CN103570627A - Indenofluorene derivative containing pyrimidyl or pyrazinyl or triazinyl group, and its application - Google Patents

Indenofluorene derivative containing pyrimidyl or pyrazinyl or triazinyl group, and its application Download PDF

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CN103570627A
CN103570627A CN201210264023.4A CN201210264023A CN103570627A CN 103570627 A CN103570627 A CN 103570627A CN 201210264023 A CN201210264023 A CN 201210264023A CN 103570627 A CN103570627 A CN 103570627A
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atom
time simultaneously
atomic time
heterocycle
aromatic
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CN103570627B (en
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邱勇
李银奎
段炼
范洪涛
任雪艳
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Tsinghua University
Beijing Visionox Technology Co Ltd
Kunshan Visionox Display Co Ltd
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Tsinghua University
Beijing Visionox Technology Co Ltd
Kunshan Visionox Display Co Ltd
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Abstract

The invention provides a novel compound having a structure represented by formula (I). In the formula (I), R1 to R5 are respectively independently selected from C1-C20 aliphatic alkyl groups or C6-C20 aromatic groups; Ar is selected from C4-C30 aromatic rings, C4-C30 N-containing heterocyclic rings, C4-C30 condensed heterocyclic aromatic hydrocarbons, C4-C30 arylamino groups or C4-C30 aryloxy groups; n is 1 or 2; A1 to A4 are N atoms or C atoms, A2 and A4 are the C atoms when the A1 and the A3 are the N atoms, or A2 and A3 are the C atoms when A1 and the A4 are the N atoms, or A1 and A3 are the C atoms when A2 and A4 are the N atoms, or A1 and A2 are the C atoms when A3 and A4 are the N atoms, or A2 is the C atom when A1, A3 and A4 are the N atoms; and L is a singly-bonded or C6-C10 aromatic ring or a C4-C10 N-containing heterocyclic ring. The compound is used in organic electroluminescent devices as an electron transfer layer material or a luminescent host material.

Description

A kind of indenofluorene analog derivative and application that contains pyrimidine or pyrazine or triazine group
Technical field
The present invention relates to a kind of novel organic materials, relate in particular to a kind of compound for organic electroluminescence device and preparation method thereof and the application of this compound in ORGANIC ELECTROLUMINESCENCE DISPLAYS technical field.
Background technology
The electron transport material that tradition is used in electroluminescent device is Alq 3, but Alq 3electronic mobility lower (greatly about 10 -6cm 2/ Vs).In order to improve the electronic transmission performance of electroluminescence device, researchist has done a large amount of exploratory study work.The people such as Yang Yang use nano level carbonic acid caesium as electric transmission and injecting material in electroluminescent device, have improved the luminous efficiency (Advanced Functional Materials, 2007,17,1966 – 1973) of device.The people such as Cao Yong synthesize FFF-Blm4(J.Am.Chem.Soc.; (Communication); 2008; 130 (11); 3282-3283.) as electric transmission and input horizon material (with Ba/Al and compare as negative electrode with Al separately), improved widely electronic injection and the transmittability of device, improved electroluminescent efficiency; The people such as Cao Yong also use to air and various chemical corrosion all stable Au as efficent electronic injection type cathode material, improved electroluminescent device electronic injection ability (Organic Electronics, 6 (2005), 118-128.).Kodak is in United States Patent (USP) (publication number US2006/0204784 and US2007/0048545), mention mixed electronic transport layer, the electron transport material of the material that adopts a kind of low lumo energy and another kind of low bright voltage and other materials form as doping such as metallic substance.Device based on this mixed electronic transport layer, efficiency and life-span etc. is all improved, but has increased the complicacy of device fabrication, is unfavorable for reducing OLED cost.
Desirable electron transport material, should have the characteristic of following several respects: have reversible electrochemical reducting reaction; HOMO and lumo energy are suitable; Electronic mobility is high; Good film-forming property; Tg is high; Preferably can blocking hole.From compound structure aspect, require molecular configuration to approach plane, the π while increasing molecular stacks between molecule-π interacts, and requires molecular structure plane completely simultaneously, prevents because molecular crystal affects film forming properties; Require molecule to contain electron deficiency structural unit, there is the good electronic capability of accepting; Molecular weight is enough large, guarantees to have higher Tg, thereby has good thermostability, and molecular weight can not be too large simultaneously, is beneficial to vacuum evaporation film forming.
Research has shown the compounds containing pyridyl, can be used as electron transport material (Chinese Patent Application No.: 200910234760.8,201010258716.3,201010512611.6, etc.).On this basis, continued to study the compound that contains the groups such as pyrimidine, pyrazine, triazine, these compounds are typical electron deficiency systems, have the good electronic capability of accepting; Indenofluorene has terphenyl structure, but owing to being fixed by a five-ring between benzene and benzene, makes three phenyl ring in same plane, and between the π molecular orbital(MO) between three phenyl ring, conjugation is fine, thereby has good transmittability.When these electron deficiency groups are connected with indenofluorene, the plane regularity of indenofluorene and large long-chain conjugated system, the π-π track heap superimposition that is conducive to molecule forms electron channel.
Therefore, electron transport material and/or the electron injection material of exploitation stability and high efficiency, thus reduced bright voltage, improve device efficiency, extend device lifetime, there is very important actual application value.
Summary of the invention
The object of the present invention is to provide a class novel cpd, this compounds can be for ORGANIC ELECTROLUMINESCENCE DISPLAYS field.
Indenofluorene has long-chain conjugated structure, and due to pentacyclic restriction, makes three phenyl ring of indenofluorene have good coplanarity, and the π-π track heap superimposition that is conducive to molecule forms electron channel.And the reduction potential of pyrimidine, pyrazine, triazine group is not lower containing heteroatomic aromaticity group than analog structure, be more conducive to accept electronics, respectively the pyrimidine of electron deficiency, pyrazine, triazine group are incorporated into into the both sides to indenofluorene, improve on the one hand electron acceptability and the mobility of this compounds, be conducive on the other hand the film-forming properties of this compounds.Therefore compound of the present invention has higher electronic transmission performance, good film-forming property, and applied device at room temperature has higher stability.In addition, this class material has the molecular orbital(MO) matching each other with luminescent dye, so this class material both can be used as electron transport material in electroluminescence device, also can be used as luminous material of main part.
A derivative, has suc as formula the structure shown in (I):
Figure BDA00001941932500021
Wherein:
R1 to R5 is independently selected from respectively the aliphatic alkyl of C1 ~ C20 or the aromatic group of C6 ~ C20;
Ar be selected from C4 ~ C30 aromatic ring, C4 ~ C30 containing N heterocycle, the annelated heterocycles aromatic hydrocarbons of C4 ~ C30, the virtue amino of C4 ~ C30 or the aryloxy of C4 ~ C30;
N is 1 or 2;
A1 to A4 is N atom or C atom;
When A1, A3 are the N atomic time simultaneously, A2 and A4 are C atom;
Or when A1, A4 are the N atomic time simultaneously, A2 and A3 are C atom;
Or when A2, A4 are the N atomic time simultaneously, A1 and A3 are C atom;
Or when A3, A4 are the N atomic time simultaneously, A1 and A2 are C atom;
Or A1, A3, A4 are the N atomic time simultaneously, A2 is C atom;
L be the aromatic ring of singly-bound or C6 ~ C10 or C4 ~ C10 containing N heterocycle.
Further, the six-membered ring group that contains A1 ~ A4 described in is selected from structural formula:
Figure BDA00001941932500031
Further, described indenofluorene derivative has structure shown in formula (II):
Figure BDA00001941932500032
Wherein:
R1 to R5 is independently selected from respectively the aliphatic alkyl of C1 ~ C20 or the aromatic group of C6 ~ C20;
Ar be selected from C4 ~ C30 aromatic ring, C4 ~ C30 containing N heterocycle, the annelated heterocycles aromatic hydrocarbons of C4 ~ C30, the virtue amino of C4 ~ C30 or the aryloxy of C4 ~ C30;
N is 1 or 2;
L be the aromatic ring of singly-bound or C6 ~ C10 or C4 ~ C10 containing N heterocycle.
Further, described indenofluorene derivative has structure shown in formula (III):
Figure BDA00001941932500033
Wherein:
R1 to R5 is independently selected from respectively the aliphatic alkyl of C1 ~ C20 or the aromatic group of C6 ~ C20;
Ar be selected from C4 ~ C30 aromatic ring, C4 ~ C30 containing N heterocycle, the annelated heterocycles aromatic hydrocarbons of C4 ~ C30, the virtue amino of C4 ~ C30 or the aryloxy of C4 ~ C30;
N is 1 or 2;
L be the aromatic ring of singly-bound or C6 ~ C10 or C4 ~ C10 containing N heterocycle.
Further, described indenofluorene derivative has structure shown in formula (IV):
Figure BDA00001941932500034
（IV）
Wherein:
R1 to R5 is independently selected from respectively the aliphatic alkyl of C1 ~ C20 or the aromatic group of C6 ~ C20;
Ar be selected from C4 ~ C30 aromatic ring, C4 ~ C30 containing N heterocycle, the annelated heterocycles aromatic hydrocarbons of C4 ~ C30, the virtue amino of C4 ~ C30 or the aryloxy of C4 ~ C30;
N is 1 or 2;
L be the aromatic ring of singly-bound or C6 ~ C10 or C4 ~ C10 containing N heterocycle.
Described aliphatic alkyl is selected from: the cycloalkyl of C3 ~ C12 or contain ethylene linkage or the alkyl of the C3 ~ C12 of acetylene bond.
Described aromatic group is selected from: pyridyl, phenyl or naphthyl.
Heteroatoms in described annelated heterocycles aromatic hydrocarbons is N atom.
In order more to clearly demonstrate content of the present invention, the preferred structure in the type of compounds that lower mask body narration the present invention relates to.
Described indenofluorene derivative, is selected from following structural formula:
Figure BDA00001941932500051
Figure BDA00001941932500061
Figure BDA00001941932500071
Figure BDA00001941932500081
Figure BDA00001941932500101
Figure BDA00001941932500111
Figure BDA00001941932500121
The present invention also provides a kind of method of preparing described indenofluorene derivative,, under argon shield, the intermediate shown in formula V or formula (VI) is obtained through linked reaction.
Figure BDA00001941932500131
Indenofluorene derivative of the present invention can be used as electric transmission layer material or luminous material of main part in organic electroluminescence device.
The present invention also provides a kind of organic electroluminescence device, comprises the first electrode and the second electrode and several organic function layers between two electrodes, and wherein, at least one deck in described organic function layer comprises the compound with following structural:
Figure BDA00001941932500132
Wherein:
R1 to R5 is independently selected from respectively the aliphatic alkyl of C1 ~ C20 or the aromatic group of C6 ~ C20;
Ar be selected from C4 ~ C30 aromatic ring, C4 ~ C30 containing N heterocycle, the annelated heterocycles aromatic hydrocarbons of C4 ~ C30, the virtue amino of C4 ~ C30 or the aryloxy of C4 ~ C30;
N is 1 or 2;
A1 to A4 is N atom or C atom;
When A1, A3 are the N atomic time simultaneously, A2 and A4 are C atom;
Or when A1, A4 are the N atomic time simultaneously, A2 and A3 are C atom;
Or when A2, A4 are the N atomic time simultaneously, A1 and A3 are C atom;
Or when A3, A4 are the N atomic time simultaneously, A1 and A2 are C atom;
Or A1, A3, A4 are the N atomic time simultaneously, A2 is C atom;
L be the aromatic ring of singly-bound or C6 ~ C10 or C4 ~ C10 containing N heterocycle.
Indenofluorene derivative of the present invention has the following advantages:
Indenofluorene derivative of the present invention has good thermostability, high electronic mobility, and film forming properties is fine, can be used as electric transmission layer material in organic electroluminescence device.
Indenofluorene derivative triplet of the present invention is higher, has and luminescent dye, and the molecular orbital(MO) that particularly phosphorescent coloring matches each other can be used as luminous material of main part in electroluminescent device.
Embodiment
The basic chemical industry raw material such as dichloro pyrimidine used, trichloropyrimidine, dichloropyrazine, cyanuric chloride, aryl boric acid, indenofluorene boric acid, indenofluorene boric acid Knit-the-brows alcohol ester, carbazole, aryl secondary amine in the present invention, all has bought in Chemicals market at home, or customized in the synthetic factory of relevant organic intermediate.Here we only synthesize the main intermediate of this patent two bromo indenofluorenes to be described below:
(1) terphenyl skeleton is synthetic
250mL there-necked flask, adds 7.6g2,5-dibromoterephthalic acid diethyl ester; 6.1g phenylo boric acid, 20.7g salt of wormwood, 0.58g tetrakis triphenylphosphine palladium; 80mL toluene, 80mL ethanol, back flow reaction 8h under nitrogen protection; stopped reaction; add moisture liquid, organic layer silica gel column chromatography is separated, sherwood oil: ethyl acetate=5:1 wash-out; obtain off-white color solid phase prod 6.06g, yield 80.9%.
(2) tetramethyl-indenofluorene is synthetic
Figure BDA00001941932500142
500mL there-necked flask, dried and clean, nitrogen protection, adds 10.0g2 wherein, 5-phenylbenzene diethyl terephthalate, the tetrahydrofuran (THF) that 200mL heavily steams, in-30 ℃ of diethyl ether solutions that drip the lithium methide of 60mL3.0mol/L.Finish and rise to 25 ℃, reaction 5h, adds methyl alcohol, adds aqueous ammonium chloride solution separatory, is concentrated into dryly after organic layer dried over mgso, obtains slight yellow oil 9.5.This oily matter is dissolved with 200mL methylene dichloride, in-5 ℃ of slow 15g methanesulfonics that drip, finish and rise to 25 ℃ of reaction 2h, add moisture liquid, organic layer silica gel column chromatography is separated, sherwood oil: ethyl acetate=10:1 wash-out, obtain white solid product 6.06g, yield 64.9%.
(3) bromo
Figure BDA00001941932500151
250mL there-necked flask, adds 3.1g indenofluorene, and 30mLDMF, in 35 ℃ of 15mLDMF solution that slowly drip 4.0gN-bromo-succinimide, finish and keep 35 ℃ of reactions to spend the night, add water, solid filtering, methyl alcohol and chloroform mixed solvent recrystallization, obtain white products 4.0g, yield 85.47%.
(4) boric acid is synthetic
Figure BDA00001941932500152
At a 500mL there-necked flask, join magnetic agitation, the protection of Ar gas; dibromo indenofluorene (the molecular weight 468 that adds 20g; 0.0428mol) and the THF of 250ml, heating makes entirely molten, is chilled to-78 ℃; drip the BuLi(concentration 2.4M of 21ml; 0.05mol), temperature maintains-78 ℃ always, drips the B (OiPr) 3 of 30ml after stirring 10min in the time of-78 ℃; stir to room temperature and add dilute acid hydrolysis, upper strata is white solid.Filter, separate solid product, water layer is neutralized to neutrality, by ethyl acetate, extracts, and extracting solution evaporate to dryness, adds diluted alkaline, by ethyl acetate, withdraws not molten impurity in alkali, and water layer is neutralized to neutrality, and adularescent solid is separated out, and filters, and obtains product.Be total to obtain 15g solid product, molecular weight 398, productive rate 86.46%.
(5) boric acid Knit-the-brows alcohol ester is synthetic
Figure BDA00001941932500153
Under nitrogen protection; the two Knit-the-brows alcohol ester 12.3g(molecular weight 254 of two boric acid; 0.0484mol); dibromo indenofluorene 10.3g(molecular weight 468; 0.0223mol), PdCl2 (dppf) is 1.8g(0.0022mol), Glacial acetic acid potassium 13g(0.133mol); anhydrous dioxane 150ml, mixes.Under 85 ° of C, stir 24h.Be chilled to room temperature, sintered filter funnel filters, and filtrate under agitation in impouring water, is collected white solid product, about 24.1g altogether, molecular weight 562, productive rate 97%.
Compou nd synthesis embodiment
Synthesizing of embodiment 1 compound 1
(1) the first step
Figure BDA00001941932500161
Under the protection of Ar gas; in the there-necked flask of a 5000ml, add 2,4,6-trichloropyrimidine 18.2g(molecular weight 182; 0.10mol); indenofluorene-2,7-hypoboric acid 17.92g(molecular weight 398,0.045mol); four (triphenylphosphine closes) palladium 6.0g(0.0052mol); the THF of 600ml, 400ml toluene, salt of wormwood 60g(0.435mol) be dissolved in the solution forming in 400ml water and add reaction flask.After under reduced pressure repeatedly taking a breath, start electric stirring, use TLC(thin-layer chromatography) monitoring reaction, after backflow 4h, react completely.Let cool, reaction system is divided two layers, work, separates organic layer, and evaporate to dryness, obtains solid product, uses toluene recrystallization, obtains 23.65g intermediate, molecular weight 604, productive rate 87%.
(2) second step
Figure BDA00001941932500162
Under the protection of Ar gas; in the there-necked flask of a 2000ml, add product 12.1g(molecular weight 604 obtained in the previous step; 0.02mol); phenylo boric acid Knit-the-brows alcohol ester 20.4g(molecular weight 204,0.1mol), four (triphenylphosphine closes) palladium 5.0g(0.0044mol); the THF of 360ml; 240ml toluene, 36g(molecular weight 138,0.26mol) salt of wormwood is dissolved in the solution forming in 240ml water and adds reaction flask.After under reduced pressure repeatedly taking a breath, start electric stirring, use TLC(thin-layer chromatography) monitoring reaction, after backflow 12h, react completely.Let cool, reaction system is divided and is done two layers, separates organic layer, and evaporate to dryness, obtains solid product, with toluene recrystallization repeatedly, obtains 8.6g product, molecular weight 770, productive rate 56%.
Product MS(m/e): 770, ultimate analysis (C 56h 42n 4): theoretical value C:87.24%, H:5.49%, N:7.27%; Measured value C:87.31%, H:5.55%, N:7.14%.
Synthesizing of embodiment 2 compounds 2
(1) the first step
Figure BDA00001941932500171
Under the protection of Ar gas; in the there-necked flask of a 5000ml, add 2; 4,6-trichloropyrimidine 18.2g(molecular weight 182,0.10mol); phenylo boric acid 28.1g(molecular weight 122; 0.23mol), four (triphenylphosphine closes) palladium 12.0g(0.0104mol), the THF of 600ml; 400ml toluene, salt of wormwood 60g(0.435mol) being dissolved in the solution forming in 400ml water adds reaction flask.After under reduced pressure repeatedly taking a breath, start electric stirring, use TLC(thin-layer chromatography) monitoring reaction, after backflow 8h, react completely.Let cool, reaction system is divided two layers, work, separates organic layer, and evaporate to dryness, obtains solid product, uses toluene recrystallization, obtains 19.9g intermediate, molecular weight 266, productive rate 75%.
(2) second step
Figure BDA00001941932500172
Under the protection of Ar gas; in the there-necked flask of a 2000ml, add product 13.3g(molecular weight 266 obtained in the previous step; 0.05mol), indenofluorene-2,7-hypoboric acid Knit-the-brows alcohol ester 11.3g(molecular weight 562; 0.02mol); four (triphenylphosphine closes) palladium 2.52g(0.0022mol), the THF of 360ml, 240ml toluene; 36g(molecular weight 138,0.26mol) salt of wormwood is dissolved in the solution forming in 240ml water and adds reaction flask.After under reduced pressure repeatedly taking a breath, start electric stirring, use TLC(thin-layer chromatography) monitoring reaction, after backflow 12h, react completely.Let cool, reaction system is divided and is done two layers, separates organic layer, and evaporate to dryness, obtains solid product, with toluene recrystallization repeatedly, obtains 8.63g product, molecular weight 770, productive rate 56%.
Product MS(m/e): 770, ultimate analysis (C 56h 42n 4): theoretical value C:87.24%, H:5.49%, N:7.27%; Measured value C:87.15%, H:5.60%, N:7.25%.
Synthesizing of embodiment 3 compounds 3
(1) the first step
Under the protection of Ar gas; carbazole 16.7g(molecular weight 167,0.1mol) is dissolved in dry DMF 180ml, drips 5.64g NaH(content 55%; 0.235mol) the solution in 180mlDMF; 20 minutes used times, stir 1h, then by 2; 4; 6-trichloropyrimidine 18.2g(molecular weight 182,0.1mol) is dissolved in the solution in 180mlDMF, with 20 minutes, adds wherein; stir 3h; in impouring water 1000ml, filtering-depositing, vacuum-drying; product is purified with silicagel column; obtain 25.4g target molecule (0.081mol), molecular weight 313, productive rate 81%.
(2) second step
Figure BDA00001941932500182
Under the protection of Ar gas; in the there-necked flask of a 5000ml, add and walk reaction product 15.6g(molecular weight 313; 0.05mol); phenylo boric acid 6.71g(molecular weight 122,0.055mol), four (triphenylphosphine closes) palladium 3.0g(0.0026mol); the THF of 150ml; 100ml toluene, salt of wormwood 15g(molecular weight 138,0.108mol) is dissolved in the solution forming in 100ml water and adds reaction flask.After under reduced pressure repeatedly taking a breath, start electric stirring, use TLC(thin-layer chromatography) monitoring reaction, after backflow 6h, react completely.Let cool, reaction system is divided two layers, work, separates organic layer, and evaporate to dryness, obtains solid product, uses toluene recrystallization, obtains 13.8g intermediate, molecular weight 355, productive rate 78%.(scalable synthesis)
(3) the 3rd steps
Under the protection of Ar gas; in the there-necked flask of a 2000ml, add product 17.75g(molecular weight 355 obtained in the previous step; 0.05mol), indenofluorene-2,7-hypoboric acid Knit-the-brows alcohol ester 11.3g(molecular weight 562; 0.02mol); four (triphenylphosphine closes) palladium 2.52g(0.0022mol), the THF of 360ml, 240ml toluene; 36g(molecular weight 138,0.26mol) salt of wormwood is dissolved in the solution forming in 240ml water and adds reaction flask.After under reduced pressure repeatedly taking a breath, start electric stirring, use TLC(thin-layer chromatography) monitoring reaction, after backflow 12h, react completely.Let cool, reaction system is divided and is done two layers, separates organic layer, and evaporate to dryness, obtains solid product, with toluene recrystallization repeatedly, obtains 7.8g product, molecular weight 948, productive rate 41%.
Product MS(m/e): 948, ultimate analysis (C 68h 48n 6): theoretical value C:86.05%, H:5.10%, N:8.85%; Measured value C:86.10%, H:5.21%, N:8.69%.
Synthesizing of embodiment 4 compounds 4
(1) the first step
Figure BDA00001941932500192
Under the protection of Ar gas; in the there-necked flask of a 5000ml, add tetrachloro intermediate (by the synthetic product of the first step in embodiment 1) 30.2g(molecular weight 604; 0.05mol); phenylo boric acid 14.64g(molecular weight 122,0.12mol), four (triphenylphosphine closes) palladium 3.0g(0.0026mol); the THF of 150ml; 100ml toluene, salt of wormwood 15g(molecular weight 138,0.108mol) is dissolved in the solution forming in 100ml water and adds reaction flask.After under reduced pressure repeatedly taking a breath, start electric stirring, use TLC(thin-layer chromatography) monitoring reaction, after backflow 6h, react completely.Let cool, reaction system is divided two layers, work, separates organic layer, and evaporate to dryness, obtains solid product, uses toluene recrystallization, obtains 25.04g intermediate, molecular weight 686, productive rate 73%.
(2) second step
Figure BDA00001941932500201
Under the protection of Ar gas; carbazole 16.7g(molecular weight 167; 0.1mol) be dissolved in dry DMF 90ml; drip 5.11g NaH(content 55%, the 0.117mol) solution in 90mlDMF, 20 minutes used times; stir 1h; then by two chloromethylated intermediate 30.9g(molecular weight 686,0.045mol) be dissolved in the solution in 90mlDMF, with 20 minutes, add wherein; stir 3h; in impouring water 500ml, filtering-depositing, vacuum-drying; product is purified with silicagel column; obtain 23.5g target molecule, molecular weight 948, productive rate 55%.
Product MS(m/e): 948, ultimate analysis (C 68h 48n 6): theoretical value C:86.05%, H:5.10%, N:8.85%; Measured value C:86.13%, H:5.15%, N:8.72%.
Synthesizing of embodiment 5 compounds 5
Figure BDA00001941932500202
Under the protection of Ar gas, in a reaction flask, add pentanoic 2.02g(molecular weight 169,0.012mol), anhydrous THF20ml.Be chilled to 00C, stir.By n-BuLi(2.4M, the 0.013mol of 5.5ml) slowly add wherein.At room temperature stir its colour changed into yellow 30 minutes.Be chilled to 00C.This solution, with 30 minutes, is slowly added to two chloromethylated intermediates (by the synthetic product of the first step in embodiment 4) 3.43g(molecular weight 686, in 50mlTHF solution 0.005mol), at 35 ° of C, stir 4h, at 50 ° of C, stir 8h, cooling, mixture is poured in water, with dichloromethane extraction, organic layer evaporate to dryness, the solid obtaining is separated by column chromatography, obtains the micro-yellow solid of 2.4g, molecular weight 952, productive rate 50%.
Product MS(m/e): 952, ultimate analysis (C 68h 52n 6): theoretical value C:85.68%, H:5.50%, N:8.82%; Measured value C:85.76%, H:5.56%, N:8.68%.
Synthesizing of embodiment 6 compounds 6
(1) the first step
Under the protection of Ar gas, in a reaction flask, add pentanoic 20.2g(molecular weight 169,0.12mol), anhydrous THF200ml.Be chilled to 0 ° of C, stir.By n-BuLi(concentration 2.4M, the 0.13mol of 55ml) slowly add wherein.At room temperature stir its colour changed into yellow 30 minutes.Be chilled to 0 ° of C.This solution, with 30 minutes, is slowly added to 2,4,6-trichloropyrimidine 20.02g(molecular weight 182, in 200mlTHF solution 0.11mol), at 0 ° of C, stir 4h, mixture is poured in water, with dichloromethane extraction, organic layer evaporate to dryness, the solid obtaining is separated by column chromatography, obtains the micro-yellow solid of 31.2g, molecular weight 315, productive rate 90%.
(2) second step
Figure BDA00001941932500212
Under the protection of Ar gas; in a there-necked flask, add and walk synthetic intermediate 15.75g(molecular weight 315; 0.05mol); phenylo boric acid 6.71g(molecular weight 122,0.055mol), four (triphenylphosphine closes) palladium 3.0g(0.0026mol); the THF of 150ml; 100ml toluene, salt of wormwood 15g(molecular weight 138,0.108mol) is dissolved in the solution forming in 100ml water and adds reaction flask.After under reduced pressure repeatedly taking a breath, start electric stirring, use TLC(thin-layer chromatography) monitoring reaction, after backflow 6h, react completely.Let cool, reaction system is divided two layers, work, separates organic layer, and evaporate to dryness, obtains solid product, uses toluene recrystallization, obtains 14.7g intermediate, molecular weight 357, productive rate 82%.
(3) the 3rd steps
Figure BDA00001941932500221
Under the protection of Ar gas; in the there-necked flask of a 2000ml, add product 17.85g(molecular weight 357 obtained in the previous step; 0.05mol), indenofluorene-2,7-hypoboric acid Knit-the-brows alcohol ester 11.3g(molecular weight 562; 0.02mol); four (triphenylphosphine closes) palladium 2.52g(0.0022mol), the THF of 360ml, 240ml toluene; 36g(molecular weight 138,0.26mol) salt of wormwood is dissolved in the solution forming in 240ml water and adds reaction flask.After under reduced pressure repeatedly taking a breath, start electric stirring, use TLC(thin-layer chromatography) monitoring reaction, after backflow 12h, react completely.Let cool, reaction system is divided and is done two layers, separates organic layer, and evaporate to dryness, obtains solid product, with toluene recrystallization repeatedly, obtains 6.48g product, molecular weight 952, productive rate 34%.
Product MS(m/e): 952, ultimate analysis (C 68h 52n 6): theoretical value C:85.68%, H:5.50%, N:8.82%; Measured value C:85.53%, H:5.48%, N:8.99%.
Synthesizing of embodiment 7 compounds 7
Synthesis step is same as embodiment 1, and just by a kind of raw material 2,4 wherein, 6-trichloropyrimidine is changed into 2,4-dichloro pyrimidine, obtains micro-yellow solid product.
Product MS(m/e): 618, ultimate analysis (C 44h 34n 4): theoretical value C:85.41%, H:5.54%, N:9.05%; Measured value C:85.46%, H:5.51%, N:9.03%.
Synthesizing of embodiment 8 compounds 8
Figure BDA00001941932500231
Synthesis step is same as embodiment 2, and just by a kind of raw material 2,4 wherein, 6-trichloropyrimidine is changed into 2,4-dichloro pyrimidine, obtains micro-yellow solid product.
Product MS(m/e): 618, ultimate analysis (C 44h 34n 4): theoretical value C:85.41%, H:5.54%, N:9.05%; Measured value C:85.32%, H:5.61%, N:9.07%.
Synthesizing of embodiment 9 compounds 9
Figure BDA00001941932500232
Under the protection of Ar gas; carbazole 16.7g(molecular weight 167; 0.1mol) be dissolved in dry DMF 90ml; drip 5.11g NaH(content 55%, the 0.117mol) solution in 90mlDMF, 20 minutes used times; stir 1h; then by two chloromethylated intermediate 24.1g(molecular weight 534,0.045mol) be dissolved in the solution in 90mlDMF, with 20 minutes, add wherein; stir 3h; in impouring water 500ml, filtering-depositing, vacuum-drying; product is purified with silicagel column; obtain 20.8g solid product, molecular weight 796, productive rate 58%.
Product MS(m/e): 796, ultimate analysis (C 56h 40n 6): theoretical value C:84.40%, H:5.06%, N:10.55%; Measured value C:84.56%, H:5.10%, N:10.34%.
Synthesizing of embodiment 10 compounds 10
Figure BDA00001941932500241
Synthesis step is same as embodiment 3, just by a kind of raw material 2,4 wherein, 6-trichloropyrimidine is changed into 2,4-dichloro pyrimidine, and there is no reacting of second step and phenylo boric acid, obtains micro-yellow solid product.
Product MS(m/e): 796, ultimate analysis (C 56h 40n 6): theoretical value C:84.40%, H:5.06%, N:10.55%; Measured value C:84.34%, H:5.16%, N:10.50%.
Synthesizing of embodiment 11 compounds 12
(1) the first step
Figure BDA00001941932500242
Under the protection of Ar gas; in the there-necked flask of a 2000ml, add 2-chloro-4; 6-phenylbenzene pyrimidine 26.6g(molecular weight 266,0.10mol), to bromobenzene boric acid Knit-the-brows alcohol ester 34g(molecular weight 282; 0.12mol); four (triphenylphosphine closes) palladium 6.0g(0.0052mol), the THF of 300ml, 200ml toluene; salt of wormwood 40g(molecular weight 138,0.29mol) is dissolved in the solution forming in 200ml water and adds reaction flask.After under reduced pressure repeatedly taking a breath, start electric stirring, use TLC(thin-layer chromatography) monitoring reaction, after backflow 5h, react completely.Let cool, reaction system is divided two layers, work, separates organic layer, and evaporate to dryness, obtains solid product, uses toluene recrystallization, obtains 27g intermediate, molecular weight 386, productive rate 70%.
(2) second step
Figure BDA00001941932500243
Synthesis step is same as the first step in embodiment 1, and just by a kind of raw material 2,4 wherein, 6-trichloropyrimidine is changed into 4,6-phenylbenzene-2-to bromophenyl pyrimidine, obtains micro-yellow solid product.
Product MS(m/e): 922, ultimate analysis (C 68h 50n 4): theoretical value C:88.47%, H:5.46%, N:6.07%; Measured value C:88.52%, H:5.44%, N:6.04%.
Synthesizing of embodiment 12 compounds 14
Figure BDA00001941932500251
Synthesis step is same as the first step in embodiment 1, and just by a kind of raw material 2,4 wherein, 6-trichloropyrimidine is changed into 4-phenyl-2-to bromophenyl pyrimidine, obtains micro-yellow solid product.
Product MS(m/e): 770, ultimate analysis (C 56h 42n 4): theoretical value C:87.24%, H:5.49%, N:7.27%; Measured value C:87.28%, H:5.56%, N:7.16%.
Synthesizing of embodiment 13 compounds 15
Figure BDA00001941932500252
Synthesis step is same as embodiment 1, and just by a kind of raw material 2,4 wherein, 6-trichloropyrimidine is changed into 2,5-dichloro pyrimidine, obtains micro-yellow solid product.
Product MS(m/e): 618, ultimate analysis (C 44h 34n 4): theoretical value C:85.41%, H:5.54%, N:9.05%; Measured value C:85.45%, H:5.48%, N:9.07%.
Synthesizing of embodiment 14 compounds 16
Figure BDA00001941932500253
Synthesis step is same as embodiment 2, and just by a kind of raw material 2,4 wherein, 6-trichloropyrimidine is changed into 2,5-dichloro pyrimidine, obtains micro-yellow solid product.
Product MS(m/e): 618, ultimate analysis (C 44h 34n 4): theoretical value C:85.41%, H:5.54%, N:9.05%; Measured value C:85.30%, H:5.61%, N:9.09%.
Synthesizing of embodiment 15 compounds 17
Figure BDA00001941932500261
In embodiment 1 the first step, by a kind of raw material 2,4 wherein, 6-trichloropyrimidine is changed into 2,5-dichloro pyrimidine, and other reagent, solvent and reaction conditions are all constant, synthesize two chloromethylated intermediates, then synthesize micro-yellow solid final product by the first step of embodiment 3.
Product MS(m/e): 796, ultimate analysis (C 56h 40n 6): theoretical value C:84.40%, H:5.06%, N:10.55%; Measured value C:84.37%, H:5.17%, N:10.46%.
Synthesizing of embodiment 16 compounds 18
Figure BDA00001941932500262
In the first step of embodiment 3, by a kind of raw material 2,4 wherein, 6-trichloropyrimidine is changed into 2,5-dichloro pyrimidine, and other reagent, solvent and reaction conditions are all constant, synthesize a chloromethylated intermediate, then synthesize micro-yellow solid final product by embodiment 1 the first step.
Product MS(m/e): 796, ultimate analysis (C 56h 40n 6): theoretical value C:84.40%, H:5.06%, N:10.55%; Measured value C:84.42%, H:5.14%, N:10.44%.
Synthesizing of embodiment 17 compounds 19
Figure BDA00001941932500271
In embodiment 1 the first step, by a kind of raw material 2 wherein, 4,6-trichloropyrimidine is changed into 2,5-dichloro pyrimidine, and other reagent, solvent and reaction conditions are all constant, synthesize two chloromethylated intermediates, re-use the synthesis step of embodiment 5, two chloromethylated intermediates are wherein changed into the intermediate that the first step synthesizes here, synthesize micro-yellow solid final product.
Product MS(m/e): 800, ultimate analysis (C 56h 44n 6): theoretical value C:83.97%, H:5.54%, N:10.49%; Measured value C:84.08%, H:5.61%, N:10.31%.
Synthesizing of embodiment 18 compounds 20
Use the synthesis step of embodiment 5, two chloromethylated intermediates are wherein changed into 2,5-dichloro pyrimidine, synthesize a chloromethylated intermediate, re-use the first step in embodiment 1, by a kind of raw material 2 wherein, 4,6-trichloropyrimidine is changed into a chloromethylated intermediate here, and other reagent, solvent and reaction conditions are all constant, synthesizes micro-yellow solid final product.
Product MS(m/e): 800, ultimate analysis (C 56h 44n 6): theoretical value C:83.97%, H:5.54%, N:10.49%; Measured value C:84.05%, H:5.48%, N:10.47%.
Synthesizing of embodiment 19 compounds 22
Figure BDA00001941932500273
Synthesis step is same as embodiment 1, and just by a kind of raw material 2,4 wherein, 6-trichloropyrimidine is changed into 5-phenyl-2-to brooethyl pyrimidine, obtains micro-yellow solid product.
Product MS(m/e): 770, ultimate analysis (C 56h 42n 4): theoretical value C:87.24%, H:5.49%, N:7.27%; Measured value C:87.23%, H:5.53%, N:7.24%.
Synthesizing of embodiment 20 compounds 25
Figure BDA00001941932500281
Synthesis step is same as embodiment 1, and just by a kind of raw material 2,4 wherein, 6-trichloropyrimidine is changed into 5-carbazole-N base-2-to brooethyl pyrimidine, obtains micro-yellow solid product.
Product MS(m/e): 948, ultimate analysis (C 68h 48n 6): theoretical value C:86.05%, H:5.10%, N:8.85%; Measured value C:86.10%, H:5.06%, N:8.84%.
Synthesizing of embodiment 21 compounds 26
Figure BDA00001941932500282
Synthesis step is same as embodiment 1, and just by a kind of raw material 2,4 wherein, 6-trichloropyrimidine is changed into 5-hexichol amido-2-to bromophenyl pyrimidine, obtains micro-yellow solid product.
Product MS(m/e): 952, ultimate analysis (C 68h 52n 6): theoretical value C:85.68%, H:5.50%, N:8.82%; Measured value C:85.54%, H:5.59%, N:8.87%.
Synthesizing of embodiment 22 compounds 27
Figure BDA00001941932500291
The step of pressing embodiment 1 is synthetic, just by a kind of raw material 2 wherein, 4,6-trichloropyrimidine is changed into 2,5-dichloropyrazine, in second step synthetic, with phenyl-boron dihydroxide and its Knit-the-brows alcohol ester, result is the same, and other reagent, solvent and reaction conditions are all constant, synthesizes micro-yellow solid final product.
Product MS(m/e): 618, ultimate analysis (C 44h 34n 4): theoretical value C:85.41%, H:5.54%, N:9.05%; Measured value C:85.39%, H:5.45%, N:9.16%.
Synthesizing of embodiment 23 compounds 28
The step of pressing embodiment 1 is synthetic, just by a kind of raw material 2 wherein, 4,6-trichloropyrimidine is changed into 3,5-dichloropyrazine, in second step synthetic, with phenyl-boron dihydroxide and its Knit-the-brows alcohol ester, result is the same, and other reagent, solvent and reaction conditions are all constant, synthesizes micro-yellow solid final product.
Product MS(m/e): 618, ultimate analysis (C 44h 34n 4): theoretical value C:85.41%, H:5.54%, N:9.05%; Measured value C:85.47%, H:5.49%, N:9.04%.
Synthesizing of embodiment 24 compounds 29
Figure BDA00001941932500301
Press the first step in embodiment 1, just by a kind of raw material 2,4 wherein, 6-trichloropyrimidine is changed into 2,5-dichloropyrazine, obtains two chloromethylated intermediates; Re-use embodiment 4 second steps, with two chloromethylated intermediates that synthesize, replace two chloromethylated intermediates in former step here, other starting material are constant, synthesize final micro-yellow solid product.
Product MS(m/e): 796, ultimate analysis (C 56h 40n 6): theoretical value C:84.40%, H:5.06%, N:10.55%; Measured value C:84.42%, H:5.14%, N:10.44%.
Synthesizing of embodiment 25 compounds 30
Figure BDA00001941932500302
Press the first step in embodiment 1, just by a kind of raw material 2,4 wherein, 6-trichloropyrimidine is changed into 3,5-dichloropyrazine, obtains two chloromethylated intermediates; Re-use embodiment 4 second steps, with two chloromethylated intermediates that synthesize, replace two chloromethylated intermediates in former step here, other starting material are constant, synthesize final micro-yellow solid product.
Product MS(m/e): 796, ultimate analysis (C 56h 40n 6): theoretical value C:84.40%, H:5.06%, N:10.55%; Measured value C:84.46%, H:5.10%, N:10.44%.
Synthesizing of embodiment 26 compounds 31
Figure BDA00001941932500311
In embodiment 1 the first step, by a kind of raw material 2 wherein, 4,6-trichloropyrimidine is changed into 2,5-dichloro pyrimidine, and other reagent, solvent and reaction conditions are all constant, synthesize two chloromethylated intermediates, re-use the synthesis step of embodiment 5, two chloromethylated intermediates are wherein changed into the intermediate that the first step synthesizes here, synthesize micro-yellow solid final product.
Product MS(m/e): 800, ultimate analysis (C 56h 44n 6): theoretical value C:83.97%, H:5.54%, N:10.49%; Measured value C:84.05%, H:5.58%, N:10.37%.
Synthesizing of embodiment 27 compounds 32
Figure BDA00001941932500312
In embodiment 1 the first step, by a kind of raw material 2 wherein, 4,6-trichloropyrimidine is changed into 3,5-dichloro pyrimidine, and other reagent, solvent and reaction conditions are all constant, synthesize two chloromethylated intermediates, re-use the synthesis step of embodiment 5, two chloromethylated intermediates are wherein changed into the intermediate that the first step synthesizes here, synthesize micro-yellow solid final product.
Product MS(m/e): 800, ultimate analysis (C 56h 44n 6): theoretical value C:83.97%, H:5.54%, N:10.49%; Measured value C:83.94%, H:5.50%, N:10.56%.
Synthesizing of embodiment 28 compounds 33
(1) the first step
In the reaction flask of an oven dry, add 2.9g(molecular weight 24; magnesium chips 0.121mol); the anhydrous THF(tetrahydrofuran (THF) of 100ml); add a little iodine; nitrogen protection, slowly drips 15.6g(molecular weight 156, the solution that 0.10mol) THF of bromobenzene and 100ml forms; after reaction starts, start stirring.Dropwise, return stirring 2h, obtains the Grignard reagent of bromobenzene.Be chilled to room temperature.By 6.1g(molecular weight 183, cyanuric chloride 0.033mol) is dissolved in the THF of 200ml, is chilled to 0-10 ℃.Under stirring, the bromobenzene Grignard reagent of preparing is above dripped in this cyanuric chloride solution.Dropwise, at 50 ℃, stir 10h.Be chilled to room temperature, by 12% the aqueous hydrochloric acid of reaction mixture impouring 500ml, remove THF under reduced pressure, filter, obtain solid product.Cross a silica gel short column, use sherwood oil: toluene (5:1) drip washing, obtains white solid product 5.4g(molecular weight 267,0.0202mol, 61%).
(2) second step
Figure BDA00001941932500322
Under nitrogen protection, by the first step product 8.03g(molecular weight 267,0.0301mol); two boric acid Knit-the-brows alcohol ester 7.9g(molecular weight 562 of indenofluorene, 0.014mol), tetra-triphenylphosphine palladium 2.0g(0.0017mol); tricyclohexyl phosphine 6.72g(molecular weight 280,0.024mol), sodium carbonate 6.7g(molecular weight 106; 0.0634mol); toluene 200ml, ethanol 100ml, 100ml; return stirring 5h, reaction finishes.Add toluene and saturated aqueous common salt, separate organic layer, evaporate to dryness, separated with silica gel short column, sherwood oil: chloroform (1:1) drip washing, product is used toluene recrystallization again, obtains the micro-yellow solid product of 7.0g.
Product MS(m/e): 772, ultimate analysis (C 54h 40n 6): theoretical value C:83.91%, H:5.22%, N:10.87%; Measured value C:83.83%, H:5.29%, N:10.88%.
Synthesizing of embodiment 29 compounds 34
Figure BDA00001941932500331
Synthetic minute two steps are carried out, and the first step step is same as the second step of embodiment 28, just in second step, two boric acid Knit-the-brows alcohol esters of starting material indenofluorene is changed to the alcohol ester to bromobenzene boric acid Knit-the-brows; Here the synthesis step of second step is also same as the second step of embodiment 28, and just that starting material 2-is chloro-4,6-phenylbenzene triazine is changed to 4-bromine triphenyl triazine, synthesizes micro-yellow solid final product.
Product MS(m/e): 924, ultimate analysis (C 66h 48n 6): theoretical value C:85.69%, H:5.23%, N:9.08%; Measured value C:85.65%, H:5.30%, N:9.05%.
Synthesizing of embodiment 30 compounds 35
Figure BDA00001941932500332
Synthesis step is same as embodiment 28, just in the first step, starting material bromobenzene is changed into methyl bromobenzene, and other reagent and raw material do not change, and synthesize micro-yellow solid final product.
Product MS(m/e): 746, ultimate analysis (C 58h 48n 6): theoretical value C:84.03%, H:5.84%, N:10.14%; Measured value C:83.98%, H:5.81%, N:10.21%.
Synthesizing of embodiment 31 compounds 36
Figure BDA00001941932500341
Synthetic minute three steps are carried out, and the first step is same as the first step in embodiment 28, just starting material bromobenzene is changed into methyl bromobenzene; Second step is same as second step in embodiment 28, just two boric acid Knit-the-brows alcohol esters of starting material indenofluorene is changed to the alcohol ester to bromobenzene boric acid Knit-the-brows, and 2-is chloro-4, and 6-phenylbenzene triazine is changed to 4-bromine triphenyl triazine; The 3rd step is synthetic is same as second step in embodiment 28, and just that 2-is chloro-4,6-phenylbenzene triazine is changed to two boric acid Knit-the-brows alcohol esters of indenofluorene, synthesizes micro-yellow solid final product.
Product MS(m/e): 980, ultimate analysis (C 70h 56n 6): theoretical value C:85.68%, H:5.75%, N:8.56%; Measured value C:85.65%, H:5.81%, N:8.54%.
Synthesizing of embodiment 32 compounds 37
Figure BDA00001941932500342
Reaction minute two steps are carried out, and the first step synthesis step is same as the second step of embodiment 28, just changes a former chlorodiphenyl base triazine into cyanuric chloride; Second step synthesis step is same as the first step in embodiment 3, just changes starting material cyanuric chloride into the first step synthesizes tetrachloro intermediate here, synthesizes micro-yellow solid final product.
Product MS(m/e): 1128, ultimate analysis (C 78h 52n 10): theoretical value C:82.96%, H:4.64%, N:12.40%; Measured value C:82.87%, H:4.55%, N:12.58%.
Synthesizing of embodiment 33 compounds 38
Figure BDA00001941932500351
Reaction minute three steps are carried out, and the first step synthesis step is same as the second step of embodiment 28, just changes a former chlorodiphenyl base triazine into cyanuric chloride; Second step is synthetic is same as the second step in embodiment 1, just tetrachloro-pyrimidine intermediate is wherein changed to tetrachloro triazine intermediate; The 3rd step synthesis step is same as the first step in embodiment 3, just changes starting material cyanuric chloride into second step synthesizes two chloromethylated intermediates here, synthesizes micro-yellow solid final product.
Product MS(m/e): 950, ultimate analysis (C 66h 46n 8): theoretical value C:83.34%, H:4.87%, N:11.78%; Measured value C:83.50%, H:4.91%, N:11.59%.
Synthesizing of embodiment 34 compounds 39
Figure BDA00001941932500352
Reaction minute two steps are carried out, and the first step synthesis step is same as the second step of embodiment 28, just changes a former chlorodiphenyl base triazine into cyanuric chloride; Second step synthesis step is same as the first step in embodiment 5, just changes starting material dichloro pyrimidine intermediate into the first step synthesizes tetrachloro triazine intermediate here, synthesizes micro-yellow solid final product.
Product MS(m/e): 1136, ultimate analysis (C 78h 60n 10): theoretical value C:82.37%, H:5.32%, N:12.31%; Measured value C:82.45%, H:5.46%, N:12.09%.
Synthesizing of embodiment 35 compounds 40
Figure BDA00001941932500361
Reaction minute three steps are carried out, and the first step synthesis step is same as the second step of embodiment 28, just changes a former chlorodiphenyl base triazine into cyanuric chloride; Second step is synthetic is same as the second step in embodiment 1, just tetrachloro-pyrimidine intermediate is wherein changed to tetrachloro triazine intermediate; The 3rd step synthesis step is same as the first step in embodiment 5, just changes the phonetic intermediate of starting material dichloro into second step synthesizes dichlorotriazine intermediate here, synthesizes micro-yellow solid final product.
Product MS(m/e): 954, ultimate analysis (C 66h 50n 8): theoretical value C:82.99%, H:5.28%, N:11.73%; Measured value C:83.05%, H:5.34%, N:11.61%.
The Application Example of the compounds of this invention below:
Embodiment 36: fabricate devices OLED-1 ~ OLED-10
The preferred implementation of fabricate devices:
(1) device design
For the convenient relatively transmission performance of these electron transport materials, the present invention has designed a simple electroluminescence device (substrate/anode/hole transmission layer (HTL)/organic luminous layer (EL)/electron transfer layer (ETL)/negative electrode), only use compound 1,2,6,10,16,23,27,29,32,33,37,38,40 as electron transport material illustration, efficent electronic transport material Bphen is material as a comparison.The structure of Bphen is:
Figure BDA00001941932500371
Substrate can be used the substrate in traditional organic luminescent device, for example: glass or plastics.In element manufacturing of the present invention, select glass substrate, ITO makes anode material.
Hole transmission layer can adopt various tri-arylamine group materials.In element manufacturing of the present invention, selected hole mobile material is NPB.
Negative electrode can adopt metal and composition thereof structure, as Mg:Ag, Ca:Ag etc., can be also electron injecting layer/metal-layer structure, as LiF/Al, Li 2the common cathode construction such as O/Al.In element manufacturing of the present invention, selected electron injection material is LiF, and cathode material is Al.
(2) fabricate devices OLED-1
Sheet glass supersound process in commercial clean-out system of ITO transparency conducting layer will be coated with; in deionized water, rinse, at acetone: ultrasonic oil removing in alcohol mixed solvent is baked to and removes moisture content completely under clean environment; by UV-light and ozone clean, and with low energy positively charged ion bundle bombarded surface;
The above-mentioned glass substrate with anode is placed in vacuum chamber, is evacuated to 1 * 10 -5～9 * 10 -3pa, on above-mentioned anode tunic, vacuum evaporation NPB is as hole transmission layer, and evaporation speed is 0.1nm/s, and evaporation thickness is 40nm;
Vacuum evaporation evaporation luminescent layer on hole transmission layer, the method for steaming altogether with double source, evaporating Al q3 and C545T, the evaporation speed of Alq3 is 0.1nm/s, the evaporation speed of C545T is 0.002nm/s,, evaporation total film thickness is 30nm;
Vacuum evaporation one deck compound 2 electron transfer layers as device OLED-1 on luminescent layer, its evaporation speed is 0.1nm/s, evaporation total film thickness is 20nm;
On electron transfer layer (ETL), vacuum evaporation evaporation LiF and Al layer are as the negative electrode of device, and thickness is respectively 0.5nm and 150nm.
Preparation preparation OLED-2 ~ OLED-10, is only the compound having changed as electron transport material as stated above.
Comparative example
Method, with embodiment 36, changes ETL material into Bphen.
Device performance is in Table 1(normal component structure: ITO/NPB(40nm)/Alq3:2wt%C545T (30nm)/ETL material (20nm)/LiF(0.5nm)/Al(150nm)):
Figure BDA00001941932500381
Table 2
Method, with embodiment 36, changes luminous material of main part into compound 23.The performance of device is in Table 3:
Table 3
Figure BDA00001941932500391
Above result shows, novel organic materials of the present invention, for organic electroluminescence device, can effectively reduce landing voltage, improves current efficiency, is well behaved electron transport material.
Although describe the present invention in conjunction with the embodiments, the present invention is not limited to above-described embodiment, should be appreciated that those skilled in the art can carry out various modifications and improvement under the guiding of the present invention's design, and claims have been summarized scope of the present invention.

Claims (12)

1. an indenofluorene derivative, is characterized in that, has suc as formula the structure shown in (I):
Wherein:
R1 to R5 is independently selected from respectively the aliphatic alkyl of C1 ~ C20 or the aromatic group of C6 ~ C20;
Ar be selected from C4 ~ C30 aromatic ring, C4 ~ C30 containing N heterocycle, the annelated heterocycles aromatic hydrocarbons of C4 ~ C30, the virtue amino of C4 ~ C30 or the aryloxy of C4 ~ C30;
N is 1 or 2;
A1 to A4 is N atom or C atom;
When A1, A3 are the N atomic time simultaneously, A2 and A4 are C atom;
Or when A1, A4 are the N atomic time simultaneously, A2 and A3 are C atom;
Or when A2, A4 are the N atomic time simultaneously, A1 and A3 are C atom;
Or when A3, A4 are the N atomic time simultaneously, A1 and A2 are C atom;
Or A1, A3, A4 are the N atomic time simultaneously, A2 is C atom;
L be the aromatic ring of singly-bound or C6 ~ C10 or C4 ~ C10 containing N heterocycle.
2. indenofluorene derivative according to claim 1, is characterized in that, the six-membered ring group that contains A1 ~ A4 is selected from structural formula:
Figure FDA00001941932400012
3. according to indenofluorene derivative described in claim 1-2, it is characterized in that, described compound has structure shown in formula (II):
Figure FDA00001941932400013
Wherein:
R1 to R5 is independently selected from respectively the aliphatic alkyl of C1 ~ C20 or the aromatic group of C6 ~ C20;
Ar be selected from C4 ~ C30 aromatic ring, C4 ~ C30 containing N heterocycle, the annelated heterocycles aromatic hydrocarbons of C4 ~ C30, the virtue amino of C4 ~ C30 or the aryloxy of C4 ~ C30;
N is 1 or 2;
A1 to A4 is N atom or C atom;
When A1, A3 are the N atomic time simultaneously, A2 and A4 are C atom;
Or when A1, A4 are the N atomic time simultaneously, A2 and A3 are C atom;
Or when A2, A4 are the N atomic time simultaneously, A1 and A3 are C atom;
Or when A3, A4 are the N atomic time simultaneously, A1 and A2 are C atom;
Or A1, A3, A4 are the N atomic time simultaneously, A2 is C atom;
L be the aromatic ring of singly-bound or C6 ~ C10 or C4 ~ C10 containing N heterocycle.
4. according to indenofluorene derivative described in claim 1-2, it is characterized in that, described compound has structure shown in formula (III):
Figure FDA00001941932400021
Wherein:
R1 to R5 is independently selected from respectively the aliphatic alkyl of C1 ~ C20 or the aromatic group of C6 ~ C20;
Ar be selected from C4 ~ C30 aromatic ring, C4 ~ C30 containing N heterocycle, the annelated heterocycles aromatic hydrocarbons of C4 ~ C30, the virtue amino of C4 ~ C30 or the aryloxy of C4 ~ C30;
N is 1 or 2;
A1 to A4 is N atom or C atom;
When A1, A3 are the N atomic time simultaneously, A2 and A4 are C atom;
Or when A1, A4 are the N atomic time simultaneously, A2 and A3 are C atom;
Or when A2, A4 are the N atomic time simultaneously, A1 and A3 are C atom;
Or when A3, A4 are the N atomic time simultaneously, A1 and A2 are C atom;
Or A1, A3, A4 are the N atomic time simultaneously, A2 is C atom;
L be the aromatic ring of singly-bound or C6 ~ C10 or C4 ~ C10 containing N heterocycle.
5. according to indenofluorene derivative described in claim 1-2, it is characterized in that, described compound has structure shown in formula (IV):
Figure FDA00001941932400022
Wherein:
R1 to R5 is independently selected from respectively the aliphatic alkyl of C1 ~ C20 or the aromatic group of C6 ~ C20;
Ar be selected from C4 ~ C30 aromatic ring, C4 ~ C30 containing N heterocycle, the annelated heterocycles aromatic hydrocarbons of C4 ~ C30, the virtue amino of C4 ~ C30 or the aryloxy of C4 ~ C30;
N is 1 or 2;
A1 to A4 is N atom or C atom;
When A1, A3 are the N atomic time simultaneously, A2 and A4 are C atom;
Or when A1, A4 are the N atomic time simultaneously, A2 and A3 are C atom;
Or when A2, A4 are the N atomic time simultaneously, A1 and A3 are C atom;
Or when A3, A4 are the N atomic time simultaneously, A1 and A2 are C atom;
Or A1, A3, A4 are the N atomic time simultaneously, A2 is C atom;
L be the aromatic ring of singly-bound or C6 ~ C10 or C4 ~ C10 containing N heterocycle.
6. according to the indenofluorene derivative described in claim 1-5, it is characterized in that, described aliphatic alkyl is selected from: the cycloalkyl of C3 ~ C12 or contain ethylene linkage or the alkyl of the C3 ~ C12 of acetylene bond.
7. according to the indenofluorene derivative described in claim 1-5, it is characterized in that, described aromatic group is selected from: pyridyl, phenyl or naphthyl.
8. according to the indenofluorene derivative described in claim 1-5, it is characterized in that, the heteroatoms in described annelated heterocycles aromatic hydrocarbons is N atom.
9. according to the arbitrary described indenofluorene derivative of claim 1-8, it is characterized in that, described compound is selected from structural formula:
Figure FDA00001941932400031
Figure FDA00001941932400041
Figure FDA00001941932400051
Figure FDA00001941932400081
Figure FDA00001941932400101
Figure FDA00001941932400111
10. a method of preparing the arbitrary described indenofluorene derivative of claim 1-9, is characterized in that, under argon shield, the intermediate shown in formula V or formula (VI) is obtained through linked reaction.
11. indenofluorene derivatives claimed in claim 1 are used as electric transmission layer material or luminous material of main part in organic electroluminescence device.
12. 1 kinds of organic electroluminescence devices, comprise the first electrode and the second electrode and several organic function layers between two electrodes, it is characterized in that, at least one deck in organic function layer comprises the compound with following structural:
Figure FDA00001941932400122
Wherein:
R1 to R5 is independently selected from respectively the aliphatic alkyl of C1 ~ C20 or the aromatic group of C6 ~ C20;
Ar be selected from C4 ~ C30 aromatic ring, C4 ~ C30 containing N heterocycle, the annelated heterocycles aromatic hydrocarbons of C4 ~ C30, the virtue amino of C4 ~ C30 or the aryloxy of C4 ~ C30;
N is 1 or 2;
A1 to A4 is N atom or C atom;
When A1, A3 are the N atomic time simultaneously, A2 and A4 are C atom;
Or when A1, A4 are the N atomic time simultaneously, A2 and A3 are C atom;
Or when A2, A4 are the N atomic time simultaneously, A1 and A3 are C atom;
Or when A3, A4 are the N atomic time simultaneously, A1 and A2 are C atom;
Or A1, A3, A4 are the N atomic time simultaneously, A2 is C atom;
L be the aromatic ring of singly-bound or C6 ~ C10 or C4 ~ C10 containing N heterocycle.
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