CN104650042A - Preparation method of binary imidazole derivative - Google Patents
Preparation method of binary imidazole derivative Download PDFInfo
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- CN104650042A CN104650042A CN201410315004.9A CN201410315004A CN104650042A CN 104650042 A CN104650042 A CN 104650042A CN 201410315004 A CN201410315004 A CN 201410315004A CN 104650042 A CN104650042 A CN 104650042A
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- synthetic method
- reaction
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- phenyl
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- 0 *C(CCCC1)[C@]1NC1C=CC=CC1 Chemical compound *C(CCCC1)[C@]1NC1C=CC=CC1 0.000 description 2
- XLEYOTUWBLZQNC-UHFFFAOYSA-N Brc1cc(-c2nc(cccc3)c3[n]2-c2ccccc2)cc(-c2nc3ccccc3[n]2-c2ccccc2)c1 Chemical compound Brc1cc(-c2nc(cccc3)c3[n]2-c2ccccc2)cc(-c2nc3ccccc3[n]2-c2ccccc2)c1 XLEYOTUWBLZQNC-UHFFFAOYSA-N 0.000 description 1
- MTDMMGZGBDTQCL-UHFFFAOYSA-N c(cc1)ccc1-[n]1c(-c2cc(-c(cc3)ccc3-[n]3c4ccccc4c4c3cccc4)cc(-c3nc4ccccc4[n]3-c3ccccc3)c2)nc2ccccc12 Chemical compound c(cc1)ccc1-[n]1c(-c2cc(-c(cc3)ccc3-[n]3c4ccccc4c4c3cccc4)cc(-c3nc4ccccc4[n]3-c3ccccc3)c2)nc2ccccc12 MTDMMGZGBDTQCL-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
- C07D403/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing three or more hetero rings
Abstract
The invention relates to a preparation method of a binary imidazo-phenylcarbazole derivative and belongs to the technical field of organic electroluminescence material synthesis. A synthetic method of the binary imidazo-phenylcarbazole derivative is improved based on the existing method; by adopting macromolecule alkali, a suitable catalyst ligand and a simple purification method, the yield can be largely improved, the purity of products is high, the purification cost is low, and the preparation method is of great significance in industrial popularization of the material.
Description
Technical field
The present invention relates to organic photoelectrical material field, particularly relate to preparation method and organic luminescent device that a class contains binary imidazole derivative.
Background technology
Organic electroluminescence device (OLED) is a kind of novel flat panel display device, has the features such as energy-conservation, fast response time, colour stable, environmental compatibility are strong, radiationless, the life-span is long, quality is light, thickness is thin.Due to developing rapidly of photoelectric communication in recent years and MultiMedia Field, organic optoelectronic material has become the core of modern society's information and electronic industry.
Research for organic EL Material is from nineteen fifty Bernose applies the observation of high current/voltage to the macromolecule membrane containing organic pigment.Nineteen sixty-five, people's Late Cambrian such as Pope Electroluminescence Properties of anthracene single crystal, this is the first electro optical phenomenon of organic compound.1987, the people such as the Tang of Kodak found, even if the organic luminescent device with separation function lamination formed by organic materials also can provide 1000cd/cm under the low voltage of 10V or less
2or more high brightness.
The present invention relates to a kind of organic electroluminescence device based on binary imidazole derivative, more specifically relate to and a kind ofly there is elctrical stability, excellent charge transport ability and high glass-transition temperature and the synthetic method of the compound based on phenyl carbazole of crystallization can be prevented.
The preparation method of binary imidazole derivative is that Japanese Patent JP2009158848A proposes, but synthesis is only suitable for laboratory applications, be not easy to industrialization, and productive rate is extremely low.Need column chromatography to purify in the preparation process of JP2009158848A report, some even wants secondary column chromatography, and productive rate is substantially all at about 40%-60%, and this synthetic method can not meet the needs of industry; US Patent No. 20140027744 also mentions the synthetic method of binary imidazo phenyl carbazole analog derivative in the patent, reaching about 80%, but still purifying with going out chromatography, being not easy to industrial needs by improving productive rate; Also report the synthetic method of binary imidazo carbazoles derivative in European patent WO2010044607A, method of purification remains column chromatography, and productive rate only has about 50%; Patent JP2009155300A, WO2013183851A and KR1020020141918A etc. all relate to binary imidazo phenyl carbazole analog derivative, but synthetic method, method of purification and productive rate are all undesirable.At present, binary imidazole derivative has become irreplaceable electron transport material in organic photoelectric equipment, due to the deficiency of synthesis technique, cannot meet industrialized demand, research for this material is only limited to device aspect, seriously hinders the industrialization promotion of material.
Summary of the invention
For the deficiency in above-mentioned field, the invention provides a kind of synthetic method of efficient synthesis binary imidazo phenyl carbazole analog derivative, the method improves on the basis of current method, easy and simple to handle, productive rate is high, product purity is high, and cost for purification is low, has great meaning to the industrialization promotion of this material.
A kind of binary imidazole derivative, the concrete structure general formula of this material as the formula (1):
general formula (1)
Wherein, A is C
14-C
20fused ring aryl, triarylamine or N-phenyl-3-carbazyl; Preferred A is N-phenyl-3-carbazyl.
The method of efficient synthesis binary imidazo phenyl analog derivative, comprise the steps: that (1) provides the intermediate B DPBI synthetic schemes of (II) for formula (I), by material dissolution in acetic acid and toluene solution, backflow is spent the night, and its reaction scheme is such as formula shown in (a); (2) by intermediate B DPBI(II) and the boric acid of different substituents carry out Suzuki linked reaction, obtain target compound (I), its reaction scheme is such as formula shown in (b).
（a）
（b）
(II) (I)
Step (1) described temperature of reaction is react 70 ~ 80h at 100 DEG C-120 DEG C.
Described reaction is carried out under nitrogen protection.
Described toluene and acetic acid make solvent.
Described reaction end adopts TLC method to detect.
Described synthetic method also comprises treatment step, and described post-processing step is cooled by reaction solution, and recrystallization, filters to obtain intermediate.
Step (2) described temperature of reaction is react 8-15h at 75 DEG C-85 DEG C.
Described solvent ratios is toluene: ethanol: water=5:1:1.
Described alkali selects cesium carbonate.
Described catalyzer four (triphenyl phosphorus) palladium: 2-dicyclohexyl phosphine-2 ', 6 '-dimethoxy-biphenyl=1:1.
Described synthetic method also comprises treatment step, and described post-processing step is reaction solution cooling, and separatory, crosses silica gel funnel, recrystallization.
The compound of this patent can come by technique the following:
(1) 5-bromine iso-phthalaldehyde, N1-phenyl benzene-1,2-diamines are joined reaction flask, add toluene and acetic acid makees solvent, stir, temperature maintains 100 ~ 120 DEG C, reacts 70 ~ 80 hours, obtains intermediate B DPBI with methyl tertiary butyl ether aftertreatment.
(2) by 4-(9H-carbazole-9-base) phenylo boric acid, BDPBI, solvent add reaction flask, stirs, inflated with nitrogen, and temperature maintains 60 DEG C-90 DEG C, reaction about 8-15h, cooling, and separatory, crosses silica gel funnel, recrystallization.
beneficial effect:
The present invention improves on original synthetic method basis, and make process simple, easy handling, reduces cost, improves productive rate, is conducive to suitability for industrialized production.Compare with other patents, (1) this invention adopts suitable solvent burden ratio on original base, improves raw material Contact area; (2) cesium carbonate macromole alkali is selected in this invention, increases speed of response while increasing alkalescence; (3) this invention employing four triphenyl phosphorus palladium catalyst and dicyclohexyl phosphine-2 ', 6 '-dimethoxy-biphenyl co-catalysis, increases catalysis intensity, accelerates Catalysis Rate, greatly improves reaction yield.
Accompanying drawing explanation
Fig. 1 is embodiment 1 nuclear-magnetism figure.
Fig. 2 embodiment 1 mass spectrum.
specific implementation method
Below in conjunction with embodiment, the present invention is described in further detail.
The preparation of intermediate B DPBI:
Under nitrogen protection condition; by 5-bromine iso-phthalaldehyde 160mmol and N1-phenyl benzene-1; 2-diamines 192mmol is dissolved in 25ml toluene and 270ml acetic acid; by solution stirring 72 hours at 110 DEG C; by reaction mixture rotary evaporation; filter, productive rate 60% with methyl tertiary butyl ether 50ml process, obtain BDPBI intermediate 100mmol.
Embodiment 1:(the inventive method)
4-(9H-carbazole-9-base is added in 500mL there-necked flask) phenylo boric acid 40mmol; BDPBI 50mmol; cesium carbonate 120mmol; add solvent (toluene: ethanol: water=180mL:36mL:36mL) in nitrogen protection, tetrakis triphenylphosphine palladium 0.8mmol, stir 30min; add part 2-dicyclohexyl phosphine-2 '; 6 '-dimethoxy-biphenyl 0.8mmol, temperature is elevated to 80 DEG C, and color is deepened gradually.Reaction 8-15 hour, some plate does not have basic material point, stopped reaction, separatory, crosses silica gel funnel, is spin-dried for solvent, uses methylene dichloride and sherwood oil to carry out recrystallization, filters, dry and obtain white powder product 36.8mmol, productive rate 92%.Nuclear-magnetism, mass spectrum determination structure.
Embodiment 2:(amplifies according to patent)
According to embodiment 1 method, amplify 10 times, obtain productive rate 89% ~ 93%, repeatedly attempt, reproducible, feasibility is large.
Comparative example 1:
Adopt four triphenyl phosphorus palladiums to make catalyzer in patent jP2009158848A, sodium carbonate does alkali, and basic/glycol dimethyl ether ether selected by solvent, and reaction 9h, productive rate, substantially all between 30%-60%, is up to 73%, and productive rate is very low.
Comparative example 2:
Adopt four triphenyl phosphorus palladiums to make catalyzer in patent JP2009155300A, sodium carbonate does alkali, and toluene/glycol dimethyl ether selected by solvent, and reaction 9h, productive rate increases, and between 77%-87%, but does not also reach ideal effect.
Comparative example 3:
Adopt four triphenyl phosphorus palladiums to make catalyzer in patent US20140027744, sodium carbonate does alkali, and toluene/glycol dimethyl ether selected by solvent, reaction 9h, and productive rate is not very desirable between 27%-82%, and technique is unstable.
Comparative example 4:
Adopt boric acid ester and halogen to react in patent WO2010044607A [1], four triphenyl phosphorus palladiums make catalyzer, and triethylamine does alkali, and tetrahydrofuran (THF) selected by solvent, and reaction 24h, productive rate is between 44.9%-82.6%.Long reaction time and productive rate is undesirable.
Claims (10)
1. based on a synthetic method for binary imidazo phenyl analog derivative,
general formula (1)
Wherein, A is C
14-C
20fused ring aryl, triarylamine or N-phenyl-3-carbazyl,
To comprise the steps: with the boric acid of intermediate B DPBI and different substituents, for raw material, to carry out Suzuki linked reaction, obtain target compound.
2. according to claim 1, preferred A substituting group is N-phenyl-3-carbazyl, comprises the steps: with intermediate B DPBI and 4-(9H-carbazole-9-base) phenylo boric acid is for raw material, add solvent, catalyzer, carries out Suzuki linked reaction, obtains following structural formula compound
。
3., according to the synthetic method described in claim 1 ~ 2, described temperature of reaction is under 60 DEG C of-90 DEG C of conditions.
4., according to the synthetic method described in claim 1 ~ 2, the described reaction times is reaction 8-15 hour.
5., according to the synthetic method described in claim 1 ~ 2, described reaction is carried out under nitrogen protection.
6., according to the synthetic method described in claim 1 ~ 2, solvent is toluene: ethanol: water=5:1:1.
7., according to the synthetic method described in claim 1 ~ 2, catalyzer is four (triphenyl phosphorus) palladium: 2-dicyclohexyl phosphine-2 ', 6 '-dimethoxy-biphenyl=1:1.
8., according to the synthetic method described in claim 1 ~ 2, the terminal of described reaction adopts TLC method to detect.
9. according to the synthetic method described in claim 1 ~ 2, described synthetic method also comprises post-processing step, and described post-processing step is reaction solution cooling, and separatory, crosses silica gel funnel, recrystallization.
10. synthetic method according to claim 9, described recrystallization solvent is methylene dichloride and sherwood oil.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201410315004.9A CN104650042A (en) | 2014-07-04 | 2014-07-04 | Preparation method of binary imidazole derivative |
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| CN201410315004.9A CN104650042A (en) | 2014-07-04 | 2014-07-04 | Preparation method of binary imidazole derivative |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105968100A (en) * | 2016-07-16 | 2016-09-28 | 吉林奥来德光电材料股份有限公司 | Imidazole derivative compound and preparation method thereof and luminescent device |
| US20210098710A1 (en) * | 2019-09-29 | 2021-04-01 | Shanghai Tianma AM-OLED Co., Ltd. | Compound, organic electroluminescent device and display equipment |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009158848A (en) * | 2007-12-27 | 2009-07-16 | Idemitsu Kosan Co Ltd | Material for organic electroluminescent element, and organic electroluminescent element using the material |
| US20130284907A1 (en) * | 2009-06-29 | 2013-10-31 | Nitto Denko Corporation | Emissive aryl-heteroaryl compounds |
| KR20140017233A (en) * | 2012-07-31 | 2014-02-11 | (주)피엔에이치테크 | Novel compound for organic electroluminescent device and organic electroluminescent device comprising the same |
| CN103804301A (en) * | 2012-11-08 | 2014-05-21 | 海洋王照明科技股份有限公司 | Bipolar blue light phosphorescence compound, preparation method and application thereof |
-
2014
- 2014-07-04 CN CN201410315004.9A patent/CN104650042A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009158848A (en) * | 2007-12-27 | 2009-07-16 | Idemitsu Kosan Co Ltd | Material for organic electroluminescent element, and organic electroluminescent element using the material |
| US20130284907A1 (en) * | 2009-06-29 | 2013-10-31 | Nitto Denko Corporation | Emissive aryl-heteroaryl compounds |
| KR20140017233A (en) * | 2012-07-31 | 2014-02-11 | (주)피엔에이치테크 | Novel compound for organic electroluminescent device and organic electroluminescent device comprising the same |
| CN103804301A (en) * | 2012-11-08 | 2014-05-21 | 海洋王照明科技股份有限公司 | Bipolar blue light phosphorescence compound, preparation method and application thereof |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105968100A (en) * | 2016-07-16 | 2016-09-28 | 吉林奥来德光电材料股份有限公司 | Imidazole derivative compound and preparation method thereof and luminescent device |
| CN105968100B (en) * | 2016-07-16 | 2019-04-19 | 吉林奥来德光电材料股份有限公司 | A kind of imidazole derivative compound and preparation method thereof and luminescent device |
| US20210098710A1 (en) * | 2019-09-29 | 2021-04-01 | Shanghai Tianma AM-OLED Co., Ltd. | Compound, organic electroluminescent device and display equipment |
| US11665959B2 (en) * | 2019-09-29 | 2023-05-30 | Wuhan Tianma Microelectronics Co., Ltd. | Compound, organic electroluminescent device and display equipment |
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