CN104650032A - Acridine derivatives, and preparation method and application thereof - Google Patents

Acridine derivatives, and preparation method and application thereof Download PDF

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CN104650032A
CN104650032A CN201510037329.XA CN201510037329A CN104650032A CN 104650032 A CN104650032 A CN 104650032A CN 201510037329 A CN201510037329 A CN 201510037329A CN 104650032 A CN104650032 A CN 104650032A
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substituted
formula
acridine
base
bromo
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CN104650032B (en
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范洪涛
李银奎
汤金明
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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Abstract

The invention relates to acridine derivatives of which the structure is disclosed as Formula (1). When the electronic transmission layer of the electroluminescent device is prepared from the material provided by the invention, the turn-on voltage of the device can be lowered, the luminescence efficiency of the device can be enhanced, and the service life of the device can be prolonged.

Description

A kind of acridine derivatives, its preparation method and application thereof
Technical field
The invention belongs to field of organic electroluminescence, be specifically related 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 Alq 3, but Alq 3electronic mobility lower (greatly about 10-6cm2/Vs).In order to improve the electronic transmission performance of electroluminescent device, researchist has done a large amount of exploratory study work.LG chemistry reports the derivative of a series of pyrene in the patent specification of China, is used as electric transmission and injecting material, improves the luminous efficiency (publication number CN 101003508A) of device in electroluminescence device.The people such as Cao Yong synthesize FFF-Blm4 (J.Am.Chem.Soc.; (Communication); 2008; 130 (11); 3282-3283) as electric transmission and input horizon material (comparing as negative electrode with independent Al with Ba/Al), significantly improve electron injection and the transmission of device, improve electroluminescence efficiency.Kodak is in United States Patent (USP) (publication number US 2006/0204784 and US 2007/0048545), mention mixed electronic transport layer, adopt the electron transport material of a kind of material of low lumo energy and another kind low bright voltage and other materials to form as metallic substance etc. adulterates.Based on the device of this mixed electronic transport layer, efficiency and life-span etc. are all improved, but are the increase in the complicacy of device fabrication, are unfavorable for reducing OLED cost.The electron transport material of exploitation stability and high efficiency and/or electron injection material, thus reduced bright voltage, improve device efficiency, extend device lifetime, there is very important actual application value.
Summary of the invention
The object of the invention is to the acridine derivatives that proposition one class is novel, this compounds may be used for ORGANIC ELECTROLUMINESCENCE DISPLAYS field.Particularly, this compounds, in display of organic electroluminescence, can be used as electron transport material.When electroluminescent device adopts material of the present invention to prepare electron transfer layer, that can reduce device opens bright voltage, improves the luminous efficiency of device, increases the work-ing life of device.
For achieving the above object, the technical scheme taked of the present invention is as follows:
A kind of acridine derivatives, has such as formula the structure shown in (1):
Wherein: Ar 1and Ar 2identical or different, be independently selected from C 6-C 30substituted or non-substituted aromatic hydrocarbon group, C 6-C 30substituted or non-substituted condensed-nuclei aromatics group, C 5-C 30substituted or non-substituted fused heterocycle group, five yuan, hexa-atomic heterocycle or substituted heterocycle, C 1-C 12substituted or non-substituted aliphatic alkyl group in one; Preferably, described replacement is replaced by alkyl, halogen, cyano group, aryl or heterocyclic aryl.
R 1-R 6identical or different, be independently selected from H, C 1-C 12substituted or non-substituted aliphatic alkyl group, C 6-C 20substituted or non-substituted aromatic hydrocarbon group, C 6-C 20substituted or non-substituted condensed-nuclei aromatics group, C 5-C 20substituted or non-substituted fused heterocycle group, five yuan, hexa-atomic heterocycle or substituted heterocycle.
Described Ar 1and Ar 2be respectively formula (2) to structure formula (11) Suo Shi:
Wherein Ar 3for H, substituted or unsubstituted aryl, substituted or unsubstituted alkyl;
L is singly-bound, substituted or unsubstituted arylidene, substituted or unsubstituted sub-heterocyclic aryl, and preferably, described replacement is replaced by alkyl, halogen, cyano group, aryl or heterocyclic aryl.
Preferably, described compound is structure shown in formula (21)-(56):
The application of described acridine derivatives in organic electroluminescence device, particularly, described acridine derivatives is used as electron transport material.
A kind of organic electroluminescence device, comprises substrate, and forms anode layer, organic luminescence function layer and cathode layer on the substrate successively; Described organic luminescence function layer comprises hole transmission layer, organic luminous layer and electron transfer layer, and described electron transfer layer is prepared from by described acridine derivatives.
Compared with prior art, the advantage of acridine derivatives of the present invention is:
Benzacridine derivative of the present invention connects condensed-nuclei aromatics or electron-withdrawing group on benzacridine precursor structure, belong to typical electron deficiency system, have and good accept electronic capability, it is again coplanar condensed-nuclei aromatics system on space structure, there is applicable HOMO and lumo energy, therefore there is good electron transfer capabilities.Therefore the compound of benzacridine class of the present invention is the electron transport material of a class excellence.
Its molecular weight of electron transport material of the present invention is between 500 and 900, and it has higher glass transition temperature Tg, thus has good thermostability, has good vacuum evaporation film-forming properties simultaneously.
Accompanying drawing explanation
Compound shown in Fig. 1 formula (22) nuclear magnetic spectrogram ( 1hNMR);
Compound shown in Fig. 2 formula (27) nuclear magnetic spectrogram ( 1hNMR);
Compound shown in Fig. 3 formula (44) nuclear magnetic spectrogram ( 1hNMR);
Compound shown in Fig. 4 formula (48) nuclear magnetic spectrogram ( 1hNMR).
Embodiment
Basic raw material used in the present invention, two (4-bromophenyl) amine, 4-bromo-benzoic acid, phenylformic acid, naphthoic acid, pyridine-2-formic acid, quinoline-2-formic acid, bromo phenanthrene, bromo anthracene derivant, bromo pyrene, bromo triphenylene etc., can buy in each large industrial chemicals market at home.Various bromo-derivative can make corresponding boronic acid compounds by usual way.
Embodiment 1
The synthesis (reference: Org.Biomol.Chem., 2010,8,326-330) of the bromo-9-phenylacridine of parent 2,7-bis-
Two (4-bromophenyl) amine 26.2g (molecular weight 327,0.08mol), phenylformic acid 9.8g (molecular weight 122,0.08mol), ZnCl 2with 16.1g (molecular weight 134,0.12mol), sand-bath heats 5 hours, stirs simultaneously, temperature 240-260 DEG C.Cooling, dissolves, mixes silica gel, and post is separated (eluent: dichloromethane/ethyl acetate=20:1), obtains 18.2g product, productive rate 55%, molecular weight 413.
Embodiment 2
The synthesis of the bromo-9-of parent 2,7-bis-(pyridine-2-base) acridine
Synthesis step is same as 1 above, and just phenylformic acid is changed into 2-naphthoic acid, other reagent is constant, obtains the bromo-9-of target parent 2,7-bis-(pyridine-2-base) acridine.Reaction path is as follows:
Embodiment 3
The synthesis of the bromo-9-of parent parent 2,7-bis-(quinoline-2-base) acridine
Synthesis step is same as 1 above, and just phenylformic acid is changed into 2-naphthoic acid, other reagent is constant, obtains the bromo-9-of target parent 2,7-bis-(quinoline-2-base) acridine.Reaction path is as follows:
Embodiment 4
The synthesis of the bromo-9-of parent parent 2,7-bis-(2-naphthyl) acridine
Synthesis step is same as 1 above, and just phenylformic acid is changed into 2-naphthoic acid, other reagent is constant, obtains the bromo-9-of target parent 2,7-bis-(2-naphthyl) acridine.Reaction path is as follows:
Embodiment 5
The synthesis of the bromo-9-of parent parent 2,7-bis-(4-bromophenyl) acridine
Synthesis step is same as 1 above, and just phenylformic acid is changed into 4-bromo-benzoic acid, other reagent is constant, obtains the bromo-9-of target parent 2,7-bis-(4-bromophenyl) acridine.Reaction path is as follows:
Embodiment 6
The synthesis of the bromo-9-of parent 2,7-bis-(4-xenyl) acridine
Synthesis step is same as 1 above, and just phenylformic acid is changed into 4-diphenic acid, other reagent is constant, obtains the bromo-9-of target parent 2,7-bis-(4-xenyl) acridine.Reaction path is as follows:
Embodiment 7
The synthesis of compound shown in formula (21)
1000 milliliters of a bite bottles, join magnetic agitation, add parent 2 shown in formula (16), the bromo-9-of 7-bis-(pyridine-2-base) acridine 8.30g (molecular weight 414,0.02mol), 4-(naphthalene-1-base) phenylo boric acid 11.0g (molecular weight 248,0.044mol), Pd (PPh 3) 4usage quantity 2.31g (molecular weight 1154,0.002mol), sodium carbonate 150ml (2M), toluene 150ml, ethanol 150ml.After argon replaces, backflow, with TLC monitoring reaction, react completely after 4 hours, cooling, separates organic layer, evaporate to dryness, pillar layer separation, ethyl acetate/petroleum ether drip washing, obtains compound shown in 11.7g formula (21), molecular weight 660, productive rate 88.4%.
Product MS (m/e): 660, ultimate analysis (C 50h 32n 2): theoretical value C:90.88%, H:4.88%, N:4.24%; 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 just a kind of raw material 4-(naphthalene-1-base) phenylo boric acid is wherein changed into pyrene-1-boric acid, the condition such as other medicine, reagent, reaction, separation is constant, obtains compound shown in formula (22).
Product MS (m/e): 656, ultimate analysis (C 50h 28n 2): theoretical value C:91.44%, H:4.30%, N:4.27%; 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 just a kind of raw material 4-(naphthalene-1-base) phenylo boric acid is wherein changed into pyrene-1-boric acid, the condition such as other medicine, reagent, reaction, separation is constant, obtains compound shown in formula (23).
Product MS (m/e): 608, ultimate analysis (C 46h 28n 2): theoretical value C:90.76%, H:4.64%, N:4.60%; 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 just a kind of raw material 4-(naphthalene-1-base) phenylo boric acid is wherein changed into 10-phenylanthracene-9-boric acid, the condition such as other medicine, reagent, reaction, separation is constant, obtains compound shown in formula (24).
Product MS (m/e): 760, ultimate analysis (C 58h 36n 2): theoretical value C:91.55%, H:4.77%, N:3.68%; 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 just a kind of raw material 4-(naphthalene-1-base) phenylo boric acid is wherein changed into triphenylene-2-boric acid, the condition such as other medicine, reagent, reaction, separation is constant, obtains compound shown in formula (25).
Product MS (m/e): 708, ultimate analysis (C 54h 32n 2): theoretical value C:91.50%, H:4.55%, N:3.95%; 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 just a kind of raw material 4-(naphthalene-1-base) phenylo boric acid is wherein changed into 5-phenylpyridine-2-boric acid, the condition such as other medicine, reagent, reaction, separation is constant, obtains compound shown in formula (26).
Product MS (m/e): 562, ultimate analysis (C 40h 26n 4): 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, just a kind of raw material 4-(naphthalene-1-base) phenylo boric acid is wherein changed into (2-phenyl-1H-benzo [d] imidazoles-1-base) phenylo boric acid, the condition such as other medicine, reagent, reaction, separation is constant, obtains compound shown in formula (27).
Product MS (m/e): 794, ultimate analysis (C 56h 38n 6): 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) shown in part Fig. 2.
Embodiment 14
The synthesis of compound shown in formula (28)
Synthesis step is same as embodiment 1, just a kind of raw material 4-(naphthalene-1-base) phenylo boric acid is wherein changed into 4-(1-phenyl-1H-benzo [d] imidazoles-2-base) phenylo boric acid, the condition such as other medicine, reagent, reaction, separation is constant, obtains compound shown in formula (28).
Product MS (m/e): 794, ultimate analysis (C 56h 38n 6): 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, just by raw material 2, the bromo-9-of 7-bis-(pyridine-2-base) acridine changes into 2, the bromo-9-of 7-bis-(quinoline-2-base) acridine, raw material 4-(naphthalene-1-base) phenylo boric acid is changed into pyrene-1-boric acid, the condition such as other medicine, reagent, reaction, separation is constant, obtains compound shown in formula (29).
Product MS (m/e): 706, ultimate analysis (C 54h 30n 2): theoretical value C:91.76%, H:4.28%, N:3.96%; 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, just by raw material 2, the bromo-9-of 7-bis-(pyridine-2-base) acridine changes into 2, the bromo-9-of 7-bis-(quinoline-2-base) acridine, raw material 4-(naphthalene-1-base) phenylo boric acid is changed into phenanthrene-9-boric acid, the condition such as other medicine, reagent, reaction, separation is constant, obtains compound shown in formula (30).
Product MS (m/e): 658, ultimate analysis (C 50h 30n 2): theoretical value C:91.16%, H:4.59%, N:4.25%; 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, just by raw material 2, the bromo-9-of 7-bis-(pyridine-2-base) acridine changes into 2, the bromo-9-of 7-bis-(quinoline-2-base) acridine, raw material 4-(naphthalene-1-base) phenylo boric acid is changed into 10-phenylanthracene-9-boric acid, the condition such as other medicine, reagent, reaction, separation is constant, obtains compound shown in formula (31).
Product MS (m/e): 810, ultimate analysis (C 62h 38n 2): theoretical value C:91.82%, H:4.72%, N:3.45%; 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, just by raw material 2, the bromo-9-of 7-bis-(pyridine-2-base) acridine changes into 2, the bromo-9-of 7-bis-(quinoline-2-base) acridine, raw material 4-(naphthalene-1-base) phenylo boric acid is changed into triphenylene-2-boric acid, the condition such as other medicine, reagent, reaction, separation is constant, obtains compound shown in formula (32).
Product MS (m/e): 758, ultimate analysis (C 58h 34n 2): theoretical value C:91.79%, H:4.52%, N:3.69%; 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, just by raw material 2, the bromo-9-of 7-bis-(pyridine-2-base) acridine changes into 2, the bromo-9-of 7-bis-(quinoline-2-base) acridine, raw material 4-(naphthalene-1-base) phenylo boric acid is changed into triphenylene-2-boric acid, the condition such as other medicine, reagent, reaction, separation is constant, obtains compound shown in formula (33).
Product MS (m/e): 690, ultimate analysis (C 52h 38n 2): theoretical value C:90.40%, H:5.54%, N:4.05%; 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, just by raw material 2, the bromo-9-of 7-bis-(pyridine-2-base) acridine changes into 2, the bromo-9-of 7-bis-(quinoline-2-base) acridine, raw material 4-(naphthalene-1-base) phenylo boric acid is changed into 4-(naphthalene-1-base) phenylo boric acid, the condition such as other medicine, reagent, reaction, separation is constant, obtains compound shown in formula (34).
Product MS (m/e): 710, ultimate analysis (C 54h 34n 2): theoretical value C:91.24%, H:4.82%, N:3.94%; 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, just by raw material 2, the bromo-9-of 7-bis-(pyridine-2-base) acridine changes into 2, the bromo-9-of 7-bis-(quinoline-2-base) acridine, raw material 4-(naphthalene-1-base) phenylo boric acid is changed into naphthalene-2-boric acid, the condition such as other medicine, reagent, reaction, separation is constant, obtains compound shown in formula (35).
Product MS (m/e): 558, ultimate analysis (C 42h 26n 2): theoretical value C:90.29%, H:4.69%, N:5.01%; 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, just by raw material 2, the bromo-9-of 7-bis-(pyridine-2-base) acridine changes into 2, the bromo-9-of 7-bis-(quinoline-2-base) acridine, raw material 4-(naphthalene-1-base) phenylo boric acid is changed into 5-phenylpyridine-2-boric acid, the condition such as other medicine, reagent, reaction, separation is constant, obtains compound shown in formula (36).
Product MS (m/e): 612, ultimate analysis (C 44h 28n 4): theoretical value C:86.25%, H:4.61%, N:9.14%; 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, just by raw material 2, the bromo-9-of 7-bis-(pyridine-2-base) acridine changes into 2, the bromo-9-of 7-bis-(quinoline-2-base) acridine, raw material 4-(naphthalene-1-base) phenylo boric acid is changed into (2-phenyl-1H-benzo [d] imidazoles-1-base) phenylo boric acid, the condition such as other medicine, reagent, reaction, separation is constant, obtains compound shown in formula (37).
Product MS (m/e): 844, ultimate analysis (C 60h 40n 6): theoretical value C:85.28%, H:4.77%, N:9.95%; 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, just by raw material 2, the bromo-9-of 7-bis-(pyridine-2-base) acridine changes into 2, the bromo-9-of 7-bis-(quinoline-2-base) acridine, raw material 4-(naphthalene-1-base) phenylo boric acid is changed into 4-(1-phenyl-1H-benzo [d] imidazoles-2-base) phenylo boric acid, the condition such as other medicine, reagent, reaction, separation is constant, obtains compound shown in formula (38).
Product MS (m/e): 844, ultimate analysis (C 60h 40n 6): theoretical value C:85.28%, H:4.77%, N:9.95%; 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, just by raw material 2, the bromo-9-of 7-bis-(pyridine-2-base) acridine changes into 2, the bromo-9-of 7-bis-(4-xenyl) acridine, raw material 4-(naphthalene-1-base) phenylo boric acid is changed into 4-(1-naphthyl) phenylo boric acid, the condition such as other medicine, reagent, reaction, separation is constant, obtains compound shown in formula (39).
Product MS (m/e): 735, ultimate analysis (C 57h 37n): theoretical value C:93.03%, H:5.07%, N:1.90%; 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, just by raw material 2, the bromo-9-of 7-bis-(pyridine-2-base) acridine changes into 2, the bromo-9-of 7-bis-(4-xenyl) acridine, raw material 4-(naphthalene-1-base) phenylo boric acid is changed into naphthalene-2-boric acid, the condition such as other medicine, reagent, reaction, separation is constant, obtains compound shown in formula (40).
Product MS (m/e): 583, ultimate analysis (C 45h 29n): theoretical value C:92.59%, H:5.01%, N:2.40%; 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, just by raw material 2, the bromo-9-of 7-bis-(pyridine-2-base) acridine changes into 2, the bromo-9-of 7-bis-(4-xenyl) acridine, raw material 4-(naphthalene-1-base) phenylo boric acid is changed into pyrene-1-boric acid, the condition such as other medicine, reagent, reaction, separation is constant, obtains compound shown in formula (41).
Product MS (m/e): 731, ultimate analysis (C 57h 33n): theoretical value C:93.54%, H:4.54%, N:1.91%; 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, just by raw material 2, the bromo-9-of 7-bis-(pyridine-2-base) acridine changes into 2, the bromo-9-of 7-bis-(2-naphthyl) acridine, raw material 4-(naphthalene-1-base) phenylo boric acid is changed into pyrene-1-boric acid, the condition such as other medicine, reagent, reaction, separation is constant, obtains compound shown in formula (42).
Product MS (m/e): 705, ultimate analysis (C 55h 31n): theoretical value C:93.59%, H:4.43%, N:1.98%; 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, just by raw material 2, the bromo-9-of 7-bis-(pyridine-2-base) acridine changes into 2, the bromo-9-of 7-bis-(2-naphthyl) acridine, raw material 4-(naphthalene-1-base) phenylo boric acid is changed into phenanthrene-9-boric acid, the condition such as other medicine, reagent, reaction, separation is constant, obtains compound shown in formula (43).
Product MS (m/e): 657, ultimate analysis (C 51h 31n): theoretical value C:93.12%, H:4.75%, N:2.13%; 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, just by raw material 2, the bromo-9-of 7-bis-(pyridine-2-base) acridine changes into 2, the bromo-9-of 7-bis-(4-xenyl) acridine, raw material 4-(naphthalene-1-base) phenylo boric acid is changed into phenanthrene-9-boric acid, the condition such as other medicine, reagent, reaction, separation is constant, obtains compound shown in formula (44).
Product MS (m/e): 683, ultimate analysis (C 53h 33n): theoretical value C:93.09%, H:4.86%, N:2.05%; 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, just by raw material 2, the bromo-9-of 7-bis-(pyridine-2-base) acridine changes into 2, the bromo-9-of 7-bis-(4-xenyl) acridine, raw material 4-(naphthalene-1-base) phenylo boric acid is changed into 10-phenylanthracene-9-boric acid, the condition such as other medicine, reagent, reaction, separation is constant, obtains compound shown in formula (45).
Product MS (m/e): 835, ultimate analysis (C 65h 41n): theoretical value C:93.38%, H:4.94%, N:1.68%; 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, just by raw material 2, the bromo-9-of 7-bis-(pyridine-2-base) acridine changes into 2, the bromo-9-of 7-bis-(4-xenyl) acridine, raw material 4-(naphthalene-1-base) phenylo boric acid is changed into 10-phenylanthracene-9-boric acid, the condition such as other medicine, reagent, reaction, separation is constant, obtains compound shown in formula (46).
Product MS (m/e): 759, ultimate analysis (C 59h 37n): theoretical value C:93.25%, H:4.91%, N:1.84%; 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, just by raw material 2, the bromo-9-of 7-bis-(pyridine-2-base) acridine changes into 2, the bromo-9-of 7-bis-(4-xenyl) acridine, raw material 4-(naphthalene-1-base) phenylo boric acid is changed into 2-phenylpyridine-5-boric acid, the condition such as other medicine, reagent, reaction, separation is constant, obtains compound shown in formula (47).
Product MS (m/e): 637, ultimate analysis (C 47h 31n 3): theoretical value C:88.51%, H:4.90%, N:6.59%; 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, just by raw material 2, the bromo-9-of 7-bis-(pyridine-2-base) acridine changes into 2, the bromo-9-of 7-bis-(2-naphthyl) acridine, raw material 4-(naphthalene-1-base) phenylo boric acid is changed into 2-phenylpyridine-5-boric acid, the condition such as other medicine, reagent, reaction, separation is constant, obtains compound shown in formula (48).
Product MS (m/e): 611, ultimate analysis (C 45h 29n 3): theoretical value C:88.35%, H:4.78%, N:6.87%; Measured value C:88.38%, H:4.76%, N:6.86%.Compound shown in formula (48) nuclear magnetic spectrogram ( 1hNMR) as shown in Figure 4.
Embodiment 35
The synthesis of compound shown in formula (49)
Synthesis step is same as embodiment 1, just by raw material 2, the bromo-9-of 7-bis-(pyridine-2-base) acridine changes into 2, the bromo-9-of 7-bis-(2-naphthyl) acridine, raw material 4-(naphthalene-1-base) phenylo boric acid is changed into (2-phenyl-1H-benzo [d] imidazoles-1-base) phenylo boric acid, the condition such as other medicine, reagent, reaction, separation is constant, obtains compound shown in formula (49).
Product MS (m/e): 843, ultimate analysis (C 61h 41n 5): theoretical value C:86.81%, H:4.90%, N:8.30%; 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, just by raw material 2, the bromo-9-of 7-bis-(pyridine-2-base) acridine changes into 2, the bromo-9-of 7-bis-(4-xenyl) acridine, raw material 4-(naphthalene-1-base) phenylo boric acid is changed into (2-phenyl-1H-benzo [d] imidazoles-1-base) phenylo boric acid, the condition such as other medicine, reagent, reaction, separation is constant, obtains compound shown in formula (50).
Product MS (m/e): 869, ultimate analysis (C 63h 43n 5): theoretical value C:86.97%, H:4.98%, N:8.05%; 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, just by raw material 2, the bromo-9-of 7-bis-(pyridine-2-base) acridine changes into 2, the bromo-9-phenylacridine of 7-bis-, raw material 4-(naphthalene-1-base) phenylo boric acid is changed into (2-phenyl-1H-benzo [d] imidazoles-1-base) phenylo boric acid, the condition such as other medicine, reagent, reaction, separation is constant, obtains compound shown in formula (51).
Product MS (m/e): 793, ultimate analysis (C 57h 39n 5): theoretical value C:86.23%, H:4.95%, N:8.82%; 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, just by raw material 2, the bromo-9-of 7-bis-(pyridine-2-base) acridine changes into 2, the bromo-9-phenylacridine of 7-bis-, raw material 4-(naphthalene-1-base) phenylo boric acid is changed into 4-(1-phenyl-1H-benzo [d] imidazoles-2-base) phenylo boric acid, the condition such as other medicine, reagent, reaction, separation is constant, obtains compound shown in formula (52).
Product MS (m/e): 793, ultimate analysis (C 57h 39n 5): theoretical value C:86.23%, H:4.95%, N:8.82%; 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, just by raw material 2, the bromo-9-of 7-bis-(pyridine-2-base) acridine changes into 2, the bromo-9-of 7-bis-(4-xenyl) acridine, raw material 4-(naphthalene-1-base) phenylo boric acid is changed into 4-(1-phenyl-1H-benzo [d] imidazoles-2-base) phenylo boric acid, the condition such as other medicine, reagent, reaction, separation is constant, obtains compound shown in formula (53).
Product MS (m/e): 869, ultimate analysis (C 63h 43n 5): theoretical value C:86.97%, H:4.98%, N:8.05%; 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, just by raw material 2, the bromo-9-of 7-bis-(pyridine-2-base) acridine changes into 2, the bromo-9-of 7-bis-(2-naphthyl) acridine, raw material 4-(naphthalene-1-base) phenylo boric acid is changed into 4-(1-phenyl-1H-benzo [d] imidazoles-2-base) phenylo boric acid, the condition such as other medicine, reagent, reaction, separation is constant, obtains compound shown in formula (54).
Product MS (m/e): 843, ultimate analysis (C 61h 41n 5): theoretical value C:86.81%, H:4.90%, N:8.30%; 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, just by raw material 2, the bromo-9-of 7-bis-(pyridine-2-base) acridine changes into 2, the bromo-9-of 7-bis-(4-bromophenyl) acridine, raw material 4-(naphthalene-1-base) phenylo boric acid is changed into naphthalene-2-boric acid, the condition such as other medicine, reagent, reaction, separation is constant, obtains compound shown in formula (55).
Product MS (m/e): 633, ultimate analysis (C 49h 31n): theoretical value C:92.86%, H:4.93%, N:2.21%; 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, just by raw material 2, the bromo-9-of 7-bis-(pyridine-2-base) acridine changes into 2, the bromo-9-of 7-bis-(4-bromophenyl) acridine, raw material 4-(naphthalene-1-base) phenylo boric acid is changed into naphthalene-1-boric acid, the condition such as other medicine, reagent, reaction, separation is constant, obtains compound shown in formula (56).
Product MS (m/e): 633, ultimate analysis (C 49h 31n): theoretical value C:92.86%, H:4.93%, N:2.21%; 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
Conveniently compare the transmission performance of these electron transport materials, the present invention devises a simple electroluminescence device, (EM1 is material of main part as luminescent material to use EM1, and non-luminescent material, object is not pursue high-level efficiency, but verify the possibility of these material practicalities), use efficent electronic transport material Bphen as comparative material.The structure of EM1 and Bphen 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, such as: glass or plastics.In organic electroluminescence device of the present invention makes, select glass substrate, ITO makes anode material.
Hole transmission layer can adopt various tri-arylamine group material.Hole mobile material selected in organic electroluminescence device of the present invention makes is NPB.NPB structure is:
Negative electrode can adopt metal and composition thereof structure, as Mg:Ag, Ca:Ag etc., is also electron injecting layer/metal-layer structure, as LiF/Al, Li 2the common cathode structures such as O/Al.Cathode material selected in organic electroluminescence device of the present invention makes is LiF/Al.
Compound in the present embodiment is as the electron transport material in organic electroluminescence device, EML is as emitting layer material, prepared multiple organic electroluminescence device altogether, its structure is: ITO/NPB (40nm)/EM1 (30nm)/ETL material (20nm)/LiF (0.5nm)/Al (150nm);
A contrast organic electroluminescence device, electron transport material selects Bphen, and all the other organic electroluminescence devices select material of the present invention.
In the present embodiment, organic electroluminescence device preparation process is as follows:
Sheet glass supersound process in commercial detergent of ITO transparency conducting layer will be coated with, rinse in deionized water, at acetone: ultrasonic oil removing in alcohol mixed solvent, be baked under clean environment and remove moisture content completely, by UV-light and ozone clean, and with low energy positively charged ion bundle bombarded surface;
The above-mentioned glass substrate with anode is placed in vacuum chamber, is evacuated to 1 × 10 -5~ 9 × 10 -3pa, on above-mentioned anode tunic, vacuum evaporation NPB is as hole transmission layer, and evaporation rate is 0.1nm/s, and evaporation thickness is 40nm;
On hole transmission layer, vacuum evaporation EM1 is as the luminescent layer of device, and evaporation rate is 0.1nm/s, and evaporation total film thickness is 30nm;
On luminescent layer, compound shown in vacuum evaporation one laminar (21), (22), (24), (27), (37), (43), (44), (47), (48), (49), (50), (53) or (55) is as the electron transport layer materials of device, with the contrast material of Bphen as device electronic transport layer material, its evaporation rate is 0.1nm/s, and evaporation total film thickness is 20nm;
The upper vacuum evaporation thickness of electron transfer layer (ETL) be the LiF of 0.5nm as electron injecting layer, thickness is the negative electrode of Al layer as device of 150nm.
Organic electroluminescence device performance sees the following form:
Compound number Require brightness cd/m 2 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
Above result shows, new organic materials of the present invention is used for organic electroluminescence device, can effectively reduce bright voltage, and improving current efficiency, is electron transport material of good performance.
Although describe the present invention in conjunction with the embodiments, the present invention is not limited to above-described embodiment, should be appreciated that, under the guiding of the present invention's design, those skilled in the art can carry out various amendment and improvement, and claims summarise scope of the present invention.

Claims (8)

1. an acridine derivatives, is characterized in that, has such as formula the structure shown in (1):
Wherein: Ar 1and Ar 2identical or different, be independently selected from C 6-C 30substituted or non-substituted aromatic hydrocarbon group, C 6-C 30substituted or non-substituted condensed-nuclei aromatics group, C 5-C 30substituted or non-substituted fused heterocycle group, five yuan, hexa-atomic heterocycle or substituted heterocycle, C 1-C 12substituted or non-substituted aliphatic alkyl group in one;
R 1-R 6identical or different, be independently selected from H, C 1-C 12substituted or non-substituted aliphatic alkyl group, C 6-C 20substituted or non-substituted aromatic hydrocarbon group, C 6-C 20substituted or non-substituted condensed-nuclei aromatics group, C 5-C 20substituted or non-substituted fused heterocycle group, five yuan, hexa-atomic heterocycle or substituted heterocycle.
2. acridine derivatives according to claim 1, is characterized in that, Ar 1and Ar 2replaced by alkyl, halogen, cyano group, aryl or heterocyclic aryl respectively.
3. acridine derivatives according to claim 1 and 2, is characterized in that, described Ar 1and Ar 2be respectively formula (2) to structure formula (11) Suo Shi:
Wherein Ar 3for H, substituted or unsubstituted aryl, substituted or unsubstituted alkyl;
L is singly-bound, substituted or unsubstituted arylidene, substituted or unsubstituted sub-heterocyclic aryl.
4. acridine derivatives according to claim 3, is characterized in that, Ar 3replaced by alkyl, halogen, cyano group, aryl or heterocyclic aryl respectively with L.
5. the acridine derivatives according to any one of claim 1-4, is characterized in that, described compound is structure shown in formula (21)-(56):
6. the application of acridine derivatives in organic electroluminescence device described in an any one of claim 1-5.
7. the application of acridine derivatives according to claim 6 in organic electroluminescence device, is characterized in that, described acridine derivatives is used as electron transport material.
8. an organic electroluminescence device, comprises substrate, and forms anode layer, organic luminescence function layer and cathode layer on the substrate successively; Described organic luminescence function layer comprises hole transmission layer, organic luminous layer and electron transfer layer, it is characterized in that:
Described electron transfer layer is prepared from by the acridine derivatives described in any one of claim 1-5.
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CN114671855A (en) * 2022-04-22 2022-06-28 云南省烟草质量监督检测站 Acridine ligand for photothermal material, cuprous iodide cluster-based coordination polymer with photo-thermal property, and preparation method and application thereof
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