CN104650032B - A kind of acridine derivatives, its preparation method and its application - Google Patents
A kind of acridine derivatives, its preparation method and its application Download PDFInfo
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- CN104650032B CN104650032B CN201510037329.XA CN201510037329A CN104650032B CN 104650032 B CN104650032 B CN 104650032B CN 201510037329 A CN201510037329 A CN 201510037329A CN 104650032 B CN104650032 B CN 104650032B
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Abstract
The present invention relates to a kind of acridine derivatives, such compound has the structure as shown in formula (1), and when electroluminescent device prepares electron transfer layer using the material of the present invention, can reduce device opens bright voltage, the luminous efficiency of device is improved, increases the service life of device.
Description
Technical field
The invention belongs to field of organic electroluminescence, and in particular to a kind of acridine derivatives, its preparation method, and its
Application in electron transport material.
Background technology
The electron transport material that tradition uses in electroluminescent device is Alq3, but Alq3Electron mobility than relatively low
(about in 10-6cm2/Vs).In order to improve the electronic transmission performance of electroluminescent device, researcher has done substantial amounts of exploration
Journal of Sex Research works.LG chemistry reports a series of derivative of pyrenes in the patent specification of China, is used in electroluminescence device
Make electric transmission and injection material, improve the luminous efficiency (publication number CN 101003508A) of device.Cao Yong et al. synthesizes
FFF-Blm4(J.Am.Chem.Soc.；(Communication)；2008；130(11)；3282-3283) as electric transmission and
Layer material (compared with Ba/Al and individually by the use of Al as negative electrode) is injected, significantly improves electron injection and the transmission of device,
Improve electroluminescence efficiency.Kodak is at United States Patent (USP) (publication number US 2006/0204784 and US 2007/0048545)
In, mixed electronic transport layer is mentioned, using a kind of material of low lumo energy and the electric transmission material of another low bright voltage
The doping such as material and other materials such as metal material forms.Based on the device of this mixed electronic transport layer, efficiency and life-span etc. are all
It is improved, but is the increase in the complexity of device fabrication, is unfavorable for reducing OLED costs.Develop the electronics of stability and high efficiency
Transmission material and/or electron injection material, so as to reduce bright voltage, device efficiency is improved, extends device lifetime, is had very heavy
The actual application value wanted.
The content of the invention
It is an object of the invention to propose a kind of new acridine derivatives, such compound can be used for organic electroluminescence hair
Light display field.Specifically, this kind of compound can be used as electron transport material in display of organic electroluminescence.Electroluminescent hair
When optical device prepares electron transfer layer using the material of the present invention, can reduce device opens bright voltage, improves the luminous of device
Efficiency, increase the service life of device.
To achieve the above object, the technical scheme that the present invention takes is as follows：
A kind of acridine derivatives, there is the structure as shown in formula (1)：
Wherein：Ar1And Ar2It is identical or different, it is respectively and independently selected from C6-C30Substituted or non-substituted aromatic hydrocarbon group, C6-
C30Substituted or non-substituted condensed-nuclei aromatics group, C5-C30Substituted or non-substituted condensed hetero ring group, five yuan, hexa-atomic miscellaneous
Ring or substituted heterocycle, C1-C12Substituted or non-substituted aliphatic alkyl group in one kind；Preferably, described substitution is
Substituted by alkyl, halogen, cyano group, aryl or heterocyclic aryl.
R1-R6It is identical or different, it is independently selected from H, C1-C12Substituted or non-substituted aliphatic alkyl group, C6-C20's
Substituted or non-substituted aromatic hydrocarbon group, C6-C20Substituted or non-substituted condensed-nuclei aromatics group,
C5-C20Substituted or non-substituted condensed hetero ring group, five yuan, hexa-atomic heterocycle or substituted heterocycle.
The Ar1For structure shown in formula (2) to formula (12)：
Ar2Selected from formula (2) to formula (11), or structure shown in formula (13) to formula (14)：
Wherein Ar3For H, substituted or unsubstituted aryl, substituted or unsubstituted alkyl；
L is singly-bound, substituted or unsubstituted arlydene, substituted or unsubstituted sub- heterocyclic aryl, it is preferable that the substitution
It is to be substituted by alkyl, halogen, cyano group, aryl or heterocyclic aryl.
Preferably, the compound is formula (21)-structure shown in (56)：
Application of the described acridine derivatives in organic electroluminescence device, specifically, the acridine derivatives are used as
Electron transport material.
A kind of organic electroluminescence device, including substrate, and sequentially form anode layer, You Jifa on the substrate
Light functional layer and cathode layer；The organic luminescence function layer includes hole transmission layer, organic luminous layer and electron transfer layer, institute
Stating electron transfer layer is prepared by described acridine derivatives.
Compared with prior art, it is the advantages of acridine derivatives of the invention：
The benzacridine derivative of the present invention is that condensed-nuclei aromatics or electron withdraw group are connected on benzacridine precursor structure,
Belong to typical short of electricity subsystem, receive electronic capability with good, be coplanar condensed-nuclei aromatics on space structure again
System, there is suitable HOMO and lumo energy, therefore there are good electron transfer capabilities.Therefore benzo of the present invention
The compound of acridine, it is a kind of excellent electron transport material.
For its molecular weight of the electron transport material of the present invention between 500 and 900, it has higher glassy state conversion temperature
Tg is spent, so as to have good heat endurance, while there is good vacuum evaporation film forming.
Brief description of the drawings
Compound shown in Fig. 1 formulas (22) nuclear magnetic spectrogram (1HNMR)；
Compound shown in Fig. 2 formulas (27) nuclear magnetic spectrogram (1HNMR)；
Compound shown in Fig. 3 formulas (44) nuclear magnetic spectrogram (1HNMR)；
Compound shown in Fig. 4 formulas (48) nuclear magnetic spectrogram (1HNMR)。
Embodiment
Basic raw material used, two (4- bromophenyls) amine, 4- bromobenzoic acids, benzoic acid, naphthoic acid, pyrrole in the present invention
Pyridine -2- formic acid, quinoline -2- formic acid, bromo phenanthrene, bromo anthracene derivant, bromo pyrene, bromo triphenylene etc., can majorization at home
Work raw materials market is bought.Corresponding boronic acid compounds can be made in various bromo-derivatives of commonsense method.
Embodiment 1
Synthesis (the bibliography of the bromo- 9- phenylacridines of parent 2,7- bis-：Org.Biomol.Chem.,2010,8,326-
330)
Two (4- bromophenyls) amine 26.2g (molecular weight 327,0.08mol), benzoic acid 9.8g (molecular weight 122,0.08mol),
ZnCl2With 16.1g (molecular weight 134,0.12mol), sand-bath is heated 5 hours, stirred simultaneously, 240-260 DEG C of temperature.Cooling, it is molten
Solution, mixes silica gel, post separation (eluent：Dichloromethane/ethyl acetate=20:1) 18.2g products, yield 55%, molecule, are obtained
Amount 413.
Embodiment 2
The synthesis of bis- bromo- 9- of parent 2,7- (pyridine -2- bases) acridine
Synthesis step is same as above 1, and benzoic acid simply is changed into 2- naphthoic acids, and other reagents are constant, obtains target mother
Bis- bromo- 9- of body 2,7- (pyridine -2- bases) acridine.Reaction path is as follows：
Embodiment 3
The synthesis of parent parent 2,7- bis- bromo- 9- (quinoline -2- bases) acridine
Synthesis step is same as above 1, and benzoic acid simply is changed into 2- naphthoic acids, and other reagents are constant, obtains target mother
Bis- bromo- 9- of body 2,7- (quinoline -2- bases) acridine.Reaction path is as follows：
Embodiment 4
The synthesis of parent parent 2,7- bis- bromo- 9- (2- naphthyls) acridine
Synthesis step is same as above 1, and benzoic acid simply is changed into 2- naphthoic acids, and other reagents are constant, obtains target mother
Body 2,7- bis- bromo- 9- (2- naphthyls) acridine.Reaction path is as follows：
Embodiment 5
The synthesis of parent parent 2,7- bis- bromo- 9- (4- bromophenyls) acridine
Synthesis step is same as above 1, benzoic acid simply is changed into 4- bromobenzoic acids, other reagents are constant, obtain target
Parent 2,7- bis- bromo- 9- (4- bromophenyls) acridine.Reaction path is as follows：
Embodiment 6
The synthesis of parent 2,7- bis- bromo- 9- (4- xenyls) acridine
Synthesis step is same as above 1, benzoic acid simply is changed into 4- diphenic acids, other reagents are constant, obtain target
Parent 2,7- bis- bromo- 9- (4- xenyls) acridine.Reaction path is as follows：
Embodiment 7
The synthesis of compound shown in formula (21)
1000 milliliters of a bite bottles, with magnetic agitation, add parent 2 shown in formula (16), bis- bromo- 9- of 7- (pyridine -2- bases) a word used for translation
Pyridine 8.30g (molecular weight 414,0.02mol), 4- (naphthalene -1- bases) phenyl boric acid 11.0g (molecular weight 248,0.044mol), Pd
(PPh3)4Usage amount 2.31g (molecular weight 1154,0.002mol), sodium carbonate 150ml (2M), toluene 150ml, ethanol 150ml.Argon
After gas displacement, backflow, monitored and reacted with TLC, reacted complete after 4 hours, cooling, separate organic layer, be evaporated, pillar layer separation,
Ethyl acetate/petroleum ether elutes, and obtains compound shown in 11.7g formulas (21), molecular weight 660, yield 88.4%.
Product MS (m/e)：660, elementary analysis (C50H32N2)：Theoretical value C：90.88%, H：4.88%, N：4.24%；It is real
Measured value C：90.84%, H：4.90%, N：4.26%.
Embodiment 8
The synthesis of compound shown in formula (22)
Synthesis step is same as embodiment 1, and a kind of raw material 4- (naphthalene -1- bases) phenyl boric acid therein simply is changed into pyrene -1-
The condition such as boric acid, other medicines, reagent, reaction, separation is constant, obtains compound shown in formula (22).
Product MS (m/e)：656, elementary analysis (C50H28N2)：Theoretical value C：91.44%, H：4.30%, N：4.27%；It is real
Measured value C：91.47%, H：4.30%, N：4.23%.Compound shown in formula (22) nuclear magnetic spectrogram (1HNMR) as shown in Figure 1.
Embodiment 9
The synthesis of compound shown in formula (23)
Synthesis step is same as embodiment 1, and a kind of raw material 4- (naphthalene -1- bases) phenyl boric acid therein simply is changed into pyrene -1-
The condition such as boric acid, other medicines, reagent, reaction, separation is constant, obtains compound shown in formula (23).
Product MS (m/e)：608, elementary analysis (C46H28N2)：Theoretical value C：90.76%, H：4.64%, N：4.60%；It is real
Measured value C：90.71%, H：4.66%, N：4.63%.
Embodiment 10
The synthesis of compound shown in formula (24)
Synthesis step is same as embodiment 1, and a kind of raw material 4- (naphthalene -1- bases) phenyl boric acid therein simply is changed into 10- benzene
The conditions such as base anthracene -9- boric acid, other medicines, reagent, reaction, separation are constant, obtain compound shown in formula (24).
Product MS (m/e)：760, elementary analysis (C58H36N2)：Theoretical value C：91.55%, H：4.77%, N：3.68%；It is real
Measured value C：91.55%, H：4.77%, N：3.68%.
Embodiment 11
The synthesis of compound shown in formula (25)
Synthesis step is same as embodiment 1, and a kind of raw material 4- (naphthalene -1- bases) phenyl boric acid therein simply is changed into Sanya
The conditions such as benzene -2- boric acid, other medicines, reagent, reaction, separation are constant, obtain compound shown in formula (25).
Product MS (m/e)：708, elementary analysis (C54H32N2)：Theoretical value C：91.50%, H：4.55%, N：3.95%；It is real
Measured value C：91.54%, H：4.53%, N：3.93%.
Embodiment 12
The synthesis of compound shown in formula (26)
Synthesis step is same as embodiment 1, and a kind of raw material 4- (naphthalene -1- bases) phenyl boric acid therein simply is changed into 5- phenyl
The conditions such as pyridine -2- boric acid, other medicines, reagent, reaction, separation are constant, obtain compound shown in formula (26).
Product MS (m/e)：562, elementary analysis (C40H26N4)：Theoretical value C：85.38%, H：
4.66%, N：9.96%；Measured value C：85.42%, H：4.64%, N：9.94%.
Embodiment 13
The synthesis of compound shown in formula (27)
Synthesis step is same as embodiment 1, and a kind of raw material 4- (naphthalene -1- bases) phenyl boric acid therein simply is changed into (2- benzene
Base -1H- benzos [d] imidazoles -1- bases) condition such as phenyl boric acid, other medicines, reagent, reaction, separation is constant, obtain formula (27) institute
Show compound.
Product MS (m/e)：794, elementary analysis (C56H38N6)：Theoretical value C：84.61%, H：4.82%, N：10.57%；
Measured value C：84.65%, H：4.84%, N：10.51%.Compound shown in formula (27) nuclear magnetic spectrogram (1HNMR) part Fig. 2 institutes
Show.
Embodiment 14
The synthesis of compound shown in formula (28)
Synthesis step is same as embodiment 1, and a kind of raw material 4- (naphthalene -1- bases) phenyl boric acid therein simply is changed into 4- (1-
Phenyl -1H- benzos [d] imidazoles -2- bases) condition such as phenyl boric acid, other medicines, reagent, reaction, separation is constant, obtain formula (28)
Shown compound.
Product MS (m/e)：794, elementary analysis (C56H38N6)：Theoretical value C：84.61%, H：4.82%, N：10.57%；
Measured value C：84.62%, H：4.86%, N：10.52%.
Embodiment 15
The synthesis of compound shown in formula (29)
Synthesis step is same as embodiment 1, and raw material 2, bis- bromo- 9- of 7- (pyridine -2- bases) acridine simply are changed into 2,7- bis-
Bromo- 9- (quinoline -2- bases) acridine, raw material 4- (naphthalene -1- bases) phenyl boric acid is changed into pyrene -1- boric acid, it is other medicines, reagent, anti-
Should, separation etc. condition it is constant, obtain compound shown in formula (29).
Product MS (m/e)：706, elementary analysis (C54H30N2)：Theoretical value C：91.76%, H：4.28%, N：3.96%；It is real
Measured value C：91.81%, H：4.26%, N：3.93%.
Embodiment 16
The synthesis of compound shown in formula (30)
Synthesis step is same as embodiment 1, and raw material 2, bis- bromo- 9- of 7- (pyridine -2- bases) acridine simply are changed into 2,7- bis-
Bromo- 9- (quinoline -2- bases) acridine, raw material 4- (naphthalene -1- bases) phenyl boric acid is changed into phenanthrene -9- boric acid, it is other medicines, reagent, anti-
Should, separation etc. condition it is constant, obtain compound shown in formula (30).
Product MS (m/e)：658, elementary analysis (C50H30N2)：Theoretical value C：91.16%, H：4.59%, N：4.25%；It is real
Measured value C：91.14%, H：4.62%, N：4.24%.
Embodiment 17
The synthesis of compound shown in formula (31)
Synthesis step is same as embodiment 1, and raw material 2, bis- bromo- 9- of 7- (pyridine -2- bases) acridine simply are changed into 2,7- bis-
Bromo- 9- (quinoline -2- bases) acridine, raw material 4- (naphthalene -1- bases) phenyl boric acid is changed into 10- phenylanthracene -9- boric acid, other medicines,
The conditions such as reagent, reaction, separation are constant, obtain compound shown in formula (31).
Product MS (m/e)：810, elementary analysis (C62H38N2)：Theoretical value C：91.82%, H：4.72%, N：3.45%；It is real
Measured value C：91.84%, H：4.75%, N：3.41%.
Embodiment 18
The synthesis of compound shown in formula (32)
Synthesis step is same as embodiment 1, and raw material 2, bis- bromo- 9- of 7- (pyridine -2- bases) acridine simply are changed into 2,7- bis-
Bromo- 9- (quinoline -2- bases) acridine, raw material 4- (naphthalene -1- bases) phenyl boric acid is changed into triphenylene -2- boric acid, other medicines, examination
The conditions such as agent, reaction, separation are constant, obtain compound shown in formula (32).
Product MS (m/e)：758, elementary analysis (C58H34N2)：Theoretical value C：91.79%, H：4.52%, N：3.69%；It is real
Measured value C：91.76%, H：4.58%, N：3.66%.
Embodiment 19
The synthesis of compound shown in formula (33)
Synthesis step is same as embodiment 1, and raw material 2, bis- bromo- 9- of 7- (pyridine -2- bases) acridine simply are changed into 2,7- bis-
Bromo- 9- (quinoline -2- bases) acridine, raw material 4- (naphthalene -1- bases) phenyl boric acid is changed into triphenylene -2- boric acid, other medicines, examination
The conditions such as agent, reaction, separation are constant, obtain compound shown in formula (33).
Product MS (m/e)：690, elementary analysis (C52H38N2)：Theoretical value C：90.40%, H：5.54%, N：4.05%；It is real
Measured value C：90.43%, H：5.50%, N：4.07%.
Embodiment 20
The synthesis of compound shown in formula (34)
Synthesis step is same as embodiment 1, and raw material 2, bis- bromo- 9- of 7- (pyridine -2- bases) acridine simply are changed into 2,7- bis-
Bromo- 9- (quinoline -2- bases) acridine, raw material 4- (naphthalene -1- bases) phenyl boric acid is changed into 4- (naphthalene -1- bases) phenyl boric acid, other medicines,
The conditions such as reagent, reaction, separation are constant, obtain compound shown in formula (34).
Product MS (m/e)：710, elementary analysis (C54H34N2)：Theoretical value C：91.24%, H：4.82%, N：3.94%；It is real
Measured value C：91.27%, H：4.80%, N：3.93%.
Embodiment 21
The synthesis of compound shown in formula (35)
Synthesis step is same as embodiment 1, and raw material 2, bis- bromo- 9- of 7- (pyridine -2- bases) acridine simply are changed into 2,7- bis-
Bromo- 9- (quinoline -2- bases) acridine, raw material 4- (naphthalene -1- bases) phenyl boric acid is changed into naphthalene -2- boric acid, it is other medicines, reagent, anti-
Should, separation etc. condition it is constant, obtain compound shown in formula (35).
Product MS (m/e)：558, elementary analysis (C42H26N2)：Theoretical value C：90.29%, H：4.69%, N：5.01%；It is real
Measured value C：90.33%, H：4.64%, N：5.03%.
Embodiment 22
The synthesis of compound shown in formula (36)
Synthesis step is same as embodiment 1, and raw material 2, bis- bromo- 9- of 7- (pyridine -2- bases) acridine simply are changed into 2,7- bis-
Bromo- 9- (quinoline -2- bases) acridine, raw material 4- (naphthalene -1- bases) phenyl boric acid is changed into 5- phenylpyridine -2- boric acid, other medicines,
The conditions such as reagent, reaction, separation are constant, obtain compound shown in formula (36).
Product MS (m/e)：612, elementary analysis (C44H28N4)：Theoretical value C：86.25%, H：4.61%, N：9.14%；It is real
Measured value C：86.23%, H：4.65%, N：9.12%.
Embodiment 23
The synthesis of compound shown in formula (37)
Synthesis step is same as embodiment 1, and raw material 2, bis- bromo- 9- of 7- (pyridine -2- bases) acridine simply are changed into 2,7- bis-
Bromo- 9- (quinoline -2- bases) acridine, raw material 4- (naphthalene -1- bases) phenyl boric acid is changed into (2- phenyl -1H- benzo [d] imidazoles -1-
Base) condition such as phenyl boric acid, other medicines, reagent, reaction, separation is constant, obtain compound shown in formula (37).
Product MS (m/e)：844, elementary analysis (C60H40N6)：Theoretical value C：85.28%, H：4.77%, N：9.95%；It is real
Measured value C：85.32%, H：4.74%, N：9.94%.
Embodiment 24
The synthesis of compound shown in formula (38)
Synthesis step is same as embodiment 1, and raw material 2, bis- bromo- 9- of 7- (pyridine -2- bases) acridine simply are changed into 2,7- bis-
Bromo- 9- (quinoline -2- bases) acridine, raw material 4- (naphthalene -1- bases) phenyl boric acid is changed into 4- (1- phenyl -1H- benzo [d] imidazoles -2-
Base) condition such as phenyl boric acid, other medicines, reagent, reaction, separation is constant, obtain compound shown in formula (38).
Product MS (m/e)：844, elementary analysis (C60H40N6)：Theoretical value C：85.28%, H：4.77%, N：9.95%；It is real
Measured value C：85.30%, H：4.73%, N：9.97%.
Embodiment 25
The synthesis of compound shown in formula (39)
Synthesis step is same as embodiment 1, and raw material 2, bis- bromo- 9- of 7- (pyridine -2- bases) acridine simply are changed into 2,7- bis-
Bromo- 9- (4- xenyls) acridine, raw material 4- (naphthalene -1- bases) phenyl boric acid is changed into 4- (1- naphthyls) phenyl boric acid, other medicines, examination
The conditions such as agent, reaction, separation are constant, obtain compound shown in formula (39).
Product MS (m/e)：735, elementary analysis (C57H37N)：Theoretical value C：93.03%, H：5.07%, N：1.90%；It is real
Measured value C：93.06%, H：5.02%, N：1.92%.
Embodiment 26
The synthesis of compound shown in formula (40)
Synthesis step is same as embodiment 1, and raw material 2, bis- bromo- 9- of 7- (pyridine -2- bases) acridine simply are changed into 2,7- bis-
Bromo- 9- (4- xenyls) acridine, raw material 4- (naphthalene -1- bases) phenyl boric acid is changed into naphthalene -2- boric acid, it is other medicines, reagent, anti-
Should, separation etc. condition it is constant, obtain compound shown in formula (40).
Product MS (m/e)：583, elementary analysis (C45H29N)：Theoretical value C：92.59%, H：5.01%, N：2.40%；It is real
Measured value C：92.55%, H：5.02%, N：2.43%.
Embodiment 27
The synthesis of compound shown in formula (41)
Synthesis step is same as embodiment 1, and raw material 2, bis- bromo- 9- of 7- (pyridine -2- bases) acridine simply are changed into 2,7- bis-
Bromo- 9- (4- xenyls) acridine, raw material 4- (naphthalene -1- bases) phenyl boric acid is changed into pyrene -1- boric acid, it is other medicines, reagent, anti-
Should, separation etc. condition it is constant, obtain compound shown in formula (41).
Product MS (m/e)：731, elementary analysis (C57H33N)：Theoretical value C：93.54%, H：4.54%, N：1.91%；It is real
Measured value C：93.58%, H：4.55%, N：1.87%.
Embodiment 28
The synthesis of compound shown in formula (42)
Synthesis step is same as embodiment 1, and raw material 2, bis- bromo- 9- of 7- (pyridine -2- bases) acridine simply are changed into 2,7- bis-
Bromo- 9- (2- naphthyls) acridine, raw material 4- (naphthalene -1- bases) phenyl boric acid is changed into pyrene -1- boric acid, other medicines, reagent, reaction,
The conditions such as separation are constant, obtain compound shown in formula (42).
Product MS (m/e)：705, elementary analysis (C55H31N)：Theoretical value C：93.59%, H：4.43%, N：1.98%；It is real
Measured value C：93.55%, H：4.48%, N：1.97%.
Embodiment 29
The synthesis of compound shown in formula (43)
Synthesis step is same as embodiment 1, and raw material 2, bis- bromo- 9- of 7- (pyridine -2- bases) acridine simply are changed into 2,7- bis-
Bromo- 9- (2- naphthyls) acridine, raw material 4- (naphthalene -1- bases) phenyl boric acid is changed into phenanthrene -9- boric acid, other medicines, reagent, reaction,
The conditions such as separation are constant, obtain compound shown in formula (43).
Product MS (m/e)：657, elementary analysis (C51H31N)：Theoretical value C：93.12%, H：4.75%, N：2.13%；It is real
Measured value C：93.10%, H：4.73%, N：2.17%.
Embodiment 30
The synthesis of compound shown in formula (44)
Synthesis step is same as embodiment 1, and raw material 2, bis- bromo- 9- of 7- (pyridine -2- bases) acridine simply are changed into 2,7- bis-
Bromo- 9- (4- xenyls) acridine, raw material 4- (naphthalene -1- bases) phenyl boric acid is changed into phenanthrene -9- boric acid, it is other medicines, reagent, anti-
Should, separation etc. condition it is constant, obtain compound shown in formula (44).
Product MS (m/e)：683, elementary analysis (C53H33N)：Theoretical value C：93.09%, H：4.86%, N：2.05%；It is real
Measured value C：93.06%, H：4.85%, N：2.09%.Compound shown in formula (44) nuclear magnetic spectrogram (1HNMR Fig. 3) is seen.
Embodiment 31
The synthesis of compound shown in formula (45)
Synthesis step is same as embodiment 1, and raw material 2, bis- bromo- 9- of 7- (pyridine -2- bases) acridine simply are changed into 2,7- bis-
Bromo- 9- (4- xenyls) acridine, raw material 4- (naphthalene -1- bases) phenyl boric acid is changed into 10- phenylanthracene -9- boric acid, other medicines, examination
The conditions such as agent, reaction, separation are constant, obtain compound shown in formula (45).
Product MS (m/e)：835, elementary analysis (C65H41N)：Theoretical value C：93.38%, H：4.94%, N：1.68%；It is real
Measured value C：93.33%, H：4.97%, N：1.70%.
Embodiment 32
The synthesis of compound shown in formula (46)
Synthesis step is same as embodiment 1, and raw material 2, bis- bromo- 9- of 7- (pyridine -2- bases) acridine simply are changed into 2,7- bis-
Bromo- 9- (4- xenyls) acridine, raw material 4- (naphthalene -1- bases) phenyl boric acid is changed into 10- phenylanthracene -9- boric acid, other medicines, examination
The conditions such as agent, reaction, separation are constant, obtain compound shown in formula (46).
Product MS (m/e)：759, elementary analysis (C59H37N)：Theoretical value C：93.25%, H：4.91%, N：1.84%；It is real
Measured value C：93.21%, H：4.97%, N：1.82%.
Embodiment 33
The synthesis of compound shown in formula (47)
Synthesis step is same as embodiment 1, and raw material 2, bis- bromo- 9- of 7- (pyridine -2- bases) acridine simply are changed into 2,7- bis-
Bromo- 9- (4- xenyls) acridine, raw material 4- (naphthalene -1- bases) phenyl boric acid is changed into 2- phenylpyridine -5- boric acid, other medicines,
The conditions such as reagent, reaction, separation are constant, obtain compound shown in formula (47).
Product MS (m/e)：637, elementary analysis (C47H31N3)：Theoretical value C：88.51%, H：4.90%, N：6.59%；It is real
Measured value C：88.56%, H：4.92%, N：6.52%.
Embodiment 34
The synthesis of compound shown in formula (48)
Synthesis step is same as embodiment 1, and raw material 2, bis- bromo- 9- of 7- (pyridine -2- bases) acridine simply are changed into 2,7- bis-
Bromo- 9- (2- naphthyls) acridine, raw material 4- (naphthalene -1- bases) phenyl boric acid is changed into 2- phenylpyridine -5- boric acid, other medicines, examination
The conditions such as agent, reaction, separation are constant, obtain compound shown in formula (48).
Product MS (m/e)：611, elementary analysis (C45H29N3)：Theoretical value C：88.35%, H：4.78%, N：6.87%；It is real
Measured value C：88.38%, H：4.76%, N：6.86%.Compound shown in formula (48) nuclear magnetic spectrogram (1HNMR Fig. 4 institutes) are seen
Show.
Embodiment 35
The synthesis of compound shown in formula (49)
Synthesis step is same as embodiment 1, and raw material 2, bis- bromo- 9- of 7- (pyridine -2- bases) acridine simply are changed into 2,7- bis-
Bromo- 9- (2- naphthyls) acridine, raw material 4- (naphthalene -1- bases) phenyl boric acid is changed into (2- phenyl -1H- benzos [d] imidazoles -1- bases) benzene
The condition such as boric acid, other medicines, reagent, reaction, separation is constant, obtains compound shown in formula (49).
Product MS (m/e)：843, elementary analysis (C61H41N5)：Theoretical value C：86.81%, H：4.90%, N：8.30%；It is real
Measured value C：86.87%, H：4.86%, N：8.27%.
Embodiment 36
The synthesis of compound shown in formula (50)
Synthesis step is same as embodiment 1, and raw material 2, bis- bromo- 9- of 7- (pyridine -2- bases) acridine simply are changed into 2,7- bis-
Bromo- 9- (4- xenyls) acridine, raw material 4- (naphthalene -1- bases) phenyl boric acid is changed into (2- phenyl -1H- benzos [d] imidazoles -1- bases)
The condition such as phenyl boric acid, other medicines, reagent, reaction, separation is constant, obtains compound shown in formula (50).
Product MS (m/e)：869, elementary analysis (C63H43N5)：Theoretical value C：86.97%, H：4.98%, N：8.05%；It is real
Measured value C：86.94%, H：4.97%, N：8.09%.
Embodiment 37
The synthesis of compound shown in formula (51)
Synthesis step is same as embodiment 1, and raw material 2, bis- bromo- 9- of 7- (pyridine -2- bases) acridine simply are changed into 2,7- bis-
Bromo- 9- phenylacridines, raw material 4- (naphthalene -1- bases) phenyl boric acid is changed into (2- phenyl -1H- benzos [d] imidazoles -1- bases) benzene boron
The condition such as acid, other medicines, reagent, reaction, separation is constant, obtains compound shown in formula (51).
Product MS (m/e)：793, elementary analysis (C57H39N5)：Theoretical value C：86.23%, H：4.95%, N：8.82%；It is real
Measured value C：86.26%, H：4.93%, N：8.81%.
Embodiment 38
The synthesis of compound shown in formula (52)
Synthesis step is same as embodiment 1, and raw material 2, bis- bromo- 9- of 7- (pyridine -2- bases) acridine simply are changed into 2,7- bis-
Bromo- 9- phenylacridines, raw material 4- (naphthalene -1- bases) phenyl boric acid is changed into 4- (1- phenyl -1H- benzos [d] imidazoles -2- bases) benzene boron
The condition such as acid, other medicines, reagent, reaction, separation is constant, obtains compound shown in formula (52).
Product MS (m/e)：793, elementary analysis (C57H39N5)：Theoretical value C：86.23%, H：4.95%, N：8.82%；It is real
Measured value C：86.26%, H：4.94%, N：8.80%.
Embodiment 39
The synthesis of compound shown in formula (53)
Synthesis step is same as embodiment 1, and raw material 2, bis- bromo- 9- of 7- (pyridine -2- bases) acridine simply are changed into 2,7- bis-
Bromo- 9- (4- xenyls) acridine, raw material 4- (naphthalene -1- bases) phenyl boric acid is changed into 4- (1- phenyl -1H- benzo [d] imidazoles -2-
Base) condition such as phenyl boric acid, other medicines, reagent, reaction, separation is constant, obtain compound shown in formula (53).
Product MS (m/e)：869, elementary analysis (C63H43N5)：Theoretical value C：86.97%, H：4.98%, N：8.05%；It is real
Measured value C：86.95%, H：4.96%, N：8.09%.
Embodiment 40
The synthesis of compound shown in formula (54)
Synthesis step is same as embodiment 1, and raw material 2, bis- bromo- 9- of 7- (pyridine -2- bases) acridine simply are changed into 2,7- bis-
Bromo- 9- (2- naphthyls) acridine, raw material 4- (naphthalene -1- bases) phenyl boric acid is changed into 4- (1- phenyl -1H- benzos [d] imidazoles -2- bases)
The condition such as phenyl boric acid, other medicines, reagent, reaction, separation is constant, obtains compound shown in formula (54).
Product MS (m/e)：843, elementary analysis (C61H41N5)：Theoretical value C：86.81%, H：4.90%, N：8.30%；It is real
Measured value C：86.85%, H：4.87%, N：8.28%.
Embodiment 41
The synthesis of compound shown in formula (55)
Synthesis step is same as embodiment 1, and raw material 2, bis- bromo- 9- of 7- (pyridine -2- bases) acridine simply are changed into 2,7- bis-
Bromo- 9- (4- bromophenyls) acridine, raw material 4- (naphthalene -1- bases) phenyl boric acid is changed into naphthalene -2- boric acid, it is other medicines, reagent, anti-
Should, separation etc. condition it is constant, obtain compound shown in formula (55).
Product MS (m/e)：633, elementary analysis (C49H31N)：Theoretical value C：92.86%, H：4.93%, N：2.21%；It is real
Measured value C：92.82%, H：4.95%, N：2.23%.
Embodiment 42
The synthesis of compound shown in formula (56)
Synthesis step is same as embodiment 1, and raw material 2, bis- bromo- 9- of 7- (pyridine -2- bases) acridine simply are changed into 2,7- bis-
Bromo- 9- (4- bromophenyls) acridine, raw material 4- (naphthalene -1- bases) phenyl boric acid is changed into naphthalene -1- boric acid, it is other medicines, reagent, anti-
Should, separation etc. condition it is constant, obtain compound shown in formula (56).
Product MS (m/e)：633, elementary analysis (C49H31N)：Theoretical value C：92.86%, H：4.93%, N：2.21%；It is real
Measured value C：92.83%, H：4.91%, N：2.26%.
Here is the Application Example of each compound of the present invention：
Embodiment 43
Comparing the transmission performance of these electron transport materials for convenience, the present invention devises a simple electroluminescence device,
Using EM1 as luminescent material, (EM1 is material of main part, and non-luminescent material, and purpose is not to pursue high efficiency, but verifies this
The practical possibility of a little materials), use efficent electronic transmission material
Bphen, which is used as, compares material.EM1 and Bphen structure is respectively:
The structure of organic electroluminescence device is in the embodiment of the present invention：
Substrate/anode/hole transmission layer (HTL)/organic luminous layer (EL)/electron transfer layer (ETL)/negative electrode.
Substrate can use the substrate in conventional organic luminescence device, such as：Glass or plastics.In the Organic Electricity of the present invention
Electroluminescence device selects glass substrate in making, and ITO makees anode material.
Hole transmission layer can use various tri-arylamine group materials.The institute in the organic electroluminescence device of the present invention makes
The hole mobile material of selection is NPB.NPB structures are：
Negative electrode can use metal and its mixture structure, such as Mg：Ag、Ca：Ag etc., also it is electron injecting layer/metal level
Structure, such as LiF/Al, Li2The common cathode structure such as O/Al.Selected by the organic electroluminescence device of the present invention makes
Cathode material is LiF/Al.
Compound in the present embodiment is as the electron transport material in organic electroluminescence device, and EML is as luminescent layer
Material, multiple organic electroluminescence devices are prepared for altogether, its structure is：ITO/NPB (40nm)/EM1 (30nm)/ETL materials
(20nm)/LiF(0.5nm)/Al(150nm)；
One contrast organic electroluminescence device, electron transport material select Bphen, the choosing of remaining organic electroluminescence device
With the material of the present invention.
Organic electroluminescence device preparation process is as follows in the present embodiment：
The glass plate for being coated with transparent conductive layer is ultrasonically treated in commercial detergent, rinsed in deionized water,
In acetone：Ultrasonic oil removing in alcohol mixed solvent, it is baked under clean environment and removes moisture content completely, it is clear with ultraviolet light and ozone
Wash, and with low energy cation beam bombarded surface；
The above-mentioned glass substrate with anode is placed in vacuum chamber, is evacuated to 1 × 10-5~9 × 10-3Pa, above-mentioned
Vacuum evaporation NPB is 40nm as hole transmission layer, evaporation rate 0.1nm/s, evaporation thickness on anode tunic；
Luminescent layers of the vacuum evaporation EM1 as device on hole transmission layer, evaporation rate 0.1nm/s, evaporation are total
Thickness is 30nm；
On luminescent layer the laminar of vacuum evaporation one (21), (22), (24), (27), (37), (43), (44), (47),
(48), electron transport layer materials of the compound as device shown in (49), (50), (53) or (55), device electricity is used as by the use of Bphen
The contrast material of son transmission layer material, its evaporation rate is 0.1nm/s, and evaporation total film thickness is 20nm；
Vacuum evaporation thickness is 0.5nm LiF as electron injecting layer, thickness 150nm on electron transfer layer (ETL)
Negative electrode of the Al layers as device.
Organic electroluminescence device performance see the table below：
| Compound number | It is required that brightness cd/m2 | Voltage V | Current efficiency cd/A |
| Bphen | 1000.00 | 5.1 | 6.0 |
| 21 | 1000.00 | 4.6 | 6.6 |
| 22 | 1000.00 | 4.4 | 6.4 |
| 24 | 1000.00 | 4.4 | 6.7 |
| 27 | 1000.00 | 4.7 | 6.6 |
| 37 | 1000.00 | 4.6 | 6.6 |
| 43 | 1000.00 | 4.5 | 6.5 |
| 44 | 1000.00 | 4.6 | 6,6 |
| 47 | 1000.00 | 4.6 | 6.5 |
| 48 | 1000.00 | 4.7 | 6.7 |
| 49 | 1000.00 | 4.5 | 6.6 |
| 50 | 1000.00 | 4.7 | 6.5 |
| 53 | 1000.00 | 4.6 | 6.5 |
| 55 | 1000.00 | 4.5 | 6.6 |
Result above shows that new organic materials of the invention are used for organic electroluminescence device, can be effectively reduced
Bright voltage, current efficiency is improved, is electron transport material of good performance.
Although the present invention is described in conjunction with the embodiments, the invention is not limited in above-described embodiment, should manage
Solution, under the guiding of present inventive concept, those skilled in the art can carry out various modifications and improvements, and appended claims summarise
The scope of the present invention.
Claims (4)
1. a kind of acridine derivatives, it is characterised in that there is formula (21)-structure shown in (56)：
A kind of 2. application of the acridine derivatives described in claim 1 in organic electroluminescence device.
3. application of the acridine derivatives according to claim 2 in organic electroluminescence device, it is characterised in that described
Acridine derivatives are used as electron transport material.
4. a kind of organic electroluminescence device, including substrate, and sequentially form anode layer, organic light emission on the substrate
Functional layer and cathode layer；The organic luminescence function layer includes hole transmission layer, organic luminous layer and electron transfer layer, and it is special
Sign is：
The electron transfer layer is prepared by the acridine derivatives described in claim 1.
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