CN104650090A - Fluorene derivative containing carbazole-3-yl group and application thereof - Google Patents

Fluorene derivative containing carbazole-3-yl group and application thereof Download PDF

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CN104650090A
CN104650090A CN201310730832.4A CN201310730832A CN104650090A CN 104650090 A CN104650090 A CN 104650090A CN 201310730832 A CN201310730832 A CN 201310730832A CN 104650090 A CN104650090 A CN 104650090A
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carbazole
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carbonatoms
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CN104650090B (en
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李银奎
汤金明
范洪涛
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Guan Eternal Material Technology Co Ltd
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Beijing Eternal Material Technology Co Ltd
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    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
    • C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
    • C07D487/04—Ortho-condensed systems
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    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
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Abstract

The invention provides a novel fluorene derivative containing a carbazole-3-yl group, which is shown in the structure of formulae (1), (2) or (3). In the structure, one of A and B is N, and the other one is a CH group or a CH group of which H is substituted by one of alkyl of C1-C12, aryl of C6-C30, heterocyclic aryl of C6-C30, -CF3 and -SCH3; Ar is selected from fluorenylidene or indenofluoreneylidene; R1 and R2 are respectively and independently selected from H, substituted or unsubstituted fatty alkyl of C1-12, fatty naphthenic base of C1-12, aryl of C6-30, methylthio, methoxyl, ethoxy or trifluoromethyl; R3 and R4 are selected from substituted fatty alkyl of C1-12, fatty naphthenic base of C1-12 or aryl of C6-30; and R4 can be selected from H. The compound is stable in property and simple in preparation process, and can be used as a phosphorescence host material in an organic electroluminescence device to obtain relatively high luminescence efficiency and relatively low turn-on voltage.

Description

A kind of fluorene derivatives containing carbazole-3-base group and application thereof
Technical field
The present invention relates to a kind of novel organic compound, and the application in ORGANIC ELECTROLUMINESCENCE DISPLAYS technical field.
Background technology
Electroluminescent material and device, through years of researches and development, have reached practical level, various material, such as hole material, electronic material, luminescent material, and display device technology of preparing has achieved considerable progress.Along with the requirement deeply with to material in practical process of research work, day by day obvious as the advantage of luminescent material with phosphorescence.The luminous efficiency of phosphor material, higher than fluorescent material 3 to 4 times, concerning many display products requiring brightness higher, is primary selection with phosphor material.Phosphorescence luminescent layer in device is steamed altogether by two class materials and is formed, and a class is material of main part, accounts for about 90% of common steaming component, and another kind of is phosphorescent coloring, accounts for about 10% of common steaming component.What tradition used is 4 at phosphorescent light body material, 4 '-N, N '-two carbazole biphenyl.This material has higher triplet, can mate well with phosphorescent coloring, but due to this material molecule amount less (molecular weight 484), make second-order transition temperature lower (Tg be about 1100C or once), in the easy crystallization of use procedure, form island, cause not bright spot, device lifetime shortens.The R and D of new phosphorescent light body material are operated in and constantly carry out, wherein have the research patent (application number 200680047266.5 in pyrimidine (pyrazine) base introducing material structure, publication number CN101331626A), also the research patent (application number 200580014777.2 introduced by pyrimidyl in material structure is had, publication number CN1951155A), obtain good improvement effect all in various degree.
Therefore, based on existing research, the phosphorescent light body material of exploitation stability and high efficiency further, thus reduced bright voltage, improve device efficiency, there is very important actual application value.
Summary of the invention
The object of the invention is to propose a kind of novel organic compound, this compounds may be used for ORGANIC ELECTROLUMINESCENCE DISPLAYS field, especially, phosphorescent light body material is used as in organic luminescence function layer in organic electroluminescence device, and then it is low to obtain driving voltage, the organic electroluminescence device that current efficiency is high, the transformation period is longer.
For solving the problems of the technologies described above, the technical solution adopted in the present invention is as follows:
Organic compound provided by the invention, namely containing imidazo ［ 1, 2-a ］ phosphorescent light body material of pyrimidine group and carbazole group, or containing imidazo ［ 1, 2-a ］ phosphorescent light body material of pyrazine group and carbazole group, there is higher molecular weight, be conducive to the raising of compound second-order transition temperature, simultaneously, imidazo [1, 2, a] pyridine groups or imidazo ［ 1, 2-a ］ pyrazine group and carbazole group directly can be connected to form compound, also fluorenylidene can be passed through, the fused ring aryl groups such as Ya Yin And fluorenyl are connected, each group on this compound is in on-plane surface state, make whole molecule on space multistory, form distortion to a certain extent, the stereoeffect irregularity of molecule, be conducive to forming unformed film, particularly on the basis having carbazole group to exist, the present invention introduces imidazo ［ 1, 2-a ］ pyrimidine group or imidazo ［ 1, 2-a ］ pyrazine group, effectively have adjusted the triplet (T1) of material.When material of the present invention is used for electroluminescent device as phosphorescence host time, electroluminescent improves significantly at everyways such as opening bright voltage, brightness, work-ing life.
The invention provides one and there is the fluorene derivatives containing carbazole-3-base group such as formula (1), structure shown in (2) or (3):
Wherein:
A and B one of them be N, another be H in CH group or CH group by carbonatoms be the alkyl of 1-12, carbonatoms is the aryl of 6-30, carbonatoms is the heterocyclic aryl ,-CF of 6-30 3,-SCH 3in a kind of group of replacement;
Ar is selected from fluorenylidene or sub-indeno fluorenyl;
R 1and R 2separately be selected from H, substituted or unsubstituted aryl, methylthio group, methoxyl group, oxyethyl group or trifluoromethyl that substituted or unsubstituted aliphatics cycloalkyl that substituted or unsubstituted aliphatic alkyl that carbonatoms is 1-12, carbonatoms are 1-12, carbonatoms are 6-30;
R 3be selected from substituted or unsubstituted aliphatic alkyl that carbonatoms is 1-12, substituted or unsubstituted aryl that substituted or unsubstituted aliphatics cycloalkyl that carbonatoms is 1-12 or carbonatoms are 6-30;
R 4be selected from H, substituted or unsubstituted aryl that substituted or unsubstituted aliphatics cycloalkyl that substituted or unsubstituted aliphatic alkyl that carbonatoms is 1-12, carbonatoms are 1-12 or carbonatoms are 6-30;
L 1and L 2independently be selected from singly-bound, substituted or unsubstituted heteroarylidene that substituted or unsubstituted arylidene that alkylidene group that carbonatoms is 1-20, carbonatoms are 6-30 or carbonatoms are 6-30.
Further, structure shown in general formula (4) can directly and imidazo ［ 1,2-a ］ pyrimidine group or the connection of imidazo ［ 1,2-a ］ pyrazine group, or, work as R 1or R 2during for H, shown in general formula (4), structure passes through R 1or R 2being connected with imidazo ［ 1,2-a ］ pyrimidine group or imidazo ［ 1,2-a ］ pyrazine group, is also just succeed in reaching an agreement structure shown in formula (4) to be connected directly between R 1or R 2position on;
Further, described R 1and R 2separately be selected from H, methyl, ethyl, propyl group, normal-butyl, n-pentyl, n-hexyl, phenyl, tolyl, ethylbenzene, xenyl, (carbazole-9-base) phenyl, naphthyl, carbazyl, N-phenyl carbazole base, fluorenyl, N-fluorenyl carbazyl, methylthio group, methoxyl group, oxyethyl group, trifluoromethyl, dibenzothiophene base or dibenzofuran group.
Further, described R 3be selected from methyl, ethyl, propyl group, normal-butyl, n-pentyl, n-hexyl, phenyl, tolyl, ethylbenzene, xenyl or naphthyl.
Further, described R 4be selected from H, methyl, ethyl, propyl group, normal-butyl, n-pentyl, n-hexyl, phenyl, tolyl, ethylbenzene, xenyl or naphthyl.
Further, when Ar is not H, the skeleton structure of described Ar is preferably from following arbitrary structure:
Further, described bridge linkage group L 1and L 2independently be selected from singly-bound, phenylene, biphenylene, naphthylidene, pyridylidene one of them.
Bridge linkage group L in general formula 1and L 2independently can also be selected from heteroatoms, the one in such as Sauerstoffatom, nitrogen-atoms or sulphur atom.
Further, formula (1), in (2) or (3) A and B one of them be N, another is that H in CH group or CH group is by methyl, ethyl, propyl group, normal-butyl, n-pentyl ,-CF 3,-SCH 3, phenyl, tolyl, ethylbenzene, xenyl, naphthyl, carbazyl, N-phenyl carbazole base monobasic CH group.
Work as R 1or R 2when not being H, described R 1or R 2be selected from following arbitrary structure:
In order to more clearly demonstrate content of the present invention, lower mask body describes the preferred structure of the compound that the present invention relates to:
Compound 1
Compound 2
Compound 3
Compound 4
Compound 5
Compound 6
Compound 7
Compound 8
Compound 9
Compound 10
Compound 11
Compound 12
Compound 13
Compound 14
Compound 15
Compound 16
Compound 17
Compound 18.
The invention provides a kind of fluorene derivatives containing carbazole-3-base group that can be applicable in organic electroluminescence device.
Further, the described fluorene derivatives containing carbazole-3-base group can be used as phosphorescent light body material in organic electroluminescence device.
Present invention also offers a kind of organic electroluminescence device, comprise substrate, and form anode layer, organic luminescence function layer and cathode layer on the substrate successively; Described organic luminescence function layer comprises hole transmission layer, organic luminous layer and electron transfer layer, and the material of main part of described organic luminous layer is the fluorene derivatives containing carbazole-3-base group described in one or more.
Further, in organic electroluminescence device, described luminescent layer is made up of material of main part and luminescent dye, and described luminescent dye is phosphorescent coloring.
The novel fluorene derivatives containing carbazole-3-base group that the present invention develops, preparation technology is simple, easy and this material has good thermostability, have the molecular orbital(MO) and triplet (T1) that match with phosphorescent coloring, be good phosphorescent light body material in organic electroluminescence device.
Specific embodiment:
Following examples 1-embodiment 19 is the synthetic example of the application:
Various imidazos [1 used in the present invention, 2-a] pyrimidine halo derivatives and imidazo [1, 2-A] pyrazine halo derivatives, such as, 5, 7-dichloro-imidazole also [1, 2-a] pyrimidine, 6-bromine imidazo [1, 2-a] pyrimidine, 3-bromine imidazo [1, 2-a] pyrimidine, the chloro-5-of 7-(methylthio group) imidazo [1, 2-c] pyrimidine, 3-bromo-6-chlorine imidazo [1, 2-a] pyrimidine, 2-(3-bromophenyl) imidazoles [1, 2-a] and pyrimidine, the chloro-2-p-tolylimidazol [1 of 6-, 2-a] and pyrimidine, 2-(4-bromophenyl)-imidazo [1, 2-a]-7-methylpyrimidine, 2-(3-bromophenyl)-imidazo [1, 2-a] pyrimidine, 2-(3-bromophenyl)-imidazo [1, 2-a]-7-methylpyrimidine, 2-(4-bromophenyl)-imidazo [1, 2-a] pyrimidine, the bromo-7-of 3-(trifluoromethyl) imidazo [1, 2-a] pyrimidine, 6-bromine imidazo [1, 2-a] pyrazine, 3-bromo-8-chlorine imidazo [1, 2-a] pyrazine, 6, the bromo-imidazoles [1 of 8-bis-, 2-a] pyrazine, the chloro-imidazo [1 of 5-, 2-a] pyrazine, 8-chlorine imidazo [1, 2-a] pyrazine, 3-bromine imidazo [1, 2-a] pyrazine, 2-bromine imidazo [1, 2-a] pyrazine, Deng, commercially available all at home, the chemical raw materials such as various aryl boric acid and Knit-the-brows alcohol ester thereof, can conveniently buy in Chemicals market at home, some special aryl boric acid derivatives and all available common organic procedures synthesis of intermediate.
Embodiment 1
The synthesis of following structural compounds,
The first step,
At one 500 milliliters of there-necked flasks, join electric stirring, Ar gas shielded; add the carbazole (molecular weight 167,0.10mol) of 16.7g, the bromo-7-of 2-iodo-9; 9-dimethyl fluorene 44g(molecular weight 398,0.11mol), cuprous iodide 1.9g(molecular weight 190; 0.01mol); salt of wormwood 28g(molecular weight 138,0.203mol), 18-hat-6 1.2g(molecular weight 264; 0.00455mol), solvent DMPU 250ml is altogether added.Return stirring 4 hours, with TLC monitoring reaction.After reacting completely, naturally stir and be cooled to less than 80 DEG C, namely add 500ml water, stir, have faint yellow solid product to separate out, leach, dry.Be separated with silica gel column chromatography, obtain micro-yellow product 35.7g, molecular weight 437, purity 98.0%, productive rate 80.2%.
Second step,
At one 500 milliliters of there-necked flasks; join magnetic agitation; Ar gas shielded; add 7-(carbazole-9-base) bromo-9, the 9-dimethyl fluorene 19.7g(molecular weight 437,0.045mol of-2-) and the THF of 120ml; be chilled to-78 DEG C; drip the nBuLi(0.05mol of 25ml2M), temperature maintains-78 DEG C always, drips the B (OiPr) of 30ml after stirring 10min-78 DEG C time 3(0.153mol), 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 15.2g solid product, molecular weight 403, productive rate 83.6%.
3rd step,
At the there-necked flask of a 1000ml, join mechanical stirring, Ar gas shielded; add 3-bromo-6-chlorine imidazo [1,2-a] pyrimidine 7.86g(molecular weight 231,0.034mol); phenylo boric acid Knit-the-brows alcohol ester 7.14g(molecular weight 204,0.035mol), catalyst P d (PPh 3) 4consumption 1.8g(molecular weight 1154,0.001556mol), aqueous sodium carbonate 120ml(2M), toluene 300ml, ethanol 150ml.Stirring and refluxing, with TLC monitoring reaction, reacts completely after reaction 1.5hs.Cooling, separates, evaporate to dryness, uses column chromatography methods separated product, the ethyl acetate of eluent 1:4: sherwood oil, obtain 7.46g faint yellow solid compound, purity 96.0%, productive rate: 92.0%.
4th step,
At the there-necked flask of a 1000ml, join mechanical stirring, Ar gas shielded; add 3-phenyl-6-chlorine imidazo [1,2-a] pyrimidine 7.16g(molecular weight 229,0.030mol); to bromobenzeneboronic acid Knit-the-brows alcohol ester 9.1g(molecular weight 282,0.032mol), catalyst P d (PPh 3) 4consumption 1.8g(molecular weight 1154,0.001556mol), aqueous sodium carbonate 120ml(2M), toluene 300ml, ethanol 150ml.Stirring and refluxing, with TLC monitoring reaction, reacts completely after reaction 3.5hs.Cooling, separates, evaporate to dryness, uses column chromatography methods separated product, the ethyl acetate of eluent 1:3: sherwood oil, obtain 9.0g faint yellow solid compound, purity 97.0%, productive rate: 83.2%.
5th step,
1000 milliliters of there-necked flasks, join magnetic agitation, add 3-phenyl-6-to bromophenyl imidazo ［ 1,2, a ］ pyrimidine 9.8g(molecular weight 349,0.028mol), 7-(carbazole-9-base)-9,9-dimethyl fluorene-2-boric acid 12.1g(molecular weight 403,0.03mol), Pd (PPh3) 4 usage quantity 1.8g(molecular weight 1154,0.00155mol), sodium carbonate 175ml(2M), toluene 175ml, ethanol 175ml.After argon replaces, backflow, with TLC monitoring reaction, react completely after 4 hours, cooling, separated basic unit, evaporate to dryness, the ethyl acetate/petroleum ether with 1/10 carries out post separation, obtains the compound 1 of 14.46g, purity 99.1%, productive rate 81.5%.
Product MS(m/e): 628, ultimate analysis (C 45h 32n 4): theoretical value C:85.96%, H:5.13%, N:8.91%; Measured value C:85.92%, H:5.11%, N:8.97%.
Embodiment 2
The synthesis of compound 1
Building-up process divides work three step, the first step is same as the 5th step reaction in embodiment 1, be to the bromo-7-of bromophenyl imidazo ［ 1,2, a ］ pyrimidine 2-iodo-9 by 3-phenyl-6-wherein, 9-dimethyl fluorene replaces, by 7-(carbazole-9-base)-9,9-dimethyl fluorene-2-boric acid with 6,9-phenylbenzene carbazole-3-boric acid replace make raw material, other raw material and process constant, obtain corresponding monobromo intermediate; Second step is same as the second step in embodiment 1, just by bromo-for 2-7-(carbazole-9 base)-9, the 9-dimethyl fluorenes monobromo intermediate of the first step synthesis here replaces making raw material, other raw material and process constant, obtain corresponding boric acid derivatives; 3rd step is same as the 5th step reaction in embodiment 1, just by 7-(carbazole-9-base wherein)-9, the 9-dimethyl fluorene-2-boric acid boric acid derivatives of second step synthesis here replaces making raw material, other raw material and process constant, obtain compound 1.
Product MS(m/e): 780, ultimate analysis (C 57h 40n 4): theoretical value C:87.66%, H:5.16%, N:7.18%; Measured value C:87.62%, H:5.13%, N:7.25%.
Embodiment 3
The synthesis of compound 2
Building-up process divides work three step, the first step is same as the 5th step reaction in embodiment 1, be to the bromo-7-of bromophenyl imidazo ［ 1,2, a ］ pyrimidine 2-iodo-9 by 3-phenyl-6-wherein, 9-dimethyl fluorene replaces, by 7-(carbazole-9-base)-9,9-dimethyl fluorene-2-boric acid with 6,9-phenylbenzene carbazole-3-boric acid replace make raw material, other raw material and process constant, obtain corresponding monobromo intermediate;
Second step,
At the there-necked flask of a 2000ml, join mechanical stirring, Ar gas shielded.Add the bromo-7-(6 of 2-, 9-phenylbenzene carbazole-3-base)-9,9-dimethyl fluorene 11.8g(molecular weight 589,0.02mol), connection pinacol borate 5.6g(molecular weight 254.2,0.022mol), Pd (dppf) Cl23.2g(0.0044mol), Potassium ethanoate 36g(molecular weight 138,0.26mol), Isosorbide-5-Nitrae dioxane 500ml.Start mechanical stirring, take a breath 3 times at reduced pressure conditions and keep Ar gas shielded afterwards, use TLC(thin-layer chromatography) monitoring reaction, to raw material completely dissolve, back flow reaction 3 hours altogether.Let cool, reaction system divides two layers, work, separates organic layer, evaporate to dryness, uses usual way process, obtains 11.2g product, productive rate 87.5%.
3rd step is same as the four-step reaction in embodiment 1, just by wherein replace making raw material to the bromobenzeneboronic acid pinacol ester pinacol borate derivative of second step synthesis here, other raw material and process constant, obtain compound 2.
Product MS(m/e): 704, ultimate analysis (C 51h 36n 4): theoretical value C:86.90%, H:5.15%, N:7.95%; Measured value C:86.92%, H:5.10%, N:7.98%.
Embodiment 4
The synthesis of compound 3
Building-up process divides work two step, the first step is same as the second step in embodiment 2, just by bromo-for 2-7-(6,9-phenylbenzene carbazole-3-base)-9, the bromo-8-(9-phenyl carbazole of 9-dimethyl fluorene 2--3-base)-6,6,12,12-tetramethyl--6,12-dihydro indeno ［ 1,2-b ］ fluorenes replace make raw material, other raw material and process constant, obtain corresponding pinacol borate derivative; Second step is same as the four-step reaction in embodiment 1, just by replacing the pinacol borate derivative of bromobenzeneboronic acid pinacol ester with second step synthesis here wherein, other raw material and process constant, obtain compound 3.
Product MS(m/e): 744, ultimate analysis (C 54h 40n 4): theoretical value C:87.07%, H:5.41%, N:7.52%; Measured value C:87.03%, H:5.42%, N:7.55%.
Embodiment 5
The synthesis of compound 4
Building-up process divides work two step, and the first step is same as the second step in embodiment 1, just by bromo-for 2-7-(6,9-phenylbenzene carbazole-3-base)-9,9-dimethyl fluorene 2-bromo-8-(6,9-phenylbenzene carbazole-3-base)-6,6,12,12-tetramethyl--6,12-dihydro indeno ［ 1,2-b ］ fluorenes replaces making raw material, other raw material and process constant, obtain corresponding pinacol borate derivative; Second step is same as the four-step reaction in embodiment 1, just by replacing the pinacol borate derivative of bromobenzeneboronic acid pinacol ester with second step synthesis here wherein, other raw material and process constant, obtain compound 4.
Product MS(m/e): 820, ultimate analysis (C 60h 44n 4): theoretical value C:87.77%, H:5.40%, N:6.82%; Measured value C:87.75%, H:5.46%, N:6.79%.
Embodiment 6
The synthesis of compound 5
Building-up process divides work two step, the first step is same as the 5th step reaction in embodiment 1, just by 7-(carbazole-9-base wherein)-9,9-dimethyl fluorene-2-boric acid 7-(6,9-phenylbenzene carbazole-3-base)-9,9-dimethyl fluorene-2-boric acid replaces, by 4-(3-phenylimidazole also [1,2-a] pyrimidine-6-base) bromobenzene 3-bromo-6-chlorine imidazo [1,2-a] pyrimidine replace make raw material, other raw material and process constant, obtain a corresponding chloromethylated intermediate; Second step is same as the 3rd step in embodiment 1, is just replaced making raw material by bromo-for 3-6-chlorine imidazo [1,2-a] pyrimidine one chloromethylated intermediate of the first step synthesis here, other raw material and process constant, obtain compound 5.
Product MS(m/e): 704, ultimate analysis (C 51h 36n 4): theoretical value C:86.90%, H:5.15%, N:7.95%; Measured value C:86.93%, H:5.16%, N:7.91%.
Embodiment 7
The synthesis of compound 6
Synthesis step is same as the four-step reaction in embodiment 1, just by wherein to bromobenzeneboronic acid pinacol ester 8-(N-phenyl carbazole-3-base)-6,6,12,12-tetramethyl--6,12-dihydro indeno ［ 1,2-b ］ fluorenes-2-pinacol borate derivative replaces, by 3-phenyl-6-chlorine imidazo [1,2-a] the bromo-7-trifluoromethyl imidazoles of pyrimidine 3-also [1,2-a] pyrimidine makes raw material, other raw material and process constant, obtain compound 6.
Product MS(m/e): 736, ultimate analysis (C 49h 35f 3n 4): theoretical value C:79.87%, H:4.79%, F:7.74%, N:7.60%; Measured value C:79.85%, H:4.76%, F:7.76%, N:7.63%.
Embodiment 8
The synthesis of compound 7
Synthesis step is same as the four-step reaction in embodiment 1, just by wherein to bromobenzeneboronic acid pinacol ester 8-(N-phenyl carbazole-3-base)-6,6,12,12-tetramethyl--6,12-dihydro indeno ［ 1,2-b ］ fluorenes-2-pinacol borate derivative replaces, by 3-phenyl-6-chlorine imidazo [1,2-a] pyrimidine 5-methylthio group-7-chlorine imidazo [1,2-a] pyrimidine makes raw material, other raw material and process constant, obtain compound 7.
Product MS(m/e): 714, ultimate analysis (C 49h 38n 4s): theoretical value C:82.32%, H:5.36%, N:7.84%, S:4.48%; Measured value C:82.36%, H:5.34%, N:7.86%, S:4.44%.
Embodiment 9
The synthesis of compound 8
Synthesis step divides work two step, and the first step is same as the four-step reaction in embodiment 1, just by wherein to bromobenzeneboronic acid pinacol ester 8-(9-phenyl carbazole-3-base)-6,6,12,12-tetramethyl--6,12-dihydro indeno ［ 1,2-b ］ replacement of fluorenes-2-pinacol borate derivative, 3-phenyl-6-chlorine imidazo [1,2-a] pyrimidine 3-bromo-6-chlorine imidazo [1,2-a] pyrimidine is replaced making raw material, other raw material and process constant, obtain a chloromethylated intermediate; Second step is same as the three-step reaction in embodiment 1, is just replaced making raw material by bromo-for 3-6-chlorine imidazo [1,2-a] pyrimidine one chloromethylated intermediate of second step synthesis here, other raw material and process constant, obtain compound 8.
Product MS(m/e): 744, ultimate analysis (C 54h 40n 4): theoretical value C:87.07%, H:5.41%, N:7.52%; Measured value C:87.03%, H:5.43%, N:7.54%.
Embodiment 10
The synthesis of compound 9
Synthesis step divides work three step, the first step is same as the four-step reaction in embodiment 1, just by 3-phenyl-6-chlorine imidazo ［ 1,2, a ］ pyrimidine 3-bromo-8-chlorine imidazo [1,2-A] pyrazine replace, other raw material and process constant, obtain 3-to bromophenyl-8-chlorine imidazo [1,2-a] pyrimidine; Second step is same as the 5th step reaction in embodiment 1, be to bromophenyl imidazo ［ 1 by 3-phenyl-6-, 2, a ］ the pyrimidine 3-of the synthesis of the first step here replaces bromophenyl-8-chlorine imidazo [1,2-a] pyrimidine, 7-(carbazole-9-base)-9,9-dimethyl fluorene-2-boric acid 7-(9-phenyl carbazole-3-base)-9,9-dimethyl fluorene-2-boric acid replace make raw material, other raw material and process constant, obtain a chloromethylated intermediate; 3rd step is same as the three-step reaction in embodiment 1, is just replaced by the chloromethylated intermediate of bromo-for 3-6-chlorine imidazo ［ 1,2, a ］ pyrimidine with second step synthesis here, other raw material and process constant, obtain compound 9.
Product MS(m/e): 704, ultimate analysis (C 51h 36n 4): theoretical value C:86.90%, H:5.15%, N:7.95%; Measured value C:86.88%, H:5.14%, N:7.98%.
Embodiment 11
The synthesis of compound 10
Synthesis step divides work three step, the first step is same as the four-step reaction in embodiment 1, just by 3-phenyl-6-chlorine imidazo ［ 1,2, a ］ pyrimidine 3-bromo-8-chlorine imidazo [1,2-A] pyrazine replace, other raw material and process constant, obtain 3-to bromophenyl-8-chlorine imidazo [1,2-a] pyrimidine; Second step is same as the 5th step reaction in embodiment 1, be to bromophenyl imidazo ［ 1 by 3-phenyl-6-, 2, a ］ the pyrimidine 3-of the synthesis of the first step here replaces bromophenyl-8-chlorine imidazo [1,2-a] pyrimidine, 7-(carbazole-9-base)-9,9-dimethyl fluorene-2-boric acid 7-(9-phenyl carbazole-3-base)-9,9-dimethyl fluorene-2-boric acid replace make raw material, other raw material and process constant, obtain a chloromethylated intermediate; 3rd step is same as the three-step reaction in embodiment 1, just by bromo-for 3-6-chlorine imidazo ［ 1,2, a ］ pyrimidine one chloromethylated intermediate of the synthesis of second step here replaces, phenylo boric acid pinacol ester 4-(carbazole-9-base) phenylo boric acid pinacol ester replace make raw material, other raw material and process constant, obtain compound 10.
Product MS(m/e): 793, ultimate analysis (C 57h 39n 5): theoretical value C:86.23%, H:4.95%, N:8.82%; Measured value C:86.26%, H:4.94%, N:8.80%.
Embodiment 12
The synthesis of compound 11
Building-up process divides work two step, the first step is same as the 3rd step in embodiment 2, just by bromo-for 3-6-chlorine imidazo [1,2-a] pyrimidine 3-bromo-8-chlorine imidazo [1,2-a] pyrazine replaces, which alcohol ester of phenylo boric acid Knit-the-brows alcohol ester N-phenyl carbazole-3-boric acid Knit-the-brows replaces making raw material, other raw material and process constant, obtain chloro midbody product; Second step is same as the four-step reaction in embodiment 1, just by wherein to bromobenzeneboronic acid pinacol ester 7-(N-phenyl carbazole-3-base)-9,9-dimethyl fluorene-2-boric acid Knit-the-brows alcohol ester replaces, 3-phenyl-6-chlorine imidazo [1,2-a] the pyrimidine chloro midbody product of the synthesis of the first step here replaces, other raw material and process constant, obtain compound 11.
Product MS(m/e): 793, ultimate analysis (C 57h 39n 5): theoretical value C:86.23%, H:4.95%, N:8.82%; Measured value C:86.25%, H:4.91%, N:8.84%.
Embodiment 13
The synthesis of compound 12
Building-up process divides work two step, the first step is same as the 3rd step in embodiment 2, just by bromo-for 3-6-chlorine imidazo [1,2-a] pyrimidine 3-bromo-8-chlorine imidazo [1,2-a] pyrazine replaces, which alcohol ester of phenylo boric acid Knit-the-brows alcohol ester diphenylene-oxide-3-boric acid Knit-the-brows replaces making raw material, other raw material and process constant, obtain chloro midbody product; Second step is same as the four-step reaction in embodiment 1, just by wherein to bromobenzeneboronic acid pinacol ester 7-(N-phenyl carbazole-3-base)-9,9-dimethyl fluorene-2-boric acid Knit-the-brows alcohol ester replaces, 3-phenyl-6-chlorine imidazo [1,2-a] the pyrimidine chloro midbody product of the synthesis of the first step here replaces, other raw material and process constant, obtain compound 12.
Product MS(m/e): 718, ultimate analysis (C 51h 34n 4o): theoretical value C:85.21%, H:4.77%, N:7.79%, O:2.23%; Measured value C:85.25%, H:4.74%, N:7.75%, O:2.26%.
Embodiment 14
The synthesis of compound 13
Building-up process divides work two step, the first step is same as the 3rd step in embodiment 2, just by bromo-for 3-6-chlorine imidazo [1,2-a] pyrimidine 3-bromo-8-chlorine imidazo [1,2-a] pyrazine replaces, which alcohol ester of phenylo boric acid Knit-the-brows alcohol ester dibenzothiophene-3-boric acid Knit-the-brows replaces making raw material, other raw material and process constant, obtain chloro midbody product; Second step is same as the four-step reaction in embodiment 1, just by wherein to bromobenzeneboronic acid pinacol ester 7-(N-phenyl carbazole-3-base)-9,9-dimethyl fluorene-2-boric acid Knit-the-brows alcohol ester replaces, 3-phenyl-6-chlorine imidazo [1,2-a] the pyrimidine chloro midbody product of the synthesis of the first step here replaces, other raw material and process constant, obtain compound 13.
Product MS(m/e): 734, ultimate analysis (C 51h 34n 4s): theoretical value C:83.35%, H:4.66%, N:7.62%, S:4.36%; Measured value C:83.38%, H:4.62%, N:7.62%, S:4.38%.
Embodiment 15
The synthesis of compound 14
Building-up process divides work two step, the first step is same as the 3rd step in embodiment 2, just by bromo-for 3-6-chlorine imidazo [1,2-a] pyrimidine 3-bromo-8-chlorine imidazo [1,2-a] pyrazine replaces, phenylo boric acid Knit-the-brows alcohol ester replaces making raw material with to phenyl phenylo boric acid Knit-the-brows alcohol ester, other raw material and process constant, obtain chloro midbody product; Second step is same as the four-step reaction in embodiment 1, just by wherein to bromobenzeneboronic acid pinacol ester 7-(N-phenyl carbazole-3-base)-9,9-dimethyl fluorene-2-boric acid Knit-the-brows alcohol ester replaces, 3-phenyl-6-chlorine imidazo [1,2-a] the pyrimidine chloro midbody product of the synthesis of the first step here replaces, other raw material and process constant, obtain compound 14.
Product MS(m/e): 704, ultimate analysis (C 51h 36n 4): theoretical value C:86.90%, H:5.15%, N:7.95%; Measured value C:86.93%, H:5.17%, N:7.90%.
Embodiment 16
The synthesis of compound 15
Building-up process divides work two step, and the first step is same as the 3rd step in embodiment 2, is just replaced making raw material by phenylo boric acid Knit-the-brows alcohol ester N-phenyl carbazole-3-boric acid Knit-the-brows alcohol ester, other raw material and process constant, obtain chloro midbody product; Second step is same as the four-step reaction in embodiment 1, just by wherein to bromobenzeneboronic acid pinacol ester 7-(N-phenyl carbazole-3-base)-9,9-dimethyl fluorene-2-boric acid Knit-the-brows alcohol ester replaces, 3-phenyl-6-chlorine imidazo [1,2-a] the pyrimidine chloro midbody product of the synthesis of the first step here replaces, other raw material and process constant, obtain compound 15.
Product MS(m/e): 793, ultimate analysis (C 57h 39n 5): theoretical value C:86.23%, H:4.95%, N:8.82%; Measured value C:86.21%, H:4.93%, N:8.86%.
Embodiment 17
The synthesis of compound 16
Building-up process divides work two step, and the first step is same as the 3rd step in embodiment 2, is just replaced making raw material by which alcohol ester of phenylo boric acid Knit-the-brows alcohol ester diphenylene-oxide-3-boric acid Knit-the-brows, other raw material and process constant, obtain chloro midbody product; Second step is same as the four-step reaction in embodiment 1, just by wherein to bromobenzeneboronic acid pinacol ester 7-(N-phenyl carbazole-3-base)-9,9-dimethyl fluorene-2-boric acid Knit-the-brows alcohol ester replaces, 3-phenyl-6-chlorine imidazo [1,2-a] the pyrimidine chloro midbody product of the synthesis of the first step here replaces, other raw material and process constant, obtain compound 16.
Product MS(m/e): 718, ultimate analysis (C 51h 34n 4o): theoretical value C:85.21%, H:4.77%, N:7.79%, O:2.23%; Measured value C:85.24%, H:4.73%, N:7.76%, O:2.27%.
Embodiment 18
The synthesis of compound 17
Building-up process divides work two step, and the first step is same as the 3rd step in embodiment 2, is just replaced making raw material by which alcohol ester of phenylo boric acid Knit-the-brows alcohol ester dibenzothiophene-3-boric acid Knit-the-brows, other raw material and process constant, obtain chloro midbody product; Second step is same as the four-step reaction in embodiment 1, just by wherein to bromobenzeneboronic acid pinacol ester 7-(N-phenyl carbazole-3-base)-9,9-dimethyl fluorene-2-boric acid Knit-the-brows alcohol ester replaces, 3-phenyl-6-chlorine imidazo [1,2-a] the pyrimidine chloro midbody product of the synthesis of the first step here replaces, other raw material and process constant, obtain compound 17.
Product MS(m/e): 734, ultimate analysis (C 51h 34n 4s): theoretical value C:83.35%, H:4.66%, N:7.62%, S:4.36%; Measured value C:83.32%, H:4.64%, N:7.65%, S:4.39%.
Embodiment 19
The synthesis of compound 18
Compound 18
Building-up process divides work two step, and the first step is same as the 3rd step in embodiment 2, is just replaced making raw material with to phenyl phenylo boric acid Knit-the-brows alcohol ester by phenylo boric acid Knit-the-brows alcohol ester, other raw material and process constant, obtain chloro midbody product; Second step is same as the four-step reaction in embodiment 1, just by wherein to bromobenzeneboronic acid pinacol ester 7-(N-phenyl carbazole-3-base)-9,9-dimethyl fluorene-2-boric acid Knit-the-brows alcohol ester replaces, 3-phenyl-6-chlorine imidazo [1,2-a] the pyrimidine chloro midbody product of the synthesis of the first step here replaces, other raw material and process constant, obtain compound 18.
Product MS(m/e): 704, ultimate analysis (C 51h 36n 4): theoretical value C:86.90%, H:5.15%, N:7.95%; Measured value C:86.92%, H:5.12%, N:7.96%.
Here is the Application Example of the compounds of this invention:
Embodiment 20
The preparation of electroluminescent device and result
The preferred implementation of fabricate devices:
(1) device layout
Conveniently compare the performance of these materials, the present invention devises a simple electroluminescence device (substrate/anode/hole injection layer (HIL)/hole transmission layer (HTL)/phosphorescence host (HOST): phosphorescent coloring (Dopant)/electron transfer layer (ETL)/electron injecting layer (EIL)/negative electrode), only use compound 1,3,4,7,9,10,11,13,16,18 as phosphorescent light body material illustration, CBP as phosphorescence host comparative material, Ir(ppy) 3as phosphorescent coloring.The structure of CBP and phosphorescent coloring 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 injection layer selects 2-TNATA.
Hole transmission layer can adopt various tri-arylamine group material.Hole mobile material selected in element manufacturing of the present invention is NPB.
Electron transport material selected in element manufacturing of the present invention is Bphen.
Wherein the structural formula of 2-TNATA, NPB, Bphen is respectively:
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.Electron injection material selected in element manufacturing of the present invention is LiF, and cathode material is Al.
(2) element manufacturing
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 -4pa, on above-mentioned anode tunic, vacuum evaporation 2-TNATA is as hole injection layer, and evaporation rate is 0.1nm/s, and evaporation thickness is 20nm; On hole injection layer, vacuum evaporation NPB is as hole transmission layer, and evaporation rate is 0.1nm/s, and evaporation thickness is 40nm;
On hole transmission layer, adopt double source vacuum evaporation phosphorescent light body material 1,3,4,7,9,10,11,13,16,18 of the present invention to be total to evaporation phosphorescent coloring Ir(ppy) simultaneously 3, phosphorescent light body material also can replace with CBP.Evaporation is as the luminescent layer of device altogether for phosphorescence host and dyestuff, and evaporation rate is 0.1nm/s, and the speed of phosphorescent coloring is 0.015nm/S, and evaporation total film thickness is 30nm;
On luminescent layer, vacuum evaporation one deck compd B phen is as the electron transfer layer of device, and its evaporation rate is 0.1nm/s, and evaporation total film thickness is 20nm;
At the upper vacuum evaporation LiF of electron transfer layer (ETL) as electron injecting layer, thickness 0.5nm.On LiF layer, evaporating Al layer is as the negative electrode of device, and thickness is 150nm.
Device performance sees the following form (device architecture: ITO/2-TNATA (20nm)/NPB(40nm)/phosphorescence host: 15%Ir(ppy) 3(30nm)/Bphen(20nm)/LiF(0.5nm)/Al(150nm))
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 phosphorescent light body 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 (13)

1., containing a fluorene derivatives for carbazole-3-base group, it is characterized in that having such as formula the structure shown in (1), (2) or (3):
Wherein:
A and B one of them be N, another be H in CH group or CH group by carbonatoms be the alkyl of 1-12, carbonatoms is the aryl of 6-30, carbonatoms is the heterocyclic aryl ,-CF of 6-30 3,-SCH 3in a kind of group of replacement;
Ar is selected from fluorenylidene or sub-indeno fluorenyl;
R 1and R 2separately be selected from H, substituted or unsubstituted aryl, methylthio group, methoxyl group, oxyethyl group or trifluoromethyl that substituted or unsubstituted aliphatics cycloalkyl that substituted or unsubstituted aliphatic alkyl that carbonatoms is 1-12, carbonatoms are 1-12, carbonatoms are 6-30;
R 3be selected from substituted or unsubstituted aliphatic alkyl that carbonatoms is 1-12, substituted or unsubstituted aryl that substituted or unsubstituted aliphatics cycloalkyl that carbonatoms is 1-12 or carbonatoms are 6-30;
R 4be selected from H, substituted or unsubstituted aryl that substituted or unsubstituted aliphatics cycloalkyl that substituted or unsubstituted aliphatic alkyl that carbonatoms is 1-12, carbonatoms are 1-12 or carbonatoms are 6-30;
L 1and L 2independently be selected from singly-bound, substituted or unsubstituted heteroarylidene that substituted or unsubstituted arylidene that alkylidene group that carbonatoms is 1-20, carbonatoms are 6-30 or carbonatoms are 6-30.
2. the fluorene derivatives containing carbazole-3-base group according to claim 1, is characterized in that, described R 1and R 2separately be selected from H, methyl, ethyl, propyl group, normal-butyl, n-pentyl, n-hexyl, phenyl, tolyl, ethylbenzene, xenyl, (carbazole-9-base) phenyl, naphthyl, carbazyl, N-phenyl carbazole base, fluorenyl, N-fluorenyl carbazyl, methylthio group, methoxyl group, oxyethyl group, trifluoromethyl, dibenzothiophene base or dibenzofuran group.
3. the fluorene derivatives containing carbazole-3-base group according to claim 1, is characterized in that, described R 3be selected from methyl, ethyl, propyl group, normal-butyl, n-pentyl, n-hexyl, phenyl, tolyl, ethylbenzene, (carbazole-9-base) phenyl, xenyl or naphthyl.
4. the fluorene derivatives containing carbazole-3-base group according to claim 1, is characterized in that, described R 4independently be selected from H, methyl, ethyl, propyl group, normal-butyl, n-pentyl, n-hexyl, phenyl, tolyl, ethylbenzene, (carbazole-9-base) phenyl, xenyl or naphthyl.
5. the fluorene derivatives containing carbazole-3-base group according to claim 1, it is characterized in that, when Ar is not H, the skeleton structure of described Ar is selected from following arbitrary structure:
6. the fluorene derivatives containing carbazole-3-base group according to claim 1, is characterized in that, described bridge linkage group L 1and L 2independently be selected from singly-bound, phenylene, biphenylene, naphthylidene, pyridylidene one of them.
7. the fluorene derivatives containing carbazole-3-base group according to claim 1, is characterized in that, A and B one of them be N, another is that H in CH group or CH group is by methyl, ethyl, propyl group, normal-butyl, n-pentyl ,-CF 3,-SCH 3, phenyl, tolyl, ethylbenzene, xenyl, naphthyl, carbazyl, N-phenyl carbazole base one of them replace CH group.
8. the fluorene derivatives containing carbazole-3-base group according to claim 1, is characterized in that, R 1or R 2when not being H, R 1or R 2be selected from following arbitrary preferred structure:
9. the fluorene derivatives containing carbazole-3-base group according to claim 1, it is characterized in that, described compound is selected from following structural formula:
Compound 1
Compound 2
Compound 3
Compound 4
Compound 5
Compound 6
Compound 7
Compound 8
Compound 9
Compound 10
Compound 11
Compound 12
Compound 13
Compound 14
Compound 15
Compound 16
Compound 17
Compound 18.
10. the fluorene derivatives containing carbazole-3-base group described in any one of claim 1-9, is applied in organic electroluminescence device.
11. a kind of fluorene derivativess containing carbazole-3-base group being applied to organic electroluminescence device according to claim 10, is characterized in that, can be used as phosphorescent light body material.
12. 1 kinds of organic electroluminescence devices, comprise substrate, and form anode layer, organic luminescence function layer and cathode layer on the substrate successively; Described organic luminescence function layer comprises hole transmission layer, organic luminous layer and electron transfer layer, it is characterized in that:
The material of main part of described organic luminous layer is that one or more are as claimed in any one of claims 1-9 wherein containing the fluorene derivatives of carbazole-3-base group.
13. a kind of organic electroluminescence devices according to claim 12, it is characterized in that, described luminescent layer is made up of material of main part and luminescent dye, and described luminescent dye is phosphorescent coloring.
CN201310730832.4A 2013-12-26 2013-12-26 A kind of fluorene kind derivative of the bases of -3- containing carbazole group and its application Active CN104650090B (en)

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CN106905221A (en) * 2017-03-04 2017-06-30 长春海谱润斯科技有限公司 A kind of benzo fluorene kind derivative and its organic luminescent device

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