CN106554322A - A kind of phenazene derivative and its application in organic electroluminescence device - Google Patents

A kind of phenazene derivative and its application in organic electroluminescence device Download PDF

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CN106554322A
CN106554322A CN201510640793.8A CN201510640793A CN106554322A CN 106554322 A CN106554322 A CN 106554322A CN 201510640793 A CN201510640793 A CN 201510640793A CN 106554322 A CN106554322 A CN 106554322A
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unsubstituted
boric acid
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azophenlyene
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CN106554322B (en
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范洪涛
李银奎
邵爽
任雪艳
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Beijing Eternal Material Technology Co Ltd
Guan Eternal Material Technology Co Ltd
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Beijing Eternal Material Technology Co Ltd
Guan Eternal Material Technology Co Ltd
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    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D241/00Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings
    • C07D241/36Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings condensed with carbocyclic rings or ring systems
    • C07D241/38Heterocyclic 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
    • C07D241/46Phenazines
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    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D401/00Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/04Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
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    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D403/00Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
    • C07D403/02Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
    • C07D403/10Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings linked by a carbon chain containing aromatic rings
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    • H10K85/00Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60Organic compounds having low molecular weight
    • H10K85/615Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
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    • H10K85/00Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60Organic compounds having low molecular weight
    • H10K85/615Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
    • H10K85/622Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing four rings, e.g. pyrene
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    • H10K85/00Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60Organic compounds having low molecular weight
    • H10K85/615Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
    • H10K85/626Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing more than one polycyclic condensed aromatic rings, e.g. bis-anthracene
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    • H10K85/00Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60Organic compounds having low molecular weight
    • H10K85/649Aromatic compounds comprising a hetero atom
    • H10K85/654Aromatic compounds comprising a hetero atom comprising only nitrogen as heteroatom
    • HELECTRICITY
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    • H10K85/00Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60Organic compounds having low molecular weight
    • H10K85/649Aromatic compounds comprising a hetero atom
    • H10K85/657Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6572Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole

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Abstract

The present invention relates to a class phenazene derivative, such compound is with the structure as shown in formula (1).The phenazene derivative 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

A kind of phenazene derivative and its application in organic electroluminescence device
Technical field
The invention belongs to field of organic electroluminescence, and in particular to a kind of phenazene derivative, its intermediate and preparation method thereof, 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 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 the patent CN 101003508A description of China, in electroluminescence It is used as electric transmission and injection material in device, 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 individually with Al as negative electrode compared with), significantly improve electron injection and the transmission of device, improve Electroluminescence efficiency.Kodak in United States Patent (USP) (publication number US 2006/0204784 and US 2007/0048545), Mixed electronic transport layer is mentioned, is passed using a kind of electronics of material of low lumo energy with another kind of low device operating voltages The doping such as defeated material and other materials such as metal material is formed.Based on the device of this mixed electronic transport layer, device efficiency is made It is improved, but is the increase in the complexity of device fabrication, is unfavorable for reducing OLED costs.Exploitation stability and high efficiency Electron transport material and/or electron injection material, play bright and running voltage so as to reduce device, improve 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 phenazene derivative of a class, such compound can be used for organic electroluminescent and show Show field.Specifically, this kind of compound can be used as electron transport material in display of organic electroluminescence.
The use of material of the present invention, can effectively reduce the running voltage of organic electroluminescence device, and improve organic electroluminescence sending out The luminous efficiency of optical device.
For achieving the above object, the technical scheme that the present invention takes is as follows:
A kind of phenazene derivative, with the structure as shown in formula (1):
Wherein:Ar1And Ar2It is identical or different, it is respectively and independently selected from H, halogen, substituted or unsubstituted C4-C30Aromatic ring Base, substituted or unsubstituted C4-C30Heteroaryl ring group, substituted or unsubstituted C4-C30Fused ring aryl, it is substituted or unsubstituted C4-C30Condensed hetero ring aryl, substituted or unsubstituted alkyl, cycloalkyl, cyano group, aromatic amine base, aliphatic secondary amido, The pyridine radicals of substituted or unsubstituted carbazole -9- bases, aromatic series and aliphatic substitution, or the phenyl that benzimidazolyl replaces; Ar1And Ar2It is asynchronously from H.
Preferably, the formula (1) is formula (2) and structure shown in formula (3):
Ar1And Ar2It is identical or different, it is respectively and independently selected from H, halogen, substituted or unsubstituted C4-C30Aromatic ring yl, take Generation or unsubstituted C4-C30Heteroaryl ring group, substituted or unsubstituted C4-C30Fused ring aryl, substituted or unsubstituted C4-C30 Condensed hetero ring aryl, substituted or unsubstituted alkyl, cycloalkyl, cyano group, aromatic amine base, aliphatic secondary amido replace Or the pyridine radicals of unsubstituted carbazole -9- bases, aromatic series and aliphatic substitution, or the phenyl that benzimidazolyl replaces;
Ar1And Ar2It is asynchronously from H.
The aromatic ring yl, heteroaryl ring group, fused ring aryl, the substituent group on condensed hetero ring aryl are aromatic ring yl, heteroaryl ring group, thick Cyclophane base or condensed hetero ring aryl, substituted or unsubstituted alkyl, cycloalkyl, secondary amine, cyano group, halogen.
The replacement or unsubstituted aryl are phenyl, o-tolyl, p-methylphenyl or tert-butyl-phenyl;It is described replacement or not Substituted heterocycle aryl be furan, benzofuran, dibenzofurans, thiophene, benzothiophene, dibenzothiophenes, carbazole, Pyridine, pyrazine, 2.4- methyl isophthalic acid .3.5 triazines or 4.6 diphenylpyrimidins etc.;The replacement or unsubstituted condensed-nuclei aromatics base For naphthyl, phenanthryl, anthryl, pyrenyl,Base, fluorenyl, triphenylenyl or 9.9- dimethyl -2- fluorenyls;Replace or do not take It is quinoline, isoquinolin, quinazoline for condensed hetero ring aryl;Substituted or unsubstituted alkyl is trifluoromethyl or alkyl.
The formula (1) is preferably with the concrete structure shown in following formula (4)-(47):
A kind of application of described phenazene derivative in organic electroluminescence device.
The phenazene derivative 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, institute The electron transport material for stating electron transfer layer is the phenazene derivative any one of claim 1-5.
Compared with prior art, the advantage containing phenazene derivative 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 (9) nuclear magnetic spectrogram (1HNMR);
Fig. 2 for compound shown in formula (15) nuclear magnetic spectrogram (1HNMR);
Fig. 3 for compound shown in formula (26) nuclear magnetic spectrogram (1HNMR);
Fig. 4 for compound shown in formula (31) nuclear magnetic spectrogram (1HNMR);
Fig. 5 for compound shown in formula (36) nuclear magnetic spectrogram (1HNMR);
Fig. 6 for compound shown in formula (45) nuclear magnetic spectrogram (1HNMR)。
Specific embodiment
Basic raw material used in the present invention, for example, 4- bromine o-phenylenediamines, 4- bromines neighbour benzoquinone (4- bromines hexamethylene -3,5- diene - 1,2- diketone), the bromo derivative of various anthracenes, the bromo derivative of diphenyl benzofluoranthrene, the bromo of diphenyl fluoranthene spread out It is the bromo derivative of biological, various triphenylene, variousBromo derivative, the bromo derivative of various pyrenes, or can be in state Interior each big industrial chemicals are commercially available, or can be synthesized with laboratory commonsense method.
Various bromo-derivatives can make corresponding boronic acid compounds with commonsense method.
A kind of phenazene derivative, with the structure as shown in formula (1):
Wherein:Ar1And Ar2It is identical or different, it is respectively and independently selected from H, halogen, substituted or unsubstituted C4-C30Aromatic ring Base, substituted or unsubstituted C4-C30Heteroaryl ring group, substituted or unsubstituted C4-C30Fused ring aryl, it is substituted or unsubstituted C4-C30Condensed hetero ring aryl, substituted or unsubstituted alkyl, cycloalkyl, cyano group, aromatic amine base, aliphatic secondary amido, The pyridine radicals of substituted or unsubstituted carbazole -9- bases, aromatic series and aliphatic substitution, or the phenyl that benzimidazolyl replaces; Ar1And Ar2It is asynchronously from H.
Preferably, the formula (1) is formula (2) and structure shown in formula (3):
Ar1And Ar2It is identical or different, it is respectively and independently selected from H, halogen, substituted or unsubstituted C4-C30Aromatic ring yl, take Generation or unsubstituted C4-C30Heteroaryl ring group, substituted or unsubstituted C4-C30Fused ring aryl, substituted or unsubstituted C4-C30 Condensed hetero ring aryl, substituted or unsubstituted alkyl, cycloalkyl, cyano group, aromatic amine base, aliphatic secondary amido replace Or the pyridine radicals of unsubstituted carbazole -9- bases, aromatic series and aliphatic substitution, or the phenyl that benzimidazolyl replaces;
Ar1And Ar2It is asynchronously from H.
The aromatic ring yl, heteroaryl ring group, fused ring aryl, the substituent group on condensed hetero ring aryl are aromatic ring yl, heteroaryl ring group, thick Cyclophane base or condensed hetero ring aryl, substituted or unsubstituted alkyl, cycloalkyl, secondary amine, cyano group, halogen.
The replacement or unsubstituted aryl are phenyl, o-tolyl, p-methylphenyl or tert-butyl-phenyl;It is described replacement or not Substituted heterocycle aryl be furan, benzofuran, dibenzofurans, thiophene, benzothiophene, dibenzothiophenes, carbazole, Pyridine, pyrazine, 2.4- methyl isophthalic acid .3.5 triazines or 4.6 diphenylpyrimidins etc.;The replacement or unsubstituted condensed-nuclei aromatics base For naphthyl, phenanthryl, anthryl, pyrenyl,Base, fluorenyl, triphenylenyl or 9.9- dimethyl -2- fluorenyls;Replace or do not take It is quinoline, isoquinolin, quinazoline for condensed hetero ring aryl;Substituted or unsubstituted alkyl is trifluoromethyl or alkyl.
The formula (1) is preferably with the concrete structure shown in following formula (4)-(47):
A kind of application of described phenazene derivative in organic electroluminescence device.
The phenazene derivative 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, institute The electron transport material for stating electron transfer layer is the phenazene derivative any one of claim 1-5.
The synthesis of 1 dibromo azophenlyene of embodiment
3.91 grams of o-phenylenediamine of 4- bromines (molecular weight 186,0.021mol), 4- bromines neighbour's benzoquinone are added in 250ml there-necked flasks 3.91 grams (molecular weight 186,0.021mol), ethanol (40 milliliters), under stirring condition, 0.2 gram of dense sulfur of Deca in 3min Sour (concentration 98%), reacts 4 hours at 65 DEG C, after reaction terminates, is cooled to room temperature, filters, washing, drying, Pillar layer separation, ethyl acetate/petroleum ether drip washing obtain 2, the 7- dibromos azophenlyene and 2,8- dibromo azophenlyene of almost equivalent, altogether 5.82 grams (molecular weight 336), gross production rate 82.4%.
Embodiment 2
The synthesis of compound shown in formula (4)
1000 milliliters of there-necked flasks, with magnetic agitation, nitrogen is protected, addition 2,8- dibromo azophenlyene 6.72g (molecular weight 336, 0.02mol), naphthalene -2- boric acid 7.4g (molecular weight 172,0.043mol), four (triphenylphosphine conjunction) palladium 2.3g (molecular weight 1154,0.002mol), the aqueous sodium carbonate 100ml of 2M, toluene 100ml, ethanol 100ml.After argon displacement, Backflow, is reacted with the monitoring of thin layer chromatography (TLC) method, and after 3.5 hours, TLC has found that the reaction of raw material bromo-derivative is complete, only There is product point.Cooling, separates organic layer, is evaporated, and pillar layer separation, ethyl acetate/petroleum ether drip washing obtain 8.1g formulas (4) compound shown in, molecular weight 432, yield 93.8%.
Product MS (m/e):432, elementary analysiss (C32H20N2):Theoretical value C:88.86%, H:4.66%, N: 6.48%;Measured value C:88.83%, H:4.67%, N:6.50%.
Embodiment 3
The synthesis of compound shown in formula (5)
Synthesis step is same as embodiment 2, and naphthalene -2- boric acid is changed into naphthalene -1- boric acid simply, and other reagents are constant, obtains formula (5) Shown compound.
Product MS (m/e):432, elementary analysiss (C32H20N2):Theoretical value C:88.86%, H:4.66%, N: 6.48%;Measured value C:88.88%, H:4.67%, N:6.45%.
Embodiment 4
The synthesis of compound shown in formula (6)
Synthesis step is same as embodiment 2, and 2,8- dibromo azophenlyene is changed into 2,7- dibromo azophenlyene simply, and other reagents are constant, Obtain compound shown in formula (6).
Product MS (m/e):432, elementary analysiss (C32H20N2):Theoretical value C:88.86%, H:4.66%, N: 6.48%;Measured value C:88.85%, H:4.69%, N:6.46%.
Embodiment 5
The synthesis of compound shown in formula (7)
Synthesis step is same as embodiment 2, and simply by raw material 2,8- dibromo azophenlyene changes into 2,7- dibromo azophenlyene, and naphthalene -2- boric acid changes It is changed into naphthalene -1- boric acid, other reagents are constant, obtains compound shown in formula (7).
Product MS (m/e):432, elementary analysiss (C32H20N2):Theoretical value C:88.86%, H:4.66%, N: 6.48%;Measured value C:88.84%, H:4.69%, N:6.47%.
Embodiment 6
The synthesis of compound shown in formula (8)
Synthesis step is same as embodiment 2, and raw naphthalene material -2- boric acid is changed into p- (naphthalene -1- bases) phenylboric acid simply, other examinations Agent is constant, obtains compound shown in formula (8).
Product MS (m/e):584, elementary analysiss (C44H28N2):Theoretical value C:90.38%, H:4.83%, N: 4.79%;Measured value C:90.34%, H:4.86%, N:4.82%.
Embodiment 7
The synthesis of compound shown in formula (9)
Synthesis step is same as embodiment 2, and raw naphthalene material -2- boric acid is changed into p- (naphthalene -2- bases) phenylboric acid simply, other examinations Agent is constant, obtains compound shown in formula (9);Its nuclear magnetic spectrogram (1HNMR) as shown in Figure 1.
Product MS (m/e):584, elementary analysiss (C44H28N2):Theoretical value C:90.38%, H:4.83%, N: 4.79%;Measured value C:90.37%, H:4.82%, N:4.81%;Its nuclear magnetic spectrogram (1HNMR) as shown in Figure 1.
Embodiment 8
The synthesis of compound shown in formula (10)
Synthesis step is same as embodiment 2, and simply by raw material 2,8- dibromo azophenlyene changes into 2,7- dibromo azophenlyene, and naphthalene -2- boric acid changes It is changed into p- (naphthalene -2- bases) phenylboric acid, other reagents are constant, obtain compound shown in formula (10).
Product MS (m/e):584, elementary analysiss (C44H28N2):Theoretical value C:90.38%, H:4.83%, N: 4.79%;Measured value C:90.33%, H:4.86%, N:4.81%.
Embodiment 9
The synthesis of compound shown in formula (11)
Synthesis step is same as embodiment 2, and simply by raw material 2,8- dibromo azophenlyene changes into 2,7- dibromo azophenlyene, and naphthalene -2- boric acid changes It is changed into p- (naphthalene -1- bases) phenylboric acid, other reagents are constant, obtain compound shown in formula (11).
Product MS (m/e):584, elementary analysiss (C44H28N2):Theoretical value C:90.38%, H:4.83%, N: 4.79%;Measured value C:90.37%, H:4.86%, N:4.77%.
Embodiment 10
The synthesis of compound shown in formula (12)
Synthesis step is same as embodiment 2, and raw naphthalene material -2- boric acid is changed into phenanthrene -9- boric acid simply, and other reagents are constant, obtain Compound shown in formula (12).
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:4.55%, N:5.22%.
Embodiment 11
The synthesis of compound shown in formula (13)
Synthesis step is same as embodiment 2, and simply by raw material 2,8- dibromo azophenlyene changes into 2,7- dibromo azophenlyene, and naphthalene -2- boric acid changes It is changed into phenanthrene -9- boric acid, other reagents are constant, obtains compound shown in formula (13).
Product MS (m/e):532, elementary analysiss (C40H24N2):Theoretical value C:90.20%, H:4.54%, N: 5.26%;Measured value C:90.24%, H:4.52%, N:5.24%.
Embodiment 12
The synthesis of compound shown in formula (14)
Synthesis step is same as embodiment 2, and raw naphthalene material -2- boric acid is changed into p- (phenanthrene -9- bases) phenylboric acid simply, other examinations Agent is constant, obtains compound shown in formula (14).
Product MS (m/e):684, elementary analysiss (C52H32N2):Theoretical value C:91.20%, H:4.71%, N: 4.09%;Measured value C:91.23%, H:4.72%, N:4.05%.
Embodiment 13
The synthesis of compound shown in formula (15)
Synthesis step is same as embodiment 2, and simply by raw material 2,8- dibromo azophenlyene changes into 2,7- dibromo azophenlyene, and naphthalene -2- boric acid changes It is changed into p- (phenanthrene -9- bases) phenylboric acid, other reagents are constant, obtain compound shown in formula (15).
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:4.74%, N:4.04%;Its nuclear magnetic spectrogram (1HNMR Fig. 2 institutes) are seen Show.
Embodiment 14
The synthesis of compound shown in formula (16)
Synthesis step is same as embodiment 2, and raw naphthalene material -2- boric acid is changed into pyrene -1- boric acid simply, and other reagents are constant, obtain Compound shown in formula (16).
Product MS (m/e):580, elementary analysiss (C44H24N2):Theoretical value C:91.01%, H:4.17%, N: 4.82%;Measured value C:91.03%, H:4.13%, N:4.84%.
Embodiment 15
The synthesis of compound shown in formula (17)
Synthesis step is same as embodiment 2, and simply by raw material 2,8- dibromo azophenlyene changes into 2,7- dibromo azophenlyene, and naphthalene -2- boric acid changes It is changed into pyrene -1- boric acid, other reagents are constant, obtains compound shown in formula (17).
Product MS (m/e):580, elementary analysiss (C44H24N2):Theoretical value C:91.01%, H:4.17%, N: 4.82%;Measured value C:91.02%, H:4.15%, N:4.83%.
Embodiment 16
The synthesis of compound shown in formula (18)
Synthesis step is same as embodiment 2, and raw naphthalene material -2- boric acid is changed into p- (pyrene -1- bases) phenylboric acid simply, other examinations Agent is constant, obtains compound shown in formula (18).
Product MS (m/e):732, elementary analysiss (C56H32N2):Theoretical value C:91.78%, H:4.40%, N: 3.82%;Measured value C:91.73%, H:4.43%, N:3.84%.
Embodiment 17
The synthesis of compound shown in formula (19)
Synthesis step is same as embodiment 2, and simply by raw material 2,8- dibromo azophenlyene changes into 2,7- dibromo azophenlyene, and naphthalene -2- boric acid changes It is changed into p- (pyrene -1- bases) phenylboric acid, other reagents are constant, obtain compound shown in formula (19).
Product MS (m/e):732, elementary analysiss (C56H32N2):Theoretical value C:91.78%, H:4.40%, N: 3.82%;Measured value C:91.74%, H:4.41%, N:3.85%.
Embodiment 18
The synthesis of compound shown in formula (20)
Synthetic reaction is allocated as two steps.The first step is same as embodiment 2, and naphthalene -2- boric acid is changed into p- (naphthalene -1- bases) benzene simply Boric acid, and 2,8- dibromo azophenlyene and p- (naphthalene -1- bases) phenylboric acid equimolar feed intake, and other reagents and reaction condition are unchanged, Pillar layer separation after reaction, obtains a bromination product;
Second step is same as embodiment 2, and simply by raw material 2,8- dibromo azophenlyene changes into the bromination product that the first step here is obtained, Naphthalene -2- boric acid changes into pyrene -1- boric acid, and the bromination product that the first step is obtained is fed intake with pyrene -1- boric acid equimolars, its Its reagent and reaction condition are unchanged, pillar layer separation after reaction, obtain compound shown in formula (20).
Product MS (m/e):582, elementary analysiss (C44H26N2):Theoretical value C:90.69%, H:4.50%, N: 4.81%;Measured value C:90.64%, H:4.52%, N:4.84%.
Embodiment 19
The synthesis of compound shown in formula (21)
Synthetic reaction is allocated as two steps.
The first step is same as embodiment 2, and simply by raw material 2,8- dibromo azophenlyene changes into 2,7- dibromo azophenlyene, and naphthalene -2- boric acid changes Feed intake for p- (naphthalene -1- bases) phenylboric acid, and 2,7- dibromo azophenlyene and p- (naphthalene -1- bases) phenylboric acid equimolar, other examinations Agent and reaction condition are unchanged, pillar layer separation after reaction, obtain a bromination product;
Second step is same as embodiment 2, and 2,8- dibromo azophenlyene is changed into the bromination product that the first step here is obtained, naphthalene simply - 2- boric acid changes into pyrene -1- boric acid, and the bromination product that the first step is obtained is fed intake with pyrene -1- boric acid equimolars, other Reagent and reaction condition are unchanged, pillar layer separation after reaction, obtain compound shown in formula (21).
Product MS (m/e):582, elementary analysiss (C44H26N2):Theoretical value C:90.69%, H:4.50%, N: 4.81%;Measured value C:90.65%, H:4.53%, N:4.82%.
Embodiment 20
The synthesis of compound shown in formula (22)
Synthesis step is same as embodiment 2, and raw naphthalene material -2- boric acid is changed into 9- phenylanthracene -10- boric acid simply, and other reagents are not Become, obtain compound shown in formula (22).
Product MS (m/e):684, elementary analysiss (C52H32N2):Theoretical value C:91.20%, H:4.71%, N: 4.09%;Measured value C:91.23%, H:4.73%, N:4.04%.
Embodiment 21
The synthesis of compound shown in formula (23)
Synthesis step is same as embodiment 2, and simply by raw material 2,8- dibromo azophenlyene changes into 2,7- dibromo azophenlyene, and naphthalene -2- boric acid changes It is changed into 9- phenylanthracene -10- boric acid, other reagents are constant, obtain compound shown in formula (23).
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:4.72%, N:4.06%.
Embodiment 22
The synthesis of compound shown in formula (24)
Synthetic reaction is allocated as two steps.
The first step is same as embodiment 2, and raw naphthalene material -2- boric acid is changed into p- (naphthalene -1- bases) phenylboric acid, and 2,8- simply Dibromo azophenlyene and p- (naphthalene -1- bases) phenylboric acid equimolar feed intake, and other reagents and reaction condition are unchanged, column chromatography after reaction Separate, obtain a bromination product;
Second step is same as embodiment 2, and 2,8- dibromo azophenlyene is changed into the bromination product that the first step here is obtained, naphthalene simply - 2- boric acid changes into 9- phenylanthracene -10- boric acid, and the bromination product that the first step is obtained and 9- phenylanthracene -10- boric acid etc. Mole feed intake, other reagents and reaction condition are unchanged, pillar layer separation after reaction, obtain compound shown in formula (24).
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:4.72%, N:4.44%.
Embodiment 23
The synthesis of compound shown in formula (25)
Synthetic reaction is allocated as two steps.
The first step is same as embodiment 2, and simply by raw material 2,8- dibromo azophenlyene changes into 2,7- dibromo azophenlyene, and naphthalene -2- boric acid changes Feed intake for p- (naphthalene -1- bases) phenylboric acid, and 2,7- dibromo azophenlyene and p- (naphthalene -1- bases) phenylboric acid equimolar, other examinations Agent and reaction condition are unchanged, pillar layer separation after reaction, obtain a bromination product;
Second step is same as embodiment 2, and 2,8- dibromo azophenlyene is changed into the bromination product that the first step here is obtained, naphthalene simply - 2- boric acid changes into 9- phenylanthracene -10- boric acid, and the bromination product that the first step is obtained and 9- phenylanthracene -10- boric acid etc. Mole feed intake, other reagents and reaction condition are unchanged, pillar layer separation after reaction, obtain compound shown in formula (25).
Product MS (m/e):634, elementary analysiss (C48H30N2):Theoretical value C:90.82%, H:4.76%, N: 4.41%;Measured value C:90.83%, H:4.74%, N:4.43%.
Embodiment 24
The synthesis of compound shown in formula (26)
Synthesis step is same as embodiment 2, and raw naphthalene material -2- boric acid is changed into 7,10- diphenyl fluoranthene -3- boric acid simply, other Reagent is constant, obtains compound shown in formula (26).
Product MS (m/e):884, elementary analysiss (C68H40N2):Theoretical value C:92.28%, H:4.56%, N: 3.17%;Measured value C:92.32%, H:4.54%, N:3.14%;Its nuclear magnetic spectrogram (1HNMR) as shown in Figure 3.
Embodiment 25
The synthesis of compound shown in formula (27)
Synthesis step is same as embodiment 2, and simply by raw material 2,8- dibromo azophenlyene changes into 2,7- dibromo azophenlyene, and naphthalene -2- boric acid changes It is changed into 7,10- diphenyl fluoranthene -3- boric acid, other reagents are constant, obtain compound shown in formula (27).
Product MS (m/e):884, elementary analysiss (C68H40N2):Theoretical value C:92.28%, H:4.56%, N: 3.17%;Measured value C:92.30%, H:4.54%, N:3.16%.
Embodiment 26
The synthesis of compound shown in formula (28)
Synthetic reaction is allocated as two steps.
The first step is same as embodiment 2, and simply by raw material 2,8- dibromo azophenlyene changes into 2,7- dibromo azophenlyene, and naphthalene -2- boric acid changes Feed intake for 2- phenylpyridine -5- boric acid, and 2,7- dibromo azophenlyene and 2- phenylpyridine -5- boric acid equimolars, other reagents and Reaction condition is unchanged, pillar layer separation after reaction, obtains a bromination product;
Second step is same as embodiment 2, and 2,8- dibromo azophenlyene is changed into the bromination product that the first step here is obtained, naphthalene simply - 2- boric acid changes into p- (9- phenylanthracene -10- bases) phenylboric acid, and the bromination product that the first step is obtained and p- (9- Phenylanthracene -10- bases) phenylboric acid equimolar feeds intake, and other reagents and reaction condition are unchanged, pillar layer separation after reaction, obtain Compound shown in formula (28).
Product MS (m/e):661, elementary analysiss (C49H31N3):Theoretical value C:88.93%, H:4.72%, N: 6.35%;Measured value C:88.91%, H:4.76%, N:6.33%.
Embodiment 27
The synthesis of compound shown in formula (29)
Synthetic reaction is allocated as two steps.
The first step is same as embodiment 2, and raw naphthalene material -2- boric acid is changed into 2- phenylpyridine -5- boric acid, and 2,8- dibromo simply Azophenlyene and 2- phenylpyridine -5- boric acid equimolars feed intake, and other reagents and reaction condition are unchanged, pillar layer separation after reaction, Obtain a bromination product;
Second step is same as embodiment 2, and 2,8- dibromo azophenlyene is changed into the bromination product that the first step here is obtained, naphthalene simply - 2- boric acid changes into p- (9- phenylanthracene -10- bases) phenylboric acid, and the bromination product that the first step is obtained and p- (9- Phenylanthracene -10- bases) phenylboric acid equimolar feeds intake, and other reagents and reaction condition are unchanged, pillar layer separation after reaction, obtain Compound shown in formula (29).
Product MS (m/e):661, elementary analysiss (C49H31N3):Theoretical value C:88.93%, H:4.72%, N: 6.35%;Measured value C:88.95%, H:4.73%, N:6.32%.
Embodiment 28
The synthesis of compound shown in formula (30)
Synthetic reaction is allocated as two steps.
The first step is same as embodiment 2, and raw naphthalene material -2- boric acid is changed into 2- phenylpyridine -5- boric acid, and 2,8- dibromo simply Azophenlyene and 2- phenylpyridine -5- boric acid equimolars feed intake, and other reagents and reaction condition are unchanged, pillar layer separation after reaction, Obtain a bromination product;
Second step is same as embodiment 2, and 2,8- dibromo azophenlyene is changed into the bromination product that the first step here is obtained, naphthalene simply - 2- boric acid changes into pyrene -1- boric acid, and the bromination product that the first step is obtained is fed intake with pyrene -1- boric acid equimolars, other Reagent and reaction condition are unchanged, pillar layer separation after reaction, obtain compound shown in formula (30).
Product MS (m/e):533, elementary analysiss (C39H23N3):Theoretical value C:87.78%, H:4.34%, N: 7.87%;Measured value C:87.81%, H:4.35%, N:7.84%.
Embodiment 29
The synthesis of compound shown in formula (31)
Synthetic reaction is allocated as two steps.
The first step is same as embodiment 2, and simply by raw material 2,8- dibromo azophenlyene changes into 2,7- dibromo azophenlyene, and naphthalene -2- boric acid changes Feed intake for 2- phenylpyridine -5- boric acid, and 2,7- dibromo azophenlyene and 2- phenylpyridine -5- boric acid equimolars, other reagents and Reaction condition is unchanged, pillar layer separation after reaction, obtains a bromination product;
Second step is same as embodiment 2, and 2,8- dibromo azophenlyene is changed into the bromination product that the first step here is obtained, naphthalene simply - 2- boric acid changes into pyrene -1- boric acid, and the bromination product that the first step is obtained is fed intake with pyrene -1- boric acid equimolars, other Reagent and reaction condition are unchanged, pillar layer separation after reaction, obtain compound shown in formula (31).
Product MS (m/e):533, elementary analysiss (C39H23N3):Theoretical value C:87.78%, H:4.34%, N: 7.87%;Measured value C:87.82%, H:4.33%, N:7.85%;Its nuclear magnetic spectrogram (1HNMR) as shown in Figure 4.
Embodiment 30
The synthesis of compound shown in formula (32)
Synthetic reaction is allocated as two steps.
The first step is same as embodiment 2, and raw naphthalene material -2- boric acid is changed into 2- phenylpyridine -5- boric acid, and 2,8- dibromo simply Azophenlyene and 2- phenylpyridine -5- boric acid equimolars feed intake, and other reagents and reaction condition are unchanged, pillar layer separation after reaction, Obtain a bromination product;
Second step is same as embodiment 2, and 2,8- dibromo azophenlyene is changed into the bromination product that the first step here is obtained, naphthalene simply - 2- boric acid changes into p- (naphthalene -1- bases) phenylboric acid, and the bromination product that the first step is obtained and p- (naphthalene -1- bases) Phenylboric acid equimolar feeds intake, and other reagents and reaction condition are unchanged, pillar layer separation after reaction, obtains formula (32) shownization Compound.
Product MS (m/e):535, elementary analysiss (C39H25N3):Theoretical value C:87.45%, H:4.70%, N: 7.84%;Measured value C:87.43%, H:4.75%, N:7.82%.
Embodiment 31
The synthesis of compound shown in formula (33)
Synthetic reaction is allocated as two steps.
The first step is same as embodiment 2, and simply by raw material 2,8- dibromo azophenlyene changes into 2,7- dibromo azophenlyene, and naphthalene -2- boric acid changes Feed intake for 2- phenylpyridine -5- boric acid, and 2,7- dibromo azophenlyene and 2- phenylpyridine -5- boric acid equimolars, other reagents and Reaction condition is unchanged, pillar layer separation after reaction, obtains a bromination product;
Second step is same as embodiment 2, and 2,8- dibromo azophenlyene is changed into the bromination product that the first step here is obtained, naphthalene simply - 2- boric acid changes into p- (naphthalene -1- bases) phenylboric acid, and the bromination product that the first step is obtained and p- (naphthalene -1- bases) Phenylboric acid equimolar feeds intake, and other reagents and reaction condition are unchanged, pillar layer separation after reaction, obtains formula (33) shownization Compound.
Product MS (m/e):535, elementary analysiss (C39H25N3):Theoretical value C:87.45%, H:4.70%, N: 7.84%;Measured value C:87.41%, H:4.73%, N:7.86%.
Embodiment 32
The synthesis of compound shown in formula (34)
Synthetic reaction is allocated as two steps.
The first step is same as embodiment 2, and raw naphthalene material -2- boric acid is changed into 2- phenylpyridine -5- boric acid, and 2,8- dibromo simply Azophenlyene and 2- phenylpyridine -5- boric acid equimolars feed intake, and other reagents and reaction condition are unchanged, pillar layer separation after reaction, Obtain a bromination product;
Second step is same as embodiment 2, and 2,8- dibromo azophenlyene is changed into the bromination product that the first step here is obtained, naphthalene simply - 2- boric acid changes into phenanthrene -9- boric acid, and the bromination product that the first step is obtained is fed intake with phenanthrene -9- boric acid equimolars, other Reagent and reaction condition are unchanged, pillar layer separation after reaction, obtain compound shown in formula (34).
Product MS (m/e):509, elementary analysiss (C37H23N3):Theoretical value C:87.21%, H:4.55%, N: 8.25%;Measured value C:87.23%, H:4.54%, N:8.23%.
Embodiment 33
The synthesis of compound shown in formula (35)
Synthetic reaction is allocated as two steps.
The first step is same as embodiment 2, and simply by raw material 2,8- dibromo azophenlyene changes into 2,7- dibromo azophenlyene, and naphthalene -2- boric acid changes Feed intake for 2- phenylpyridine -5- boric acid, and 2,7- dibromo azophenlyene and 2- phenylpyridine -5- boric acid equimolars, other reagents and Reaction condition is unchanged, pillar layer separation after reaction, obtains a bromination product;
Second step is same as embodiment 2, and 2,8- dibromo azophenlyene is changed into the bromination product that the first step here is obtained, naphthalene simply - 2- boric acid changes into phenanthrene -9- boric acid, and the bromination product that the first step is obtained is fed intake with phenanthrene -9- boric acid equimolars, other Reagent and reaction condition are unchanged, pillar layer separation after reaction, obtain compound shown in formula (35).
Product MS (m/e):509, elementary analysiss (C37H23N3):Theoretical value C:87.21%, H:4.55%, N: 8.25%;Measured value C:87.22%, H:4.51%, N:8.27%.
Embodiment 34
The synthesis of compound shown in formula (36)
Synthetic reaction is allocated as two steps.
The first step is same as embodiment 2, and simply by raw material 2,8- dibromo azophenlyene changes into 2,7- dibromo azophenlyene, and naphthalene -2- boric acid changes For 4- (2- phenyl -1H- benzos [d] imidazoles -1- bases) phenylboric acid, and 2,7- dibromo azophenlyene and 4- (2- phenyl -1H- benzos [d] imidazoles - 1- bases) phenylboric acid equimolar feeds intake, and other reagents and reaction condition are unchanged, pillar layer separation after reaction, obtain bromo product Thing;
Second step is same as embodiment 2, and 2,8- dibromo azophenlyene is changed into the bromination product that the first step here is obtained, naphthalene simply - 2- boric acid changes into phenanthrene -9- boric acid, and the bromination product that the first step is obtained is fed intake with phenanthrene -9- boric acid equimolars, other Reagent and reaction condition are unchanged, pillar layer separation after reaction, obtain compound shown in formula (36).
Product MS (m/e):624, elementary analysiss (C45H28N4):Theoretical value C:86.51%, H:4.52%, N: 8.97%;Measured value C:86.53%, H:4.54%, N:8.93%;Its nuclear magnetic spectrogram (1HNMR) as shown in Figure 5.
Embodiment 35
The synthesis of compound shown in formula (37)
Synthetic reaction is allocated as two steps.
The first step is same as embodiment 2, and raw naphthalene material -2- boric acid is changed into 4- (2- phenyl -1H- benzos [d] imidazoles -1- bases) benzene simply Boric acid, and 2,8- dibromo azophenlyene and 4- (2- phenyl -1H- benzos [d] imidazoles -1- bases) phenylboric acid equimolar feed intake, other reagents Unchanged with reaction condition, pillar layer separation after reaction obtains a bromination product;
Second step is same as embodiment 2, and 2,8- dibromo azophenlyene is changed into the bromination product that the first step here is obtained, naphthalene simply - 2- boric acid changes into phenanthrene -9- boric acid, and the bromination product that the first step is obtained is fed intake with phenanthrene -9- boric acid equimolars, other Reagent and reaction condition are unchanged, pillar layer separation after reaction, obtain compound shown in formula (37).
Product MS (m/e):624, elementary analysiss (C45H28N4):Theoretical value C:86.51%, H:4.52%, N: 8.97%;Measured value C:86.54%, H:4.52%, N:8.94%.
Embodiment 36
The synthesis of compound shown in formula (38)
Synthetic reaction is allocated as two steps.
The first step is same as embodiment 2, and raw naphthalene material -2- boric acid is changed into 4- (2- phenyl -1H- benzos [d] imidazoles -1- bases) benzene simply Boric acid, and 2,8- dibromo azophenlyene and 4- (2- phenyl -1H- benzos [d] imidazoles -1- bases) phenylboric acid equimolar feed intake, other reagents Unchanged with reaction condition, pillar layer separation after reaction obtains a bromination product;
Second step is same as embodiment 2, and 2,8- dibromo azophenlyene is changed into the bromination product that the first step here is obtained, naphthalene simply - 2- boric acid changes into p- (naphthalene -1- bases) phenylboric acid, and the bromination product that the first step is obtained and p- (naphthalene -1- bases) Phenylboric acid equimolar feeds intake, and other reagents and reaction condition are unchanged, pillar layer separation after reaction, obtains formula (38) shownization Compound.
Product MS (m/e):650, elementary analysiss (C47H30N4):Theoretical value C:86.74%, H:4.65%, N: 8.61%;Measured value C:86.72%, H:4.64%, N:8.64%.
Embodiment 37
The synthesis of compound shown in formula (39)
Synthetic reaction is allocated as two steps.
The first step is same as embodiment 2, and simply by raw material 2,8- dibromo azophenlyene changes into 2,7- dibromo azophenlyene, and naphthalene -2- boric acid changes For 4- (2- phenyl -1H- benzos [d] imidazoles -1- bases) phenylboric acid, and 2,7- dibromo azophenlyene and 4- (2- phenyl -1H- benzos [d] imidazoles - 1- bases) phenylboric acid equimolar feeds intake, and other reagents and reaction condition are unchanged, pillar layer separation after reaction, obtain bromo product Thing;
Second step is same as embodiment 2, and 2,8- dibromo azophenlyene is changed into the bromination product that the first step here is obtained, naphthalene simply - 2- boric acid changes into p- (naphthalene -1- bases) phenylboric acid, and the bromination product that the first step is obtained and p- (naphthalene -1- bases) Phenylboric acid equimolar feeds intake, and other reagents and reaction condition are unchanged, pillar layer separation after reaction, obtains formula (39) shownization Compound.
Product MS (m/e):650, elementary analysiss (C47H30N4):Theoretical value C:86.74%, H:4.65%, N: 8.61%;Measured value C:86.76%, H:4.61%, N:8.63%.
Embodiment 38
The synthesis of compound shown in formula (40)
Synthetic reaction is allocated as two steps.
The first step is same as embodiment 2, and raw naphthalene material -2- boric acid is changed into 4- (2- phenyl -1H- benzos [d] imidazoles -1- bases) benzene simply Boric acid, and 2,8- dibromo azophenlyene and 4- (2- phenyl -1H- benzos [d] imidazoles -1- bases) phenylboric acid equimolar feed intake, other reagents Unchanged with reaction condition, pillar layer separation after reaction obtains a bromination product;
Second step is same as embodiment 2, and 2,8- dibromo azophenlyene is changed into the bromination product that the first step here is obtained, naphthalene simply - 2- boric acid changes into pyrene -1- boric acid, and the bromination product that the first step is obtained is fed intake with pyrene -1- boric acid equimolars, other Reagent and reaction condition are unchanged, pillar layer separation after reaction, obtain compound shown in formula (40).
Product MS (m/e):648, elementary analysiss (C47H28N4):Theoretical value C:87.01%, H:4.35%, N: 8.64%;Measured value C:87.04%, H:4.34%, N:8.62%.
Embodiment 39
The synthesis of compound shown in formula (41)
Synthetic reaction is allocated as two steps.
The first step is same as embodiment 2, and simply by raw material 2,8- dibromo azophenlyene changes into 2,7- dibromo azophenlyene, and naphthalene -2- boric acid changes For 4- (2- phenyl -1H- benzos [d] imidazoles -1- bases) phenylboric acid, and 2,7- dibromo azophenlyene and 4- (2- phenyl -1H- benzos [d] imidazoles - 1- bases) phenylboric acid equimolar feeds intake, and other reagents and reaction condition are unchanged, pillar layer separation after reaction, obtain bromo product Thing;
Second step is same as embodiment 2, and 2,8- dibromo azophenlyene is changed into the bromination product that the first step here is obtained, naphthalene simply - 2- boric acid changes into pyrene -1- boric acid, and the bromination product that the first step is obtained is fed intake with pyrene -1- boric acid equimolars, other Reagent and reaction condition are unchanged, pillar layer separation after reaction, obtain compound shown in formula (41).
Product MS (m/e):648, elementary analysiss (C47H28N4):Theoretical value C:87.01%, H:4.35%, N: 8.64%;Measured value C:87.03%, H:4.36%, N:8.61%.
Embodiment 40
The synthesis of compound shown in formula (42)
Synthetic reaction is allocated as two steps.
The first step is same as embodiment 2, and raw naphthalene material -2- boric acid is changed into 4- (2- phenyl -1H- benzos [d] imidazoles -1- bases) benzene simply Boric acid, and 2,8- dibromo azophenlyene and 4- (2- phenyl -1H- benzos [d] imidazoles -1- bases) phenylboric acid equimolar feed intake, other reagents Unchanged with reaction condition, pillar layer separation after reaction obtains a bromination product;
Second step is same as embodiment 2, and 2,8- dibromo azophenlyene is changed into the bromination product that the first step here is obtained, naphthalene simply - 2- boric acid changes into triphenylene -2- boric acid, and the bromination product that the first step is obtained is thrown with triphenylene -2- boric acid equimolar Expect, other reagents and reaction condition are unchanged, and pillar layer separation after reaction obtains compound shown in formula (42).
Product MS (m/e):674, elementary analysiss (C49H30N4):Theoretical value C:87.22%, H:4.48%, N: 8.30%;Measured value C:87.24%, H:4.43%, N:8.33%.
Embodiment 41
The synthesis of compound shown in formula (43)
Synthetic reaction is allocated as two steps.
The first step is same as embodiment 2, and simply by raw material 2,8- dibromo azophenlyene changes into 2,7- dibromo azophenlyene, and naphthalene -2- boric acid changes For 4- (2- phenyl -1H- benzos [d] imidazoles -1- bases) phenylboric acid, and 2,7- dibromo azophenlyene and 4- (2- phenyl -1H- benzos [d] miaows Azoles -1- bases) phenylboric acid equimolar feeds intake, and other reagents and reaction condition are unchanged, pillar layer separation after reaction, obtain a bromo Product;
Second step is same as embodiment 2, and 2,8- dibromo azophenlyene is changed into the bromination product that the first step here is obtained, naphthalene simply - 2- boric acid changes into triphenylene -2- boric acid, and the bromination product that the first step is obtained is thrown with triphenylene -2- boric acid equimolar Expect, other reagents and reaction condition are unchanged, and pillar layer separation after reaction obtains compound shown in formula (43).
Product MS (m/e):674, elementary analysiss (C49H30N4):Theoretical value C:87.22%, H:4.48%, N: 8.30%;Measured value C:87.23%, H:4.45%, N:8.32%.
Embodiment 42
The synthesis of compound shown in formula (44)
Synthetic reaction is allocated as two steps.
The first step is same as embodiment 2, and raw naphthalene material -2- boric acid is changed into 2- phenylpyridine -5- boric acid, and 2,8- bis- simply Bromine azophenlyene and 2- phenylpyridine -5- boric acid equimolars feed intake, and other reagents and reaction condition are unchanged, pillar layer separation after reaction, Obtain a bromination product;
Second step is same as embodiment 2, and 2,8- dibromo azophenlyene is changed into the bromination product that the first step here is obtained, naphthalene simply - 2- boric acid changes into triphenylene -2- boric acid, and the bromination product that the first step is obtained is thrown with triphenylene -2- boric acid equimolar Expect, other reagents and reaction condition are unchanged, and pillar layer separation after reaction obtains compound shown in formula (44).
Product MS (m/e):559, elementary analysiss (C41H25N3):Theoretical value C:87.99%, H:4.50%, N: 7.51%;Measured value C:87.94%, H:4.52%, N:7.54%.
Embodiment 43
The synthesis of compound shown in formula (45)
Synthetic reaction is allocated as two steps.
The first step is same as embodiment 2, and simply by raw material 2,8- dibromo azophenlyene changes into 2,7- dibromo azophenlyene, and naphthalene -2- boric acid changes Feed intake for 2- phenylpyridine -5- boric acid, and 2,7- dibromo azophenlyene and 2- phenylpyridine -5- boric acid equimolars, other reagents and Reaction condition is unchanged, pillar layer separation after reaction, obtains a bromination product;
Second step is same as embodiment 2, and 2,8- dibromo azophenlyene is changed into the bromination product that the first step here is obtained, naphthalene simply - 2- boric acid changes into triphenylene -2- boric acid, and the bromination product that the first step is obtained is thrown with triphenylene -2- boric acid equimolar Expect, other reagents and reaction condition are unchanged, and pillar layer separation after reaction obtains compound shown in formula (45).
Product MS (m/e):559, elementary analysiss (C41H25N3):Theoretical value C:87.99%, H:4.50%, N: 7.51%;Measured value C:87.96%, H:4.52%, N:7.52%;Its nuclear magnetic spectrogram (1HNMR Fig. 1 institutes) are seen Show.
Embodiment 44
The synthesis of compound shown in formula (46)
Synthesis step is same as embodiment 2, and raw naphthalene material -2- boric acid is changed into triphenylene -2- boric acid simply, and other reagents are constant, Obtain compound shown in formula (46).
Product MS (m/e):632, elementary analysiss (C48H28N2):Theoretical value C:91.11%, H:4.46%, N: 4.43%;Measured value C:91.14%, H:4.42%, N:4.44%.
Embodiment 45
The synthesis of compound shown in formula (47)
Synthesis step is same as embodiment 2, and simply by raw material 2,8- dibromo azophenlyene changes into 2,7- dibromo azophenlyene, and naphthalene -2- boric acid changes It is changed into triphenylene -2- boric acid, other reagents are constant, obtains compound shown in formula (47).
Product MS (m/e):632, elementary analysiss (C48H28N2):Theoretical value C:91.11%, H:4.46%, N: 4.43%;Measured value C:91.12%, H:4.43%, N:4.45%.
The Application Example of each compound of the invention is presented herein below:
Embodiment 46
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 sun On the tunic of pole, 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 (4), formula (6), formula (12), formula (13), formula (16), formula (22), Formula (26), formula (34), formula (36), formula (46) or electron transfer layer material of the compound as device shown in formula (47) 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 (4) 1000.00 5.7 6.8
Formula (6) 1000.00 5.7 6.9
Formula (12) 1000.00 5.6 6.8
Formula (13) 1000.00 5.5 7.1
Formula (16) 1000.00 5.6 7.2
Formula (22) 1000.00 5.6 7.1
Formula (26) 1000.00 5.7 7.1
Formula (34) 1000.00 5.6 7.3
Formula (36) 1000.00 5.7 7.2
Formula (46) 1000.00 5.6 7.3
Formula (47) 1000.00 5.7 7.1
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 phenazene derivative, it is characterised in that with the structure as shown in formula (1):
Wherein:Ar1And Ar2It is identical or different, it is respectively and independently selected from H, halogen, substituted or unsubstituted C4-C30Aromatic ring Base, substituted or unsubstituted C4-C30Heteroaryl ring group, substituted or unsubstituted C4-C30Fused ring aryl, it is substituted or unsubstituted C4-C30Condensed hetero ring aryl, substituted or unsubstituted alkyl, cycloalkyl, cyano group, aromatic amine base, aliphatic secondary amido, The pyridine radicals of substituted or unsubstituted carbazole -9- bases, aromatic series and aliphatic substitution, or the phenyl that benzimidazolyl replaces; Ar1And Ar2It is asynchronously from H.
2. phenazene derivative according to claim 1, it is characterised in that the formula (1) is formula (2) and formula (3) Shown structure:
Ar1And Ar2It is identical or different, it is respectively and independently selected from H, halogen, substituted or unsubstituted C4-C30Aromatic ring yl, take Generation or unsubstituted C4-C30Heteroaryl ring group, substituted or unsubstituted C4-C30Fused ring aryl, substituted or unsubstituted C4-C30 Condensed hetero ring aryl, substituted or unsubstituted alkyl, cycloalkyl, cyano group, aromatic amine base, aliphatic secondary amido replace Or the pyridine radicals of unsubstituted carbazole -9- bases, aromatic series and aliphatic substitution, or the phenyl that benzimidazolyl replaces;
Ar1And Ar2It is asynchronously from H.
3. phenazene derivative according to claim 1 and 2, it is characterised in that the aromatic ring yl, heteroaryl ring group, Fused ring aryl, the substituent group on condensed hetero ring aryl be aromatic ring yl, heteroaryl ring group, fused ring aryl or condensed hetero ring aryl, replace or Unsubstituted alkyl, cycloalkyl, secondary amine, cyano group, halogen.
4. the phenazene derivative according to any one of claim 1-3, it is characterised in that the replacement or unsubstituted virtue Alkyl is phenyl, o-tolyl, p-methylphenyl or tert-butyl-phenyl;It is described replacement or unsubstituting heterocycle aryl be furan, Benzofuran, dibenzofurans, thiophene, benzothiophene, dibenzothiophenes, carbazole, pyridine, pyrazine, 2.4- methyl isophthalic acid .3.5 Triazine or 4.6 diphenylpyrimidins etc.;It is described replacement or unsubstituted condensed-nuclei aromatics base be naphthyl, phenanthryl, anthryl, pyrenyl, Base, fluorenyl, triphenylenyl or 9.9- dimethyl -2- fluorenyls;Replace or unsubstituted condensed hetero ring aryl be quinoline, isoquinolin, Quinazoline;Substituted or unsubstituted alkyl is trifluoromethyl or alkyl.
5. phenazene derivative according to claim 1, it is characterised in that the formula (1) with following formula (4)- (47) concrete structure shown in:
6. application of the phenazene derivative described in a kind of any one of claim 1-5 in organic electroluminescence device.
7. application of a kind of phenazene derivative according to claim 6 in organic electroluminescence device, its feature exist In the phenazene derivative 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 phenazene derivative any one of claim 1-5.
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