CN104650117B - A kind of organic compound and its application in organic electroluminescence device - Google Patents
A kind of organic compound and its application in organic electroluminescence device Download PDFInfo
- Publication number
- CN104650117B CN104650117B CN201310733664.4A CN201310733664A CN104650117B CN 104650117 B CN104650117 B CN 104650117B CN 201310733664 A CN201310733664 A CN 201310733664A CN 104650117 B CN104650117 B CN 104650117B
- Authority
- CN
- China
- Prior art keywords
- raw material
- compound
- pyrimidine
- boric acid
- alcohol esters
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- RLYVRUUUOXHYQV-UHFFFAOYSA-N Bc(cc1)ccc1-c(cn1)c[n]2c1ncc2-c1ccccc1 Chemical compound Bc(cc1)ccc1-c(cn1)c[n]2c1ncc2-c1ccccc1 RLYVRUUUOXHYQV-UHFFFAOYSA-N 0.000 description 1
- FFAJZEIADCUOGO-UHFFFAOYSA-N Brc(cc1)ccc1-c(cn1)c[n]2c1ncc2-c1ccccc1 Chemical compound Brc(cc1)ccc1-c(cn1)c[n]2c1ncc2-c1ccccc1 FFAJZEIADCUOGO-UHFFFAOYSA-N 0.000 description 1
- YOUGPRUWTRPZTC-UHFFFAOYSA-N CC1(C)OB(C2=CCC(C3)C33N=CC(Cl)=CN23)OC1(C)C Chemical compound CC1(C)OB(C2=CCC(C3)C33N=CC(Cl)=CN23)OC1(C)C YOUGPRUWTRPZTC-UHFFFAOYSA-N 0.000 description 1
- GKJYBVXLRNFDHU-UHFFFAOYSA-N CC1(C)ON(c(cc2)ccc2-c2ccccc2)OC1(C)C Chemical compound CC1(C)ON(c(cc2)ccc2-c2ccccc2)OC1(C)C GKJYBVXLRNFDHU-UHFFFAOYSA-N 0.000 description 1
- DHDHJYNTEFLIHY-UHFFFAOYSA-N c(cc1)ccc1-c1c(ccc(c2ncc3)c3-c3ccccc3)c2ncc1 Chemical compound c(cc1)ccc1-c1c(ccc(c2ncc3)c3-c3ccccc3)c2ncc1 DHDHJYNTEFLIHY-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D519/00—Heterocyclic compounds containing more than one system of two or more relevant hetero rings condensed among themselves or condensed with a common carbocyclic ring system not provided for in groups C07D453/00 or C07D455/00
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Nitrogen Condensed Heterocyclic Rings (AREA)
Abstract
The present invention relates to a class such as formula（Ⅰ）Shown organic compound, wherein：One of A and B are N, and another H in CH groups or CH groups is by C1 12 alkyl, C6 30 aryl, C6 30 heterocyclic aryl, CF3、‑SCH3In a kind of substituted group；N values 1 or 2；Ar is selected from substitution or unsubstituted C4 30 fused ring aryl or sub- fused ring aryl；L is selected from one of singly-bound, C6 30 arlydene or sub- heterocyclic aryl, oxygen atom, nitrogen-atoms or sulphur atom；Ar1And Ar2Independently selected from H, or phenyl, naphthyl, the xenyl that can be substituted, five, one of hexa-member heterocycle group or C1 12 aliphatic alkyl.The present invention also protects application of such compound in organic electroluminescence device, especially OLED electron transport material, can significantly reduce driving voltage, improves current efficiency.
Description
Technical field
The present invention relates to a kind of new organic materials, and its application in ORGANIC ELECTROLUMINESCENCE DISPLAYS technical field.
Background technology
Electroluminescent material and device pass through years of researches and development, have reached practical level, various materials,
Such as hole material, electronic material, luminescent material, display device technology of preparing has been achieved for considerable progress.Similarly,
The all types of electron transport materials that transmittability is stronger, stability is higher, all have been reported that in article and patent.In general,
Electron transport material is all the plane aromatic compound with big conjugated structure, and they have mostly preferably receives electronics
Ability, while under certain forward bias again can effectively transmit electronics.Used electron transport material mainly has 8-
Hydroxyquinoline aluminum class compound, furodiazole compound, quinoxaline compound, the polymer of nitrile group-containing, other nitrogen heterocyclic rings
Compound etc.（Chem.Mater.2004,16,4556-4573, J Mater.Chem.2005,15,94-106）.It is newer at present
Report has the condensed-nuclei aromatics electron transport material that phenylpyridyl replaces（Application publication number CN101891673A, data of publication of application
2010,11,24）, the condensed-nuclei aromatics electron transport material of benzimidazole group substitution（Application number 200910234761.2, application
Day 2009,11,13）, etc..
Therefore, based on existing research, the electron transport material of stability and high efficiency is further developed, so as to reduce bright electricity
Pressure, improves device efficiency, with critically important actual application value.
The content of the invention
It is an object of the invention to provide a class novel organic compound, such compound can be used for organic electroluminescent
Display field, specifically, this kind of compound is in organic electroluminescence device, as electron transport material.
The present invention be withParent, imidazo [1,2-a] pyrimidine radicals of electron deficient are used as Deng condensed-nuclei aromatics derivatives group
Group or imidazo [1,2-a] pyrazine group form the new compound of a class as electron deficient substituent, and such compound has very
Good electronic transmission performance.There is larger conjugated structure Deng condensed-nuclei aromatics, when the condensed-nuclei aromatics of these conjugated structures is used as mother
Body, when combining to form new material molecule with electron deficient substituent, these condensed-nuclei aromatics can keep preferable plane regularity,
And the highest occupied molecular orbital(HOMO) of these molecules（HOMO）And lowest unoccupied molecular orbital（LUMO）It is mainly distributed on parent thick
On PAH, these big and regular planar conjugates are conducive to transmission of the electronics in molecular orbit.Electron deficient imidazo [1,
2-a] pyrimidine（Pyrazine）The presence of group in the molecule, makes molecule that electron deficient state is integrally presented, be conducive to electronics injection and
Transmission.The compound of the present invention has higher electronic transmission performance, and the electroluminescence device made of the material has good electricity
Photoluminescence efficiency, device lifetime is also longer.
Therefore, the technical scheme that the present invention takes is：
A kind of organic compound, with such as formula（Ⅰ）Shown structure：
Wherein：
One of A and B are N, and another is that H in CH groups or CH groups is 6-30 by C1-12 alkyl, carbon number
Aryl, carbon number be 6-30 heterocyclic aryl ,-CF3、-SCH3In a kind of substituted group；
N values 1 or 2；
Ar be selected from naphthyl, phenyl, xenyl, naphthyl, the monobasic naphthyl of phenyl napthyl, naphthylene,Base, phenyl,
Xenyl, naphthyl, phenyl napthyl it is monobasicBase, it is sub-Base, benzo anthryl, phenyl, xenyl, naphthyl, phenyl napthyl
Monobasic benzo anthryl, benzo anthrylene, dibenzo anthryl, phenyl, xenyl, naphthyl, phenyl napthyl it is monobasic
Dibenzo anthryl, dibenzo anthrylene, phenanthryl, phenyl, xenyl, naphthyl, the monobasic phenanthryl of phenyl napthyl, phenanthrylene,
Benzo phenanthryl, phenyl, xenyl, naphthyl, the monobasic benzo phenanthryl of phenyl napthyl, benzo phenanthrylene, perylene base, phenyl, connection
Phenyl, naphthyl, the monobasic perylene base of phenyl napthyl, sub- perylene base, pyrenyl, one of phenyl, xenyl, naphthyl, phenyl napthyl take
The pyrenyl in generation, sub- pyrenyl, Sanya phenyl, phenyl, xenyl, naphthyl, the monobasic Sanya phenyl of phenyl napthyl, sub- triphenylene
One of base；
L is bridge linkage group, the arlydene for being 6-30 selected from singly-bound, carbon number, the substitution virtue of three that carbon number is 6-30
Three substituted heterocycle aryl that sub- heterocyclic aryl, the carbon number that base, carbon number are 6-30 are 6-30, oxygen atom, nitrogen-atoms or
One of sulphur atom；
Ar1And Ar2Separately it is selected from H, phenyl, C1-12Alkyl ,-CF3、-SCH3, phenyl, xenyl, naphthyl wherein
A kind of phenyl of substituent group, naphthyl, C1-12Alkyl ,-CF3、-SCH3, phenyl, xenyl, naphthyl one of which substituent group
Naphthyl, one of five yuan or hexa-member heterocycle group, the aliphatic alkyl of 1-12 carbon atom.
Further, the compound has formula（Ⅱ）Or（Ⅲ）Described structure：
Further, the bridge linkage group L is selected from singly-bound, phenylene, biphenylene, naphthylene, sub- pyridine radicals, oxygen original
One of son, nitrogen-atoms or sulphur atom.
In order to illustrate more clearly of present invention, lower mask body narration the present invention relates to organic compound choosing it is preferred
Structure is：
The invention provides a kind of organic compound that can be applied in organic electroluminescence device.
The organic compound of the present invention has higher electron transfer capabilities, and electronics is used as in organic electroluminescence device
Transmission material.
Present invention also offers a kind of organic electroluminescence device, including substrate, and sequentially form on the substrate
Anode layer, organic luminescence function layer and cathode layer；Described organic luminescence function layer includes hole transmission layer, organic luminous layer
And electron transfer layer,
The electron transport material of the electron transfer layer is described organic compound.
Further, the electron transport material in organic electroluminescence device can also be by the compound of the application and other
Compound is used cooperatively, collectively as electron transport material.
Preparation is simple for the compounds of this invention, and these compounds have good heat endurance, high electricity
Transport factor, the electroluminescent device electroluminescence efficiency made of the material is significantly improved, while the life-span of device also carries significantly
Height, can be used as electron transport material in organic electroluminescence device.
The organic compound of the present invention can also be used as the material of other functional layers in the devices, can such as make in luminescent layer
For material of main part.
Brief description of the drawings
Fig. 1 is the highest occupied molecular orbital(HOMO) of compound 1 in the embodiment of the present invention；
Fig. 2 is the lowest unoccupied molecular orbital of compound 1 in the embodiment of the present invention；
Fig. 3 is the highest occupied molecular orbital(HOMO) of compound of the embodiment of the present invention 9；
Fig. 4 is the lowest unoccupied molecular orbital of compound of the embodiment of the present invention 9.
Embodiment
Various imidazos [1,2-a] pyrimidine halo derivatives and imidazo [1,2-A] pyrazine halo used in the present invention
Derivative, for example, 5,7- dichloro-imidazoles simultaneously [1,2-a] pyrimidine, 6- bromines imidazo [1,2-a] pyrimidine, 3- bromines imidazo [1,2-a]
Pyrimidine, 7- chloro- 5- (methyl mercapto) imidazo [1,2-c] pyrimidine, bromo- 6- chlorine imidazo [1, the 2-a] pyrimidines of 3-, 5,7- dichloro-imidazoles
And [1,2-A] pyrimidine, 2- (3- bromophenyls) imidazoles [1,2-a] and pyrimidine, the chloro- 2-p- tolylimidazols [1,2-a] of 6- and pyrimidine,
2- (4- bromophenyls)-imidazo [1,2-a] -7- methylpyrimidines, 2- (3- bromophenyls)-imidazo [1,2-a] pyrimidine, 2- (3- bromines
Phenyl)-imidazo [1,2-a] -7- methylpyrimidines, 2- (4- bromophenyls)-imidazo [1,2-a] pyrimidine, the chloro- 2- mebendazoles of 6-
And [1,2-a] pyrimidine, 2- (4- bromophenyls) -7- methylimidazoles [1,2-a] and pyrimidine, 3- bromo- 7- (trifluoromethyl) imidazo [1,
2-a] pyrimidine, 6- bromines imidazo [1,2-A] pyrazine, bromo- 8- chlorine imidazo [1, the 2-A] pyrazines of 3-, 6,8- bis- bromo- imidazoles [1,2-
A] pyrazine, the chloro- imidazos of 5- [1,2-A] pyrazine, 8- chlorine imidazo [1,2-a] pyrazine, 3- bromines imidazo [1,2-a] pyrazine, 2-
Bromine imidazo [1,2-a] pyrazine, etc. commercially available at home, various halo condensed-nuclei aromatics, aryl boric acid and its Knit-the-brows alcohol esters
Deng chemical raw material, can conveniently it buy in chemical products market at home；Some special aryl boric acid derivatives and intermediate
It can use common organic procedures synthesis.
Embodiment 1
The synthesis of compound 1
The first step,
In the there-necked flask of a 2000ml, with mechanical agitation, Ar gas shieldeds.Add bromo- 6- chlorine imidazo [1,2-A] pyrimidines of 3-
4.62g（Molecular weight 231,0.02mol）, connection pinacol borate 5.6g（Molecular weight 254.2,0.022mol）, Pd (dppf)
Cl23.2g（0.0044mol）, potassium acetate 36g（Molecular weight 138,0.26mol）, Isosorbide-5-Nitrae dioxane 500ml.Machinery is started to stir
Mix, keep Ar gas shieldeds after taking a breath 3 times at reduced pressure conditions, use TLC（Thin-layer chromatography）Monitoring reaction, to raw material be wholly absent for
Only, after flowing back 3 hours, reaction is complete.Let cool, reaction system is allocated as two layers, separates organic layer, is evaporated, obtain 5.31g products,
Yield 92.1%.
Second step,
In the there-necked flask of a 1000ml, with mechanical agitation, Ar gas shieldeds add 6,12- dibromos Chrysene5.76g（Point
Son amount 384,0.015mol）, above the first step synthesis 6- chlorine imidazo [1,2-A] pyrimidine -3- boric acid Knit-the-brows alcohol esters 9.21g
（Molecular weight 279,0.033mol）, catalyst Pd (PPh3)4Consumption 1.8g（Molecular weight 1154,0.001556mol）, sodium carbonate
Solution 120ml（2M）, toluene 300ml, ethanol 150ml.It is stirred at reflux, is monitored and reacted with TLC, has been reacted after coreaction 3.5hs
Entirely.Cooling, separates, is evaporated, use column chromatography methods separation product, eluent uses 1：1 ethyl acetate：Petroleum ether, obtains 6.7g
Yellow solid compound, purity 97.0%, yield：81.2%.
3rd step,
In the there-necked flask of a 1000ml, with mechanical agitation, Ar gas shieldeds add two chloromethylated intermediates of second step generation above
7.95g（Molecular weight 530,0.015mol）, 4- biphenylboronic acid Knit-the-brows alcohol esters 9.24g（Molecular weight 280,0.033mol）, catalyst
Pd(PPh3)4Consumption 1.8g（Molecular weight 1154,0.001556mol）, aqueous sodium carbonate 120ml（2M）, toluene 300ml, ethanol
150ml.It is stirred at reflux, is monitored and reacted with TLC, reacts complete after coreaction 6hs.Cooling, separates, is evaporated, use column chromatography methods
Separation product, eluent uses 1：1 ethyl acetate：Petroleum ether, obtains 9.23g faint yellow solid compounds, purity 99.0%, production
Rate：79.5%.
Product MS（m/e）：766, elementary analysis（C54H36N6）：Theoretical value C：84.57%, H：4..47%, N：10.96%；
Measured value C：84.60%, H：4.46%, N：10.94%.
Embodiment 2
The synthesis of compound 2
The first step,
Building-up process is same as the second step of embodiment 1, simply by a kind of raw material 6- chlorine imidazo [1,2-a] pyrimidine therein-
3- boric acid Knit-the-brows alcohol esters replace making raw material with 4- bromobenzeneboronic acid Knit-the-brows alcohol esters, and remaining reagent is unchanged, react 1.5 hours, and reaction is
It has been completed that, obtain the Bromo-intermediates of white solid two.
Second step,
Building-up process is same as the second step of embodiment 1, and simply by a kind of raw material 6 therein, 12- dibromos Chrysene uses first
Two Bromo-intermediates of step synthesis are replaced making raw material, and remaining reagent is unchanged, react 2 hours, and reaction has been completed, and obtains slightly yellow
Solid dichloro- intermediate.
3rd step,
Building-up process is same as the second step of embodiment 1, simply by raw material 4- biphenylboronic acids Knit-the-brows alcohol ester phenyl boric acids therein
Knit-the-brows alcohol esters are replaced, and two chloromethylated intermediates that two chloromethylated intermediates are synthesized with second step here are replaced making raw material, remaining reagent
It is unchanged, obtain compound as white solid 2.
Product MS（m/e）：766, elementary analysis（C54H36N6）：Theoretical value C：84.57%, H：4..47%, N：10.96%；
Measured value C：84.59%, H：4.50%, N：10.91%.
Embodiment 3
The synthesis of compound 3
The first step,
Building-up process is same as the first step of embodiment 1, simply by bromo- 6- chlorine imidazo [1, the 2-A] pyrimidines of raw material 3- therein
Use 2-（P-bromophenyl）Simultaneously [1,2-A] pyrimidine is replaced -7- methylimidazoles, obtains slightly yellow solid chemical compound.
Second step,
Building-up process is same as the second step of embodiment 1, and a kind of raw material 4- biphenylboronic acids Knit-the-brows alcohol esters therein simply are used into the
The slightly yellow solid chemical compound borate that one-step synthesis goes out is replaced, and remaining reagent is unchanged, obtains faint yellow solid compound 3.
Product MS（m/e）：642, elementary analysis（C44H30N6）：Theoretical value C：82.22%, H：4..70%, N：13.08%；
Measured value C：82.24%, H：4.72%, N：13.04%.
Embodiment 4
The synthesis of compound 4
Building-up process is same as the second step of embodiment 1, simply by a kind of raw material 4- biphenylboronic acids Knit-the-brows alcohol esters 3- therein
（7- methylimidazoles simultaneously [1,2-A] pyrimidine -2-base）Borate ester is replaced, and remaining reagent is unchanged, obtains faint yellow solid compound
4。
Product MS（m/e）：642, elementary analysis（C44H30N6）：Theoretical value C：82.22%, H：4..70%, N：13.08%；
Measured value C：82.20%, H：4.75%, N：13.05%.
Embodiment 5
The synthesis of compound 5
Building-up process is same as the second step of embodiment 1, simply by a kind of raw material 4- biphenylboronic acids Knit-the-brows alcohol esters 4- therein
（7- trifluoromethyl imidazoles simultaneously [1,2-A] pyrimidin-3-yl）Borate ester is replaced, and remaining reagent is unchanged, obtains faint yellow solid
Compound 5.
Product MS（m/e）：750, elementary analysis（C44H24F6N6）：Theoretical value C：70.40%, H：3.22%, F：15.18%；
N：11.20%；Measured value C：70.42%, H：3.24%, F：15.15%；N：11.19%.
Embodiment 6
The synthesis of compound 6
Building-up process is same as the second step of embodiment 1, simply by a kind of raw material 4- biphenylboronic acids Knit-the-brows alcohol esters 4- therein
（2-（P-methylphenyl）Imidazo [1,2-A] pyrimidine -6- bases）Phenyl boric acid Knit-the-brows alcohol esters are replaced, and remaining reagent is unchanged, obtains yellowish
Color solid chemical compound 6.
Product MS（m/e）：794, elementary analysis（C56H38N6）：Theoretical value C：84.61%, H：4.82%, N：10.57%；
Measured value C：84.59%, H：4.81%, N：10.60%.
Embodiment 7
The synthesis of compound 7
The first step,
In the there-necked flask of a 500ml, with mechanical agitation, Ar gas shieldeds add bromo- 6- chlorine imidazo [1, the 2-a] pyrimidines of 3-
7.6g（Molecular weight 231,0.033mol）, phenyl boric acid Knit-the-brows alcohol esters 6.73g（Molecular weight 204,0.033mol）, catalyst Pd
(PPh3)4Consumption 1.8g（Molecular weight 1154,0.001556mol）, aqueous sodium carbonate 100ml（2M）, toluene 150ml, ethanol
100ml.It is stirred at reflux, is monitored and reacted with TLC, reacts complete after reaction 1.5hs.Cooling, separates, is evaporated, use column chromatography methods
Separation product, eluent uses 1：1 ethyl acetate：Petroleum ether, obtains the slightly yellow solid chemical compounds of 7.3g, purity 99.2%, production
Rate：95.64%.
Second step,
Building-up process is same as previous step, simply by the bromo- 6- of raw material 3- therein chloro- imidazo [1,2-a] pyrimidine 3-
Phenyl -6- chlorine imidazo [1,2-c] pyrimidine is replaced, 4- bromobenzeneboronic acid Knit-the-brows alcohol esters make raw material instead of phenyl boric acid Knit-the-brows alcohol esters, its
Remaining reagent is unchanged, obtains faint yellow solid bromo-derivative.
3rd step,
In one 1000 milliliters of there-necked flasks, with mechanical agitation, Ar gas shieldeds add the faint yellow bromo-derivative that previous step synthesizes
8.4g（Molecular weight 349,0.024mol）, the anhydrous THF of 100ml are cooled to -78 DEG C, the lower BuLi that 12ml is added dropwise of stirring（2.4M,
0.0288mol）, temperature maintains -78 DEG C, 12ml B (OiPr) is added dropwise after stirring 10min at -78 DEG C always3（Molecular weight
188.07, proportion 0.9574,0.061mol）, stir to room temperature（Use 3hrs）, dilute acid hydrolysis is added, water layer is separated, in being neutralized to
Property, sodium chloride is added, the THF being dissolved in water is removed under reduced pressure, there is white solid precipitation, is filtered, product 7.2g solids 4- is obtained（3-
Phenylimidazole simultaneously [1,2-a] pyrimidine -6- bases）Phenyl boric acid, yield 95.5%.
4th step,
In the there-necked flask of a 1000ml, with mechanical agitation, Ar gas shieldeds add 6,12- dibromos Chrysene13.5g（Point
Son amount 384,0.035mol）, 4-（1- naphthyls）Phenyl boric acid 8.7g（Molecular weight 248,0.035mol）, catalyst Pd (PPh3)4Consumption
1.8g（Molecular weight 1154,0.001556mol）, aqueous sodium carbonate 120ml（2M）, toluene 250ml, ethanol 150ml.Stir back
Stream, is monitored with TLC and reacted, and reacts complete after reaction 1.5hs.Cooling, separates, is evaporated, use column chromatography methods separation product, elutes
Agent uses 1：5 ethyl acetate：Petroleum ether, obtains 17.5g faint yellow solids 6-（4-（1- naphthyls）Phenyl）- 12- bromine Chrysene,
Molecular weight of product 508, purity 97.2%, yield：95.4%.
5th step,
Building-up process is same as the step of the present embodiment the 4th, simply by a kind of raw material 6 therein, 12- dibromo Chrysene 6-
（4-（1- naphthyls）Phenyl）- 12- bromines Chrysene is replaced, 4-（1- naphthyls）Phenyl boric acid 4-（Simultaneously [1,2-a] is phonetic for 3- phenylimidazoles
Pyridine -6- bases）Phenyl boric acid replaces making raw material, and remaining reagent is unchanged, obtains faint yellow solid compound 7.
Product MS（m/e）：699, elementary analysis（C52H33N3）：Theoretical value C：89.24%, H：4.75%, N：6.01%；It is real
Measured value C：89.26%, H：4.72%, N：6.02%.
Embodiment 8
The synthesis of compound 8
Building-up process is same as the second step of embodiment 1, simply by a kind of raw material 6 therein, 12- dibromo Chrysene 6-
（4-（1- naphthyls）Phenyl）- 12- bromines Chrysene is replaced, 6- chlorine imidazo [1,2-A] pyrimidine -3- boric acid Knit-the-brows alcohol esters 4-
（7- methylimidazoles simultaneously [1,2-a] pyrimidine -2-base）Phenyl boric acid replaces making raw material, and remaining reagent is unchanged, obtains faint yellow solid
Compound 8.
Product MS（m/e）：637, elementary analysis（C47H31N3）：Theoretical value C：88.51%, H：4.90%, N：6.59%；It is real
Measured value C：88.49%, H：4.88%, N：6.63%.
Embodiment 9
The synthesis of compound 9
Building-up process is allocated as three steps, and the first step is same as the first step of embodiment 1, simply by the bromo- 6- chlorine imidazoles of initiation material 3-
And [1,2-A] pyrimidine is replaced with bromo- 8- chlorine imidazo [1, the 2-A] pyrazines of 3-, remaining reagent is unchanged, obtain 8- chlorine imidazo [1,
2-A] pyrazine -3- pinacol borates；Second step is same as the second step of embodiment 1, simply by a kind of raw material 6- chlorine imidazoles therein
And [1,2-A] pyrimidine -3- boric acid Knit-the-brows alcohol esters are replaced making raw material with 8- chlorine imidazo [1,2-A] pyrazine -3- pinacol borates,
Obtain corresponding two chloromethylated intermediate；3rd step is same as the second step of embodiment 1, simply by a kind of raw material 6 therein, 12- dibromos
Chrysene is replaced with two chloromethylated intermediates synthesized with second step here, 6- chlorine imidazo [1,2-A] pyrimidine -3- boric acid Knit-the-brows alcohol
Ester 4-（1- naphthyls）Phenyl boric acid replaces making raw material, and remaining reagent is unchanged, obtain yellow solid compound 9.
Product MS（m/e）：866, elementary analysis（C62H38N6）：Theoretical value C：85.89%, H：4.42%, N：9.69%；It is real
Measured value C：85.91%, H：4.41%, N：9.68%.
Embodiment 10
The synthesis of compound 10
Building-up process is allocated as three steps, and the first step is same as the step of embodiment 7 the 4th, simply by initiation material 4-（1- naphthyls）Benzene boron
Acid is replaced with 2- naphthalene boronic acids, and remaining reagent is unchanged, obtains 6-（2- naphthyls）- 12- bromos Chrysene；Second step is same as embodiment
1 second step, simply by a kind of raw material 6- chlorine imidazo [1,2-A] pyrimidine -3- boric acid Knit-the-brows alcohol esters 8- chlorine imidazos therein
[1,2-A] pyrazine -3- pinacol borates are replaced, the 6- that 6,12- dibromo Chrysene are synthesized with the first step here（2- naphthyls）-
12- bromos Chrysene replaces making raw material, obtains a corresponding chloromethylated intermediate；3rd step is same as the second step of embodiment 1, simply will
A kind of raw material 6 therein, 12- dibromos Chrysene is replaced with the chloromethylated intermediate synthesized with second step here, 6- chlorine imidazos
[1,2-A] pyrimidine -3- boric acid Knit-the-brows alcohol esters 4-（1- naphthyls）Phenyl boric acid replaces making raw material, and remaining reagent is unchanged, obtains yellow
Solid chemical compound 10.
Product MS（m/e）：673, elementary analysis（C50H31N3）：Theoretical value C：89.13%, H：4.64%, N：6.24%；It is real
Measured value C：89.11%, H：4.63%, N：6.26%.
Embodiment 11
The synthesis of compound 11
Building-up process is allocated as two steps, and the first step is same as the second step of embodiment 1, simply by raw material 6- chlorine imidazos therein
[1,2-A] pyrimidine -3- boric acid Knit-the-brows alcohol esters are replaced making raw material with 8- chlorine imidazo [1,2-A] pyrazine -3- pinacol borates, and 6,
12- dibromos Chrysene uses 1,6- dibromos pyrene to replace, and obtains corresponding two chloromethylated intermediate；Second step is same as the second step of embodiment 1,
Simply by a kind of raw material 6 therein, 12- dibromos Chrysene is replaced with two chloromethylated intermediates synthesized with the first step here, 6- chlorine
Imidazo [1,2-A] pyrimidine -3- boric acid Knit-the-brows alcohol esters 4-（1- naphthyls）Phenyl boric acid replaces making raw material, and remaining reagent is unchanged, obtains
To slightly yellow solid chemical compound 11.
Product MS（m/e）：840, elementary analysis（C60H36N6）：Theoretical value C：85.69%, H：4.32%, N：9.99%；It is real
Measured value C：85.71%, H：4.33%, N：9.96%.
Embodiment 12
The synthesis of compound 12
Building-up process is allocated as two steps, and the first step is same as the second step of embodiment 1, simply by raw material 6- chlorine imidazos therein
[1,2-A] pyrimidine -3- boric acid Knit-the-brows alcohol esters 4-（6- chlorine imidazo [1,2-A] pyrimidin-3-yl）Phenyl boric acid replaces making raw material, and 6,
12- dibromos Chrysene uses 1,6- dibromos pyrene to replace, and obtains corresponding two chloromethylated intermediate；Second step is same as the second step of embodiment 1,
Simply by a kind of raw material 6 therein, 12- dibromos Chrysene is replaced with two chloromethylated intermediates synthesized with the first step here, 6- chlorine
Imidazo [1,2-A] pyrimidine -3- boric acid Knit-the-brows alcohol esters are replaced making raw material with phenyl boric acid, and remaining reagent is unchanged, obtains slightly yellow solid
Body compound 12.
Product MS（m/e）：740, elementary analysis（C52H32N6）：Theoretical value C：84.30%, H：4.35%, N：11.34%；
Measured value C：84.34%, H：4.33%, N：11.33%.
Embodiment 13
The synthesis of compound 13
Building-up process is same as the second step of embodiment 1, simply by raw material 6- chlorine imidazo [1,2-A] pyrimidine -3- boron therein
Sour Knit-the-brows alcohol esters 4-（7- methylimidazoles simultaneously [1,2-A] pyrimidine -2-base）Phenyl boric acid is replaced, and 6,12- dibromo Chrysene use 1,
6- dibromos pyrene replaces making raw material, and remaining reagent is unchanged, obtains slightly yellow solid chemical compound 13.
Product MS（m/e）：616, elementary analysis（C42H28N6）：Theoretical value C：81.80%, H：4.57%, N：13.63%；
Measured value C：81.82%, H：4.54%, N：113.64%.
Embodiment 14
The synthesis of compound 14
Building-up process is same as the second step of embodiment 1, simply by raw material 6- chlorine imidazo [1,2-A] pyrimidine -3- boron therein
Sour Knit-the-brows alcohol esters 4-（7- trifluoromethyl imidazoles simultaneously [1,2-A] pyrimidin-3-yl）Phenyl boric acid is replaced, 6,12- dibromo Chrysene
Replaced making raw material with 1,6- dibromos pyrene, remaining reagent is unchanged, obtains slightly yellow solid chemical compound 14.
Product MS（m/e）：724, elementary analysis（C42H22F6N6）：Theoretical value C：69.61%, H：3.06%, F：15.73%,
N：11.60%；Measured value C：69.64%, H：3.05%, F：15.70%, N：11.61%.
Embodiment 15
The synthesis of compound 15
Building-up process is same as the second step of embodiment 1, simply by raw material 6- chlorine imidazo [1,2-A] pyrimidine -3- boron therein
Sour Knit-the-brows alcohol esters 4-（2-（P-methylphenyl）Imidazo [1,2-A] pyrimidine -6- bases）Phenyl boric acid is replaced, 6,12- dibromos
Chrysene uses 1,6- dibromos pyrene to replace making raw material, and remaining reagent is unchanged, obtains slightly yellow solid chemical compound 15.
Product MS（m/e）：687, elementary analysis（C51H33N3）：Theoretical value C：89.06%, H：4.84%, N：6.10%；It is real
Measured value C：89.05%, H：4.88%, N：6.07%.
Embodiment 16
The synthesis of compound 16
Building-up process is same as the second step of embodiment 1, simply by raw material 6- chlorine imidazo [1,2-A] pyrimidine -3- boron therein
Sour Knit-the-brows alcohol esters 4-（6- phenylimidazoles simultaneously [1,2-A] pyrimidin-3-yl）Phenyl boric acid is replaced, and 6,12- dibromo Chrysene use 5,
8- dibromos benzophenanthrene replaces making raw material, and remaining reagent is unchanged, obtains slightly yellow solid chemical compound 16.
Product MS（m/e）：766, elementary analysis（C54H34N6）：Theoretical value C：84.57%, H：4.47%, N：10.96%；
Measured value C：84.55%, H：4.46%, N：10.99%.
Embodiment 17
The synthesis of compound 17
Building-up process is same as the second step of embodiment 1, simply by raw material 6- chlorine imidazo [1,2-A] pyrimidine -3- boron therein
Sour Knit-the-brows alcohol esters 4-（7- phenylimidazoles simultaneously [1,2-A] pyrimidine -5- bases）Phenyl boric acid is replaced, and 6,12- dibromo Chrysene use 5,
8- dibromos benzophenanthrene replaces making raw material, and remaining reagent is unchanged, obtains slightly yellow solid chemical compound 17.
Product MS（m/e）：766, elementary analysis（C54H34N6）：Theoretical value C：84.57%, H：4.47%, N：10.96%；
Measured value C：84.59%, H：4.45%, N：10.96%.
Embodiment 18
The synthesis of compound 18
Building-up process is same as the second step of embodiment 1, simply by raw material 6- chlorine imidazo [1,2-A] pyrimidine -3- boron therein
Sour Knit-the-brows alcohol esters 4-（7- methylimidazoles simultaneously [1,2-A] pyrimidine -2-base）Phenyl boric acid is replaced, and 6,12- dibromo Chrysene use 5,
8- dibromos benzophenanthrene replaces making raw material, and remaining reagent is unchanged, obtains slightly yellow solid chemical compound 18.
Product MS（m/e）：642, elementary analysis（C44H30N6）：Theoretical value C：82.22%, H：4.70%, N：13.08%；
Measured value C：82.25%, H：4.73%, N：13.02%.
Embodiment 19
The synthesis of compound 19
Building-up process is same as the second step of embodiment 1, simply by raw material 6- chlorine imidazo [1,2-A] pyrimidine -3- boron therein
Sour Knit-the-brows alcohol esters 4-（7- trifluoromethyl imidazoles simultaneously [1,2-A] pyrimidin-3-yl）Phenyl boric acid is replaced, 6,12- dibromo Chrysene
Replaced making raw material with 5,8- dibromos benzophenanthrene, remaining reagent is unchanged, obtains slightly yellow solid chemical compound 19.
Product MS（m/e）：750, elementary analysis（C44H24F6N6）：Theoretical value C：70.40%, H：3.22%, F：15.18%,
N：11.20%；Measured value C：70.42%, H：3.19%, F：15.16%, N：11.23%.
Embodiment 20
The synthesis of compound 20
Building-up process is same as the second step of embodiment 1, simply by raw material 6- chlorine imidazo [1,2-A] pyrimidine -3- boron therein
Sour Knit-the-brows alcohol esters 4-（7- trifluoromethyl imidazoles simultaneously [1,2-A] pyrimidin-3-yl）Phenyl boric acid is replaced, 6,12- dibromo Chrysene
Replaced making raw material with 5,8- dibromos benzophenanthrene, remaining reagent is unchanged, obtains slightly yellow solid chemical compound 19.
Product MS（m/e）：766, elementary analysis（C54H34N6）：Theoretical value C：85.57%, H：4.47%, N：10.96%；
Measured value C：85.56%, H：4.45%, N：10.99%.
Embodiment 21
The synthesis of compound 21
Building-up process is same as the second step of embodiment 1, simply by raw material 6- chlorine imidazo [1,2-A] pyrimidine -3- boron therein
Sour Knit-the-brows alcohol esters 4-（2-（P-methylphenyl）Imidazo [1,2-A] pyrimidine -6- bases）Phenyl boric acid replaces making raw material, 6,12- dibromos
Chrysene uses 5,8- dibromos benzophenanthrene to replace, and remaining reagent is unchanged, obtains slightly yellow solid chemical compound 19.
Product MS（m/e）：810, elementary analysis（C57H42N6）：Theoretical value C：84.42%, H：5.22%, N：10.36%；
Measured value C：84.45%, H：5.20%, N：10.35%.
Embodiment 22
The synthesis of compound 22
Building-up process is allocated as two steps, and the first step is same as the second step of embodiment 1, simply by raw material 6- chlorine imidazos therein
[1,2-A] pyrimidine -3- boric acid Knit-the-brows alcohol esters are replaced with 6- chlorine imidazo [1,2-A] pyrimidine -3- boric acid Knit-the-brows alcohol esters, and 6,12- bis-
Bromine Chrysene uses the bromine perylenes of 3,9- bis- to replace making raw material, obtains two chloromethylated intermediates；Second step is same as the second step of embodiment 1, simply
Raw material 6- chlorine imidazo [1,2-A] pyrimidine -3- boric acid Knit-the-brows alcohol esters therein are replaced with 4- biphenylboronic acid Knit-the-brows alcohol esters, 6,
12- dibromos Chrysene replaces making raw material with the here first two obtained chloromethylated intermediates, and remaining reagent is unchanged, obtains slightly yellow solid
Body compound 22.
Product MS（m/e）：790, elementary analysis（C56H34N6）：Theoretical value C：85.04%, H：4.33%, N：10.63%；
Measured value C：85.06%, H：4.34%, N：10.60%.
Embodiment 23
The synthesis of compound 23
Building-up process is allocated as two steps, and the first step is same as the second step of embodiment 1, simply by raw material 6- chlorine imidazos therein
[1,2-A] pyrimidine -3- boric acid Knit-the-brows alcohol esters 4-（6- chlorine imidazo [1,2-A] pyrimidin-3-yl）Phenyl boric acid is replaced, and 6,12- bis-
Bromine Chrysene uses the bromine perylenes of 3,9- bis- to replace making raw material, obtains two chloromethylated intermediates；Second step is same as the second step of embodiment 1, simply
Raw material 6- chlorine imidazo [1,2-A] pyrimidine -3- boric acid Knit-the-brows alcohol esters therein are replaced with phenyl boric acid Knit-the-brows alcohol esters, 6,12- bis-
Bromine Chrysene replaces making raw material with the here first two obtained chloromethylated intermediates, and remaining reagent is unchanged, obtains slightly yellow solidification
Compound 23.
Product MS（m/e）：790, elementary analysis（C56H34N6）：Theoretical value C：85.04%, H：4.33%, N：10.63%；
Measured value C：85.03%, H：4.30%, N：10.67%.
Embodiment 24
The synthesis of compound 24
Building-up process is same as the second step of embodiment 1, simply by raw material 6- chlorine imidazo [1,2-A] pyrimidine -3- boron therein
Sour Knit-the-brows alcohol esters 4-（7- methylimidazoles simultaneously [1,2-A] pyrimidine -2-base）Phenyl boric acid is replaced, and 6,12- dibromo Chrysene use 3,
9- bis- Xiu perylenes replace making raw material, and remaining reagent is unchanged, obtains faint yellow solid compound 24.
Product MS（m/e）：666, elementary analysis（C46H30N6）：Theoretical value C：82.86%, H：4.54%, N：12.60%；
Measured value C：82.89%, H：4.53%, N：12.58%.
Embodiment 25
The synthesis of compound 25
Building-up process is same as the second step of embodiment 1, simply by raw material 6- chlorine imidazo [1,2-A] pyrimidine -3- boron therein
Sour Knit-the-brows alcohol esters 3-（7- methylimidazoles simultaneously [1,2-A] pyrimidine -2-base）Phenyl boric acid is replaced, and 6,12- dibromo Chrysene use 3,
9- bis- Xiu perylenes replace making raw material, and remaining reagent is unchanged, obtains faint yellow solid compound 25.
Product MS（m/e）：666, elementary analysis（C46H30N6）：Theoretical value C：82.86%, H：4.54%, N：12.60%；
Measured value C：82.87%, H：4.51%, N：12.62%.
Embodiment 26
The synthesis of compound 26
Building-up process is same as the second step of embodiment 1, simply by raw material 6- chlorine imidazo [1,2-A] pyrimidine -3- boron therein
Sour Knit-the-brows alcohol esters 4-（3- phenylimidazoles simultaneously [1,2-A] pyrimidine -6- bases）Phenyl boric acid is replaced, and 6,12- dibromo Chrysene use 3,
9- bis- Xiu perylenes replace making raw material, and remaining reagent is unchanged, obtains faint yellow solid compound 26.
Product MS（m/e）：723, elementary analysis（C54H33N3）：Theoretical value C：89.60%, H：4.59%, N：5.81%；It is real
Measured value C：89.62%, H：4.60%, N：5.78%.
Embodiment 27
The synthesis of compound 27
Building-up process is allocated as two steps, and the first step is same as the second step of embodiment 1, simply by raw material 6- chlorine imidazos therein
[1,2-A] pyrimidine -3- boric acid Knit-the-brows alcohol esters are replaced with 8- chlorine imidazo [1,2-A] pyrazine -3- boric acid Knit-the-brows alcohol esters, and 6,12- bis-
Bromine Chrysene uses the bromine perylenes of 3,9- bis- to replace making raw material, obtains two chloromethylated intermediates；Second step is same as the second step of embodiment 1, simply
By raw material 6- chlorine imidazo [1,2-A] pyrimidine -3- boric acid Knit-the-brows alcohol esters 4- therein（1- naphthyls）Phenyl boric acid Knit-the-brows alcohol ester generations
Replace, 6,12- dibromo Chrysene replace making raw material with the here first two obtained chloromethylated intermediates, and remaining reagent is unchanged, obtains light
Yellow solid compound 27.
Product MS（m/e）：890, elementary analysis（C64H38N6）：Theoretical value C：86.27%, H：4.30%, N：9.43%；It is real
Measured value C：86.25%, H：4.27%, N：9.48%.
Embodiment 28
The synthesis of compound 28
Building-up process is same as the second step of embodiment 1, simply by raw material 6- chlorine imidazo [1,2-A] pyrimidine -3- boron therein
Sour Knit-the-brows alcohol esters 4-（Imidazo [1,2-A] pyrazine -3- bases）Phenyl boric acid is replaced, 6,12- dibromo Chrysene 2,7- dibromos
Triphenylene replaces making raw material, and remaining reagent is unchanged, obtains faint yellow solid compound 28.
Product MS（m/e）：614, elementary analysis（C42H26N6）：Theoretical value C：82.06%, H：4.26%, N：13.67%；
Measured value C：82.03%, H：4.24%, N：13.73%.
Embodiment 29
The synthesis of compound 29
Building-up process is allocated as two steps, and the first step is same as the second step of embodiment 1, simply by a kind of raw material 6 therein, 12- bis-
Bromine Chrysene uses 2,7- dibromos triphenylene to replace making raw material, obtains two chloromethylated intermediates；Second step is same as the second step of embodiment 1,
Simply raw material 6- chlorine imidazo [1,2-A] pyrimidine -3- boric acid Knit-the-brows alcohol esters therein are replaced with 4- biphenylboronic acid Knit-the-brows alcohol esters,
Two chloromethylated intermediates that 6,12- dibromo Chrysene are obtained with the first step here replace making raw material, and remaining reagent is unchanged, obtain yellowish
Color solid chemical compound 29.
Product MS（m/e）：766, elementary analysis（C54H34N6）：Theoretical value C：84.57%, H：4.47%, N：10.96%；
Measured value C：84.59%, H：4.43%, N：10.98%.
Embodiment 30
The synthesis of compound 30
Building-up process is allocated as two steps, and the first step is same as the second step of embodiment 1, simply by raw material 6- chlorine imidazos therein
[1,2-A] pyrimidine -3- boric acid Knit-the-brows alcohol esters are replaced with 8- chlorine imidazo [1,2-A] pyrazine -3- boric acid Knit-the-brows alcohol esters, and 6,12- bis-
Bromine Chrysene uses 2,7- dibromos triphenylene to replace making raw material, obtains two chloromethylated intermediates；Second step is same as the second step of embodiment 1,
Simply by raw material 6- chlorine imidazo [1,2-A] pyrimidine -3- boric acid Knit-the-brows alcohol esters 4- therein（1- naphthyls）Phenyl boric acid Knit-the-brows alcohol
Ester is replaced, and 6,12- dibromo Chrysene replace making raw material with the here first two obtained chloromethylated intermediates, and remaining reagent is unchanged, obtains
To slightly yellow solid chemical compound 30.
Product MS（m/e）：749, elementary analysis（C56H35N3）：Theoretical value C：89.69%, H：4.70%, N：5.61%；It is real
Measured value C：89.65%, H：4.71%, N：5.64%.
Embodiment 31
The synthesis of compound 31
Building-up process is allocated as two steps, and the first step is same as the second step of embodiment 1, simply by raw material 6- chlorine imidazos therein
[1,2-A] pyrimidine -3- boric acid Knit-the-brows alcohol esters 4-（1- naphthyls）Phenyl boric acid Knit-the-brows alcohol esters are replaced, and 6,12- dibromo Chrysene are used
2,7- dibromo triphenylenes replace making raw material, obtain monobromo intermediate；Second step is same as the second step of embodiment 1, simply will be therein
Raw material 6- chlorine imidazo [1,2-A] pyrimidine -3- boric acid Knit-the-brows alcohol esters 4-（Imidazo [1,2-A] pyrazine -2- bases）Phenyl boric acid Knit-the-brows
Alcohol ester is replaced, and the monobromo intermediate that 6,12- dibromo Chrysene are synthesized with the first step here replaces making raw material, and remaining reagent is not
Become, obtain slightly yellow solid chemical compound 31.
Product MS（m/e）：623, elementary analysis（C46H29N3）：Theoretical value C：88.58%, H：4.69%, N：6.73%；It is real
Measured value C：88.62%, H：4.68%, N：6.70%.
Embodiment 32
The synthesis of compound 32
Building-up process is allocated as two steps, and the first step is same as the second step of embodiment 1, simply by raw material 6- chlorine imidazos therein
[1,2-A] pyrimidine -3- boric acid Knit-the-brows alcohol esters 4-（6- chlorine imidazo [1,2-A] pyrimidin-3-yl）Phenyl boric acid Knit-the-brows alcohol esters are replaced,
6,12- dibromo Chrysene use 2,7- dibromos triphenylene to replace making raw material, obtain two chloromethylated intermediates；Second step is same as embodiment 1
Second step, simply by raw material 6- chlorine imidazo [1,2-A] pyrimidine -3- boric acid Knit-the-brows alcohol esters therein with phenyl boric acid Knit-the-brows alcohol ester generations
Replace, two chloromethylated intermediates that 6,12- dibromo Chrysene are synthesized with the first step here replace making raw material, and remaining reagent is unchanged, obtains
Slightly yellow solid chemical compound 32.
Product MS（m/e）：766, elementary analysis（C54H34N6）：Theoretical value C：84.57%, H：4.47%, N：10.96%；
Measured value C：84.54%, H：4.46%, N：11.00%.
Embodiment 33
The synthesis of compound 33
Building-up process is allocated as two steps, and the first step is same as the second step of embodiment 1, simply by raw material 6- chlorine imidazos therein
[1,2-A] pyrimidine -3- boric acid Knit-the-brows alcohol esters are replaced with 8- chlorine imidazo [1,2-A] pyrazine -3- boric acid Knit-the-brows alcohol esters, and 6,12- bis-
Bromine Chrysene uses 2,7- dibromos triphenylene to replace making raw material, obtains two chloromethylated intermediates；Second step is same as the second step of embodiment 1,
Simply raw material 6- chlorine imidazo [1,2-A] pyrimidine -3- boric acid Knit-the-brows alcohol esters therein are replaced with 4- biphenylboronic acid Knit-the-brows alcohol esters,
Two chloromethylated intermediates that 6,12- dibromo Chrysene are synthesized with the first step here replace making raw material, and remaining reagent is unchanged, obtain micro- Huang
Color solid chemical compound 33.
Product MS（m/e）：766, elementary analysis（C54H34N6）：Theoretical value C：84.57%, H：4.47%, N：10.96%；
Measured value C：84.55%, H：4.48%, N：10.97%.
Embodiment 34
The synthesis of compound 34
Building-up process is allocated as two steps, and the first step is same as the second step of embodiment 1, simply by raw material 6- chlorine imidazos therein
[1,2-A] pyrimidine -3- boric acid Knit-the-brows alcohol esters are replaced with 8- chlorine imidazo [1,2-A] pyrazine -3- boric acid Knit-the-brows alcohol esters, and 6,12- bis-
Bromine Chrysene uses 2,7- dibromos phenanthrene to replace making raw material, obtains two chloromethylated intermediates；Second step is same as the second step of embodiment 1, simply
Raw material 6- chlorine imidazo [1,2-A] pyrimidine -3- boric acid Knit-the-brows alcohol esters therein are replaced with 4- biphenylboronic acid Knit-the-brows alcohol esters, 6,
Two chloromethylated intermediates that 12- dibromos Chrysene is obtained with the first step here replace making raw material, and remaining reagent is unchanged, obtain slightly yellow
Solid chemical compound 34.
Product MS（m/e）：716, elementary analysis（C50H32N6）：Theoretical value C：83.78%, H：4.50%, N：11.72%；
Measured value C：83.75%, H：4.51%, N：11.74%.
Embodiment 35
The synthesis of compound 35
Building-up process is allocated as two steps, and the first step is same as the second step of embodiment 1, simply by raw material 6- chlorine imidazos therein
[1,2-A] pyrimidine -3- boric acid Knit-the-brows alcohol esters are replaced with 4- (6- chlorine imidazo [1,2-A] pyrimidin-3-yl) phenyl boric acid Knit-the-brows alcohol esters,
6,12- dibromo Chrysene use 2,7- dibromos phenanthrene to replace making raw material, obtain two chloromethylated intermediates；Second step is same as embodiment 1 second
Step, simply replaces raw material 6- chlorine imidazo [1,2-A] pyrimidine -3- boric acid Knit-the-brows alcohol esters therein with phenyl boric acid Knit-the-brows alcohol esters,
Two chloromethylated intermediates that 6,12- dibromo Chrysene are obtained with the first step here replace making raw material, and remaining reagent is unchanged, obtain micro- Huang
Color solid chemical compound 35.
Product MS（m/e）：716, elementary analysis（C50H32N6）：Theoretical value C：83.78%, H：4.50%, N：11.72%；
Measured value C：83.79%, H：4.52%, N：11.69%.
Embodiment 36
The synthesis of compound 36
Building-up process is allocated as two steps, and the first step is same as the second step of embodiment 1, simply by raw material 6 therein, 12- dibromos
Chrysene uses 2,7- dibromos phenanthrene to replace making raw material, obtains two chloromethylated intermediates；Second step is same as the second step of embodiment 1, simply will
Raw material 6- chlorine imidazo [1,2-A] pyrimidine -3- boric acid Knit-the-brows alcohol esters therein are replaced with 4- biphenylboronic acid Knit-the-brows alcohol esters, and 6,12-
Two chloromethylated intermediates that dibromo Chrysene is obtained with the first step here replace making raw material, and remaining reagent is unchanged, obtain slightly yellow solid
Body compound 36.
Product MS（m/e）：716, elementary analysis（C50H32N6）：Theoretical value C：83.78%, H：4.50%, N：11.72%；
Measured value C：83.80%, H：4.53%, N：11.67%.
Embodiment 37
The synthesis of compound 37
Building-up process is allocated as two steps, and the first step is same as the second step of embodiment 1, simply by raw material 6- chlorine imidazos therein
[1,2-A] pyrimidine -3- boric acid Knit-the-brows alcohol esters are replaced with 8- chlorine imidazo [1,2-A] pyrazine -3- boric acid Knit-the-brows alcohol esters, and 6,12- bis-
Bromine Chrysene uses 2,7- dibromos phenanthrene to replace making raw material, obtains two chloromethylated intermediates；Second step is same as the second step of embodiment 1, simply
By raw material 6- chlorine imidazo [1,2-A] pyrimidine -3- boric acid Knit-the-brows alcohol esters 4- therein（1- naphthyls）Phenyl boric acid Knit-the-brows alcohol ester generations
Replace, two chloromethylated intermediates that 6,12- dibromo Chrysene are obtained with the first step here replace making raw material, and remaining reagent is unchanged, obtains
Slightly yellow solid chemical compound 37.
Product MS（m/e）：699, elementary analysis（C52H33N3）：Theoretical value C：89.24%, H：4.75%, N：6.01%；It is real
Measured value C：89.21%, H：4.74%, N：6.05%.
Embodiment 38
The synthesis of compound 38
The first step,
In one 500 milliliters of there-necked flasks, with magnetic agitation, the bromo- 6- chlorine miaows of 3- are added by above-mentioned amount successively after nitrogen displacement
Azoles simultaneously [1,2-a] pyrimidine 9.24g（Molecular weight 231,0.040mol）、THF230ml.Butyl lithium 20ml is added dropwise at -78 DEG C（It is dense
Spend 2.5M, 0.05mol）, after stirring 10 minutes, add benzo anthraquinone 4.9g（Molecular weight 258,0.019mol）.It is natural after adding
Room temperature is warming up to, solution is in dark yellow.The hydrolysis of 200ml water is added, is extracted with ethyl acetate, solvent evaporated.Add acetic acid
300ml, KI and each 30g of sodium hypophosphite, backflow.Reaction 2 hours, cooling, cooling is filtered out, and obtains dark yellow solid product.With 15/
100 water/THF boils 1 hour, lets cool and filters out, repeated multiple times, obtains 4.26g dark yellow solid products, molecular weight 530, purity
95.0%, yield 40.2%.It is a collection of by this scaling synthesis, so that the next step needs.
Second step,
In the there-necked flask of a 1000ml, with mechanical agitation, Ar gas shieldeds add the dichloro- intermediate of first step generation
7.95g（Molecular weight 530,0.015mol）, 4- biphenylboronic acid Knit-the-brows alcohol esters 9.24g（Molecular weight 280,0.033mol）, catalyst
Pd(PPh3)4Consumption 1.8g（Molecular weight 1154,0.001556mol）, aqueous sodium carbonate 120ml（2M）, toluene 300ml, ethanol
150ml.It is stirred at reflux, is monitored and reacted with TLC, reacts complete after coreaction 5hs.Cooling, separates, is evaporated, use column chromatography methods
Separation product, eluent uses 1：1 ethyl acetate：Petroleum ether, obtains 9.32g dark yellow solids compound 38.Purity 99.2%,
Yield：80.5%.
Product MS（m/e）：766, elementary analysis（C54H34N6）：Theoretical value C：84.57%, H：4.47%, N：10.96%；
Measured value C：84.55%, H：4.46%, N：10.99%.
Embodiment 39
The synthesis of compound 39
Building-up process is divided into two steps, and the first step is same as the first step of embodiment 38, simply by the bromo- 6- chlorine imidazos of raw material 3-
[1,2-a] pyrimidine 4-（6- chlorine imidazo [1,2-a] pyrimidin-3-yl）Bromobenzene is replaced, and obtains two chloromethylated intermediates；Second step is synthesized
The second step of embodiment 1 is same as, the first step is same as the second step of embodiment 1, it is simply that raw material 6- chlorine imidazo [1,2-A] therein is phonetic
Pyridine -3- boric acid Knit-the-brows alcohol esters are replaced with phenyl boric acid Knit-the-brows alcohol esters, 6,12- dibromo Chrysene synthesized with the first step here two
Chloromethylated intermediate replaces making raw material, obtains yellow solid compound 39.
Product MS（m/e）：766, elementary analysis（C54H34N6）：Theoretical value C：84.57%, H：4.47%, N：10.96%；
Measured value C：84.59%, H：4.46%, N：10.95%.
Embodiment 40
The synthesis of compound 40
Building-up process is same as the first step of embodiment 38, simply by bromo- 6- chlorine imidazo [1,2-a] the pyrimidine 4- of raw material 3-
（2-（P-methylphenyl）Imidazo [1,2-a] pyrimidine -6- bases）Bromobenzene is replaced, and obtains yellow solid compound 40.
Product MS（m/e）：794, elementary analysis（C56H38N6）：Theoretical value C：84.61%, H：4.82%, N：10.57%；
Measured value C：84.64%, H：4.80%, N：10.56%.
Embodiment 41
The Application Example of each compound of the present invention
Compare the transmission performance of these electron transport materials for convenience, the present invention devises a simple electroluminescence device,
Use CBP doping Ir (ppy)3As luminescent material, using efficent electronic transmission material Bphen as comparing material, Bphen,
CBP and Ir (ppy)3Structure be respectively:
The structure of organic electroluminescence device is in the embodiment of the present invention：
Substrate/anode/hole transmission layer（HTL）/ organic luminous layer（EL）/ electron transfer layer (ETL)/negative electrode.
Substrate can use the substrate in conventional organic luminescence device, for example：Glass or plastics.In the Organic Electricity of the present invention
Electroluminescence device selects glass substrate in making, and ITO makees anode material.
Hole transmission layer can use various tri-arylamine group materials.The institute in the organic electroluminescence device of the present invention makes
The hole mobile material of selection is NPB.
Negative electrode can use metal and its mixture structure, such as Mg：Ag、Ca：Ag etc. or electron injecting layer/gold
Belong to Rotating fields, such as LiF/Al, Li2The common cathode structure such as O/Al.It is selected in the organic electroluminescence device of the present invention makes
Cathode material is LiF/Al.
Embodiment 42
Compound in the present embodiment is as the electron transport material in organic electroluminescence device, and EML is used as luminescent layer
Material, is prepared for multiple organic electroluminescence devices altogether, and its structure is：ITO/NPB（40nm）/CBP:Ir(ppy)3(30nm)/
ETL materials（20nm）/LiF（0.5nm）/Al（150nm）；
One contrast organic electroluminescence device, electron transport material selects Bphen, the choosing of remaining organic electroluminescence device
With the material of the present invention.
Organic electroluminescence device preparation process is as follows in the present embodiment：
The glass plate of transparent conductive layer will be coated with ultrasonically treated in commercial detergent, rinsed in deionized water,
In acetone：Ultrasonic oil removing in alcohol mixed solvent, is baked under clean environment and removes moisture content completely, clear with ultraviolet light and ozone
Wash, and with low energy cation beam bombarded surface；
The above-mentioned glass substrate with anode is placed in vacuum chamber, 1 × 10 is evacuated to-5~9 × 10-3Pa, above-mentioned
Vacuum evaporation NPB is as hole transmission layer on anode tunic, and evaporation rate is 0.1nm/s, and evaporation thickness is 40nm；
Method the vacuum evaporation CBP and Ir (ppy) 3 steamed altogether using double source on hole transmission layer is as the luminous of device
Layer, CBP evaporation rates are 0.1nm/s, Ir (ppy)3Evaporation rate is 0.015nm/s, and evaporation total film thickness is 30nm；
The stratification compound 1,6,9,11,18,22,23,29,34,39 of vacuum evaporation one or Bphen are used as device on luminescent layer
The electron transfer layer of part, its evaporation rate is 0.1nm/s, and evaporation total film thickness is 20nm；
In electron transfer layer（ETL）Upper vacuum evaporation thickness for 0.5nm LiF as electron injecting layer, thickness is 150nm
Al layers as device negative electrode.
Organic electroluminescence device performance see the table below：
| Compound number | It is required that brightness cd/m2 | Voltage V | Current density A/m2 | Current efficiency cd/A |
| Bphen | 5000.00 | 5.7 | 155.28 | 32.2 |
| 1 | 5000.00 | 5,2 | 137.36 | 36.4 |
| 6 | 5000.00 | 5,1 | 142.45 | 35.1 |
| 9 | 5000.00 | 5.3 | 134.05 | 37.3 |
| 11 | 5000.00 | 5.0 | 138.12 | 36.2 |
| 18 | 5000.00 | 4.9 | 126.90 | 39.4 |
| 22 | 5000.00 | 5.0 | 123.45 | 40.5 |
| 23 | 5000.00 | 5.4 | 117.92 | 42.4 |
| 29 | 5000.00 | 5.1 | 134.77 | 37.1 |
| 34 | 5000.00 | 5.3 | 127.22 | 39.3 |
| 39 | 5000.00 | 5.2 | 135.87 | 36.8 |
Result above shows that new organic materials of the invention are used for organic electroluminescence device, can effectively reduce
Landing voltage, improves current efficiency, is electron transport material of good performance.
Although the present invention is described in conjunction with the embodiments, the invention is not limited in above-described embodiment, it should manage
Solution, under the guiding of present inventive concept, those skilled in the art can carry out various modifications and improvements, and appended claims are summarised
The scope of the present invention.
Claims (4)
1. a kind of organic compound, it is characterised in that the organic compound is selected from following structural formula：
2. application of the organic compound described in claim 1 in organic electroluminescence device.
3. application according to claim 2, it is characterised in that the organic compound is used as electron transport material.
4. a kind of organic electroluminescence device, including substrate, and sequentially form anode layer, organic light emission on the substrate
Functional layer and cathode layer；Described organic luminescence function layer includes hole transmission layer, organic luminous layer and electron transfer layer, its
It is characterised by：
The electron transport material of the electron transfer layer is one or more organic compounds as claimed in claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310733664.4A CN104650117B (en) | 2013-12-26 | 2013-12-26 | A kind of organic compound and its application in organic electroluminescence device |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310733664.4A CN104650117B (en) | 2013-12-26 | 2013-12-26 | A kind of organic compound and its application in organic electroluminescence device |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104650117A CN104650117A (en) | 2015-05-27 |
| CN104650117B true CN104650117B (en) | 2017-08-01 |
Family
ID=53241806
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310733664.4A Active CN104650117B (en) | 2013-12-26 | 2013-12-26 | A kind of organic compound and its application in organic electroluminescence device |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104650117B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111925366B (en) * | 2019-05-13 | 2024-04-09 | 广东阿格蕾雅光电材料有限公司 | An imidazolyl nitrogen heterocyclic compound and its application |
| CN115322189B (en) * | 2021-09-28 | 2023-11-28 | 四川阿格瑞新材料有限公司 | Spiro compound and application thereof |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101219987A (en) * | 2003-01-10 | 2008-07-16 | 出光兴产株式会社 | Nitrogen-containing heterocyclic derivative and organic electroluminescent device using the same |
| CN101265260A (en) * | 2007-03-13 | 2008-09-17 | 三星Sdi株式会社 | Imidazopyrimidine compound and organic light-emitting device using organic layer containing same |
| CN101291582A (en) * | 2005-09-02 | 2008-10-22 | 艾博特公司 | Novel imidazo based heterocycles |
| US20090153035A1 (en) * | 2007-06-15 | 2009-06-18 | Jung-Han Shin | Heteroaromatic cycle-containing compound, method of preparing the same and organic light emitting device comprising the same |
| CN101656300A (en) * | 2008-08-18 | 2010-02-24 | 三星移动显示器株式会社 | Organic light emitting diode including light-efficiency-improvement layer |
| CN102473856A (en) * | 2010-04-12 | 2012-05-23 | 出光兴产株式会社 | Organic electroluminescent element |
| US20120286246A1 (en) * | 2011-05-13 | 2012-11-15 | Samsung Mobile Display Co., Ltd. | Condensed-cyclic compound, organic light-emitting device comprising the same, and flat panel display apparatus |
| US20130299794A1 (en) * | 2010-12-31 | 2013-11-14 | Ho-Kuk Jung | Compound for organic optoelectronic device, organic light emitting diode including the same and display including the organic light emitting diode |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4025468B2 (en) * | 1999-07-29 | 2007-12-19 | 三井化学株式会社 | Organic electroluminescence device |
| EP2463352B1 (en) * | 2005-09-08 | 2018-05-02 | Toray Industries, Inc. | Light emitting device material and light emitting device |
| JP5076328B2 (en) * | 2006-02-06 | 2012-11-21 | 東レ株式会社 | Light emitting element |
| JP5006606B2 (en) * | 2006-09-13 | 2012-08-22 | 双葉電子工業株式会社 | COMPOUND FOR ORGANIC EL ELEMENT AND ORGANIC EL ELEMENT |
| JP2009096771A (en) * | 2007-10-18 | 2009-05-07 | Mitsubishi Chemicals Corp | Diarylpyrene compound, material for organic electroluminescent device, composition for organic electroluminescent device, and organic electroluminescent device |
| JP2010195708A (en) * | 2009-02-25 | 2010-09-09 | Toyo Ink Mfg Co Ltd | Compound having carbazolyl group and use thereof |
| KR101375361B1 (en) * | 2010-12-30 | 2014-03-27 | (주)씨에스엘쏠라 | Organic light compound and organic light device using the same |
| KR20120096382A (en) * | 2011-02-22 | 2012-08-30 | (주)씨에스엘쏠라 | Organic light compound and organic light device using the same |
-
2013
- 2013-12-26 CN CN201310733664.4A patent/CN104650117B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101219987A (en) * | 2003-01-10 | 2008-07-16 | 出光兴产株式会社 | Nitrogen-containing heterocyclic derivative and organic electroluminescent device using the same |
| CN101291582A (en) * | 2005-09-02 | 2008-10-22 | 艾博特公司 | Novel imidazo based heterocycles |
| CN101265260A (en) * | 2007-03-13 | 2008-09-17 | 三星Sdi株式会社 | Imidazopyrimidine compound and organic light-emitting device using organic layer containing same |
| US20090153035A1 (en) * | 2007-06-15 | 2009-06-18 | Jung-Han Shin | Heteroaromatic cycle-containing compound, method of preparing the same and organic light emitting device comprising the same |
| CN101656300A (en) * | 2008-08-18 | 2010-02-24 | 三星移动显示器株式会社 | Organic light emitting diode including light-efficiency-improvement layer |
| CN102473856A (en) * | 2010-04-12 | 2012-05-23 | 出光兴产株式会社 | Organic electroluminescent element |
| US20130299794A1 (en) * | 2010-12-31 | 2013-11-14 | Ho-Kuk Jung | Compound for organic optoelectronic device, organic light emitting diode including the same and display including the organic light emitting diode |
| US20120286246A1 (en) * | 2011-05-13 | 2012-11-15 | Samsung Mobile Display Co., Ltd. | Condensed-cyclic compound, organic light-emitting device comprising the same, and flat panel display apparatus |
Non-Patent Citations (3)
| Title |
|---|
| Bioisosteric Transformations and Permutations in the Triazolopyrimidine Scaffold To Identify the Minimum Pharmacophore Required for Inhibitory Activity against Plasmodium falciparum Dihydroorotate Dehydrogenase;Alka Marwaha, 等;《Journal of Medicinal Chemistry》;20120809;第55卷(第17期);图3，化合物6 * |
| Direct Arylation Reactions Catalyzed by Pd(OH)2/C: Evidence for a Soluble Palladium Catalyst;Mathieu Parisien, 等;《Journal of Organic Chemistry》;20050812;第70卷(第19期);第7581页，表2，化合物30 * |
| Nucleophilic substitutions of 5-chloro-7-methyl-2-phenylimidazo[1,2-a-] pyrimidines;vo Theodor Pyl, 等;《Justus Liebigs Annalen der Chemie》;19661231;第699卷;第129页，表1，化合物Nr.l * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104650117A (en) | 2015-05-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101407493B (en) | A kind of organic material and its application in organic electroluminescence device | |
| CN103183638B (en) | One compounds, its method for making and the organic electroluminescence device containing it | |
| CN104650032B (en) | A kind of acridine derivatives, its preparation method and its application | |
| CN104673276B (en) | A kind of luminous organic material and its application | |
| CN103664906B (en) | A kind of 6,6-dimethyl-6H-benzo [cd] pyrene derivatives and application thereof | |
| CN104650116B (en) | A kind of organic compound and its application in organic electroluminescence device | |
| CN103665014B (en) | 6-trimethylphenyl-6H-6-boroheterobenzo[cd]pyrene derivatives and application thereof | |
| CN103570629A (en) | Benzanthracene derivatives containing pyrimidinyl, pyrazinyl or triazinyl groups and applications thereof | |
| CN103664894A (en) | 6H-naphtho-[2,1,8,7-klmn]Ar derivatives and application thereof | |
| CN110526901A (en) | A kind of luminous organic material and its application for preparing organic electroluminescence device | |
| CN103570627B (en) | A kind of indenofluorene analog derivative and application containing pyrimidine or pyrazine or triazine group | |
| CN112079841A (en) | Organic compound, electroluminescent material and application thereof | |
| CN106554319A (en) | A kind of * analog derivatives containing quinazoline group and its application | |
| CN107652272A (en) | It is a kind of using ketone structure as the organic compound of parent nucleus and its application in OLED | |
| CN104649954B (en) | A kind of phenanthro- carbazole derivates and its application in organic electroluminescence device | |
| CN104650089B (en) | A kind of fluorene kind derivative of base group containing carbazole 9 and its application | |
| CN104650117B (en) | A kind of organic compound and its application in organic electroluminescence device | |
| CN109651435A (en) | A kind of bipolarity organic photoelectric functional material and preparation method | |
| CN109705126A (en) | A kind of compound and application for organic electroluminescence device | |
| Huang et al. | Efficient orange-red thermally activated delayed fluorescence material containing a cyano group | |
| CN110526905A (en) | A kind of compound containing ketone and its application on organic electroluminescence device | |
| CN109748880A (en) | The compound and its application on organic electroluminescence device of a kind of fluorenes of dimethylanthracene containing spiral shell and nitrogenous hexa-member heterocycle | |
| CN104513192B (en) | A kind of benzo anthra [9,1-bc] carbazole derivates and its application | |
| CN104650090B (en) | A kind of fluorene kind derivative of the bases of -3- containing carbazole group and its application | |
| CN110396051A (en) | A kind of organic small molecule hole injection/transport material and its preparation method and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| ASS | Succession or assignment of patent right |
Owner name: GU'AN ETERNAL MATERIAL TECHNOLOGY CO., LTD. Effective date: 20150630 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20150630 Address after: 100192 Beijing city Haidian District West Road No. 66 small Zhongguancun Dongsheng Technology Park North Territory D District No. 2 Building 3 layer Applicant after: BEIJING ETERNAL MATERIAL TECHNOLOGY CO., LTD. Applicant after: GU'AN ETERNAL MATERIAL TECHNOLOGY CO., LTD. Address before: 100192 Beijing city Haidian District West Road No. 66 small Zhongguancun Dongsheng Technology Park North Territory D District No. 2 Building 3 layer Applicant before: BEIJING ETERNAL MATERIAL TECHNOLOGY CO., LTD. |
|
| TA01 | Transfer of patent application right |
Effective date of registration: 20170612 Address after: 100192 Beijing city Haidian District West Road No. 66 small Zhongguancun Dongsheng Technology Park North Territory D District No. 2 Building 3 layer Applicant after: BEIJING ETERNAL MATERIAL TECHNOLOGY CO., LTD. Address before: 100192 Beijing city Haidian District West Road No. 66 small Zhongguancun Dongsheng Technology Park North Territory D District No. 2 Building 3 layer Applicant before: BEIJING ETERNAL MATERIAL TECHNOLOGY CO., LTD. Applicant before: GU'AN ETERNAL MATERIAL TECHNOLOGY CO., LTD. |
|
| TA01 | Transfer of patent application right | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |