CN103570627B - A kind of indenofluorene analog derivative and application containing pyrimidine or pyrazine or triazine group - Google Patents

A kind of indenofluorene analog derivative and application containing pyrimidine or pyrazine or triazine group Download PDF

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CN103570627B
CN103570627B CN201210264023.4A CN201210264023A CN103570627B CN 103570627 B CN103570627 B CN 103570627B CN 201210264023 A CN201210264023 A CN 201210264023A CN 103570627 B CN103570627 B CN 103570627B
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indenofluorene
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CN103570627A (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 kind of novel cpd, its structure formula (I) represents.Wherein R1 to R5 is independently selected from the aliphatic alkyl of C1 ~ C20 or the aromatic group of C6 ~ C20; Ar is selected from the aromatic ring of C4 ~ C30, the aryloxy containing N heterocycle, the annelated heterocycles aromatic hydrocarbons of C4 ~ C30, the virtue amino of C4 ~ C30 or C4 ~ C30 of C4 ~ C30; N is 1 or 2; A1 to A4 is atom N or C atom; When A1, A3 are atom N simultaneously, A2 and A4 is C atom; Or when A1, A4 are atom N simultaneously, A2 and A3 is C atom; Or when A2, A4 are atom N simultaneously, A1 and A3 is C atom; Or when A3, A4 are atom N simultaneously, A1 and A2 is C atom; Or when A1, A3, A4 are atom N, A2 is C atom simultaneously; L be the aromatic ring of singly-bound or C6 ~ C10 or C4 ~ C10 containing N heterocycle.This compounds is used as electron transport layer materials or light emitting host material in organic electroluminescence device.

Description

A kind of indenofluorene analog derivative and application containing pyrimidine or pyrazine or triazine group
Technical field
The present invention relates to a kind of new organic materials, particularly relate 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 uses 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 YangYang use nano level cesium carbonate as electric transmission and injecting material in electroluminescent device, improve the luminous efficiency (AdvancedFunctionalMaterials, 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 (comparing as negative electrode with independent Al with Ba/Al), significantly improve electron injection and the transmittability of device, improve electroluminescent efficiency; The people such as Cao Yong also with to air and all stable Au of various chemical corrosion as efficent electronic injection type cathode material, improve the electron injection ability (OrganicElectronics, 6 (2005), 118-128.) of electroluminescent device.Kodak is in United States Patent (USP) (publication number US2006/0204784 and US2007/0048545), mention mixed electronic transport layer, adopt the electron transport material of a kind of material of low lumo energy and another kind low bright voltage and other materials to form as metallic substance etc. adulterates.Based on the device of this mixed electronic transport layer, efficiency and life-span etc. are all improved, but are the increase in the complicacy of device fabrication, are 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 suitable; Electronic mobility is high; Good film-forming property; Tg is high; Preferably can blocking hole.From compound structure aspect, require that molecular configuration is close to plane, π-π when increasing molecular stacks between molecule interacts, requires that molecular structure can not plane completely simultaneously, prevents from affecting film forming properties because of molecular crystal; Require that molecule contains electron deficiency structural unit, have and good accept electronic capability; Molecular weight is enough large, ensures to have higher Tg, thus has good thermostability, and molecular weight can not be too large simultaneously, is beneficial to vacuum evaporation film forming.
Study the compounds that indicates containing pyridyl, can be used as electron transport material (Chinese Patent Application No.: 200910234760.8,201010258716.3,201010512611.6, etc.).On this basis, continue to have studied the compound containing groups such as pyrimidine, pyrazine, triazines, these compounds are typical electron deficiency systems, have the good electronic capability that accepts; Indenofluorene has terphenyl structure, but owing to being fixed by a five-ring between benzene and benzene, makes three phenyl ring be in same plane, and between the π molecular orbital(MO) between three phenyl ring, conjugation is fine, thus has good transmittability.When these electron deficiency groups are connected with indenofluorene, the plane regularity of indenofluorene and large long conjugation system, be conducive to the π-π rail-stack of molecule and form electron channel.
Therefore, the electron transport material of exploitation stability and high efficiency and/or electron injection material, 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 may be used for ORGANIC ELECTROLUMINESCENCE DISPLAYS field.
Indenofluorene has long conjugation structure, and due to pentacyclic restriction, makes three of indenofluorene phenyl ring have good coplanarity, is conducive to the π-π rail-stack of molecule and forms electron channel.And the reduction potential of pyrimidine, pyrazine, triazine group is not lower containing heteroatomic aromatic radical 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 electron acceptability and the mobility of this compounds on the one hand, be conducive to the film-forming properties of this compounds on the other hand.Therefore compound of the present invention has higher electronic transmission performance, good film-forming property, and the device applied at room temperature has higher stability.In addition, this kind of material has the molecular orbital(MO) matched each other with luminescent dye, so this kind of material both can be used as electron transport material in electroluminescence device, also can be used as light emitting host material.
A kind of indenofluorene derivative, has such as formula the structure shown in (I):
Wherein:
R1 to R5 is independently selected from the aliphatic alkyl of C1 ~ C20 or the aromatic group of C6 ~ C20;
Ar is selected from the aromatic ring of C4 ~ C30, the aryloxy containing N heterocycle, the annelated heterocycles aromatic hydrocarbons of C4 ~ C30, the virtue amino of C4 ~ C30 or C4 ~ C30 of C4 ~ C30;
N is 1 or 2;
A1 to A4 is atom N or C atom;
When A1, A3 are atom N simultaneously, A2 and A4 is C atom;
Or when A1, A4 are atom N simultaneously, A2 and A3 is C atom;
Or when A2, A4 are atom N simultaneously, A1 and A3 is C atom;
Or when A3, A4 are atom N simultaneously, A1 and A2 is C atom;
Or when A1, A3, A4 are atom N, A2 is C atom simultaneously;
L be the aromatic ring of singly-bound or C6 ~ C10 or C4 ~ C10 containing N heterocycle.
Further, the described six-membered ring group containing A1 ~ A4 is selected from structural formula:
Further, described indenofluorene derivative has structure shown in formula (II):
Wherein:
R1 to R5 is independently selected from the aliphatic alkyl of C1 ~ C20 or the aromatic group of C6 ~ C20;
Ar is selected from the aromatic ring of C4 ~ C30, the aryloxy containing N heterocycle, the annelated heterocycles aromatic hydrocarbons of C4 ~ C30, the virtue amino of C4 ~ C30 or C4 ~ C30 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):
Wherein:
R1 to R5 is independently selected from the aliphatic alkyl of C1 ~ C20 or the aromatic group of C6 ~ C20;
Ar is selected from the aromatic ring of C4 ~ C30, the aryloxy containing N heterocycle, the annelated heterocycles aromatic hydrocarbons of C4 ~ C30, the virtue amino of C4 ~ C30 or C4 ~ C30 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):
Wherein:
R1 to R5 is independently selected from the aliphatic alkyl of C1 ~ C20 or the aromatic group of C6 ~ C20;
Ar is selected from the aromatic ring of C4 ~ C30, the aryloxy containing N heterocycle, the annelated heterocycles aromatic hydrocarbons of C4 ~ C30, the virtue amino of C4 ~ C30 or C4 ~ C30 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 alkyl of the cycloalkyl of C3 ~ C12 or the C3 ~ C12 containing ethylene linkage or acetylene bond.
Described aromatic group is selected from: pyridyl, phenyl or naphthyl.
Heteroatoms in described annelated heterocycles aromatic hydrocarbons is atom N.
In order to more clearly demonstrate content of the present invention, lower mask body describes the preferred structure in the type of compounds that the present invention relates to.
Described indenofluorene derivative, is selected from following structural formula:
Present invention also offers a kind of method preparing described indenofluorene derivative, namely under argon shield, the intermediate shown in formula (V) or formula (VI) is obtained through linked reaction.
Indenofluorene derivative of the present invention can be used as electron transport layer materials or light emitting host material in organic electroluminescence device.
Present invention also offers a kind of organic electroluminescence device, comprise the first electrode and the second electrode and several organic function layers between two electrodes, wherein, at least one deck in described organic function layer comprises the compound with following structural:
Wherein:
R1 to R5 is independently selected from the aliphatic alkyl of C1 ~ C20 or the aromatic group of C6 ~ C20;
Ar is selected from the aromatic ring of C4 ~ C30, the aryloxy containing N heterocycle, the annelated heterocycles aromatic hydrocarbons of C4 ~ C30, the virtue amino of C4 ~ C30 or C4 ~ C30 of C4 ~ C30;
N is 1 or 2;
A1 to A4 is atom N or C atom;
When A1, A3 are atom N simultaneously, A2 and A4 is C atom;
Or when A1, A4 are atom N simultaneously, A2 and A3 is C atom;
Or when A2, A4 are atom N simultaneously, A1 and A3 is C atom;
Or when A3, A4 are atom N simultaneously, A1 and A2 is C atom;
Or when A1, A3, A4 are atom N, A2 is C atom simultaneously;
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, in organic electroluminescence device, can be used as electron transport layer materials.
Indenofluorene derivative triplet of the present invention is higher, has and luminescent dye, and particularly the molecular orbital(MO) that matches each other of phosphorescent coloring, can be used as light emitting host material in electroluminescent device.
Embodiment
The basic chemical industry raw materials such as dichloro pyrimidine used in the present invention, trichloropyrimidine, dichloropyrazine, cyanuric chloride, aryl boric acid, indenofluorene boric acid, indenofluorene boric acid Knit-the-brows alcohol ester, carbazole, secondary aryl amine, all can buy in Chemicals market at home, or customized in relevant organic intermediate synthesis factory.Here the synthesis of the main intermediate two bromo indenofluorene of this patent is only described below by we:
(1) synthesis of terphenyl skeleton
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 water separatory, and 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) synthesis of tetramethyl-indenofluorene
500mL there-necked flask, dried and clean, nitrogen protection, adds 10.0g2 wherein, 5-diphenyl terephthalic acid diethyl ester, the tetrahydrofuran (THF) that 200mL heavily steams, and drips the diethyl ether solution of the lithium methide of 60mL3.0mol/L in-30 DEG C.Finish and rise to 25 DEG C, reaction 5h, adds methyl alcohol, adds aqueous ammonium chloride solution separatory, be concentrated into dry after organic layer dried over mgso, obtain slight yellow oil 9.5.This oily matter 200mL methylene dichloride is dissolved, slowly drips 15g methanesulfonic in-5 DEG C, finish and rise to 25 DEG C of reaction 2h, add water separatory, and 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
250mL there-necked flask, adds 3.1g indenofluorene, 30mLDMF, slowly drips the 15mLDMF solution of 4.0gN-bromo-succinimide in 35 DEG C, finish maintenance 35 DEG C 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) synthesis of boric acid
At a 500mL there-necked flask, join magnetic agitation, Ar gas shielded; add the dibromo indenofluorene (molecular weight 468 of 20g; 0.0428mol) and the THF of 250ml, heating makes entirely molten, is chilled to-78 DEG C; drip BuLi (the concentration 2.4M of 21ml; 0.05mol), temperature maintains-78 DEG C always, drips the B (OiPr) 3 of 30ml after stirring 10min-78 DEG C time; stir and add dilute acid hydrolysis to room temperature, upper strata is white solid.Filter, separate solid product, water layer is neutralized to neutrality, and extract by ethyl acetate, extracting solution evaporate to dryness, adds diluted alkaline, and withdraw not molten impurity in alkali by ethyl acetate, water layer is neutralized to neutrality, and adularescent solid is separated out, and filters, obtains product.Be total to obtain 15g solid product, molecular weight 398, productive rate 86.46%.
(5) synthesis of boric acid Knit-the-brows alcohol ester
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.24h is stirred at 85 DEG C.Be chilled to room temperature, sintered filter funnel filters, and filtrate, under agitation in impouring water, collects white solid product, altogether about 24.1g, molecular weight 562, productive rate 97%.
Compou nd synthesis embodiment
The synthesis of embodiment 1 compound 1
(1) the first step
Under Ar gas shielded; 2,4,6-trichloropyrimidine 18.2g (molecular weight 182 is added in the there-necked flask of a 5000ml; 0.10mol); indenofluorene-2,7-hypoboric acid 17.92g (molecular weight 398,0.045mol); four (triphenylphosphine conjunction) palladium 6.0g (0.0052mol); the THF of 600ml, 400ml toluene, salt of wormwood 60g (0.435mol) is dissolved in the solution formed in 400ml water and adds reaction flask.After under reduced pressure repeatedly taking a breath, start electric stirring, with TLC (thin-layer chromatography) monitoring reaction, after backflow 4h, react completely.Let cool, reaction system divides two layers, work, separates organic layer, evaporate to dryness, obtains solid product, with re crystallization from toluene, obtains 23.65g intermediate, molecular weight 604, productive rate 87%.
(2) second step
Under Ar gas shielded; product 12.1g (molecular weight 604 obtained in the previous step is added in the there-necked flask of a 2000ml; 0.02mol); phenylo boric acid Knit-the-brows alcohol ester 20.4g (molecular weight 204,0.1mol), four (triphenylphosphine conjunction) 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 formed in 240ml water and adds reaction flask.After under reduced pressure repeatedly taking a breath, start electric stirring, with TLC (thin-layer chromatography) monitoring reaction, after backflow 12h, react completely.Let cool, reaction system divides two layers, work, separates organic layer, 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%.
The synthesis of embodiment 2 compound 2
(1) the first step
Under Ar gas shielded; 2 are added in the there-necked flask of a 5000ml; 4,6-trichloropyrimidine 18.2g (molecular weight 182,0.10mol); phenylo boric acid 28.1g (molecular weight 122; 0.23mol), four (triphenylphosphine conjunction) palladium 12.0g (0.0104mol), THF of 600ml; 400ml toluene, salt of wormwood 60g (0.435mol) is dissolved in the solution formed in 400ml water and adds reaction flask.After under reduced pressure repeatedly taking a breath, start electric stirring, with TLC (thin-layer chromatography) monitoring reaction, after backflow 8h, react completely.Let cool, reaction system divides two layers, work, separates organic layer, evaporate to dryness, obtains solid product, with re crystallization from toluene, obtains 19.9g intermediate, molecular weight 266, productive rate 75%.
(2) second step
Under Ar gas shielded; product 13.3g (molecular weight 266 obtained in the previous step is added in the there-necked flask of a 2000ml; 0.05mol), indenofluorene-2,7-hypoboric acid Knit-the-brows alcohol ester 11.3g (molecular weight 562; 0.02mol); four (triphenylphosphine conjunction) 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 formed in 240ml water and adds reaction flask.After under reduced pressure repeatedly taking a breath, start electric stirring, with TLC (thin-layer chromatography) monitoring reaction, after backflow 12h, react completely.Let cool, reaction system divides two layers, work, separates organic layer, 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%.
The synthesis of embodiment 3 compound 3
(1) the first step
Under Ar gas shielded; carbazole 16.7g (molecular weight 167,0.1mol) is dissolved in dry DMF 180ml, drips 5.64gNaH (content 55%; solution 0.235mol) 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, adds wherein with 20 minutes; stir 3h; in impouring water 1000ml, filtering-depositing, vacuum-drying; product silica column purification; obtain 25.4g target molecule (0.081mol), molecular weight 313, productive rate 81%.
(2) second step
Under Ar gas shielded; reaction product 15.6g (molecular weight 313 is walked on adding in the there-necked flask of a 5000ml; 0.05mol); phenylo boric acid 6.71g (molecular weight 122,0.055mol), four (triphenylphosphine conjunction) 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 formed in 100ml water and adds reaction flask.After under reduced pressure repeatedly taking a breath, start electric stirring, with TLC (thin-layer chromatography) monitoring reaction, after backflow 6h, react completely.Let cool, reaction system divides two layers, work, separates organic layer, evaporate to dryness, obtains solid product, with re crystallization from toluene, obtains 13.8g intermediate, molecular weight 355, productive rate 78%.(scalable synthesis)
(3) the 3rd steps
Under Ar gas shielded; product 17.75g (molecular weight 355 obtained in the previous step is added in the there-necked flask of a 2000ml; 0.05mol), indenofluorene-2,7-hypoboric acid Knit-the-brows alcohol ester 11.3g (molecular weight 562; 0.02mol); four (triphenylphosphine conjunction) 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 formed in 240ml water and adds reaction flask.After under reduced pressure repeatedly taking a breath, start electric stirring, with TLC (thin-layer chromatography) monitoring reaction, after backflow 12h, react completely.Let cool, reaction system divides two layers, work, separates organic layer, 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%.
The synthesis of embodiment 4 compound 4
(1) the first step
Under Ar gas shielded; four chloromethylated intermediates (product by the first step synthesis in embodiment 1) 30.2g (molecular weight 604 is added in the there-necked flask of a 5000ml; 0.05mol); phenylo boric acid 14.64g (molecular weight 122; 0.12mol); four (triphenylphosphine conjunction) 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 formed in 100ml water and adds reaction flask.After under reduced pressure repeatedly taking a breath, start electric stirring, with TLC (thin-layer chromatography) monitoring reaction, after backflow 6h, react completely.Let cool, reaction system divides two layers, work, separates organic layer, evaporate to dryness, obtains solid product, with re crystallization from toluene, obtains 25.04g intermediate, molecular weight 686, productive rate 73%.
(2) second step
Under Ar gas shielded; carbazole 16.7g (molecular weight 167; 0.1mol) be dissolved in dry DMF 90ml; drip 5.11gNaH (content 55%, the 0.117mol) solution in 90mlDMF, 20 minutes used times; stir 1h; then two chloromethylated intermediate 30.9g (molecular weight 686,0.045mol) are dissolved in the solution in 90mlDMF, added wherein with 20 minutes; stir 3h; in impouring water 500ml, filtering-depositing, vacuum-drying; product silica column purification; 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%.
The synthesis of embodiment 5 compound 5
Under Ar gas shielded, in a reaction flask, add pentanoic 2.02g (molecular weight 169,0.012mol), anhydrous THF20ml.Be chilled to 00C, stir.The n-BuLi (2.4M, 0.013mol) of 5.5ml is slowly added wherein.At room temperature stir 30 minutes, its colour changed into yellow.Be chilled to 00C.By this solution with 30 minutes, slowly add in the 50mlTHF solution of two chloromethylated intermediates (product by the first step synthesis in embodiment 4) 3.43g (molecular weight 686,0.005mol), 4h is stirred at 35 DEG C, stir 8h at 50 DEG C, cooling, mixture is poured in water, with dichloromethane extraction, organic layer evaporate to dryness, the solid pillar layer separation obtained, 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%.
The synthesis of embodiment 6 compound 6
(1) the first step
Under Ar gas shielded, in a reaction flask, add pentanoic 20.2g (molecular weight 169,0.12mol), anhydrous THF200ml.Be chilled to 0 DEG C, stir.The n-BuLi (concentration 2.4M, 0.13mol) of 55ml is slowly added wherein.At room temperature stir 30 minutes, its colour changed into yellow.Be chilled to 0 DEG C.By this solution with 30 minutes, slowly add 2,4,6-trichloropyrimidine 20.02g (molecular weight 182, in 200mlTHF solution 0.11mol), stir 4h at 0 DEG C, mixture is poured in water, with dichloromethane extraction, organic layer evaporate to dryness, the solid pillar layer separation obtained, obtains the micro-yellow solid of 31.2g, molecular weight 315, productive rate 90%.
(2) second step
Under Ar gas shielded; intermediate 15.75g (the molecular weight 315 walking synthesis is added in a there-necked flask; 0.05mol); phenylo boric acid 6.71g (molecular weight 122,0.055mol), four (triphenylphosphine conjunction) 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 formed in 100ml water and adds reaction flask.After under reduced pressure repeatedly taking a breath, start electric stirring, with TLC (thin-layer chromatography) monitoring reaction, after backflow 6h, react completely.Let cool, reaction system divides two layers, work, separates organic layer, evaporate to dryness, obtains solid product, with re crystallization from toluene, obtains 14.7g intermediate, molecular weight 357, productive rate 82%.
(3) the 3rd steps
Under Ar gas shielded; product 17.85g (molecular weight 357 obtained in the previous step is added in the there-necked flask of a 2000ml; 0.05mol), indenofluorene-2,7-hypoboric acid Knit-the-brows alcohol ester 11.3g (molecular weight 562; 0.02mol); four (triphenylphosphine conjunction) 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 formed in 240ml water and adds reaction flask.After under reduced pressure repeatedly taking a breath, start electric stirring, with TLC (thin-layer chromatography) monitoring reaction, after backflow 12h, react completely.Let cool, reaction system divides two layers, work, separates organic layer, 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%.
The synthesis of embodiment 7 compound 7
Synthesis step is same as embodiment 1, just a kind of raw material 2,4,6-trichloropyrimidine is wherein 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%.
The synthesis of embodiment 8 compound 8
Synthesis step is same as embodiment 2, just a kind of raw material 2,4,6-trichloropyrimidine is wherein 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%.
The synthesis of embodiment 9 compound 9
Under Ar gas shielded; carbazole 16.7g (molecular weight 167; 0.1mol) be dissolved in dry DMF 90ml; drip 5.11gNaH (content 55%, the 0.117mol) solution in 90mlDMF, 20 minutes used times; stir 1h; then two chloromethylated intermediate 24.1g (molecular weight 534,0.045mol) are dissolved in the solution in 90mlDMF, added wherein with 20 minutes; stir 3h; in impouring water 500ml, filtering-depositing, vacuum-drying; product silica column purification; 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%.
The synthesis of embodiment 10 compound 10
Synthesis step is same as embodiment 3, just a kind of raw material 2,4,6-trichloropyrimidine is wherein changed into 2,4-dichloro pyrimidine, and without the reaction 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%.
The synthesis of embodiment 11 compound 12
(1) the first step
Under Ar gas shielded; 2-chloro-4 is added in the there-necked flask of a 2000ml; 6-diphenylpyrimidin 26.6g (molecular weight 266,0.10mol), to bromobenzeneboronic acid Knit-the-brows alcohol ester 34g (molecular weight 282; 0.12mol); four (triphenylphosphine conjunction) 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 formed in 200ml water and adds reaction flask.After under reduced pressure repeatedly taking a breath, start electric stirring, with TLC (thin-layer chromatography) monitoring reaction, after backflow 5h, react completely.Let cool, reaction system divides two layers, work, separates organic layer, evaporate to dryness, obtains solid product, with re crystallization from toluene, obtains 27g intermediate, molecular weight 386, productive rate 70%.
(2) second step
Synthesis step is same as the first step in embodiment 1, just a kind of raw material 2,4,6-trichloropyrimidine is wherein 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%.
The synthesis of embodiment 12 compound 14
Synthesis step is same as the first step in embodiment 1, just a kind of raw material 2,4,6-trichloropyrimidine is wherein 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%.
The synthesis of embodiment 13 compound 15
Synthesis step is same as embodiment 1, just a kind of raw material 2,4,6-trichloropyrimidine is wherein 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%.
The synthesis of embodiment 14 compound 16
Synthesis step is same as embodiment 2, just a kind of raw material 2,4,6-trichloropyrimidine is wherein 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%.
The synthesis of embodiment 15 compound 17
In embodiment 1 the first step, by a kind of raw material 2,4 wherein, 6-trichloropyrimidine changes 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%.
The synthesis of embodiment 16 compound 18
In the first step of embodiment 3, by a kind of raw material 2,4 wherein, 6-trichloropyrimidine changes 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%.
The synthesis of embodiment 17 compound 19
In embodiment 1 the first step, by a kind of raw material 2 wherein, 4,6-trichloropyrimidine changes 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 here synthesizes, 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%.
The synthesis of embodiment 18 compound 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 changes 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%.
The synthesis of embodiment 19 compound 22
Synthesis step is same as embodiment 1, just a kind of raw material 2,4,6-trichloropyrimidine is wherein 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%.
The synthesis of embodiment 20 compound 25
Synthesis step is same as embodiment 1, just a kind of raw material 2,4,6-trichloropyrimidine is wherein 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%.
The synthesis of embodiment 21 compound 26
Synthesis step is same as embodiment 1, just a kind of raw material 2,4,6-trichloropyrimidine is wherein 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%.
The synthesis of embodiment 22 compound 27
Synthesize by the step of embodiment 1, just by a kind of raw material 2 wherein, 4,6-trichloropyrimidine changes into 2,5-dichloropyrazine, in the synthesis of second step, 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%.
The synthesis of embodiment 23 compound 28
Synthesize by the step of embodiment 1, just by a kind of raw material 2 wherein, 4,6-trichloropyrimidine changes into 3,5-dichloropyrazine, in the synthesis of second step, 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%.
The synthesis of embodiment 24 compound 29
By the first step in embodiment 1, just a kind of raw material 2,4,6-trichloropyrimidine is wherein changed into 2,5-dichloropyrazine, obtain two chloromethylated intermediates; Re-use embodiment 4 second step, replace two chloromethylated intermediates in former step here with two chloromethylated intermediates synthesized, 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%.
The synthesis of embodiment 25 compound 30
By the first step in embodiment 1, just a kind of raw material 2,4,6-trichloropyrimidine is wherein changed into 3,5-dichloropyrazine, obtain two chloromethylated intermediates; Re-use embodiment 4 second step, replace two chloromethylated intermediates in former step here with two chloromethylated intermediates synthesized, 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%.
The synthesis of embodiment 26 compound 31
In embodiment 1 the first step, by a kind of raw material 2 wherein, 4,6-trichloropyrimidine changes 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 here synthesizes, 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%.
The synthesis of embodiment 27 compound 32
In embodiment 1 the first step, by a kind of raw material 2 wherein, 4,6-trichloropyrimidine changes 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 here synthesizes, 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%.
The synthesis of embodiment 28 compound 33
(1) the first step
2.9g (molecular weight 24 is added in a reaction flask of drying; magnesium chips 0.121mol); the anhydrous THF (tetrahydrofuran (THF)) of 100ml; add a little iodine; nitrogen protection, the solution that the THF slowly dripping 15.6g (molecular weight 156,0.10mol) bromobenzene and 100ml is formed; after reaction starts, start stirring.Dropwise, return stirring 2h, obtain the Grignard reagent of bromobenzene.Be chilled to room temperature.The cyanuric chloride of 6.1g (molecular weight 183,0.033mol) is dissolved in the THF of 200ml, is chilled to 0-10 DEG C.Under stirring, by the bromobenzene Grignard reagent dropwise prepared above in this cyanuric chloride solution.Dropwise, at 50 DEG C, stir 10h.Be chilled to room temperature, by the aqueous hydrochloric acid of 12% of reaction mixture impouring 500ml, remove THF under reduced pressure, filter, obtain solid product.Cross a short column of silica gel, with sherwood oil: toluene (5:1) drip washing, obtains white solid product 5.4g (molecular weight 267,0.0202mol, 61%).
(2) second step
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 562,0.014mol) of indenofluorene, 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 terminates.Add toluene and saturated aqueous common salt, separate organic layer, evaporate to dryness, be separated with short column of silica gel, sherwood oil: chloroform (1:1) drip washing, product uses re crystallization from toluene 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%.
The synthesis of embodiment 29 compound 34
Synthesis point two steps are carried out, and the first step step is same as the second step of embodiment 28, is just changed to bromobenzeneboronic acid Knit-the-brows alcohol ester by two boric acid Knit-the-brows alcohol esters of starting material indenofluorene in second step; Here the synthesis step of second step is also same as the second step of embodiment 28, just chloro-for starting material 2-4,6-phenylbenzene triazines 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%.
The synthesis of embodiment 30 compound 35
Synthesis step is same as embodiment 28, and just change into methyl bromobenzene by starting material bromobenzene in a first step, 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%.
The synthesis of embodiment 31 compound 36
Synthesis point three steps are carried out, and the first step is same as the first step in embodiment 28, just changes into methyl bromobenzene by starting material bromobenzene; Second step is same as second step in embodiment 28, is just changed to bromobenzeneboronic acid Knit-the-brows alcohol ester by two boric acid Knit-the-brows alcohol esters of starting material indenofluorene, chloro-for 2-4,6-phenylbenzene triazines are changed to 4-bromine triphenyl triazine; 3rd step synthesis is same as second step in embodiment 28, just chloro-for 2-4,6-phenylbenzene triazines 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%.
The synthesis of embodiment 32 compound 37
Reaction point 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 starting material cyanuric chloride is changed into four chloromethylated intermediates that the first step here synthesizes, 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%.
The synthesis of embodiment 33 compound 38
Reaction point 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 synthesizes the second step be same as in embodiment 1, just tetrachloro-pyrimidine intermediate is wherein changed to four chlorotriazine intermediates; 3rd step synthesis step is same as the first step in embodiment 3, just starting material cyanuric chloride is changed into two chloromethylated intermediates that second step here synthesizes, 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%.
The synthesis of embodiment 34 compound 39
Reaction point 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 starting material dichloro pyrimidine intermediate is changed into the four chlorotriazine intermediates that the first step here synthesizes, 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%.
The synthesis of embodiment 35 compound 40
Reaction point 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 synthesizes the second step be same as in embodiment 1, just tetrachloro-pyrimidine intermediate is wherein changed to four chlorotriazine intermediates; 3rd step synthesis step is same as the first step in embodiment 5, just phonetic for starting material dichloro intermediate is changed into the dichlorotriazine intermediate that second step here synthesizes, 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%.
Here is the Application Example of the compounds of this invention:
Embodiment 36: fabricate devices OLED-1 ~ OLED-10
The preferred implementation of fabricate devices:
(1) device layout
Conveniently compare the transmission performance of these electron transport materials, the present invention devises 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 material as a comparison.The structure of Bphen is:
Substrate can use the substrate in conventional organic luminescence device, such as: 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 material.Hole mobile material selected in element manufacturing of the present invention 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 structures such as O/Al.Electron injection material selected in element manufacturing of the present invention is LiF, and cathode material is Al.
(2) fabricate devices OLED-1
Sheet glass supersound process in commercial detergent of ITO transparency conducting layer will be coated with, rinse in deionized water, at acetone: ultrasonic oil removing in alcohol mixed solvent, be baked under clean environment and remove moisture content completely, 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 rate 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, the evaporation rate of evaporating Al q3 and C545T, Alq3 is the evaporation rate of 0.1nm/s, C545T is 0.002nm/s, evaporation total film thickness is 30nm;
On luminescent layer, vacuum evaporation one deck compound 2 is as the electron transfer layer of device OLED-1, and its evaporation rate is 0.1nm/s, and evaporation total film thickness is 20nm;
At the upper vacuum evaporation evaporation LiF of electron transfer layer (ETL) and the Al layer negative electrode as device, thickness is respectively 0.5nm and 150nm.
Preparation preparation OLED-2 ~ OLED-10, is only change the compound 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)):
Table 2
Method, with embodiment 36, changes light emitting host material into compound 23.The performance of device is in table 3:
Table 3
Above result shows, new organic materials of the present invention is used for organic electroluminescence device, can effectively reduce landing voltage, and improving current efficiency, is electron transport material of good performance.
Although describe the present invention in conjunction with the embodiments, the present invention is not limited to above-described embodiment, should be appreciated that, under the guiding of the present invention's design, those skilled in the art can carry out various amendment and improvement, and claims summarise scope of the present invention.

Claims (3)

1. an indenofluorene derivative, is characterized in that, described compound is selected from structural formula:
2. indenofluorene derivative according to claim 1 is used as electron transport layer materials or light emitting host material in organic electroluminescence device.
3. an organic electroluminescence device, 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:
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