CN103589421B - Organic electroluminescent material and preparation method thereof - Google Patents
Organic electroluminescent material and preparation method thereof Download PDFInfo
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- CN103589421B CN103589421B CN201310551993.7A CN201310551993A CN103589421B CN 103589421 B CN103589421 B CN 103589421B CN 201310551993 A CN201310551993 A CN 201310551993A CN 103589421 B CN103589421 B CN 103589421B
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- KUBSCXXKQGDPPD-UHFFFAOYSA-N Brc(cc1c2ccccc22)ccc1[n]2-c1ccccc1 Chemical compound Brc(cc1c2ccccc22)ccc1[n]2-c1ccccc1 KUBSCXXKQGDPPD-UHFFFAOYSA-N 0.000 description 1
- XGEGRVQLIXEIHB-UHFFFAOYSA-N c(cc1)ccc1-[n](c1ccccc1c1c2)c1ccc2N(c1c-2cccc1)c1cccc3c1c-2ccc3 Chemical compound c(cc1)ccc1-[n](c1ccccc1c1c2)c1ccc2N(c1c-2cccc1)c1cccc3c1c-2ccc3 XGEGRVQLIXEIHB-UHFFFAOYSA-N 0.000 description 1
- MCXFBJRDLNFXHM-UHFFFAOYSA-N c(cc1-2)ccc1Nc1cccc3cccc-2c13 Chemical compound c(cc1-2)ccc1Nc1cccc3cccc-2c13 MCXFBJRDLNFXHM-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention relates to an organic electroluminescent material and a preparation method thereof, and solves the technical problem that the luminous efficiency of the conventional luminescent material cannot meet requirements of an OLED (Organic Light Emitting Diode). The organic electroluminescent material is a novel material which is synthesized by introducing C14-C20 condensed ring aryl group, triarylated amine or N-phenyl-3-carbazolyl based on 7H-benzacridine. Compared with 7H-benzacridine, the synthesized green organic electroluminescent material has a bigger plane structure and a conjugated system, and can change electron transition energy level, thereby changing luminescent spectrum and obviously improving luminous efficiency. The preparation method of the organic electroluminescent material is simple in synthesis and purification, low in cost, and can meet requirements of industrial development.
Description
Technical field
The present invention relates to organic photoelectrical material field, be specifically related to electroluminescent organic material of a kind of benzacridine class and preparation method thereof.
Background technology
Organic electroluminescent refers to that organic materials is under electric field action, is subject to electric current and exciting of electric field and the phenomenon of luminescence.Organic electroluminescent LED (OLED) is the technique of display of new generation utilizing this phenomenon to realize display.Since U.S. Kodak company's T ang C.W. and Vanslyke S.A. in 1987 has made the organic electroluminescence device of first excellent property, ORGANIC ELECTROLUMINESCENCE DISPLAYS has caused the great interest of people due to advantage that it has.
In the research of OLED, the selection of organic materials plays conclusive effect.The organic materials used in OLED mainly contains hole-injecting material, hole mobile material, luminescent material, electron transport material and electron injection material etc., and luminescent material is main raw wherein.Lot of domestic and international research institution, enterprise are that the over-all properties improving constantly luminescent material has carried out a large amount of research work, achieve abundant achievement in research.But the luminescent properties of the luminescent material of research and development at present still can not meet the requirement of OLED.
Acridine compound is large ring conjugated system, has rigid planar structure, is a kind of good fluorescent reagent.At present the research of acridine compound is mainly concentrated on, be used for, in the application of Mian Yi ∕ DNA analysis, having very high luminous detection sensitivity used as luminescence probe.Acridine compound also because having good insecticidal activity, antimalarial active, anti-tumor activity, and is widely used in antibacterial, anti-inflammatory and antineoplastic agent etc.But the research at present acridine compound being applied to field of organic electroluminescence is less.
Summary of the invention
The present invention is the technical problem that the luminous efficiency solving existing luminescent material still can not meet the requirement of OLED, and provide a kind of luminous efficiency higher, benzacridine class, electroluminescent organic material and preparation method thereof.
In order to solve the problems of the technologies described above, technical scheme of the present invention is specific as follows:
A kind of electroluminescent organic material, the concrete structure general formula of this material as the formula (1):
In formula, A is C
14-C
20fused ring aryl, triarylamine or N-phenyl-3-carbazyl; Preferred A is 2-phenanthryl, 2-anthryl, 4-perylene base or 2-pyrenyl.
Above-mentioned preferred electroluminescent organic material of the present invention, concrete structural formula corresponds to the chemical structural formula of following 001-006 respectively:
Be exactly the concrete structure formation of this compound more above, but this series compound does not limit to and these listed chemical structures.Every based on structural formula (1), the arbitrary combination of the concrete structure provided before A group is respectively all should be included.
The preparation method of electroluminescent organic material, is characterized in that, concrete steps and the condition of this preparation method are as follows:
In molar ratio for 1:1.5 ~ 2.0 take the bromo-derivative of 7H-benzacridine and A, then add potassium tert.-butoxide, acid chloride and tri-tert phosphorus, dissolve with toluene solution; Wherein, the mol ratio of potassium tert.-butoxide and 7H-benzacridine is 1.2 ~ 1.6:1, and the mol ratio of acid chloride and 7H-benzacridine is 0.02 ~ 0.04:1, and the mol ratio of tri-tert phosphorus and 7H-benzacridine is 0.02 ~ 0.04:1;
Under nitrogen protection condition, be 80 DEG C ~ 90 DEG C by the mixing solutions of reactant in temperature, react 10 ~ 15 hours; Filter the mixing solutions of reactant, refine the crude product obtained with silica gel chromatography, then with toluene, recrystallization is carried out to the crude product obtained, after drying, obtain benzacridine compounds.
The invention has the beneficial effects as follows:
1, electroluminescent organic material provided by the invention is based on 7H-benzacridine, introduces C on this basis
14-C
20fused ring aryl, triarylamine or N-phenyl-3-carbazyl synthesis a class new Organic Electro Luminescent Materials.Compared with 7H-benzacridine, the electroluminescent organic material of the present invention's synthesis has larger two dimensional structure and conjugated system, luminous peak position can be regulated by regulating transition of electron, obtain required Green organic electroluminescent material, and luminous efficiency significantly improving.
We are respectively by comparative sample 7H-benzacridine, and the luminous efficiency of the benzacridine compounds 001-006 synthesized with the embodiment of the present invention compares.Its result is: the luminous efficiency of 7H-benzacridine in dilute solution is 80%, luminous efficiency is in the film 49%, and the luminous efficiency in the benzacridine compounds dilute solution of embodiment of the present invention synthesis is up to 97%, luminous efficiency is in the film up to 64%.Compared by data, we find that electroluminescent organic material provided by the invention is the material that a class luminous efficiency is higher, can meet the requirement of OLED, have extraordinary application prospect.
2, the preparation method of electroluminescent organic material provided by the invention, the method is synthesized and is purified fairly simple, with low cost, can meet industrialization development demand.The productive rate of product increases substantially, and purity is high, and HPLC purity is greater than 98%.
Embodiment
Electroluminescent organic material provided by the invention is that be obtained by reacting benzacridine compounds, its concrete synthetic route is as follows with the bromo-derivative of 7H-benzacridine and A for raw material:
The synthetic route of 7H-benzacridine is as follows:
Under nitrogen protection condition, will containing Na
2cO
3(1400g) water 6.5L, joins N-(8-bromonaphthalene-1-base) ethanamide 660g(2.50mol) in solution, (6-methoxy basic ring six-1,5-diene-1-base) boric acid 505g(2.50mol), and 144g(Ph
3p)
4pd(125mmol, 5mol%) methyl ether 14ml.Mixture is refluxed 18 hours, then solvent is evaporated.8L water is added to resistates, by methylene dichloride (2 × 5L) extracting twice, this extract Na
2sO
4drying is also evaporated.Column chromatography, with petrol ether/ethyl acetate mixture (1:1), re-crystallizing in ethyl acetate, obtains pure N-(8-(2-p-methoxy-phenyl) naphthalene-1-base) ethanamide 308.82g, productive rate 55% is clear crystal.
Under 0 DEG C of condition, by boron tribromide 1.5L(1M methylene dichloride, 1.50mol) be added drop-wise to N-(8-(2-p-methoxy-phenyl) naphthalene-1-base) ethanamide 308.82g(1.06mol) in 4L dichloromethane solution, mixture is at room temperature stirred 18 hours, is then poured into water.Add saturated sodium bicarbonate, by ethyl acetate (2 × 3L) extracting twice.Merge organic extract liquid, use Na
2sO
4drying, and in underpressure distillation, column chromatography, with ethyl acetate/dichloromethane mixture (1:1) as eluent, obtains white solid N-(8-(2-hydroxy phenyl) naphthalene-1-base) ethanamide 271.77g, productive rate 92%.
N-(8-(2-hydroxy phenyl) naphthalene-1-base) ethanamide 271.77g(0.98mol) solution stir 40 hours under reflux at the mixture of the hydrazine hydrate 4.0L of Pentyl alcohol 6.0L and 80%, the then pressure of vapourisation under reduced pressure.Column chromatography, by ethyl acetate/petroleum ether (1:1) as eluent, obtains brown product 7H-benzacridine 173.82g, productive rate 79%.
Embodiment 1: the synthesis of compound 001
Concrete synthetic route is as follows:
Take 7H-benzacridine 21.72g, 2-bromine pyrene 42.47g, potassium tert.-butoxide 13.46g, acid chloride (II) 0.41g, tri-tert phosphorus 0.45g, dissolve with 250ml toluene, under nitrogen protection, in 80 DEG C of reactions 10 hours.Filtering reacting solution, refines the crude product obtained with silica gel chromatography, then carries out recrystallization with toluene to the solid obtained, and dry, obtain 35.48g white-yellowish solid compound 001, productive rate more than 85%, HPLC purity is greater than 98%.Mass spectrum: calculated value is 417.50; Test value is 417.52.Ultimate analysis: calculated value is C:92.06%; H:4.59%; N:3.35%; Test value is C:92.07%; H:4.60%; N:3.33%.
Embodiment 2: the synthesis of compound 002
Concrete synthetic route is as follows:
Take 7H-benzacridine 21.72g, 4-bromine triphenylamine 51.87g, potassium tert.-butoxide 14.36g, acid chloride (II) 0.48g, tri-tert phosphorus 0.54g, dissolve with 250ml toluene, in 82 DEG C of reactions 11 hours.Filtering reacting solution, refines the crude product obtained with silica gel chromatography, carry out recrystallization with toluene to the solid obtained, and dry, obtain 39.15g white-yellowish solid compound 002, productive rate more than 85%, HPLC purity is greater than 98%.Mass spectrum: calculated value is 460.57; Test value is 460.56.Ultimate analysis: calculated value is C:88.67%; H:5.25%; N:6.08%; Test value is C:88.69%; H:5.24%; N:6.07%.
Embodiment 3: the synthesis of compound 003
Concrete synthetic route is as follows:
Take 7H-benzacridine 21.72g, 2-bromine anthracene 43.71g, potassium tert.-butoxide 15.26g, acid chloride (II) 0.56g, tri-tert phosphorus 0.63g, dissolve with 250ml toluene, in 84 DEG C of reactions 12 hours.Filtering reacting solution, refines the crude product obtained with silica gel chromatography, carry out recrystallization with toluene to the solid obtained, and dry, obtain 33.84g white-yellowish solid compound 003, productive rate more than 86%, HPLC purity is greater than 98%.Mass spectrum: calculated value is 397.51; Test value is 397.52.Ultimate analysis: calculated value is C:90.64%; H:5.83%; N:3.52%; Test value is C:90.62%; H:5.84%; N:3.53%.
Embodiment 4: the synthesis of compound 004
Concrete synthetic route is as follows:
Take 7H-benzacridine 21.72g, 2-bromine luxuriant and rich with fragrance 46.64g, potassium tert.-butoxide 16.16g, acid chloride (II) 0.64g, tri-tert phosphorus 0.72g, dissolved with 250ml toluene, in 86 DEG C of reactions 13 hours.Filtering reacting solution, refines the crude product obtained with silica gel chromatography, carry out recrystallization with toluene to the solid obtained, and dry, obtain 33.83g white-yellowish solid compound 004, productive rate more than 86%, HPLC purity is greater than 98%.Mass spectrum: calculated value is 393.48; Test value is 393.45.Ultimate analysis: calculated value is C:91.57%; H:4.87%; N:3.56%; Test value is C:91.56%; H:4.89%; N:3.55%.
Embodiment 5: the synthesis of compound 005
Concrete synthetic route is as follows:
Take 7H-benzacridine 21.72g, 2-Xiu perylene 62.93g, potassium tert.-butoxide 17.06g, acid chloride (II) 0.72g, tri-tert phosphorus 0.81g, dissolve with 250ml toluene, in 88 DEG C of reactions 14 hours.Filtering reacting solution, refines the crude product obtained with silica gel chromatography, carry out recrystallization with toluene to the solid obtained, and dry, obtain 38.80g white-yellowish solid compound 005, productive rate more than 83%, HPLC purity is greater than 98%.Mass spectrum: calculated value is 467.56; Test value is 467.54.Ultimate analysis: calculated value is C:92.48%; H:4.53%; N:3.00%; Test value is C:92.46%; H:4.54%; N:3.01%.
Embodiment 6: the synthesis of compound 006
Concrete synthetic route is as follows:
Take 7H-benzacridine 21.72g, the bromo-9-phenyl of 3--9H-carbazole 64.44g, potassium tert.-butoxide 17.95g, acid chloride (II) 0.80g, tri-tert phosphorus 0.90g, dissolve with 250ml toluene, in 90 DEG C of reactions 15 hours.Filtering reacting solution, refines the crude product obtained with silica gel chromatography, carry out recrystallization with toluene to the solid obtained, and dry, obtain 38.51g white-yellowish solid compound 006, productive rate more than 84%, HPLC purity is greater than 98%.Mass spectrum: calculated value is 460.57; Test value is 460.55.Ultimate analysis: calculated value is C:88.67%; H:5.25%; N:6.08%; Test value is C:88.65%; H:5.26%; N:6.09%.
Simultaneous test
It is 1 × 10 that compound 001-006 prepared by comparative sample 7H-benzacridine, embodiment 1-6 is mixed with concentration by respectively
-6the solution of mol/L, use Edinburdh-FLS920 equipment, spin-coating method is made into film, tests their luminous efficiency successively, and concrete data are as following table.
The luminous efficiency of table 1 acridine compound 001-006 and comparative sample
| Compound | Luminous efficiency in dilute solution | Luminous efficiency in film |
| Comparative sample | 80% | 49% |
| 001 | 92% | 60% |
| 002 | 91% | 62% |
| 003 | 93% | 61% |
| 004 | 93% | 63% |
| 005 | 94% | 59% |
| 006 | 97% | 64% |
As can be seen from the data of table 1, the luminous efficiency of 7H-benzacridine in dilute solution is 80%, luminous efficiency is in the film 49%, and the luminous efficiency in the benzacridine compounds dilute solution of embodiment of the present invention synthesis is up to 97%, and luminous efficiency is in the film up to 64%.Namely the luminous efficiency of benzacridine compounds provided by the invention in dilute solution, the luminous efficiency in film are all significantly improved.Compared by data, we find that electroluminescent organic material provided by the invention is the material that a class luminous efficiency is higher, can meet the requirement of OLED, have extraordinary application prospect.
Should be understood that, application of the present invention is not limited to above-mentioned citing, for those of ordinary skills, can be improved according to the above description or convert, and all these improve and convert the protection domain that all should belong to claims of the present invention.
Claims (2)
1. an electroluminescent organic material, is characterized in that, the concrete structure general formula of this material is such as formula shown in (1):
In formula, A is 2-phenanthryl, 2-anthryl, 4-perylene base, 2-pyrenyl or N-phenyl-3-carbazyl.
2. the preparation method of electroluminescent organic material according to claim 1, is characterized in that, concrete steps and the condition of this preparation method are as follows:
In molar ratio for 1:1.5 ~ 2.0 take the bromo-derivative of 7H-benzacridine and A, then add potassium tert.-butoxide, acid chloride and tri-tert phosphorus, dissolve with toluene solution; Wherein, the mol ratio of potassium tert.-butoxide and 7H-benzacridine is 1.2 ~ 1.6:1, and the mol ratio of acid chloride and 7H-benzacridine is 0.02 ~ 0.04:1, and the mol ratio of tri-tert phosphorus and 7H-benzacridine is 0.02 ~ 0.04:1;
Under nitrogen protection condition, be 80 DEG C ~ 90 DEG C by the mixing solutions of reactant in temperature, react 10 ~ 15 hours; Filter the mixing solutions of reactant, refine the crude product obtained with silica gel chromatography, then with toluene, recrystallization is carried out to the crude product obtained, after drying, obtain benzacridine compounds.
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|---|---|---|---|---|
| WO2018138306A1 (en) * | 2017-01-30 | 2018-08-02 | Merck Patent Gmbh | Materials for organic electroluminescent devices |
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| KR102203099B1 (en) * | 2013-08-13 | 2021-01-15 | 삼성디스플레이 주식회사 | Condensed compound and organic light emitting diode comprising the same |
| KR102277659B1 (en) * | 2014-07-03 | 2021-07-15 | 덕산네오룩스 주식회사 | Compound for organic electronic element, organic electronic element using the same, and an electronic device thereof |
| CN107250087B (en) * | 2015-02-03 | 2022-01-18 | 株式会社Lg化学 | Electroactive material |
| CN110684524A (en) * | 2019-10-31 | 2020-01-14 | 武汉天马微电子有限公司 | Electroluminescent compound, thermal activation delayed fluorescence material and application thereof |
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| KR101873447B1 (en) * | 2011-06-22 | 2018-07-03 | 삼성디스플레이 주식회사 | Novel compound and organic light emitting device containing same |
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| KR102559144B1 (en) | 2017-01-30 | 2023-07-24 | 메르크 파텐트 게엠베하 | Materials for Organic Electroluminescent Devices |
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