated up in a steamer 10 hours.
New class 9 provided by the invention, two (triphen amido) fluorene derivativess of 9-can be applicable to electroluminescent organic material.This compounds be a class excellent performance help the hole-transfer material, itself and hole-transfer materials such as traditional TPD and NPB are united use, can reduce the bright voltage that rises of photodiode greatly, and brightness and current efficiency do not made significant difference.
Of the present invention 9, two (triphen amido) the fluorene derivatives preparation technologies of 9-are simple, the yield height, be easy to purifying, and compound has excellent chemical property, high thermostability and good hole-transfer performance, be used with widely used hole-transfer material TPD or NPB, form compound hole transport layer, can obtain the device that bright voltage is lower than 3V.
Description of drawings
Fig. 1 be product among the embodiment 1 (numbering XB10) as TPD help hole transport layer the time device voltage and brightness curve
Fig. 2 be product among the embodiment 1 (numbering XB10) as NPB help hole transport layer the time device voltage and brightness curve
Embodiment
Following examples help and understand the present invention, but are not limited to content of the present invention.
Under the argon shield; in the 100mL reaction flask, add 338mg (1mmol) 2 successively; 7-two bromo-9-Fluorenones; 3.43g (14mmol) triphenylamine and 91mg (1mmol) methanesulfonic; after gas displacement in the reaction flask is rare gas element; mixture heating up to 140 ℃, and under this temperature stir about 8 hours, obtain red tan solution; cool to room temperature; add the methylene dichloride dissolving, with the saturated aqueous sodium carbonate washing and with anhydrous sodium sulfate drying with after concentrating, column chromatography (silica gel; sherwood oil/dichloromethane/ethyl acetate wash-out) separate 0.633g 2; 7-two bromo-9, two (triphen amido) fluorenes of 9-, yield 78.1%.
Under-78 ℃, 3.24g (10mmol) triphenylamine bromine is added n-BuLi, react after 1 hour, add 2.82g (15mmol) boric acid three Virahol esters, stirred 2 hours, temperature rises to room temperature, continue to stir 1 hour, product adds the mixture of ethylene glycol/toluene after concentrating, return and heated up in a steamer 10 hours.Add water after being chilled to room temperature.Also with anhydrous sodium sulfate drying with after concentrating, column chromatography for separation gets 1.53g triphenylamine list boric acid ester, yield 48.6% for toluene extraction, saturated common salt water washing.
Under the argon shield, in the 100mL reaction flask, add above-mentioned synthetic 2 successively, 7-two bromo-9,9-two (triphen amido) fluorenes 0.81g (1mmol), triphenylamine list boric acid ester 1.26g (4mmol) and 115mg (0.1mmol) Pd (PPh
3)
4, the gas displacement in the reaction flask is rare gas element after, add the Na of 10mL toluene, 10mL glycol dimethyl ether and 4mL 2M
2CO
3The aqueous solution, mixture return and heat up in a steamer 36 hours.Add water 30mL after being chilled to room temperature, ethyl acetate extraction (2 * 50mL).Merge organic phase, the saturated common salt water washing and with anhydrous sodium sulfate drying, concentrate after, column chromatography (silica gel, sherwood oil/methylene dichloride eluent) separate 696mg product 2,7,9,9-four (triphen amido) fluorenes, yield 61.2%.Fusing point 194.7-196.1 ℃.
1H?NMR(CDCl
3)：δ7.80(d，J＝7.8Hz，2H)，8.72(s，1H)，7.57-7.64(m，4H)，7.19-7.30(m，16H)，7.12-7.17(m，16H)，7.02-7.08(m，12H)，6.96-7.00(m，4H)，6.93(d，J＝9.0Hz，2H)；
13C?NMR(CDCl
3)：δ64.7，120.53，120.55，122.9，123.07，123.11，123.9，124.5，126.3，127.9，129.1，129.3，129.4，135.3，138.7，139.7，140.1，146.3，147.2，147.68，147.73，152.5；MALDI-MS：1138(M
+)，1061，894，817，740；FT-IR(KBr)：v(cm
-1)1590，1492，1274，814，751，694。Electron spectrum data: UV-vis, λ
Max=373nm (methylene dichloride); PL, λ
Max=437nm (methylene dichloride).
Embodiment 22, two (the 2-naphthyls)-9 of 7-, and the Synthetic 2 of two (triphen amido) fluorenes of 9-, 7-two bromo-9, two (triphen amido) the fluorenes preparation methods of 9-are identical with embodiment 1.
Under the argon shield; in reaction flask, add 10.35g (50mmol) 2-bromonaphthalene successively; 1.32g (55mmol) magnesium chips and 100mL tetrahydrofuran (THF); return and heat up in a steamer reaction after 4 hours, be cooled to-78 ℃, add 14.1g (75mmol) boric acid three Virahol esters; stirred 2 hours; temperature rises to room temperature, continues to stir 10 hours, obtains green solution.Add 2N hydrochloric acid soln 500mL, stirring at room added water after 2 hours.Also with anhydrous sodium sulfate drying with after concentrating, the toluene recrystallization gets 3.18g 2-naphthyl list boric acid ester, yield 37% for extracted with diethyl ether, saturated common salt water washing.
Under the argon shield, in the 100mL reaction flask, add above-mentioned synthetic 2 successively, 7-two bromo-9,9-two (triphen amido) fluorenes 0.81g (1mmol), 2-naphthyl list boric acid ester 0.516g (3mmol) and 0.213g (0.2mmol) Pd (PPh
3)
4, after the gas displacement in the question response bottle is rare gas element, add the Na of 10mL toluene, 10mL glycol dimethyl ether and 4mL 2M
2CO
3The aqueous solution, mixture return and heat up in a steamer 24 hours.Add water 30mL, ethyl acetate extraction after being chilled to room temperature.Merge organic phase and use the saturated common salt water washing, anhydrous sodium sulfate drying, concentrate after, column chromatography (silica gel, sherwood oil/dichloromethane/ethyl acetate eluent) separate 506mg product 2, two (the 2-naphthyls)-9 of 7-, 9-pair of (triphen amido) fluorenes, yield 56%.
1H?NMR(CDCl
3)：δ8.05(s，2H)，7.93-7.89(m，8H)，7.80(s，2H)，7.78-7.74(m，4H)，7.54-7.46(m，4H)，7.26-7.18(m，12H)，7.08(d，J＝7.8Hz，8H)，7.0-6.95(m，8H)。
Embodiment 3 triphenylamines-fluorene compound as TPD help hole transport layer the time luminescent device manufacturing and performance
With TPD is hole transport layer, and triphenylamine-fluorene compound that previous embodiment 1 is obtained (numbering XB10) is as helping hole transport layer, Alq
3Being luminescent layer and electron transfer layer, is anode with the ito glass, and aluminum fluoride is an electron injecting layer, and aluminium is negative electrode, prepares luminescent device by the vacuum evaporation mode.The voltage and the brightness curve of device are seen Fig. 1.
Symbol among the figure is respectively:
With NPB is hole transport layer, and triphenylamine-fluorene compound that previous embodiment 1 is obtained (numbering XB10) is as helping hole transport layer, Alq
3Being luminescent layer and electron transfer layer, is anode with the ito glass, and aluminum fluoride is an electron injecting layer, and aluminium is negative electrode, prepares luminescent device by the vacuum evaporation mode.The voltage and the brightness curve of device are seen Fig. 2.
NPB is among the figure:
Claims (9)
1. a class has the compound of fluorenes-triphenylamine type structure, it is characterized in that having following chemical structure:
Wherein Ar is
2. the preparation method with compound of fluorenes-triphenylamine type structure as claimed in claim 1 is characterized in that being made by following method:
In containing the organic solvent of mineral alkali, in the presence of the mixture of organic palladium catalyzer or organic palladium catalyzer and organophosphorus ligand, 2,7-two chloro-9, two (triphen amido) fluorenes or 2 of 9-, 7-two bromo-9, organic boronic or its ester prepared in reaction of two (triphen amido) fluorenes of 9-and Ar; Ar according to claim 1 in the formula.
3. preparation method as claimed in claim 2 is characterized in that described 60～150 ℃ of reactions 10～48 hours, described 2 of being reflected at, 7-two chloro-9, two (triphen amido) fluorenes or 2 of 9-, 7-two bromo-9, organic boronic or its ester mol ratio of two (triphen amido) fluorenes of 9-and Ar are 1: 3～1: 4; Ar according to claim 1 in the formula.
4. preparation method as claimed in claim 2, it is characterized in that described 2,7-two chloro-9, two (triphen amido) fluorenes or 2 of 9-, 7-two bromo-9, two (triphen amido) fluorenes of 9-are prepared by following method: under methanesulfonic catalysis, triphenylamine and 2,7-dichloro 9-Fluorenone or 2,7-two bromo-9-Fluorenone prepared in reaction 2,7-two chloro-9, two (triphen amido) fluorenes or 2 of 9-, 7-two bromo-9, two (triphen the amido)-fluorenes of 9-.
5. preparation method as claimed in claim 2 is characterized in that the organic boronic of described Ar or its ester are prepared by following method: in organic solvent, ArBr reacts with the boron alkoxide acid esters under the n-Butyl Lithium effect, obtains the product of organic boronic or its ester; Ar according to claim 1 in the formula.
6. as claim 2,3,4 or 5 described preparation methods, it is characterized in that described organic palladium catalyzer is the title complex of palladium metal and organic phosphine.
7. as claim 2,3,4 or 5 described preparation methods, it is characterized in that described organic solvent is tetrahydrofuran (THF), glycol dimethyl ether, benzene, toluene or their mixture; Described organic palladium catalyzer is Pd (PPh
3)
4Or Pd (PPh
3)
2Cl
2, the mixture of described organic palladium and organophosphorus ligand is Pd
2(dba)
3With P (t-Bu)
3Mixture; Described mineral alkali is the aqueous solution of alkali metal hydroxide or alkaline carbonate.
8. as claim 2,3,4 or 5 described preparation methods, it is characterized in that described organic solvent is the mixture of toluene and glycol dimethyl ether, the volume ratio of this mixture is 1: 1; Described organic palladium catalyzer is Pd (PPh
3)
4Described mineral alkali is the aqueous sodium carbonate of 2M.
9. the purposes of a compound as claimed in claim 1 is characterized in that, helps the hole-transfer material as Organic Light Emitting Diode.
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| CN101538209B (en) * | 2009-04-22 | 2014-07-23 | 中国科学院上海有机化学研究所 | Novel X-shaped anthracene compound containing triphenylamine and flourenyl as well as preparation and application thereof |
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| CN102924522B (en) * | 2011-08-09 | 2015-12-16 | 海洋王照明科技股份有限公司 | Containing triphenylamine organic semiconductor material, its preparation method and application |
| CN102924514A (en) * | 2011-08-09 | 2013-02-13 | 海洋王照明科技股份有限公司 | Triphenylamine-containing organic semiconductor material, preparation method and applications thereof |
| CN102924513A (en) * | 2011-08-09 | 2013-02-13 | 海洋王照明科技股份有限公司 | Triphenylamine-containing organic semiconductor material, preparation method and applications thereof |
| CN102358745A (en) * | 2011-08-11 | 2012-02-22 | 河南省科学院化学研究所有限公司 | Method for preparing series of 2-boric acid-9,9-disubstituted fluorene |
| CN102491998B (en) * | 2011-12-02 | 2014-04-30 | 中国科学院长春应用化学研究所 | Bivalent palladium complex, preparation method for bivalent palladium complex, polyfluorene and preparation method for polyfluorene |
| KR102198635B1 (en) | 2012-04-20 | 2021-01-05 | 가부시키가이샤 한도오따이 에네루기 켄큐쇼 | Organic compound, light-emitting element, light-emitting device, electronic device, and lighting device |
| CN104016934B (en) * | 2014-06-19 | 2015-09-09 | 泰州市嘉新新材料有限公司 | One class has the macrocylc compound of triphenylamine by the both sides coupling of Fluorenone |
| CN105709692A (en) * | 2014-12-05 | 2016-06-29 | 中国石油化工股份有限公司 | Copper based metal organic skeleton material and preparation method thereof |
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| JPH07145372A (en) * | 1993-10-01 | 1995-06-06 | Toyo Ink Mfg Co Ltd | Hole-transport mateiral and its use |
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