CN106554320A - A kind of condensed-nuclei aromatics derivant of quinoxaline group and its application - Google Patents
A kind of condensed-nuclei aromatics derivant of quinoxaline group and its application Download PDFInfo
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- WIHHVKUARKTSBU-UHFFFAOYSA-N Nc(c(N)c1)ccc1Br Chemical compound Nc(c(N)c1)ccc1Br WIHHVKUARKTSBU-UHFFFAOYSA-N 0.000 description 1
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D241/00—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings
- C07D241/36—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings condensed with carbocyclic rings or ring systems
- C07D241/38—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings condensed with carbocyclic rings or ring systems with only hydrogen or carbon atoms directly attached to the ring nitrogen atoms
- C07D241/40—Benzopyrazines
- C07D241/42—Benzopyrazines with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the hetero ring
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- C07D241/36—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings condensed with carbocyclic rings or ring systems
- C07D241/38—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings condensed with carbocyclic rings or ring systems with only hydrogen or carbon atoms directly attached to the ring nitrogen atoms
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D241/00—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings
- C07D241/36—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings condensed with carbocyclic rings or ring systems
- C07D241/38—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings condensed with carbocyclic rings or ring systems with only hydrogen or carbon atoms directly attached to the ring nitrogen atoms
- C07D241/40—Benzopyrazines
- C07D241/44—Benzopyrazines with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to carbon atoms of the hetero ring
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- H10K85/60—Organic compounds having low molecular weight
- H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
- H10K85/622—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing four rings, e.g. pyrene
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- H—ELECTRICITY
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- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
- H10K85/623—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing five rings, e.g. pentacene
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- 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
- H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
- H10K85/626—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing more than one polycyclic condensed aromatic rings, e.g. bis-anthracene
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- H—ELECTRICITY
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- 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
Abstract
The present invention relates to a kind of condensed-nuclei aromatics derivant containing quinoxaline group, such compound is with the structure as shown in formula (1).The condensed-nuclei aromatics derivant containing quinoxaline group of the present invention, is suitable for making ETL materials in electroluminescent display.The use of material of the present invention, can effectively reduce the running voltage of organic electroluminescence device, and improve the luminous efficiency of organic electroluminescence device.
Description
Technical field
The invention belongs to field of organic electroluminescence, and in particular to a kind of condensed-nuclei aromatics derivant containing quinoxaline group and its
Application in electron transport material.
Background technology
The electron transport material that tradition is used in electroluminescent device is Alq3, but Alq3Electron mobility it is (bigger than relatively low
About in 10-6cm2/Vs).In order to improve the electronic transmission performance of electroluminescent device, research worker has done substantial amounts of exploration
Research work.
LG chemistry reports a series of derivant of pyrenes in CN 101003508A, is used as electronics biography in electroluminescence device
Defeated and injection material, improves the luminous efficiency of device.Cao Yong et al. synthesizes FFF-Blm4 (J.Am.Chem.Soc.；
(Communication)；2008；130(11)；3282-3283) as electric transmission and injection layer material (with Ba/Al and independent
Compared as negative electrode with Al), electron injection and the transmission of device are significantly improved, electroluminescence efficiency is improve.Kodak
Company mentions mixed electronic transmission in United States Patent (USP) (publication number US 2006/0204784 and US 2007/0048545)
Layer, it is such as golden with the electron transport material and other materials of another kind of low bright voltage using a kind of material of low lumo energy
The doping such as category material are formed.Based on the device of this mixed electronic transport layer, it is improved device efficiency, but increased device
The complexity of part manufacturing process, is unfavorable for reducing OLED costs.The electron transport material and/or electronics of exploitation stability and high efficiency
Injection material, plays bright and running voltage so as to reduce device, improves device efficiency, extend device lifetime, with critically important
Actual application value.
The content of the invention
It is an object of the invention to propose the new condensed-nuclei aromatics derivant containing quinoxaline group of a class, such compound can use
Make electron transport material, the use of material of the present invention can effectively reduce the running voltage of organic electroluminescence device, and carry
The luminous efficiency of high organic electroluminescence device.
For achieving the above object, the technical scheme that the present invention takes is as follows：
A kind of condensed-nuclei aromatics derivant containing quinoxaline group, with the structure shown in formula (1)：
Wherein：Ar is selected from C10-C50Condensed-nuclei aromatics group or condensed hetero ring aromatic hydrocarbon group；
L is selected from singly-bound, substituted or unsubstituted arlydene, substituted or unsubstituted sub- heterocyclic aryl.
R1And R2It is identical or different, it is respectively and independently selected from H, aryl, heterocyclic arene base, condensed-nuclei aromatics base, or condensed hetero ring
Aryl, substituted or unsubstituted alkyl, cyano group；R1And R2Cyclization can be also connected with each other, becomes aromatic ring or aliphatic ring.
Preferably, the Ar is group shown in formula (2) to formula (6)：
Wherein, Ar1And Ar2It is identical or different, it is respectively and independently selected from H, C4-C30Aromatic ring yl, heteroaryl ring group, condensed-nuclei aromatics
Base or condensed hetero ring aryl；
R3To R10It is identical or different, it is respectively and independently selected from H, aryl, heterocyclic arene base, condensed-nuclei aromatics base, or condensed hetero ring
Aryl, substituted or unsubstituted alkyl, cyano group.
It is further preferred that the compound is structure shown in formula (7) to formula (11)：
Wherein, Ar1And Ar2It is identical or different, H is independently selected from, is replaced or unsubstituted C4-C30Aromatic ring yl, heteroaryl ring group,
Replace or unsubstituted condensed-nuclei aromatics base or condensed hetero ring aryl；
L is singly-bound, substituted or unsubstituted arlydene, substituted or unsubstituted sub- heterocyclic aryl；
R3To R10It is identical or different, H is respectively and independently selected from, is replaced or unsubstituted aryl, replaced or unsubstituting heterocycle aromatic hydrocarbons
Base, replaces or unsubstituted condensed-nuclei aromatics base or condensed hetero ring aryl, substituted or unsubstituted alkyl, cyano group.
Preferably, the unsubstituted alkyl is methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl group, Zhong Ding
Base, the tert-butyl group, 2- Methylethyls, amyl group or cyclohexyl；
The substituted alkyl is trifluoromethyl；
The replacement or unsubstituted aryl are phenyl, o-tolyl, p-methylphenyl, tert-butyl-phenyl etc..Replace or do not take
It is furan, benzofuran, dibenzofurans, thiophene, benzothiophene, dibenzothiophenes, carbazole, pyrrole for heterocyclic arene base
Pyridine, pyrazine, 2.4- methyl isophthalic acid .3.5 triazines, 4.6 diphenylpyrimidins；
The replacement or unsubstituted condensed-nuclei aromatics base are naphthyl, phenanthryl, anthryl, pyrenyl, 9.9- dimethyl -2- fluorenyls.Take
Generation or unsubstituted condensed hetero ring aryl be quinoline, after isoquinolin or quinazoline.
Described above being substituted by is monosubstituted or polysubstituted.
The compound is preferably formula (12)-structure shown in (54)：
A kind of application of described condensed-nuclei aromatics derivant containing quinoxaline group in organic electroluminescence device.
The condensed-nuclei aromatics derivant containing quinoxaline group can be used as electron transport material.
A kind of organic electroluminescence device, including substrate, and sequentially form anode layer on the substrate, organic light emission
Functional layer and cathode layer；The 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 the described condensed-nuclei aromatics derivant containing quinoxaline group.
Compared with prior art, the advantage of the condensed-nuclei aromatics derivant of quinoxaline group of the invention is：
The condensed-nuclei aromatics derivant of the quinoxaline group of the present invention belongs to typical short of electricity subsystem, with suitable HOMO
And lumo energy, thus receive electronic capability with good.Coplanar condensed-nuclei aromatics system on space structure,
With good electron transfer capabilities.Therefore the compound of benzacridine class of the present invention, is that the excellent electronics of a class is passed
Defeated material.
Experiment shows, when in the present invention, the condensed-nuclei aromatics derivant of quinoxaline group is used as electron transport material, with Bphen
Compare as electron transport material, the driving voltage of device declines, and effectively reduces device operating voltages, improve lumen effect
Rate, reduces the power consumption of device, is electron transport material of good performance.
Description of the drawings
Fig. 1 for compound shown in formula (14) nuclear magnetic spectrogram (1HNMR)；
Fig. 2 for compound shown in formula (22) nuclear magnetic spectrogram (1HNMR)；
Fig. 3 for compound shown in formula (24) nuclear magnetic spectrogram (1HNMR)；
Fig. 4 for compound shown in formula (26) nuclear magnetic spectrogram (1HNMR)；
Fig. 5 for compound shown in formula (36) nuclear magnetic spectrogram (1HNMR)；
Fig. 6 for compound shown in formula (52) nuclear magnetic spectrogram (1HNMR)。
Specific embodiment
Basic raw material used in the present invention, for example, 4- bromine o-phenylenediamines, diphenylthanedione, 1,2- cyclohexanedione, hexafluoro
Diacetyl, diacetyl, diaminomaleonitrile, the bromo derivative of various anthracenes, the bromo derivative of diphenyl benzofluoranthrene, two
It is the bromo derivative of phenyl fluoranthene, the bromo derivative of various triphenylenes, variousBromo derivative, the bromo of various pyrenes
Derivant, etc., or each big industrial chemicals can be commercially available at home, or can be synthesized with laboratory commonsense method.
Various bromo-derivatives can make corresponding boronic acid compounds with commonsense method.
The condensed-nuclei aromatics derivant containing quinoxaline group of the present invention, with the structure shown in formula (1)：
Wherein：Ar is selected from C10-C50Condensed-nuclei aromatics group or condensed hetero ring aromatic hydrocarbon group；
L is selected from singly-bound, substituted or unsubstituted arlydene, substituted or unsubstituted sub- heterocyclic aryl.
R1And R2It is identical or different, it is respectively and independently selected from H, aryl, heterocyclic arene base, condensed-nuclei aromatics base, or condensed hetero ring
Aryl, substituted or unsubstituted alkyl, cyano group；R1And R2Cyclization can be also connected with each other, becomes aromatic ring or aliphatic ring.
Preferably, the Ar is group shown in formula (2) to formula (6)：
Wherein, Ar1And Ar2It is identical or different, it is respectively and independently selected from H, C4-C30Aromatic ring yl, heteroaryl ring group, condensed-nuclei aromatics
Base or condensed hetero ring aryl；
R3To R10It is identical or different, it is respectively and independently selected from H, aryl, heterocyclic arene base, condensed-nuclei aromatics base, or condensed hetero ring
Aryl, substituted or unsubstituted alkyl, cyano group.Described replacement can be monosubstituted or polysubstituted.
It is further preferred that the compound is structure shown in formula (7) to formula (11)：
Wherein, Ar1And Ar2It is identical or different, H is independently selected from, is replaced or unsubstituted C4-C30Aromatic ring yl, heteroaryl ring group,
Replace or unsubstituted condensed-nuclei aromatics base or condensed hetero ring aryl；
L is singly-bound, substituted or unsubstituted arlydene, substituted or unsubstituted sub- heterocyclic aryl；
R3To R10It is identical or different, H is respectively and independently selected from, is replaced or unsubstituted aryl, replaced or unsubstituting heterocycle aromatic hydrocarbons
Base, replaces or unsubstituted condensed-nuclei aromatics base or condensed hetero ring aryl, substituted or unsubstituted alkyl, cyano group.
Preferably, the unsubstituted alkyl is methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl group, Zhong Ding
Base, the tert-butyl group, 2- Methylethyls, amyl group or cyclohexyl；
The substituted alkyl is trifluoromethyl；
The replacement or unsubstituted aryl are phenyl, o-tolyl, p-methylphenyl, tert-butyl-phenyl etc..Replace or do not take
It is furan, benzofuran, dibenzofurans, thiophene, benzothiophene, dibenzothiophenes, carbazole, pyrrole for heterocyclic arene base
Pyridine, pyrazine, 2.4- methyl isophthalic acid .3.5 triazines, 4.6 diphenylpyrimidins；
The replacement or unsubstituted condensed-nuclei aromatics base are naphthyl, phenanthryl, anthryl, pyrenyl, 9.9- dimethyl -2- fluorenyls.Take
Generation or unsubstituted condensed hetero ring aryl be quinoline, after isoquinolin or quinazoline.
The compound is preferably formula (12)-structure shown in (54)：
A kind of application of described condensed-nuclei aromatics derivant containing quinoxaline group in organic electroluminescence device.
The condensed-nuclei aromatics derivant containing quinoxaline group can be used as electron transport material.
A kind of organic electroluminescence device, including substrate, and sequentially form anode layer on the substrate, organic light emission
Functional layer and cathode layer；The 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 the virtue of the condensed ring containing quinoxaline group described in any one of claim 1-4
Hydrocarbon derivative.
The synthesis of 1 various quinoxaline boronic acid derivatives intermediate of embodiment
The synthesis of 1,6- bromo- 2,3- diphenylquinoxalines
3.91 grams of o-phenylenediamine of 4- bromines (molecular weight 186,0.021mol), diphenyl second two are added in 250ml there-necked flasks
4.41 grams of ketone (molecular weight 210,0.021mol), ethanol (40 milliliters), under stirring condition, in 3min, 0.2 gram of Deca is dense
Sulphuric acid, reacts 4 hours at 65 DEG C, after reaction terminates, is cooled to room temperature, filters, successively with 50ml ethanol, 50ml
Petroleum ether, obtains 6.66 grams of bromo- 2, the 3- diphenylquinoxalines of midbody compound 6- (molecular weight 360), yield 88.1%.
2,7- bromo- 1, the synthesis of 2,3,4- tetrahydrochysene azophenlyene
Reactions steps are same as the synthesis of bromo- 2, the 3- diphenylquinoxalines of 6-, and diphenylthanedione is changed to 1,2- cyclohexanediones simply,
Obtain the bromo- 1,2,3,4- tetrahydrochysenes azophenlyene of intermediate 7-.
The synthesis of 3,6- bromo- 2,3- dimethylquinoxalins
Reactions steps are same as the synthesis of bromo- 2, the 3- diphenylquinoxalines of 6-, diphenylthanedione is changed to diacetyl simply, is obtained
The bromo- 2,3- dimethylquinoxalins of intermediate 6-.
The synthesis of 4,6- bromine quinoxalines
Reactions steps are same as the synthesis of bromo- 2, the 3- diphenylquinoxalines of 6-, diphenylthanedione is changed to Biformyl simply, is obtained
Intermediate 6- bromine quinoxalines.
The synthesis of 5,6- bromo- 2,3- bis- (trifluoromethyl) quinoxalines
Reactions steps are same as the synthesis of bromo- 2, the 3- diphenylquinoxalines of 6-, and diphenylthanedione is changed to hexafluoro diacetyl simply,
Obtain bromo- 2,3- bis- (trifluoromethyl) quinoxalines of intermediate 6-.
The synthesis of 6,6- bromo- 2,3- dicyanos quinoxalines
Reactions steps are same as the synthesis of bromo- 2, the 3- diphenylquinoxalines of 6-, and diphenylthanedione is changed to diaminomaleonitrile simply,
Obtain the bromo- 2,3- dicyanos quinoxalines of intermediate 6-.
Embodiment 2
The synthesis of compound shown in formula (12)
1000 milliliters of there-necked flasks, with magnetic agitation, nitrogen protection, add bromo- 2, the 3- dimethylquinoxalins 4.72g (molecules of 6-
Amount 236,0.02mol), 9,10- bis- (naphthalene -2- bases) anthracene -2- boric acid 11.0g (molecular weight 474,0.022mol), four ((three
Phenylphosphine is closed) palladium 1.16g (molecular weight 1154,0.001mol), the aqueous sodium carbonate 80ml of 2M, toluene 80ml,
Ethanol 80ml.After argon displacement, backflow is reacted with the monitoring of thin layer chromatography (TLC) method, and after 4 hours, TLC has found
The reaction of raw material bromo-derivative is complete, only product point.25 DEG C are cooled to, organic layer is separated, are evaporated, pillar layer separation, second
Acetoacetic ester/petroleum ether drip washing, obtains compound shown in 11.7g formulas (12), molecular weight 586, yield 87.4%.
Product MS (m/e)：586, elementary analysiss (C44H30N2)：Theoretical value C：90.07%, H：5.15%, N：
4.77%；Measured value C：90.04%, H：5.13%, N：4.83%.
Embodiment 3
The synthesis of compound shown in formula (13)
Synthesis step is same as embodiment 2, and 6- bromo- 2,3- dimethylquinoxalins are changed into bromo- 1,2,3, the 4- tetrahydrochysene azophenlyene of 7- simply,
Other reagents are constant, obtain compound shown in formula (13).
Product MS (m/e)：612, elementary analysiss (C46H32N2)：Theoretical value C：90.16%, H：5.26%, N：
4.57%；Measured value C：90.12%, H：5.22%, N：4.66%.
Embodiment 4
The synthesis of compound shown in formula (14)
Synthesis step is same as embodiment 2, and 6- bromo- 2,3- dimethylquinoxalins are changed into bromo- 2, the 3- diphenylquinoxalines of 6- simply,
Other reagents are constant, obtain compound shown in formula (14).
Product MS (m/e)：710, elementary analysiss (C54H34N2)：Theoretical value C：91.24%, H：4.82%, N：
3.94%；Measured value C：91.27%, H：4.84%, N：3.89%；Its nuclear magnetic spectrogram (1HNMR) see Fig. 1
It is shown.
Embodiment 5
The synthesis of compound shown in formula (15)
Synthesis step is same as embodiment 2, and 6- bromo- 2,3- dimethylquinoxalins are changed into bromo- 2, the 3- bis- (trifluoromethyl) of 6- simply
Quinoxaline, other reagents are constant, obtain compound shown in formula (15).
Product MS (m/e)：710, elementary analysiss (C44H24F6N2)：Theoretical value C：76.08%, H：3.48%, F:
16.41%, N：4.03%；Measured value C：76.03%, H：3.46%, F:16.44%, N：4.07%.
Embodiment 6
The synthesis of compound shown in formula (16)
Synthesis step is same as embodiment 2, and 6- bromo- 2,3- dimethylquinoxalins are changed into bromo- 2, the 3- dicyanos quinoxalines of 6- simply,
Other reagents are constant, obtain compound shown in formula (16).
Product MS (m/e)：608, elementary analysiss (C44H24N4)：Theoretical value C：86.82%, H：3.97%, N：
9.20%；Measured value C：86.83%, H：3.94%, N：9.23%.
Embodiment 7
The synthesis of compound shown in formula (17)
Synthesis step is same as embodiment 2, and 6- bromo- 2,3- dimethylquinoxalins are changed into 6- bromine quinoxalines, other reagents simply
It is constant, obtain compound shown in formula (17).
Product MS (m/e)：558, elementary analysiss (C42H26N2)：Theoretical value C：90.29%, H：4.69%, N：5.02%；
Measured value C：90.26%, H：4.67%, N：5.07%.
Embodiment 8
The synthesis of compound shown in formula (18)
Synthesis step is same as embodiment 2, and simply by a kind of raw material 9 therein, 10- bis- (naphthalene -2- bases) anthracene -2- boric acid is changed into
The conditions such as 9- (naphthalene -2- bases) -10- (to (1- naphthyls) phenyl) anthracene -2- boric acid, other medicines, reagent, reaction, separation
It is constant, obtain compound shown in formula (18).
Product MS (m/e)：662, elementary analysiss (C50H34N2)：Theoretical value C：90.60%, H：5.17%, N：4.23%；
Measured value C：90.63%, H：5.16%, N：4.21%.
Embodiment 9
The synthesis of compound shown in formula (19)
Synthesis step is same as embodiment 2, and raw material 6- bromo- 2,3- dimethylquinoxalins are changed into bromo- 1,2,3, the 4- tetrahydrochysenes of 7- simply
Azophenlyene, 9,10- bis- (naphthalene -2- bases) anthracene -2- boric acid change into 9- (naphthalene -2- bases) -10- (to (1- naphthyls) phenyl) anthracene -2-
The conditions such as boric acid, other medicines, reagent, reaction, separation are constant, obtain compound shown in formula (19).
Product MS (m/e)：688, elementary analysiss (C52H36N2)：Theoretical value C：90.67%, H：5.27%, N：4.07%；
Measured value C：90.66%, H：5.30%, N：4.04%.
Embodiment 10
The synthesis of compound shown in formula (20)
Synthesis step is same as embodiment 2, and raw material 6- bromo- 2,3- dimethylquinoxalins are changed into bromo- 2, the 3- diphenyl quinolines of 6- simply
Quinoline, 9,10- bis- (naphthalene -2- bases) anthracene -2- boric acid change into 9- (naphthalene -2- bases) -10- (to (1- naphthyls) phenyl) anthracene -2-
The conditions such as boric acid, other medicines, reagent, reaction, separation are constant, obtain compound shown in formula (20).
Product MS (m/e)：786, elementary analysiss (C60H38N2)：Theoretical value C：91.57%, H：4.87%, N：3.56%；
Measured value C：91.55%, H：4.86%, N：3.59%.
Embodiment 11
The synthesis of compound shown in formula (21)
Synthesis step is same as embodiment 2, and raw material 6- bromo- 2,3- dimethylquinoxalins are changed into bromo- 2,3-, the bis- (trifluoros of 6- simply
Methyl) quinoxaline, 9,10- bis- (naphthalene -2- bases) anthracene -2- boric acid changes into 9- (naphthalene -2- bases) -10- (to (1- naphthyls) benzene
Base) anthracene -2- boric acid, the condition such as other medicines, reagent, reaction, separation is constant, obtains compound shown in formula (21).
Product MS (m/e)：770, elementary analysiss (C60H28F6N2)：Theoretical value C：77.91%, H：3.66%, F：14.79%,
N：3.63%；Measured value C：77.95%, H：3.62%, F：14.75%, N：3.68%.
Embodiment 12
The synthesis of compound shown in formula (22)
Synthesis step is same as embodiment 2, and raw material 6- bromo- 2,3- dimethylquinoxalins are changed into bromo- 2, the 3- dicyanos quinolines of 6- simply
Quinoline, 9,10- bis- (naphthalene -2- bases) anthracene -2- boric acid change into 9- (naphthalene -2- bases) -10- (to (1- naphthyls) phenyl) anthracene -2-
The conditions such as boric acid, other medicines, reagent, reaction, separation are constant, obtain compound shown in formula (22).
Product MS (m/e)：684, elementary analysiss (C50H28N4)：Theoretical value C：87.70%, H：4.12%, N：8.18%；
Measured value C：87.75%, H：4.15%, N：8.20%；Its nuclear magnetic spectrogram (1HNMR) as shown in Figure 2.
Embodiment 13
The synthesis of compound shown in formula (23)
Synthesis step is same as embodiment 2, and raw material 6- bromo- 2,3- dimethylquinoxalins are changed into 6- bromine quinoxalines simply, and 9,10-
Two (naphthalene -2- bases) anthracene -2- boric acid changes into 9- (naphthalene -2- bases) -10- (to (1- naphthyls) phenyl) anthracene -2- boric acid, other
The conditions such as medicine, reagent, reaction, separation are constant, obtain compound shown in formula (23).
Product MS (m/e)：634, elementary analysiss (C48H30N2)：Theoretical value C：90.82%, H：4.76%, N：4.41%；
Measured value C：90.84%, H：4.73%, N：4.43%.
Embodiment 14
The synthesis of compound shown in formula (24)
Synthesis step is same as embodiment 2, and raw material 6- bromo- 2,3- dimethylquinoxalins are changed into 6- bromine quinoxalines simply, and 9,10-
Two (naphthalene -2- bases) anthracene -2- boric acid changes into 7,12- diphenyl benzo [k] fluoranthene -3- boric acid, other medicines, reagent, reaction,
The conditions such as separation are constant, obtain compound shown in formula (24).
Product MS (m/e)：532, elementary analysiss (C40H24N2)：Theoretical value C：90.20%, H：4.54%, N：5.26%；
Measured value C：90.23%, H：4.53%, N：5.24%；Its nuclear magnetic spectrogram (1HNMR) as shown in Figure 3.
Embodiment 15
The synthesis of compound shown in formula (25)
Synthesis step is same as embodiment 2, and raw material 6- bromo- 2,3- dimethylquinoxalins are changed into bromo- 2, the 3- diphenyl quinolines of 6- simply
Quinoline, 9,10- bis- (naphthalene -2- bases) anthracene -2- boric acid change into 7,12- diphenyl benzo [k] fluoranthene -3- boric acid, other medicines, examination
The conditions such as agent, reaction, separation are constant, obtain compound shown in formula (25).
Product MS (m/e)：684, elementary analysiss (C52H32N2)：Theoretical value C：91.20%, H：4.71%, N：4.09%；
Measured value C：91.22%, H：4.73%, N：4.05%.
Embodiment 16
The synthesis of compound shown in formula (26)
Synthesis step is same as embodiment 2, and raw material 6- bromo- 2,3- dimethylquinoxalins are changed into bromo- 1,2,3, the 4- tetrahydrochysenes of 7- simply
Azophenlyene, 9,10- bis- (naphthalene -2- bases) anthracene -2- boric acid change into 7,12- diphenyl benzo [k] fluoranthene -3- boric acid, other medicines, examination
The conditions such as agent, reaction, separation are constant, obtain compound shown in formula (26).
Product MS (m/e)：586, elementary analysiss (C44H30N2)：Theoretical value C：90.07%, H：5.15%, N：4.77%；
Measured value C：90.08%, H：5.13%, N：4.79%；Its nuclear magnetic spectrogram (1HNMR) as shown in Figure 4.
Embodiment 17
The synthesis of compound shown in formula (27)
Synthesis step is same as embodiment 2, and raw material 6- bromo- 2,3- dimethylquinoxalins are changed into bromo- 2, the 3- dicyanos quinolines of 6- simply
Quinoline, 9,10- bis- (naphthalene -2- bases) anthracene -2- boric acid change into 7,12- diphenyl benzo [k] fluoranthene -3- boric acid, other medicines, examination
The conditions such as agent, reaction, separation are constant, obtain compound shown in formula (27).
Product MS (m/e)：582, elementary analysiss (C42H22N4)：Theoretical value C：86.58%, H：3.81%, N：9.62%；
Measured value C：86.54%, H：3.86%, N：9.60%.
Embodiment 18
The synthesis of compound shown in formula (28)
Synthesis step is same as embodiment 2, and raw material 6- bromo- 2,3- dimethylquinoxalins are changed into bromo- 2,3-, the bis- (trifluoros of 6- simply
Methyl) quinoxaline, 9,10- bis- (naphthalene -2- bases) anthracene -2- boric acid changes into 7,12- diphenyl benzo [k] fluoranthene -3- boric acid, other
The conditions such as medicine, reagent, reaction, separation are constant, obtain compound shown in formula (28).
Product MS (m/e)：668, elementary analysiss (C42H22F6N2)：Theoretical value C：75.45%, H：3.32%, F：17.05%,
N：4.19%；Measured value C：75.47%, H：3.34%, F：17.02%, N：4.17%.
Embodiment 19
The synthesis of compound shown in formula (29)
Synthesis step is same as embodiment 2, and raw material 6- bromo- 2,3- dimethylquinoxalins are changed into bromo- 2, the 3- diphenyl quinolines of 6- simply
Quinoline, 9,10- bis- (naphthalene -2- bases) anthracene -2- boric acid change into 7,10- diphenyl fluoranthene -3- boric acid, other medicines, reagent, anti-
Should, separate etc. condition it is constant, obtain compound shown in formula (29).
Product MS (m/e)：634, elementary analysiss (C48H30N2)：Theoretical value C：90.82%, H：4.76%, N：4.41%；
Measured value C：90.84%, H：4.73%, N：4.43%.
Embodiment 20
The synthesis of compound shown in formula (30)
Synthesis step is same as embodiment 2, and raw material 6- bromo- 2,3- dimethylquinoxalins are changed into bromo- 1,2,3, the 4- tetrahydrochysenes of 7- simply
Azophenlyene, 9,10- bis- (naphthalene -2- bases) anthracene -2- boric acid change into 7,10- diphenyl fluoranthene -3- boric acid, other medicines, reagent, anti-
Should, separate etc. condition it is constant, obtain compound shown in formula (30).
Product MS (m/e)：536, elementary analysiss (C40H28N2)：Theoretical value C：89.52%, H：5.26%, N：5.22%；
Measured value C：89.54%, H：5.23%, N：5.23%.
Embodiment 21
The synthesis of compound shown in formula (31)
Synthesis step is same as embodiment 2, and raw material 6- bromo- 2,3- dimethylquinoxalins are changed into bromo- 2, the 3- dicyanos quinolines of 6- simply
Quinoline, 9,10- bis- (naphthalene -2- bases) anthracene -2- boric acid change into 7,10- diphenyl fluoranthene -3- boric acid, other medicines, reagent, anti-
Should, separate etc. condition it is constant, obtain compound shown in formula (31).
Product MS (m/e)：532, elementary analysiss (C38H20N4)：Theoretical value C：85.70%, H：3.79%, N：10.52%；
Measured value C：85.72%, H：3.75%, N：10.53%.
Embodiment 22
The synthesis of compound shown in formula (32)
Synthesis step is same as embodiment 2, and raw material 6- bromo- 2,3- dimethylquinoxalins are changed into bromo- 2,3-, the bis- (trifluoros of 6- simply
Methyl) quinoxaline, 9,10- bis- (naphthalene -2- bases) anthracene -2- boric acid changes into 7,10- diphenyl fluoranthene -3- boric acid, other medicines,
The conditions such as reagent, reaction, separation are constant, obtain compound shown in formula (32).
Product MS (m/e)：618, elementary analysiss (C38H20F6N2)：Theoretical value C：73.78%, H：3.26%, F：18.43%,
N：4.53%；Measured value C：73.75%, H：3.29%, F：18.41%, N：4.55%.
Embodiment 23
The synthesis of compound shown in formula (33)
Synthesis step is same as embodiment 2, and raw material 6- bromo- 2,3- dimethylquinoxalins are changed into bromo- 1,2,3, the 4- tetrahydrochysenes of 7- simply
Azophenlyene, 9,10- bis- (naphthalene -2- bases) anthracene -2- boric acid change into 7- (naphthalene -2- bases) triphenylene -2- boric acid, other medicines, reagent,
The conditions such as reaction, separation are constant, obtain compound shown in formula (33).
Product MS (m/e)：536, elementary analysiss (C40H28N2)：Theoretical value C：89.52%, H：5.26%, N：5.22%；
Measured value C：89.54%, H：5.23%, N：5.23%.
Embodiment 24
The synthesis of compound shown in formula (34)
Synthesis step is same as embodiment 2, and raw material 6- bromo- 2,3- dimethylquinoxalins are changed into bromo- 2,3-, the bis- (trifluoros of 6- simply
Methyl) quinoxaline, 9,10- bis- (naphthalene -2- bases) anthracene -2- boric acid changes into 7- (naphthalene -2- bases) triphenylene -2- boric acid, other medicines
The conditions such as product, reagent, reaction, separation are constant, obtain compound shown in formula (34).
Product MS (m/e)：618, elementary analysiss (C38H20F6N2)：Theoretical value C：73.78%, H：3.26%, F：18.43%,
N：4.53%；Measured value C：73.74%, H：3.28%, F：18.42%, N：4.56%.
Embodiment 25
The synthesis of compound shown in formula (31)
Synthesis step is same as embodiment 2, and raw material 6- bromo- 2,3- dimethylquinoxalins are changed into bromo- 2, the 3- dicyanos quinolines of 6- simply
Quinoline, 9,10- bis- (naphthalene -2- bases) anthracene -2- boric acid change into 7- (naphthalene -2- bases) triphenylene -2- boric acid, other medicines, reagent,
The conditions such as reaction, separation are constant, obtain compound shown in formula (31).
Product MS (m/e)：532, elementary analysiss (C38H20N4)：Theoretical value C：85.70%, H：3.79%, N：10.52%；
Measured value C：85.73%, H：3.77%, N：10.50%.
Embodiment 26
The synthesis of compound shown in formula (36)
Synthesis step is same as embodiment 2, and raw material 6- bromo- 2,3- dimethylquinoxalins are changed into bromo- 2, the 3- diphenyl quinolines of 6- simply
Quinoline, 9,10- bis- (naphthalene -2- bases) anthracene -2- boric acid change into 7- (naphthalene -2- bases) triphenylene -2- boric acid, other medicines, reagent,
The conditions such as reaction, separation are constant, obtain compound shown in formula (36).
Product MS (m/e)：634, elementary analysiss (C48H30N2)：Theoretical value C：90.82%, H：4.76%, N：4.41%；
Measured value C：90.85%, H：4.72%, N：4.43%；Its nuclear magnetic spectrogram (1HNMR) as shown in Figure 5.
Embodiment 27
The synthesis of compound shown in formula (37)
Synthesis step is same as embodiment 2, and simply by raw material 9,10- bis- (naphthalene -2- bases) anthracene -2- boric acid changes into 7- (naphthalene -2- bases)
The conditions such as triphenylene -2- boric acid, other medicines, reagent, reaction, separation are constant, obtain compound shown in formula (37).
Product MS (m/e)：510, elementary analysiss (C38H26N2)：Theoretical value C：89.38%, H：5.13%, N：5.49%；
Measured value C：89.36%, H：5.16%, N：5.48%.
Embodiment 28
The synthesis of compound shown in formula (38)
Synthesis step is same as embodiment 2, and simply by raw material 9,10- bis- (naphthalene -2- bases) anthracene -2- boric acid changes into 7- (to (naphthalene
- 1- bases) phenyl) triphenylene -2- boric acid, the condition such as other medicines, reagent, reaction, separation is constant, obtains formula (38)
Shown compound.
Product MS (m/e)：586, elementary analysiss (C44H30N2)：Theoretical value C：90.07%, H：5.15%, N：4.77%；
Measured value C：90.10%, H：5.16%, N：4.74%.
Embodiment 29
The synthesis of compound shown in formula (39)
Synthesis step is same as embodiment 2, and raw material 6- bromo- 2,3- dimethylquinoxalins are changed into bromo- 2, the 3- diphenyl quinolines of 6- simply
Quinoline, 9,10- bis- (naphthalene -2- bases) anthracene -2- boric acid change into 7- (to (naphthalene -1- bases) phenyl) triphenylene -2- boric acid, other
The conditions such as medicine, reagent, reaction, separation are constant, obtain compound shown in formula (39).
Product MS (m/e)：710, elementary analysiss (C54H34N2)：Theoretical value C：91.24%, H：4.82%, N：3.94%；
Measured value C：91.21%, H：4.84%, N：3.95%.
Embodiment 30
The synthesis of compound shown in formula (40)
Synthesis step is same as embodiment 2, and raw material 6- bromo- 2,3- dimethylquinoxalins are changed into bromo- 2, the 3- dicyanos quinolines of 6- simply
Quinoline, 9,10- bis- (naphthalene -2- bases) anthracene -2- boric acid change into 7- (to (naphthalene -1- bases) phenyl) triphenylene -2- boric acid, other
The conditions such as medicine, reagent, reaction, separation are constant, obtain compound shown in formula (40).
Product MS (m/e)：608, elementary analysiss (C44H24N4)：Theoretical value C：86.82%, H：3.97%, N：9.20%；
Measured value C：86.84%, H：3.93%, N：9.23%.
Embodiment 31
The synthesis of compound shown in formula (41)
Synthesis step is same as embodiment 2, and raw material 6- bromo- 2,3- dimethylquinoxalins are changed into bromo- 2,3-, the bis- (trifluoros of 6- simply
Methyl) quinoxaline, 9,10- bis- (naphthalene -2- bases) anthracene -2- boric acid changes into 7- (to (naphthalene -1- bases) phenyl) triphenylene -2-
The conditions such as boric acid, other medicines, reagent, reaction, separation are constant, obtain compound shown in formula (41).
Product MS (m/e)：694, elementary analysiss (C44H24F6N2)：Theoretical value C：76.08%, H：3.48%, F：16.41%,
N：4.03%；Measured value C：76.05%, H：3.46%, F：16.43%, N：4.06%.
Embodiment 32
The synthesis of compound shown in formula (42)
Synthesis step is same as embodiment 2, and raw material 6- bromo- 2,3- dimethylquinoxalins are changed into bromo- 1,2,3, the 4- tetrahydrochysenes of 7- simply
Azophenlyene, 9,10- bis- (naphthalene -2- bases) anthracene -2- boric acid change into 7- (to (naphthalene -1- bases) phenyl) triphenylene -2- boric acid, other
The conditions such as medicine, reagent, reaction, separation are constant, obtain compound shown in formula (42).
Product MS (m/e)：612, elementary analysiss (C46H32N2)：Theoretical value C：90.16%, H：5.26%, N：4.57%；
Measured value C：90.18%, H：5.23%, N：4.59%.
Embodiment 33
The synthesis of compound shown in formula (43)
Synthesis step is same as embodiment 2, and raw material 6- bromo- 2,3- dimethylquinoxalins are changed into 6- bromine quinoxalines simply, and 9,10-
Two (naphthalene -2- bases) anthracene -2- boric acid changes into 7- (to (naphthalene -1- bases) phenyl) triphenylene -2- boric acid, other medicines, reagent,
The conditions such as reaction, separation are constant, obtain compound shown in formula (43).
Product MS (m/e)：558, elementary analysiss (C42H26N2)：Theoretical value C：90.29%, H：4.69%, N：5.01%；
Measured value C：90.32%, H：4.65%, N：5.03%.
Embodiment 34
The synthesis of compound shown in formula (44)
Synthesis step is same as embodiment 2, and raw material 6- bromo- 2,3- dimethylquinoxalins are changed into bromo- 2, the 3- dicyanos quinolines of 6- simply
Quinoline, 9,10- bis- (naphthalene -2- bases) anthracene -2- boric acid change into 12- (naphthalene -2- bases)- 6- boric acid, other medicines, reagent,
The conditions such as reaction, separation are constant, obtain compound shown in formula (44).
Product MS (m/e)：532, elementary analysiss (C38H20N4)：Theoretical value C：85.70%, H：3.79%, N：10.52%；
Measured value C：85.73%, H：3.77%, N：10.50%.
Embodiment 35
The synthesis of compound shown in formula (45)
Synthesis step is same as embodiment 2, and raw material 6- bromo- 2,3- dimethylquinoxalins are changed into bromo- 2,3-, the bis- (trifluoros of 6- simply
Methyl) quinoxaline, 9,10- bis- (naphthalene -2- bases) anthracene -2- boric acid changes into 12- (naphthalene -2- bases)- 6- boric acid, other medicines,
The conditions such as reagent, reaction, separation are constant, obtain compound shown in formula (45).
Product MS (m/e)：618, elementary analysiss (C38H20F6N2)：Theoretical value C：73.78%, H：3.26%, F：18.43%,
N：4.53%；Measured value C：73.74%, H：3.28%, F：18.41%, N：4.57%.
Embodiment 36
The synthesis of compound shown in formula (46)
Synthesis step is same as embodiment 2, and simply by raw material 9,10- bis- (naphthalene -2- bases) anthracene -2- boric acid changes into 12- (naphthalene -2-
Base)The conditions such as -6- boric acid, other medicines, reagent, reaction, separation are constant, obtain compound shown in formula (46).
Product MS (m/e)：510, elementary analysiss (C38H26N2)：Theoretical value C：89.38%, H：5.13%, N：5.49%；
Measured value C：89.35%, H：5.17%, N：5.48%.
Embodiment 37
The synthesis of compound shown in formula (47)
Synthesis step is same as embodiment 2, and raw material 6- bromo- 2,3- dimethylquinoxalins are changed into bromo- 1,2,3, the 4- tetrahydrochysenes of 7- simply
Azophenlyene, 9,10- bis- (naphthalene -2- bases) anthracene -2- boric acid change into 12- (naphthalene -2- bases)- 6- boric acid, other medicines, reagent,
The conditions such as reaction, separation are constant, obtain compound shown in formula (47).
Product MS (m/e)：536, elementary analysiss (C40H28N2)：Theoretical value C：89.52%, H：5.26%, N：5.22%；
Measured value C：89.54%, H：5.23%, N：5.23%.
Embodiment 38
The synthesis of compound shown in formula (48)
Synthesis step is same as embodiment 2, and raw material 6- bromo- 2,3- dimethylquinoxalins are changed into bromo- 2, the 3- diphenyl quinolines of 6- simply
Quinoline, 9,10- bis- (naphthalene -2- bases) anthracene -2- boric acid change into 12- (naphthalene -2- bases)- 6- boric acid, other medicines, reagent,
The conditions such as reaction, separation are constant, obtain compound shown in formula (48).
Product MS (m/e)：536, elementary analysiss (C40H28N2)：Theoretical value C：89.52%, H：5.26%, N：5.22%；
Measured value C：89.54%, H：5.23%, N：5.23%.
Embodiment 39
The synthesis of compound shown in formula (49)
Synthesis step is same as embodiment 2, and raw material 6- bromo- 2,3- dimethylquinoxalins are changed into 6- bromine quinoxalines simply, and 9,10-
Two (naphthalene -2- bases) anthracene -2- boric acid changes into 12- (naphthalene -2- bases)- 6- boric acid, other medicines, reagent, reaction, separation
It is constant etc. condition, obtain compound shown in formula (49).
Product MS (m/e)：482, elementary analysiss (C36H22N2)：Theoretical value C：89.60%, H：4.60%, N：5.81%；
Measured value C：89.57%, H：4.56%, N：5.87%.
Embodiment 40
The synthesis of compound shown in formula (50)
Synthesis step is same as embodiment 2, and raw material 6- bromo- 2,3- dimethylquinoxalins are changed into bromo- 2,3-, the bis- (trifluoros of 6- simply
Methyl) quinoxaline, 9,10- bis- (naphthalene -2- bases) anthracene -2- boric acid changes into 12- (to (naphthalene -1- bases) phenyl)- 6- boric acid,
The conditions such as other medicines, reagent, reaction, separation are constant, obtain compound shown in formula (50).
Product MS (m/e)：694, elementary analysiss (C44H24F6N2)：Theoretical value C：76.08%, H：3.48%, F：16.41%,
N：4.03%；Measured value C：76.04%, H：3.46%, F：16.43%, N：4.07%.
Embodiment 41
The synthesis of compound shown in formula (51)
Synthesis step is same as embodiment 2, and raw material 6- bromo- 2,3- dimethylquinoxalins are changed into bromo- 2, the 3- dicyanos quinolines of 6- simply
Quinoline, 9,10- bis- (naphthalene -2- bases) anthracene -2- boric acid change into 12- (to (naphthalene -1- bases) phenyl)- 6- boric acid, other medicines
The conditions such as product, reagent, reaction, separation are constant, obtain compound shown in formula (51).
Product MS (m/e)：608, elementary analysiss (C44H24N4)：Theoretical value C：86.82%, H：3.97%, N：9.20%；
Measured value C：86.84%, H：3.93%, N：9.23%.
Embodiment 42
The synthesis of compound shown in formula (52)
Synthesis step is same as embodiment 2, and raw material 6- bromo- 2,3- dimethylquinoxalins are changed into bromo- 2, the 3- diphenyl quinolines of 6- simply
Quinoline, 9,10- bis- (naphthalene -2- bases) anthracene -2- boric acid change into 12- (to (naphthalene -1- bases) phenyl)- 6- boric acid, other medicines
The conditions such as product, reagent, reaction, separation are constant, obtain compound shown in formula (52).
Product MS (m/e)：710, elementary analysiss (C54H34N2)：Theoretical value C：91.24%, H：4.82%, N：3.94%；
Measured value C：91.22%, H：4.85%, N：3.93%；Its nuclear magnetic spectrogram (1HNMR) as shown in Figure 6.
Embodiment 43
The synthesis of compound shown in formula (53)
Synthesis step is same as embodiment 2, and raw material 6- bromo- 2,3- dimethylquinoxalins are changed into bromo- 1,2,3, the 4- tetrahydrochysenes of 7- simply
Azophenlyene, 9,10- bis- (naphthalene -2- bases) anthracene -2- boric acid change into 12- (to (naphthalene -1- bases) phenyl)- 6- boric acid, other medicines
The conditions such as product, reagent, reaction, separation are constant, obtain compound shown in formula (53).
Product MS (m/e)：612, elementary analysiss (C46H32N2)：Theoretical value C：90.16%, H：5.26%, N：4.57%；
Measured value C：90.18%, H：5.24%, N：4.58%.
Embodiment 44
The synthesis of compound shown in formula (54)
Synthesis step is same as embodiment 2, and simply by raw material 9,10- bis- (naphthalene -2- bases) anthracene -2- boric acid changes into 12- (to (naphthalene
- 1- bases) phenyl)The conditions such as -6- boric acid, other medicines, reagent, reaction, separation are constant, obtain shown in formula (54)
Compound.
Product MS (m/e)：586, elementary analysiss (C44H30N2)：Theoretical value C：90.07%, H：5.15%, N：4.77%；
Measured value C：90.08%, H：5.18%, N：4.74%.
The Application Example of each compound of the invention is presented herein below：
Embodiment 45
Compare the transmission performance of these electron transport materials for convenience, the present invention devises a simple electroluminescence device, use
Used as luminescent material, (EM1 is material of main part to EM1, and non-luminescent material, and purpose is not to pursue high efficiency, but checking
The practical probability of these materials), using efficent electronic transmission material Bphen as comparing material.EM1's and Bphen
Structure is respectively:
In the embodiment of the present invention, the structure of organic electroluminescence device is：
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 electroluminescence of the present invention
Luminescent device selects glass substrate, ITO to make anode material in making.
Hole transmission layer can adopt various tri-arylamine group materials.It is selected in the organic electroluminescence device of the present invention makes
Hole mobile material be NPB.NPB structures are：
Negative electrode can adopt metal and its mixture structure, such as Mg：Ag、Ca：Ag etc., or electron injecting layer/
Metal-layer structure, such as LiF/Al, Li2The common cathode structure such as O/Al.In the organic electroluminescence device of the present invention makes
Selected cathode material is LiF/Al.
, used as the electron transport material in organic electroluminescence device, EML is used as luminescent layer material for compound in the present embodiment
Material, is prepared for multiple organic electroluminescence devices altogether, and its structure is：ITO/NPB(40nm)/EM1(30nm)/ETL
Material (20nm)/LiF (0.5nm)/Al (150nm)；
One contrast organic electroluminescence device, electron transport material select Bphen, and remaining organic electroluminescence device is selected
The material of the present invention.
In the present embodiment, organic electroluminescence device preparation process is as follows：
The glass plate of the transparent conductive layer supersound process in commercial detergent will be coated with, be rinsed in deionized water,
Acetone：In alcohol mixed solvent, ultrasonic oil removing, is baked under clean environment and completely removes moisture content, clear with ultraviolet light and ozone
Wash, and with mental retardation cation beam bombarded surface；
The above-mentioned glass substrate with anode is placed in vacuum intracavity, 1 × 10 is evacuated to-5～9 × 10-3Pa, in above-mentioned anode
On tunic, used as hole transmission layer, evaporation rate is 0.1nm/s to vacuum evaporation NPB, and evaporation thickness is 40nm；
Luminescent layers of the vacuum evaporation EM1 as device on the hole transmission layer, evaporation rate is 0.1nm/s, is deposited with total film
Thick is 30nm；
On the luminescent layer one laminar of vacuum evaporation (13), formula (14), formula (16), formula (25), formula (27), formula (33),
Formula (35), formula (36), formula (44), formula (46) or electron transfer layer material of the compound as device shown in formula (52)
Material, transmits the contrast material of layer material with Bphen as device electronic, and its evaporation rate is 0.1nm/s, is deposited with total film thickness
For 20nm；
On electron transfer layer (ETL), vacuum evaporation thickness is the LiF of 0.5nm as electron injecting layer, and thickness is 150nm
Al layers as device negative electrode.
Organic electroluminescence device performance see the table below：
| Compound number | Require brightness cd/m2 | Voltage V | Current efficiency cd/A |
| Bphen | 1000.00 | 6.2 | 6.1 |
| Formula (13) | 1000.00 | 5.7 | 6.8 |
| Formula (14) | 1000.00 | 5.6 | 6.9 |
| Formula (16) | 1000.00 | 5.6 | 7.0 |
| Formula (25) | 1000.00 | 5.8 | 7.2 |
| Formula (27) | 1000.00 | 5.7 | 7.1 |
| Formula (33) | 1000.00 | 5.6 | 6.9 |
| Formula (35) | 1000.00 | 5.6 | 7.1 |
| Formula (36) | 1000.00 | 5.7 | 7.3 |
| Formula (44) | 1000.00 | 5.7 | 7.0 |
| Formula (46) | 1000.00 | 5.7 | 7.1 |
| Formula (52) | 1000.00 | 5.5 | 7.0 |
Result above shows that the new organic materials of the present invention are used for organic electroluminescence device, can effectively reduce device
Running voltage, improves current efficiency, is electron transport material of good performance.
Although describe the present invention in conjunction with the embodiments, above-described embodiment is the invention is not limited in, it will be appreciated that
Under the guiding of present inventive concept, those skilled in the art can carry out various modifications and improvements, and claims summarise this
The scope of invention.
Claims (8)
1. a kind of condensed-nuclei aromatics derivant containing quinoxaline group, it is characterised in that with the structure shown in formula (1)：
Wherein：Ar is selected from C10-C50Condensed-nuclei aromatics group or condensed hetero ring aromatic hydrocarbon group；
L is selected from singly-bound, substituted or unsubstituted arlydene, substituted or unsubstituted sub- heterocyclic aryl.
R1And R2It is identical or different, it is respectively and independently selected from H, aryl, heterocyclic arene base, condensed-nuclei aromatics base, or condensed hetero ring
Aryl, substituted or unsubstituted alkyl, cyano group；R1And R2Cyclization can be also connected with each other, becomes aromatic ring or aliphatic ring.
2. the condensed-nuclei aromatics derivant containing quinoxaline group according to claim 1, it is characterised in that the Ar is
Group shown in formula (2) to formula (6)：
Wherein, Ar1And Ar2It is identical or different, it is respectively and independently selected from H, C4-C30Aromatic ring yl, heteroaryl ring group, condensed-nuclei aromatics
Base or condensed hetero ring aryl；
R3To R10It is identical or different, it is respectively and independently selected from H, aryl, heterocyclic arene base, condensed-nuclei aromatics base, or condensed hetero ring
Aryl, substituted or unsubstituted alkyl, cyano group.
3. the condensed-nuclei aromatics derivant containing quinoxaline group according to claim 2, it is characterised in that the chemical combination
Thing is structure shown in formula (7) to formula (11)：
Wherein, Ar1And Ar2It is identical or different, H is independently selected from, is replaced or unsubstituted C4-C30Aromatic ring yl, heteroaryl ring group,
Replace or unsubstituted condensed-nuclei aromatics base or condensed hetero ring aryl；
L is singly-bound, substituted or unsubstituted arlydene, substituted or unsubstituted sub- heterocyclic aryl；
R3To R10It is identical or different, H is respectively and independently selected from, is replaced or unsubstituted aryl, replaced or unsubstituting heterocycle aromatic hydrocarbons
Base, replaces or unsubstituted condensed-nuclei aromatics base or condensed hetero ring aryl, substituted or unsubstituted alkyl, cyano group.
4. the condensed-nuclei aromatics derivant containing quinoxaline group according to any one of claim 1-3, it is characterised in that
The unsubstituted alkyl is methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl group, sec-butyl, tertiary fourth
Base, 2- Methylethyls, amyl group or cyclohexyl；
The substituted alkyl is trifluoromethyl；
The replacement or unsubstituted aryl are phenyl, o-tolyl, p-methylphenyl, tert-butyl-phenyl etc..Replace or do not take
It is furan, benzofuran, dibenzofurans, thiophene, benzothiophene, dibenzothiophenes, carbazole, pyrrole for heterocyclic arene base
Pyridine, pyrazine, 2.4- methyl isophthalic acid .3.5 triazines, 4.6 diphenylpyrimidins；
The replacement or unsubstituted condensed-nuclei aromatics base are naphthyl, phenanthryl, anthryl, pyrenyl, 9.9- dimethyl -2- fluorenyls.Take
Generation or unsubstituted condensed hetero ring aryl be quinoline, after isoquinolin or quinazoline.
5. the condensed-nuclei aromatics derivant containing quinoxaline group according to claim 4, it is characterised in that the compound is
Formula (12)-structure shown in (54)：
6. the condensed-nuclei aromatics derivant containing quinoxaline group described in a kind of any one of claim 1-4 is in organic electroluminescent
Application in device.
7. application of the condensed-nuclei aromatics derivant according to claim 5 in organic electroluminescence device, its feature exist
In the condensed-nuclei aromatics derivant containing quinoxaline group can be used as electron transport material.
8. a kind of organic electroluminescence device, including substrate, and sequentially form anode layer on the substrate, organic
Light emitting functional layer and cathode layer；The organic luminescence function layer includes hole transmission layer, organic luminous layer and electron transfer layer,
It is characterized in that：
The electron transport material of the electron transfer layer is the virtue of the condensed ring containing quinoxaline group described in any one of claim 1-4
Hydrocarbon derivative.
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| CN202010042537.XA CN111205234A (en) | 2015-09-30 | 2015-09-30 | Condensed ring aromatic hydrocarbon derivative with quinoxaline group and application thereof |
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| CN107954942A (en) * | 2017-12-08 | 2018-04-24 | 北京鼎材科技有限公司 | Benzopyrazines substitutes anthracene derivant and organic electroluminescence device |
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| CN111187225B (en) | 2021-06-11 |
| CN111187225A (en) | 2020-05-22 |
| CN111205234A (en) | 2020-05-29 |
| CN106554320B (en) | 2020-07-07 |
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