CN1562999A - Compound of biindole heterocycles, preparation method and application in use for organic electroluminescence material - Google Patents
Compound of biindole heterocycles, preparation method and application in use for organic electroluminescence material Download PDFInfo
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Abstract
This invention relates to metal for prepn. of bis-indole heterocycle type organic electroluminescence material with characteristic of having indok-aromatic heterocycle-indole structure. advantages are: easy synthesis and purification, high opto-thermo stability, easy to be dissolved in organic solvent, high fluorescent light, high-hole conduction property, being used as hole conduction layer and luminous layer of OLED. In the prepn., indole boric acid or its ester and dihalogenated aromatic hydrocarbon or dihalogenated aromatic heterocycle compound are proceed Suzuki coupling reaction to obtain said product.
Description
Technical field
The present invention relates to the new two indoles heterocyclic compounds of a class, is that starting raw material makes by benzazolyl compounds.Compound provided by the present invention is a class potential electroluminescent material.
Background technology
Electroluminescent organic material (OLED) has been subjected to the close attention of scientific and technological circle and industrial community because of its huge applications prospect in flat-panel monitor.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, 1995,273,884; Journal of the American 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, hole transport layer adopts the lower triphenylamine compounds of oxidizing potential more; Luminescent layer utilizes luminescent dye or its blends such as red, green, blue; Electron transfer layer Duo Yong Er oxazole compounds etc.In addition, cooperate electronics blocking material or hole barrier materials, to adjust glow color and brightness.
Form in all materials of Organic Light Emitting Diode, 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.
Two indoles hetero-aromatic ring compounds have the chemical structure similar with triphenylamine, and the electrochemical oxidation current potential is also approaching with triphenylamine, but are better than triphenylamine on synthetic and purification process.Preparation cost is also low than triphen amine material simultaneously.Based on this, the present invention uses two indoles hetero-aromatic ring compounds as electroluminescent material.
Two indoles hetero-aromatic ring compounds are common in (Journal of OrganicChemistry in the marine indole Alkaloid, 2002,67,9392-9396), it is a class potential medicine, the contriver once described the synthetic of an other class double-indole hetero-aromatic ring compounds in detail in the patent that is had (Chinese invention patent ZL 98122898.8, two indoles heterogeneous ring compounds, preparation method and its usage), and drug effect.
Summary of the invention
The present invention is intended to the two indoles heterogeneous ring compounds of new class are applied to electroluminescent organic material, to widen the purposes of this compounds as the expansion of above-mentioned Chinese invention patent.
Novel electroluminescent material provided by the present invention has following general structure:
Wherein, R
1, R
2Be H, C
1～C
6Alkyl, C
5～C
7Cycloalkyl, C
1～C
6Alkyl silyl, benzyl, C
1～C
18Carbonic acyl radical, benzoyl, the benzenesulfonyl of alkyl.R
1, R
2Can be the same or different; R ' is H, C
1～C
6Alkyl, C
1～C
6Alkoxyl group, C
5～C
7Cycloalkyl, preferred R
1, R
2Be H, C
1～C
6The bright base of alkyl, cyclopentyl, cyclohexyl, vinyl, propenyl, alkene, ethynyl, C
1～C
6Alkyl silyl, benzyl, C
1～C
6Carbonic acyl radical, benzoyl, the benzenesulfonyl of alkyl.Preferred R ' is H, C
1～C
6Alkyl, C
1～C
6Alkoxyl group, cyclopentyl, cyclohexyl, vinyl, propenyl, allyl group, ethynyl.Ar is for replacing or do not have the aromatic ring or the hetero-aromatic ring of replacement, and its structure is:
In the following formula, R is H, C
1～C
6Alkyl, C
5～C
7Cycloalkyl, phenyl, benzyl.Preferred R is H, C
1～C
6Alkyl, cyclopentyl, cyclohexyl, phenyl, benzyl.
Of the present invention pair of indoles heterogeneous ring compound can prepare by following method:
Indoles boric acid or its ester
With dihalo aromatic hydrocarbons X-Ar-X (X be Cl or
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, the mol ratio preferred 1 of indoles boric acid or its ester and dihalo aromatic hydrocarbons X-Ar-X (X is Cl or Br): 1-1.5, the organic palladium catalyst levels is preferably 5-10mol% (with respect to dihalo aromatic hydrocarbons), and the mineral alkali consumption is preferably the twice (mol ratio) of indoles boric acid or its ester.
R in the structural formula of aforementioned reactant and product
1During for H, preparation method of the present invention also can further comprise: in organic solvent, and previous reaction product, alkali and R
1Br or R
3Br (R
1, R
2Be not H) reaction, the mol ratio of aforementioned each component preferably is followed successively by 1: 1～5: 1～2.5, obtains product
(R
1, R
2Be not H).This reaction is preferably carried out in room temperature, preferred reaction 1～6h, the hydride or the oxyhydroxide of described alkali preferred as alkali or alkaline-earth metal, for example NaH etc.
Wherein, R ', R
1, R
2, Ar, R definition unless otherwise indicated, all as previously mentioned.
The mixture of described organic palladium and organophosphorus ligand can be Pd
2(dba)
3With P (t-Bu)
3Mixture
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 can be Pd (PPh
3)
4, Pd (PPh
3)
2Cl
2Or Pd
2(dba)
3/ P (t-Bu)
3, be preferably Pd (PPh
3)
4
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.
Of the present invention couple of indoles heterogeneous ring compound preparation technology is simple, and the yield height is easy to purifying.And compound has optical property preferably, and chemical property and carbazole and triphenylamine compounds are similar, can be used as electroluminescent organic material.
Table 1 is the performance of the luminescent device of a kind of pair of indoles heterogeneous ring compound preparation.
The performance that table 1. is the luminescent device of hole transport layer by two indoles heterogeneous ring compounds
[notes]
[notes] device constitutes: ITO/Y-1/Perylene/TPBi/Alq
3/ MgAg
ITO is an indium tin oxide-coated glass, Perylene Ji perylene, Alq
3=three (oxine closes aluminium);
By table 1 as seen, the alternative NPB of two indoles heterogeneous ring compounds is as hole transport layer, and the device that is obtained has higher luminous intensity and luminous efficiency.
Embodiment
Following examples help and understand the present invention, but are not limited to content of the present invention.
Embodiment 1 3-methoxyl group-2, two (N-benzyl-3 '-indoles) pyrazines of 5-synthetic
Under the argon shield; in the 100mL reaction flask, add successively 825mg (3mmol) N-tertiary butyl dimethyl silica-based-3-indoles boric acid glycol ester (presses Journal of Organic Chemistry; 1994; 59; the preparation of 10-11 institute report method), 268mg (1mmol) 3-methoxyl group-2,5-two bromo-pyrazines and 116mg (0.1mmol) Pd (PPh
3)
4, the gas displacement in the reaction flask is rare gas element after, add 20mL toluene and 20mL glycol dimethyl ether, the back that stirs adds the aqueous sodium carbonate of 3mL 2M.Mixture heating up is to 80-100 ℃, and under this temperature stir about 24 hours.Add water 30mL after being chilled to room temperature.Ethyl acetate extraction (2 * 50mL); Merge organic phase, saturated common salt water washing and with behind the anhydrous sodium sulfate drying, pressure reducing and steaming organic solvent.Residue dissolves with tetrahydrofuran (THF), the tetrahydrofuran solution of adding TBAF (tetrabutyl ammonium fluoride) (1M, 3mL, 3mmol), stirring at room adds water 20mL after 6 hours, ethyl acetate extraction (2 * 30mL), merge organic phase, the saturated common salt water washing is also with anhydrous sodium sulfate drying with after concentrating, column chromatography (silica gel, sherwood oil/methylene dichloride wash-out) separate 327mg 3-methoxyl group-2, two (3 '-indoles)-pyrazines of 5-, yield 96%.
Get above-mentioned synthetic 3-methoxyl group-2, two (3 '-indoles)-pyrazine 267mg (0.79mmol) of 5-are dissolved in the 15mL dry DMF, add NaH (4 equivalent) under the room temperature, stir to add benzyl bromine (4 equivalent) after 15 minutes.Mixture adds the 200mL shrend reaction of going out after stirring 4 hours under the 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 the 365mg product, yield 89%.Fusing point 268.4-268.8 ℃.
1H?NMR(CDCl
3)：δ8.88-8.92(m，1H)，8.72(s，1H)，8.53-8.56(m，1H)，8.19(s，1H)，7.80(s，1H)，7.23-7.37(m，12H)，7.17-7.21(m，4H)，5.44(s，2H)，5.41(s，2H)，4.26(s，3H)；
13C?NMR(CDCl
3)：δ50.61，50.64，53.9，110.0，110.4，111.7，114.1，121.11，121.15，122.1，122.8，123.6，126.5，126.8，127.1，127.7，127.9，128.0，128.1，129.0，129.1，131.7，132.1，136.9，137.0，137.1，137.4.137.6，155.9；FT-IR(KBr)：ν(cm
-1)1551，1397，1365，1092，738。Electron spectrum data: UV-vis, λ
Max=388nm (toluene); PL, λ
Max=431nm (methylene dichloride).
Embodiment 2 2-dimethylaminos-3, two (N-benzyl-3 '-the indoles)-pyrazines of 5-synthetic
Under the argon shield, in the 200mL reaction flask, add successively 3.85g (14mmol) N-tertiary butyl dimethyl silica-based-3-indoles boric acid glycol ester, 1.267g (4.6mmol) 3-methoxyl group-2,5-two bromo-pyrazines, 531mg (0.46mmol) Pd (PPh
3)
4Reaction flask with inert gas replacement after, add 40mL toluene and 40mL glycol dimethyl ether, after stirring evenly, add the aqueous sodium carbonate of 14mL 2M.Mixture heating up is to 80-100 ℃, and under this temperature stir about 24 hours.After reaction mixture is chilled to room temperature, add water 50mL, with ethyl acetate extraction (2 * 50mL).Merge organic phase, with the saturated common salt water washing with behind the anhydrous sodium sulfate drying, the pressure reducing and steaming organic solvent.Residue is dissolved in tetrahydrofuran (THF), the tetrahydrofuran solution of adding TBAF (14mmol), stirring at room adds water 30mL after 6 hours for 1M, 14mL, and ethyl acetate extraction (2 * 30mL), merge organic phase, use the saturated common salt water washing, anhydrous sodium sulfate drying concentrates.Residual column chromatography (silica gel, the sherwood oil/methylene dichloride wash-out) purifying of using mixedly gets 1.46g 2-dimethylamino-3, two (3 '-indoles)-pyrazines of 5-, yield 90%.
Get above-mentioned synthetic 2-dimethylamino-3, two (N-benzyl-3 '-the indoles)-pyrazine 806mg (2.28mmol) of 5-are dissolved in the 20mL dry DMF, add NaH (4 equivalent), stir under the room temperature to add benzyl bromine (4 equivalent) after 15 minutes.Stir after 4 hours and to add about 200mL shrend reaction of going out.Mixture ethyl acetate extraction (2 * 50mL).Merge organic phase, behind saturated common salt water washing and anhydrous sodium sulfate drying, removal of solvent under reduced pressure.Residue (silica gel, sherwood oil/methylene dichloride wash-out) purifying gets the 744mg product, yield 61%.Fusing point 190.7-190.9 ℃.EI-MS m/z (%): 533 (M
+, 100);
1H NMR (CDCl
3): δ 8.40-8.43 (m, 1H), 8.34 (s, 1H), 8.23-8.26 (m, 1H), 7.94 (s, 1H), 7.66 (s, 1H), 7.08-7.25 (m, 16H), 5.31 (s, 2H), 5.30 (s, 2H), 2.74 (s, 6H); 1
3C NMR (CDCl
3): δ 41.6,50.6, and 110.1,110.4,114.6,114.8,120.8,120.9,121.9,122.5,122.6,123.2,126.5,127.1,127.2,127.5,127.6,128.0,129.11,129.13,130.2,133.6,137.0,137.4,137.6,141.2,142.0,154.0; Ultimate analysis. calculated value, C
36H
31N
5: C, 81.02; H, 5.86; N, 13.12; Measured value: C, 80.58; H, 5.84; N, 13.12; FT-IR (KBr): ν (cm
-1) 1536,1171,742,728.
Electron spectrum data: UV-vis, λ
Max=302nm, 383nm (toluene); PL, λ
Max=460nm (methylene dichloride).
Embodiment 32, two (N-benzyl-3 '-the indoles)-pyrazines of 5-synthetic
Under the argon shield, 3.3g (12mmol) N-tertiary butyl dimethyl is silica-based-3-indoles boric acid, 952mg (4mmol) 2, and 5-two bromo-pyrazines, 463mg (0.4mmol) Pd (PPh
3)
4Add successively in the 200mL reaction flask, reaction flask adds with rare gas element and fills the back and add 50mL toluene and 50mL glycol dimethyl ether, stirs well the aqueous sodium carbonate that the back adds 12mL 2M.Mixture heating up is to 80-100 ℃, and under this temperature stir about 24 hours.Add water 50mL after being chilled to room temperature, with ethyl acetate extraction (2 * 50mL).Merge organic phase and with the saturated common salt water washing, behind the anhydrous sodium sulfate drying, the pressure reducing and steaming organic solvent.Residue dissolves with tetrahydrofuran (THF), adds tetrahydrofuran solution (1M, the 12mL of TBAF, 12mmol), stirring at room adds water 20mL, ethyl acetate extraction (2 * 30mL) after 6 hours, merge organic phase and with the saturated common salt water washing, behind anhydrous sodium sulfate drying, the pressure reducing and steaming organic solvent.Enriched material gets 760mg 2 through column chromatography purification, two (3 '-indoles)-pyrazines (62%) of 5-.Under the room temperature, 654mg (2.11mmol) 2, two (3 '-indoles)-pyrazines of 5-are dissolved in the 15mL dry DMF, add NaH (4 equivalent), stir under the room temperature to add benzyl bromine (4 equivalent) after 15 minutes; Stirring at room adds the shrend reaction of going out after 4 hours, add about 200mL water, uses ethyl acetate extraction (2 * 50mL) then.The organic phase that merges is with the saturated common salt water washing and use anhydrous sodium sulfate drying.Concentrate back column chromatography (silica gel, sherwood oil/methylene dichloride wash-out) and get 490mg product, yield 49%.212 ℃ of fusing points (decomposition).EI-MS m/z (%): 490 (M
+, 56.9), 91 (100);
1H NMR (CDCl
3): δ 9.00 (s, 2H), 8.38-8.41 (m, 2H), 7.80 (s, 2H), 7.18-7.37 (m, 16H), 5.40 (s, 4H);
13C NMR (CDCl
3): δ 50.40,110.2, and 113.8,121.1,121.4,122.6,126.0,126.8,127.8,128.0,128.8,136.6,137.3,140.8,146.6; The HRMS calculated value, C
34H
26N
4490.2151, measured value, 490.2169; FT-IR (KBr): FT-IR (KBr): ν (cm
-1), 1552,1454,1382,1145,743.Electron spectrum data: UV-vis, λ
Max=381nm (toluene); PL, λ
Max=435nm (methylene dichloride).
Embodiment 4 5-methoxyl groups-2, two (N-benzyl-3 '-the indoles)-pyrimidines of 4-synthetic
Under the argon shield, 945mg (3mmol) N-p-toluenesulfonyl-3-indoles boric acid (Heterocycles1992,34,1169), 179mg (1mmol) 5-methoxyl group-2,4-two chloro-pyrimidines, 9.2mg (0.01mmol) Pd
2(dba)
3, 580mg KF adds in the 100mL reaction flask successively, gas adds 4.9 microlitre P (t-Bu) in the reaction flask behind inert gas replacement
3, the 10mL tetrahydrofuran (THF).Mixture heating up is to 80-100 ℃, and under this temperature stir about 48 hours.Be chilled to suction filtration after the room temperature.Behind the pressure reducing and steaming organic solvent, the residue dissolve with methanol, add NaOH (10 equivalent), reflux to stir after 2 hours underpressure distillation and remove methyl alcohol, after adding water, with ethyl acetate extraction (2 * 30mL), merge organic phase and with the saturated common salt water washing, behind the anhydrous sodium sulfate drying, the pressure reducing and steaming organic solvent.Enriched material gets 232mg 5-methoxyl group-2 with column chromatography purification, two (3 '-indoles)-pyrimidines (78%) of 4-.Under the room temperature, 153mg 2,5-methoxyl group-2, and two (3 '-indoles)-pyrimidines of 4-are dissolved in the 10mL dry DMF, add NaH (4 equivalent), stir under the room temperature to add benzyl bromine (4 equivalent) after 15 minutes; Stirring at room adds the shrend reaction of going out after 4 hours, add about 100mL water, uses ethyl acetate extraction (2 * 50mL) then.The organic phase that merges is with the saturated common salt water washing and use anhydrous sodium sulfate drying.Concentrate back column chromatography (silica gel, sherwood oil/methylene dichloride wash-out) and get 221mg product, yield 83%.Fusing point 259.9-260.3 ℃.EI-MS m/z (%): 520 (M
+, 60.6), 91 (100);
1H NMR (CDCl
3): δ 8.96-9.00 (m, 1H), 8.78-8.81 (m, 1H), 8.39 (s, 1H), 8.27 (s, 1H), 8.12 (s, 1H), 7.17-7.34 (m, 16H), 5.44 (s, 4H), 5.35 (s, 4H), 4.04 (s, 1H);
13C NMR (CDCl
3): δ 50.7,50.8, and 110.10,110.12,111.3,116.6,121.0,121.5,122.4,123.0,123.1,124.0,126.9,127.1,127.4,127.7,128.0,129.06,129.08,129.09,130.7,134.5,136.8,137.0,137.1,137.56,137.6,138.6,147.2,151.4,151.0; The HRMS calculated value, C
35H
28N
4O:540.2257, measured value, 520.2251; FT-IR (KBr): ν (cm
-1), 1536,1450,1389,1174,1018,740,728,696.Electron spectrum data: UV-vis, λ
Max=321nm (toluene); PL, λ
Max=407nm (methylene dichloride).
Embodiment 54, two (the N-benzyls-3 '-indoles)-2,1 of 7-, 3-diazosulfide synthetic
Under the argon shield, 3.3g (12mmol) N-tertiary butyl dimethyl is silica-based-3-indoles boric acid, 1176mg (4mmol) 4, and 5-two bromo-2,1,3-diazosulfide, 463mg (0.4mmol) Pd (PPh
3)
4Add successively in the 200mL reaction flask, reaction flask adds with rare gas element and fills the back and add 50mL toluene and 50mL glycol dimethyl ether, stirs well the aqueous sodium carbonate that the back adds 12mL 2M.Mixture heating up is to 80-100 ℃, and under this temperature stir about 24 hours.Add water 50mL after being chilled to room temperature, with ethyl acetate extraction (2 * 50mL).Merge organic phase and with the saturated common salt water washing, behind the anhydrous sodium sulfate drying, the pressure reducing and steaming organic solvent.Residue dissolves with tetrahydrofuran (THF), adds tetrahydrofuran solution (1M, the 12mL of TBAF, 12mmol), stirring at room adds water 20mL, ethyl acetate extraction (2 * 30mL) after 6 hours, merge organic phase and with the saturated common salt water washing, behind anhydrous sodium sulfate drying, the pressure reducing and steaming organic solvent.Enriched material gets 4 through column chromatography purification, two (3 '-indoles)-2,1 of 7-, 3-diazosulfide, yield 62%.Under the room temperature, 4 of 2.11mmol, two (3 '-indoles)-2,1 of 7-, the 3-diazosulfide is dissolved in the 15mL dry DMF, adds NaH (4 equivalent), stirs under the room temperature to add benzyl bromine (4 equivalent) after 15 minutes; Stirring at room adds the shrend reaction of going out after 4 hours, add about 200mL water, uses ethyl acetate extraction (2 * 50mL) then.The organic phase that merges is with the saturated common salt water washing and use anhydrous sodium sulfate drying.Concentrate back column chromatography (silica gel, sherwood oil/methylene dichloride wash-out) and get required product, yield 70%.MALDI m/z:546 (M
+);
1H NMR (CDCl
3): δ 8.32 (s, 2H), 8.14-8.19 (m, 4H), 7.24-7.42 (m, 16H), 5.50 (s, 4H); Ultimate analysis, C
36H
26N
4S, calculated value (%), C, 79.09, H, 4.79, N, 10.25; Measured value, C, 78.77, H, 4.84, N, 10.19.Electron spectrum data: UV-vis, λ
Max=465nm (methylene dichloride); PL, λ
Max=610nm (methylene dichloride).
Embodiment 6 bis-benzazolyl compounds are as the luminescent device of hole transport layer
As hole transport layer, with hole blocking layer TPBi and luminescent layer Perylene combination, is anode with ito glass with bis-benzazolyl compounds that previous embodiment obtained, and the magnesium silver alloys is a negative electrode, prepares luminescent device by the vacuum evaporation mode.The performance of typical device sees Table 1.
Claims (10)
1. a class has the compound of indoles-heterocycle-indoles type structure, it is characterized in that having following chemical structure:
Wherein, R
1, R
2Be H, C
1～C
6Alkyl, C
5～C
7Cycloalkyl, C
1～C
6Alkyl silyl, benzyl, C
1～C
18Carbonic acyl radical, benzoyl, the benzenesulfonyl of alkyl.R
1, R
2Can be the same or different; R ' is H, C
1～C
6Alkyl, C
1～C
6Alkoxyl group, C
5～C
7Cycloalkyl, Ar=
In the following formula, R is H, C
1～C
6Alkyl, C
5～C
7Cycloalkyl, phenyl, benzyl.
2. compound as claimed in claim 1 is characterized in that described R
1, R
2Be H, C
1～C
6The bright base of alkyl, cyclopentyl, cyclohexyl, vinyl, propenyl, alkene, ethynyl, C
1～C
6Alkyl silyl, benzyl, C
1～C
6Carbonic acyl radical, benzoyl, the benzenesulfonyl of alkyl, R
1, R
2Can be the same or different; R ' and R " be H, C
1～C
6Alkyl, C
1～C
6Alkoxyl group, cyclopentyl, cyclohexyl, vinyl, propenyl, allyl group, ethynyl, R ', R " can be the same or different; R is H, C
1～C
6Alkyl, cyclopentyl, cyclohexyl, phenyl, benzyl.
3. the preparation method of the compound of indoles-heterocycle as claimed in claim 1-indoles type structure is characterized in that being made by following method (1) or method (1), (2):
(1). in containing the organic solvent of mineral alkali, in the presence of the mixture of organic palladium or organic palladium and organophosphorus ligand, molecular formula is
Indoles boric acid or its ester and molecular formula be the dihalo aromatic hydrocarbons prepared in reaction of X-Ar-X (X is Cl or Br); .
(2). in organic solvent, the product (R of (1)
1Be H), alkali and R
1Br or R
2Br (R
1, R
2Be not H) reaction.
4. preparation method as claimed in claim 3 is characterized in that being made by following method (1) or method (1), (2):
(1). in containing the organic solvent of mineral alkali, in the presence of the mixture of the title complex of the title complex of palladium metal and organic phosphine or palladium metal and organic phosphine and organophosphorus ligand, molecular formula is
Indoles boric acid or its ester and molecular formula be 1 for dihalo aromatic hydrocarbons mol ratio for X-Ar-X (X is Cl or Br): during 1-1.5, in 60-150 ℃ of reaction 10-48 hour down;
(2). in organic solvent, the product of (1) (R1 is H), alkali and R
1Br or R
2Br (R
1, R
2For H) react under the room temperature.
5. as claim 3 or 4 described preparation methods, it is characterized in that (2) described alkali is the hydride or the oxyhydroxide of basic metal or alkaline-earth metal.
6. preparation method as claimed in claim 3 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 or organic palladium and organophosphorus ligand, molecular formula is
Indoles boric acid or its ester and the molecular formula dihalo aromatic hydrocarbons mol ratio that is X-Ar-X (X is Cl or Br) be 1: during 1-1.5, in 80-100 ℃ of reaction 10-48 hour down.
7. preparation method as claimed in claim 3 is characterized in that described organic palladium catalyst levels is 5-10mol% (with respect to a dihalo aromatic hydrocarbons), and the mineral alkali consumption is the twice (mol ratio) of described indoles boric acid or its ester.
8. preparation method as claimed in claim 3 is characterized in that described organic solvent is tetrahydrofuran (THF), glycol dimethyl ether, benzene, toluene; Described organic palladium catalyzer can be Pd (PPh
3)
4, Pd (PPh
3)
2Cl
2, the mixture of described organic palladium and organophosphorus ligand can be Pd
2(dba)
3With P (t-Bu)
3Mixture; Described mineral alkali is the aqueous solution of alkali metal hydroxide or alkaline carbonate.
9. preparation method as claimed in claim 3 is characterized in that described organic solvent is the mixture of 1: 1 (volume ratio) of toluene and glycol dimethyl ether; Described organic palladium catalyzer is Pd (PPh
3)
4Described mineral alkali is the aqueous sodium carbonate of 2M.
10. the purposes of indoles-heterocycle as claimed in claim 1-indoles type structural compounds is characterized in that, as electroluminescent organic material.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100177455A CN100384835C (en) | 2004-04-16 | 2004-04-16 | Compound of biindole heterocycles, preparation method and application in use for organic electroluminescence material |
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| CNB2004100177455A CN100384835C (en) | 2004-04-16 | 2004-04-16 | Compound of biindole heterocycles, preparation method and application in use for organic electroluminescence material |
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| CN100384835C CN100384835C (en) | 2008-04-30 |
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| WO2008123540A2 (en) * | 2007-03-30 | 2008-10-16 | Fujifilm Corporation | Organic electroluminescent device |
| CN100465159C (en) * | 2006-07-27 | 2009-03-04 | 鞍山科技大学 | Synthesis of 3-substituted phenyl indole compound |
| WO2009157428A1 (en) * | 2008-06-23 | 2009-12-30 | 住友化学株式会社 | Phosphorescent light-emitting composition and light-emitting element comprising the composition |
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| CN104725296A (en) * | 2013-12-24 | 2015-06-24 | 北京鼎材科技有限公司 | Indole derivative and application thereof to organic electroluminescence |
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| JPH06212151A (en) * | 1993-01-14 | 1994-08-02 | Toyo Ink Mfg Co Ltd | Organic electroluminescent element |
| JP2000219677A (en) * | 1999-01-28 | 2000-08-08 | Mitsubishi Paper Mills Ltd | Organic photoconductive compound and electrophotographic photoreceptor using the same |
| JP4090874B2 (en) * | 2000-10-05 | 2008-05-28 | 新日鐵化学株式会社 | Organic electroluminescence device |
| US6670053B2 (en) * | 2002-02-26 | 2003-12-30 | Eastman Kodak Company | Organic electroluminescent devices with high luminance |
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| CN100465159C (en) * | 2006-07-27 | 2009-03-04 | 鞍山科技大学 | Synthesis of 3-substituted phenyl indole compound |
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| WO2008123540A2 (en) * | 2007-03-30 | 2008-10-16 | Fujifilm Corporation | Organic electroluminescent device |
| KR101627543B1 (en) * | 2007-03-30 | 2016-06-07 | 유디씨 아일랜드 리미티드 | Organic electroluminescent device |
| CN101646746B (en) * | 2007-03-30 | 2013-03-27 | Udc爱尔兰有限公司 | Organic electroluminescent device |
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| US8890122B2 (en) | 2007-03-30 | 2014-11-18 | Udc Ireland Limited | Organic electroluminescent device |
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| CN104725296A (en) * | 2013-12-24 | 2015-06-24 | 北京鼎材科技有限公司 | Indole derivative and application thereof to organic electroluminescence |
| CN104725296B (en) * | 2013-12-24 | 2019-11-29 | 北京鼎材科技有限公司 | Indole derivatives and its application in field of organic electroluminescence |
| CN104017571A (en) * | 2014-06-11 | 2014-09-03 | 郑州大学 | Organic electroluminescent material and application thereof |
| CN104017571B (en) * | 2014-06-11 | 2016-02-17 | 郑州大学 | Electroluminescent organic material and application thereof |
| JP2016210753A (en) * | 2015-05-13 | 2016-12-15 | 国立大学法人横浜国立大学 | Indolyl benzothiadiazole derivative, method for producing indolyl benzothiadiazole derivative and organic fluorescent material |
| CN106467458A (en) * | 2016-07-27 | 2017-03-01 | 江苏三月光电科技有限公司 | A kind of compound based on diaryl ketone and its application on organic electroluminescence device |
| CN106467458B (en) * | 2016-07-27 | 2019-05-24 | 江苏三月光电科技有限公司 | A kind of compound based on diaryl ketone and its application on organic electroluminescence device |
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