CN108047235B - A kind of aromatic heterocyclic compounds and its application - Google Patents

A kind of aromatic heterocyclic compounds and its application Download PDF

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CN108047235B
CN108047235B CN201711484681.3A CN201711484681A CN108047235B CN 108047235 B CN108047235 B CN 108047235B CN 201711484681 A CN201711484681 A CN 201711484681A CN 108047235 B CN108047235 B CN 108047235B
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孙军
张宏科
刘凯鹏
王小伟
刘骞峰
高仁孝
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Xi'an Ruilian New Material Co Ltd
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Abstract

The present invention provides a kind of aromatic heterocyclic compounds, is indicated by general formula (1), in formula, Y1For oxygen atom or sulphur atom；Y2For oxygen atom, sulphur atom, NR3Or CR1R2, wherein R1、R2Respectively one of hydrogen atom, methyl, ethyl, propyl, tert-butyl, phenyl, R3For hydrogen atom or phenyl；X11~X20Respectively nitrogen-atoms or CR4, and X11~X20In at least one be and L1The carbon atom combined with singly-bound, wherein R4For hydrogen atom, halogen atom or cyano；X17~X20In at least one be nitrogen-atoms.A kind of aromatic heterocyclic compounds provided by the invention have the structure similar with dibenzofuran derivative, dibenzothiophene derivatives, it can be improved electron-transporting, organic EL element high brightness, low-voltage, high efficiency, long service life may be implemented, can be widely used in OLED luminescent device and display device and used as luminescent layer material of main part.

Description

A kind of aromatic heterocyclic compounds and its application
Technical field
The present invention relates to field of light emitting materials more particularly to a kind of aromatic heterocyclic compounds and its applications.
Background technique
As a kind of self luminous electronic component, organic electroluminescent OLED (Organic Light Emission Diodes) show illumination component luminescence mechanism be under the action of DC electric field, will be electric by organic semiconductor functional material One kind of the novel photoelectric information technology of luminous energy can be converted into.Its luminous color can for individual red, green, blue, yellow light or Person is combination white light.The maximum feature of OLED luminescence display technology is that ultra-thin, ultralight amount, face shines and Flexible Displays, can use In manufacture monochrome or full-color display, as new type light source technology, illuminating product can also be made or novel backlight source technology is used In manufacture liquid crystal display.
According to principle of luminosity, organic electroluminescent device (organic EL element) can be divided into fluorescent type and phosphorescence type is these two types of. Voltage is applied for organic EL element, injects hole from anode and the electronics from cathode, they in luminescent layer again In conjunction with formation exciton.According to electron spin statistic law, singlet exciton and triplet exciton are generated with the ratio of 25%:75%. Fluorescent type is because used singlet exciton to shine, therefore its internal quantum can only achieve 25%.Thermal activities delayed fluorescence (TADF) material is the third generation luminous organic material developed after organic fluorescence materials and organic phosphorescent material.Such material Generally have lesser singlet-triplet poor (Δ Est), triplet excitons can be transformed into list by sowing distrust among one's enemies gap and passing through Line state excitonic luminescence can make full use of the singlet exciton and triplet excitons for being electrically excited lower formation, the interior quantum effect of device Rate can achieve 100%, while material structure is controllable, and property is stablized, cheap to be not necessarily to precious metal, in the field OLEDs It has a extensive future.
In order to prepare high performance OLED luminescent device, needs to select and use high performance OLED functional material, correspond to For the OLED functional material of different role, the basic demand needed to have is as follows:
1, there is good thermal stability, i.e., material will not decompose during long-time is deposited, while material being required to have There is good process reproducibility；
2, the OLED luminescent device of collocation OLED functional material production is with good performance, that is, requires better effect Rate, longer service life and lower voltage.This requires materials need to have suitable HOMO, LUMO, suitable triplet state energy Amount.
In recent years, it although the development of OLED functional material achieves some breakthroughs, is applied as illumination or display, Excavation and the better material of innovation performance are needed, phosphorescent OLED system is especially can be applied to and having for TADF system is grown Service life, the organic functional material of efficient more preferable performance.
Summary of the invention
The purpose of the present invention is overcoming the deficiencies in the prior art, providing one kind can be improved organic electroluminescence The aromatic heterocyclic compounds of part service efficiency and service life.
A kind of aromatic heterocyclic compounds provided by the invention are indicated by the following general formula (1):
[changing 1]
In formula (1),
Y1For oxygen atom or sulphur atom；
Y2For oxygen atom, sulphur atom, NR3Or CR1R2, wherein R1、R2Respectively hydrogen atom, methyl, ethyl, propyl, tertiary fourth One of base, phenyl, R3For hydrogen atom or phenyl；
X11~X20Respectively nitrogen-atoms or CR4, and X11~X20In at least one be and L1With singly-bound combine carbon atom, Wherein, R4For hydrogen atom, halogen atom or cyano；
A is the group indicated by the following general formula (2) or (3),
[changing 2]
-HAr (2)
[changing 3]
In formula (3), L1For divalent~sexavalence linking group, the integer that n is 1~5；
In formula (2) or (3), HAr is the nitrogenous polycyclic group indicated by the following general formula (4),
[changing 4]
In formula (4), Ar1And Ar2Respectively third aryl；X1~X3Respectively nitrogen-atoms or CR5；Wherein, R5For hydrogen atom, Halogen atom, cyano, the first aryl, substituted or unsubstituted at ring carbon that substituted or unsubstituted ring carbons number is 6~30 It is alkyl that the first heterocycle that atomicity is 5~30, substituted or unsubstituted carbon atom number are 1~30, substituted or unsubstituted Alkynyl that alkenyl that carbon atom number is 2~30, substituted or unsubstituted carbon atom number are 2~30, substituted or unsubstituted carbon are former Arylsilyl groups that subnumber is 3~30, substituted or unsubstituted carbon atom number are one of 6~30 aryloxy group.
Preferably, the linking group be substituted or unsubstituted cyclization C atomicity be 6~30 the second aryl, replace Or unsubstituted cyclization C atomicity is 5~30 the second heterocycle or 2~3 second aryl and 2~3 described second The group that heterocycle combines.
Preferably, in the general formula (3), when n is 1, L1For singly-bound or the linking group of divalent；When n is 2~5, L1It is three Valence~sexavalence linking group.
Preferably, in the general formula (1), X17~X20In at least one be nitrogen-atoms.
Preferably, Y1For oxygen atom or sulphur atom；Y2For oxygen atom or CR1R2, wherein R1For methyl, R2For methyl；X11~ X20Respectively CR4, wherein R4For hydrogen atom；X1~X3Respectively nitrogen-atoms；Ar1And Ar2Respectively phenyl.
Preferably, Y1For oxygen atom；Y2For CR1R2, wherein R1For methyl, R2For methyl；X17~X20In at least one be nitrogen Atom, remaining is CR4, X11~X16Respectively CR4, wherein R4For hydrogen atom；X1~X3Respectively nitrogen-atoms；Ar1And Ar2Respectively For phenyl.
The present invention also provides materials made of a kind of aromatic heterocyclic compounds described above in organic electroluminescent Application in element.
The present invention also provides a kind of organic electroluminescent devices, comprising:
Anode and cathode relative to each other；
At least one organic layer between the anode and the cathode；
Wherein the organic layer includes luminescent layer, and the luminescent layer includes that aromatic heterocyclic compounds described above are made Material.
Preferably, the organic layer further includes hole blocking layer and electron transfer layer；Wherein, the hole blocking layer or electricity Sub- transport layer separately includes material made of aromatic heterocyclic compounds described above.
Aromatic heterocyclic compounds described above have similar with dibenzofuran derivative, dibenzothiophene derivatives Structure.
The present invention also provides a kind of organic electroluminescent devices as described above in organic electroluminescence display device and method of manufacturing same In application.
The beneficial effects of the present invention are: a kind of aromatic heterocyclic compounds provided by the invention have and dibenzofurans The similar structure of derivative, dibenzothiophene derivatives, can be improved electron-transporting, and it is highlighted that organic EL element may be implemented Degree, low-voltage, high efficiency and long service life, meanwhile, the thermostabilization with higher of material made of the compound of the present invention Property, it is remarkably improved the stability of photoluminescence of luminescent device, can be widely used in OLED luminescent device and display device as hair Photosphere material of main part uses.
Detailed description of the invention
Fig. 1 is a kind of structural schematic diagram of organic electroluminescent device of the invention.
Description of symbols:
1- cathode；2- transparent conductive film；3- hole injection layer；
4- hole transmission layer；5- luminescent layer；6- hole blocking layer；
7- electron transfer layer；8- electron injecting layer；9- anode.
Specific embodiment
It in order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below will be in the embodiment of the present invention Technical solution be explicitly described, it is clear that described embodiments are some of the embodiments of the present invention, rather than whole Embodiment.Based on the embodiments of the present invention, those of ordinary skill in the art are obtained without making creative work The every other embodiment obtained, shall fall within the protection scope of the present invention.Unless otherwise specified, technological means used is in embodiment Conventional means well-known to those skilled in the art.
Hereinafter, being illustrated to each group in the general formula (1)~(4).
Substituted or unsubstituted ring carbons number is the first aryl that C atomicity is 6~30 and the second aryl group point For example there are: phenyl, 1- naphthalene, 2- naphthalene, 1- anthryl, 2- anthryl, 9- anthryl, benzo anthryl, 1- phenanthryl, 2- phenanthryl, 3- are luxuriant and rich with fragrance Base, 4- phenanthryl, tetraphenyl, pyrenyl, 1- bend base, 2- bends base, 3- bends base, 4- bends base, 5- bends base, benzo [c] phenanthryl, 1-9,10- Benzo phenanthryl, 2-9,10- benzo phenanthryl, 3-9,10- benzo phenanthryl, 4-9,10- benzo phenanthryl, 1- fluorenyl, 2- fluorenyl, 3- fluorenes Base, 4- fluorenyl, o- terphenyl, m- terphenyl, benzo fluorenyl, dibenzo fluorenyl, 2- biphenylyl, 3- biphenylyl, 4- biphenylyl, o- terphenyl, m- terphenyl -4- base, m- terphenyl -3- base, m- terphenyl -2- base, p- three Benzene -4- base, p- terphenyl -3- base, p- terphenyl -2- base, m- tetraphenyl, 3- fluoranthene base, 4- fluoranthene base, 8- fluoranthene base, 9- Fluoranthene base, benzofluoranthrene base, o- tolyl, m- tolyl, p- tolyl, 2,3- xylyl, 3,4- xylyl, 2, 5- xylyl, 2,4,6- trimethylphenyls, o- cumenyl, m- cumenyl, p- cumenyl, p- tert-butyl, 9,9- Dimethyl -1- fluorenyl, 9,9- dimethyl -2- fluorenyl, 9,9- dimethyl -4- fluorenyl, 9,9- phenylbenzene -2- fluorenyl, 9,9- union II Benzene -3- fluorenyl, 9,9- phenylbenzene -4- fluorenyl.
Third aryl group, for example there are: phenyl, 1,2- xenyl, 1,3- xenyl, Isosorbide-5-Nitrae-xenyl, 1- naphthalene, 2- naphthalene Base, 1- anthryl, 2- anthryl, 9- anthryl, benzo anthryl, 1- phenanthryl, 2- phenanthryl, 3- phenanthryl, 4- phenanthryl, tetraphenyl, pyrenyl, 1- are bent Base, 2- bend base, 3- bends base, 4- bends base, 5- bends base, benzo [c] phenanthryl, 1-9,10- benzo phenanthryl, 2-9,10- benzo phenanthryl, 3- 9,10- benzo phenanthryl, 4-9,10- benzo phenanthryl, 1- fluorenyl, 2- fluorenyl, 3- fluorenyl, 4- fluorenyl, o- terphenyl, m- three Phenyl, benzo fluorenyl, dibenzo fluorenyl, 2- biphenylyl, 3- biphenylyl, 4- biphenylyl, o- terphenyl, m- three Benzene -4- base, m- terphenyl -3- base, m- terphenyl -2- base, p- terphenyl -4- base, p- terphenyl -3- base, p- three Benzene -2- base, m- tetraphenyl, 3- fluoranthene base, 4- fluoranthene base, 8- fluoranthene base, 9- fluoranthene base, benzofluoranthrene base, o- tolyl, M- tolyl, p- tolyl, 2,3- xylyl, 3,4- xylyl, 2,5- xylyl, 2, it is 4,6- trimethylphenyls, o- Cumenyl, m- cumenyl, p- cumenyl, p- tert-butyl, 9,9- dimethyl -1- fluorenyl, 9,9- dimethyl -2- fluorenes Base, 9,9- dimethyl -4- fluorenyl, 9,9- phenylbenzene -2- fluorenyl, 9,9- phenylbenzene -3- fluorenyl, 9,9- phenylbenzene -4- fluorenyl.
Substituted or unsubstituted ring carbons number be 5~30 the first heterocycle and the second heterocycle respectively for example there are: Pyrrole radicals, pyrazinyl, pyridyl group, indyl, isoindolyl, imidazole radicals, furyl, benzofuranyl, isobenzofuran-base, two Benzofuranyl, dibenzothiophene, quinolyl, isoquinolyl, quinoxalinyl, carbazyl, phenanthridinyl, acridinyl, phenanthroline The mute piperazine base of base, phenazinyl, phenothiazinyl, pheno, mute oxazolyl, mute di azoly, furan a word used for translation base, benzothienyl and pyridine ring, pyrazine It is ring, pyrimidine ring, pyridazine ring, indole ring, quinoline ring, acridine ring, pyrrolidine ring, carbazole ring, furan nucleus, thiphene ring, mute azoles ring, mute Diazole ring, thiazole ring, Thiadiazole, benzothiazole ring, triazole ring, imidazole ring, benzimidazole ring, pyranoid ring, dibenzofurans The group of the ring of formation.Further specifically have: azepine carbazole and furans, azepine carbazole bithiophene, azepine carbazole and fluorenes, azepine Dibenzofurans and furans, azepine dibenzofurans bithiophene, azepine dibenzofurans and fluorenes, azepine dibenzofurans and click Azoles, azepine dibenzothiophenes bithiophene, azepine dibenzothiophenes and furans, azepine dibenzothiophenes and fluorenes, azepine dibenzo thiophene Pheno and carbazole, azepine fluorenes and fluorenes, azepine fluorenes and furans, azepine fluorenes bithiophene, azepine fluorenes and carbazole etc. and 5-member heterocyclic ring containing nitrogen, nitrogen Position any combination.
The alkyl that substituted or unsubstituted carbon atom number is 1~30, for example there are: methyl, ethyl, propyl, isopropyl, fourth Base, isobutyl group, tert-butyl, amyl, hexyl, cyclopropyl, cyclobutyl, cyclopenta, cyclohexyl etc..
The alkenyl that substituted or unsubstituted carbon atom number is 2~30, for example there are: vinyl, acrylic, cyclobutenyl, oil base, Eicosapentaenoic base, 26 carbon, six alkenyl, styryl, 2,2- diphenylacetylene, 1,2,2- triphenyl vinyls, 2- benzene Base -2- acrylic etc..Preferred vinyl in above-mentioned alkenyl.
For example there are acetenyl, propinyl, 2- phenylacetylene bases etc. for the alkynyl that substituted or unsubstituted carbon atom number is 2~30. Preferred acetenyl in above-mentioned alkynyl.
For example there are dialkyl silyls, alkyl for the arylsilyl groups that substituted or unsubstituted carbon atom number is 3~30 Diarylsilyl, diarye silyl.
Substituted or unsubstituted carbon atom number is that for example there are phenoxy groups for 6~30 aryloxy group.
It is as follows by the concrete example of singly linked group with group A in general formula (1):
[changing 5]
Group represented by A is by general formula (2) or (3) in general formula (1)；Wherein, L in general formula (3)1Linking group it is specific Such as it is lower shown:
[changing 6]
The concrete example of group represented by general formula (3) is as follows:
[changing 7]
HAr is the nitrogenous polycyclic group indicated by general formula (4), the nitrogenous polycyclic group of general formula (4) in its formula of (2) or (3) Concrete example is as follows:
[changing 8]
The present invention is as follows with the concrete example of general formula (1) compound represented:
[changing 9]
[changing 10]
[changing 11]
[changing 12]
[changing 13]
[changing 14]
A kind of organic electroluminescent device provided by the invention, wherein containing heteroaromatic chemical combination shown in general formula (1) Object, in the case where no specific limitation, the organic electroluminescent device can be phosphorescent devices and be also possible to fluorescent device It either include thermal activities delayed fluorescence (TADF) material devices.
Fig. 1 shows an example of organic electroluminescence device.Organic electroluminescent member according to one embodiment Part successively includes anode 9, organic layer and cathode 1, and organic layer successively includes transparent conductive film 2, hole injection layer 3, hole biography Defeated layer 4, luminescent layer 5, hole blocking layer 6, electron transfer layer 7 and electron injecting layer 8；Anode 9 can be by with high official letter number Indium tin oxide (ITO) helps hole injection, and cathode 1 can be the metal electrode of the low official letter number such as aluminium, magnesium, silver.In organic layer Including at least one layer of compound, which can be used as the use of 5 main body of luminescent layer, when using as 5 main body of luminescent layer Can the independent compound, be also possible to the compound other organic materials of arranging in pairs or groups and constitute hybrid agents and use.As master The fluorescent material that can arrange in pairs or groups when body use uses, and the phosphor material that can also arrange in pairs or groups uses or collocation TADF materials'use.It is described Compound can also be used as hole blocking layer 6 to use, or use as electron transfer layer 7.The organic light emission member Part further includes hole injection layer 3, hole transmission layer 4, electronic barrier layer, electron transfer layer 7 and electron injecting layer 8, electrically conducting transparent The auxiliary functional layers such as film 2 improve the photoelectric properties of device.Below by way of device embodiments and comparative example 1, the present invention will be described in detail The concrete application effect of the organic electroluminescent functional material of synthesis in the devices.
Embodiment 1: compound 1
The synthesis of compound 1:
(1) intermediate 1 (compound 1) synthetic intermediate 2 (compound 2)
This boric acid of 30g O-methoxy, 43g bromophenyl first are sequentially added in the 1L there-necked flask equipped with thermometer, condenser pipe Sour methyl esters, 55g k2CO3With 13g TBABA, 300ml toluene, 100ml ethyl alcohol and 50ml water are then sequentially added, is replaced with nitrogen 1.15g Pd (PPH is added in air in reaction flask under nitrogen protection state3)4, heating is opened, magnetic agitation is heated to (78 ~80 DEG C) back flow reaction, sample detection after 8h is reacted, until stopping reaction when raw material fully reacting, after being cooled to room temperature progress Reason, by reaction solution filtering, stratification, aqueous layer merges organic phase after being extracted with 100ml toluene, is washed to neutrality, use is anhydrous Na2SO4Dry 1h, is filtered to remove desiccant and obtains filter cake, filter cake is eluted with a small amount of toluene, merging filtrate, mistake after filtrate is concentrated Column purification obtains target product intermediate 2.
Intermediate 2 be colourless liquid 44g, yield 92%,1H NMR spectra analyzes result are as follows:1H NMR (400MHz, CDC13) δ 7.86 (dd, J=7.7,1H), 7.52 (td, J=7.6,1H), 7.37 (td, J=7.6,1H), 7.34-7.28 (m, 2H), 7.23 (dt, J=6.2,1H), 7.02 (t, J=7.4,1H), 6.88 (d, J=8.2,1H), 3.69 (s, 3H), 3.63 (s, 3H)。
(2) intermediate 2 (compound 2) synthetic intermediate 3 (compound3)
200ml THF is added in 500ml there-necked flask, 40g intermediate 2 is then added, in nitrogen displacement reaction flask Air, reaction system are cooled to 0 DEG C, and MeMgBr (3M in THF) 110ml is slowly added dropwise under nitrogen protection state, keeps this After temperature 1h, it is warming up to and is stirred to react 12h under room temperature.Monitoring raw material stops reaction when reacting completely, and saturation NH is added4Cl Solution quenching reaction, the reaction solution stratification that will be obtained, aqueous layer are extracted with dichloromethane 2 times, each 50ml, merge organic Phase washes primary, anhydrous Na with saturated common salt2SO4Dry 1h is filtered to remove desiccant, and column is crossed after filtrate concentration and obtains target production Object intermediate 3.
Intermediate 3 be colourless liquid 33g, yield 83%,1H NMR spectra analyzes result are as follows:1H NMR (400MHz, CDC13) δ 7.86 (dd, J=7.7,1H), 7.52 (td, J=7.6,1H), 7.37 (td, J=7.6,1H), 7.34-7.28 (m, 2H), 7.23 (dt, J=6.2,1H), 7.02 (t, J=7.4,1H), 6.88 (d, J=8.2,1H), 3.63 (s, 3H), 1.88 (s, 1H), 1.47 (s, 6H).
(3) intermediate 3 (compound3) synthetic intermediate 4 (compound4)
AcOH 300ml is added in 1L there-necked flask, 33g intermediate 3 is then added, is cooled to 0 DEG C of stirring 10min, then Phosphatase 24 00ml is added, reaction system, which is warming up to, is stirred at room temperature 3h, after TLC monitoring raw material reacts completely, is added into reaction system NaOH solution adjusts PH to neutrality, then extracts 3 water phases with DCM, each 500ml merges organic phase and washed with saturated common salt Once, anhydrous Na2SO4Dry 1h, is filtered, and is crossed silicagel column after concentration filtrate and is obtained target product intermediate 4.
Intermediate 4 be white solid 25g, yield 80%,1H NMR spectra analyzes result are as follows:1H NMR (400MHz, CDC13) δ 7.86 (dd, J=7.7,1H), 7.52 (td, J=7.6,1H), 7.37 (td, J=7.6,1H), 7.34-7.28 (m, 2H), 7.23 (dt, J=6.2,1H), 7.02 (t, J=7.4,1H), 6.88 (d, J=8.2,1H), 4.30 (s, 3H), 1.53 (s, 6H)。
(4) intermediate 4 (compound 4) synthetic intermediate 5 (compound5)
25g intermediate 4 is added in the 500ml there-necked flask equipped with 150ml DCM, with the sky in nitrogen displacement reaction flask Gas is down to -5 DEG C, by BBr3It is dissolved in DCM, is slowly added to reaction system under nitrogen protection, this temperature is kept to continue after being added dropwise Reaction, until stopping reaction when TLC monitoring raw material fully reacting；Slowly add water quenching reaction, stratification, water under condition of ice bath It is mutually extracted with DCM, merges organic phase, washed once with saturated common salt, then anhydrous Na2SO4Dry 1h, is filtered to remove desiccant, Silicagel column, which is crossed, after filtrate concentration obtains target product intermediate 5.
Intermediate 5 is white solid 23g, yield 96%, 1H NMR spectra analysis result are as follows: 1H NMR (400MHz, CDC13) δ 7.86 (dd, J=7.7,1H), 7.52 (td, J=7.6,1H), 7.37 (td, J=7.6,1H), 7.34-7.28 (m, 2H), 7.23 (dt, J=6.2,1H), 7.02 (t, J=7.4,1H), 6.88 (d, J=8.2,1H), 5.33 (s, 1H), 1.53 (s, 6H)。
(5) intermediate 5 (compound5) synthetic intermediate 6 (compound6)
DMSO is added in the 250ml there-necked flask equipped with thermometer, condenser pipe, then sequentially adds 23g intermediate 5,31g K2CO3, 3g 18- crown- 6, iodo- 4 aminopyridine of 38g 3,5- bis-, with the air in reaction system with nitrogen, in nitrogen protection Lower addition CuI is heated to stopping stirring after 100 DEG C of reaction 6h, TLC monitoring raw materials react completely, is down to room temperature.In reaction system The water that 3 times of volumes are added makes product precipitate, and filtering, gained crude product is washed 3 times, each 400ml after being completely dissolved with DCM, It is concentrated after organic phase is dry, crude product crosses silicagel column and obtains target product intermediate 6.
Intermediate 6 be faint yellow solid 41g, yield 87%,1H NMR spectra analyzes result are as follows:1H NMR (400MHz, CDC13) δ 8.56 (s, 1H), 8.11 (s, 1H), 7.86 (dd, J=7.7,1.1,1H), 7.52 (td, J=7.6,1.3,1H), 7.37 (td, J=7.6,1.1,1H), 7.34-7.28 (m, 2H), 7.23 (dt, J=6.2,3.1,1H), 7.02 (t, J=7.4, 1H), 6.88 (d, J=8.2,1H), 4.13 (s, 2H), 1.53 (s, 6H).
(6) intermediate 6 (compound6) synthetic intermediate 7 (compound7)
The dilute sulfuric acid 200ml of mass fraction 25% is added in 500ml there-necked flask, 40g intermediate 6, reaction is then added System is cooled to -5~0 DEG C, is slowly added to dissolved with 7g NaNO2Aqueous solution 30ml, be heated to 80 after keeping this thermotonus 2h DEG C continue to be stirred to react 2h, TLC monitoring raw material stops reacting when react completely, is down to room temperature.It is 9 that NaOH solution, which is added, and adjusts PH ~10, reaction solution is extracted 3 times, each 100ml with DCM, merges organic phase, is washed with saturated common salt primary, and organic phase is with anhydrous Na2SO4It is concentrated after drying, crude product crosses silica gel column purification and obtains target product intermediate 7.
Intermediate 7 be gray solid 30g, yield 78%,1H NMR spectra analyzes result are as follows:1H NMR (400MHz, CDC13) δ 8.72 (s, 1H), 8.35 (s, 1H), 7.86 (dd, J=7.7,1H), 7.52 (td, J=7.6,1H), 7.37 (td, J =7.6,1H), 7.34-7.28 (m, 2H), 7.23 (dt, J=6.2,1H), 7.02 (t, J=7.4,1H), 1.53 (s, 6H).
(7) intermediate 7 (compound7) synthesizes compound 1
15g intermediate 7,10g 3,5- diphenyl benzene boron are added in the 500ml there-necked flask equipped with thermometer, condenser pipe Acid, 11g K2CO3, then 2.4g TBAB sequentially adds 120ml toluene, 40ml ethyl alcohol, 20ml water, with nitrogen displacement reaction flask In air, 0.21g Pd (PPH is added under nitrogen protection state3)4, heating is opened, magnetic agitation is heated to (78~80 DEG C) Back flow reaction, sample detection after 6h are cooled to room temperature and are post-processed until stopping reaction when raw material fully reacting, reaction solution mistake Filter, stratification, aqueous layer are extracted with 50ml toluene, merge organic phase, ultrapure to be washed to neutrality, anhydrous Na2SO4Dry 1h, mistake Desiccant is filtered out, filter cake is eluted with a small amount of toluene, merging filtrate, and silicagel column is crossed after concentration and obtains compound 1.
Compound 1 be white solid 16g, yield 86%,1H NMR spectra analyzes result are as follows:1H NMR (400MHz, CDC13) δ 8.67 (s, 1H), 8.28 (s, 1H), 7.86 (dd, J=7.7,1H), 7.42-7.50 (m, 9H), 7.37 (td, J= 7.6,1H), 7.34-7.22 (m, 7H), 7.02 (dd, J=7.7,1H), 1.53 (s, 6H).
Embodiment 2: compound 2
The synthesis of compound 2:
15g intermediate 7,10g 1,3,5-triazines -4,6- are added in the 500ml there-necked flask equipped with thermometer, condenser pipe Diphenyl -2- boric acid, 11g K2CO3, then 2.4g TBAB sequentially adds 120ml toluene, 40ml ethyl alcohol, 20ml water uses nitrogen The air in reaction flask is replaced, 0.21g Pd (PPH is added under nitrogen protection state3)4, open heating.Magnetic agitation is heated to (78-80 DEG C) back flow reaction, sample detection after 6h are cooled to room temperature and are post-processed until stopping reaction when raw material fully reacting, Reaction solution filtering, stratification, aqueous layer are extracted with 50ml toluene, merge organic phase, ultrapure to be washed to neutrality, anhydrous Na2SO4 Dry 1h, is filtered to remove desiccant, and filter cake is eluted with a small amount of toluene, merging filtrate, and silicagel column is crossed after concentration and obtains compound 2.
Compound 2 be light green solid 17g, yield 91%,1H NMR spectra analyzes result are as follows:1H NMR (400MHz, CDC13) δ 8.67 (s, 1H), 8.28 (s, 1H), 7.86 (dd, J=7.7,1H), 7.61 (dd, J=7.7,1H), 7.42-7.48 (m, 6H), 7.37 (td, J=7.6,1H), 7.34-7.22 (m, 6H), 7.02 (dd, J=7.7,1H), 1.53 (s, 6H).
Embodiment 3: compound 3
The synthesis of compound 3:
(1) intermediate 8 (compound8) synthetic intermediate 9 (compound9)
15g intermediate 8 is sequentially added in the 1L there-necked flask equipped with thermometer, condenser pipe, 30g c pyridine -4- boric acid, The bromo- 3- methoxyl group methyl formate of 60g 2-, 51g K2CO3, then 1.3g TBAB sequentially adds 300ml toluene, 100ml ethyl alcohol, 1.15g Pd (PPH is added with the air in nitrogen displacement reaction flask in 50ml water under nitrogen protection state3)4, open heating, magnetic Power stirring, is heated to (78~80 DEG C) back flow reaction, and sample detection after 8h is cooled to until stopping reaction when raw material fully reacting Room temperature is post-processed, reaction solution filtering, stratification.Water phase is extracted with 100ml toluene, is merged organic phase, is washed to neutrality, Anhydrous Na2SO4Dry 1h, is filtered to remove desiccant, and filter cake is eluted with a small amount of toluene, merging filtrate, during mistake silicagel column obtains after concentration Mesosome 9.
Intermediate 9 be white solid 53g, yield 89%,1H NMR spectra analyzes result are as follows:1H NMR (400MHz, CDC13) δ 8.65 (dd, J=7.7,2H), 7.59 (m, 3H), 7.22 (dt, J=6.2,1H), 7.02 (dd, J=6.2,1H), 3.88 (s, 3H), 3.73 (s, 3H).
(2) intermediate 9 (compound9) synthetic intermediate 10 (compound10)
300ml THF is sequentially added in 1L there-necked flask, 53g intermediate 9 is then added, in nitrogen displacement reaction flask Air, reaction system are down to 0 DEG C, and MeMgBr (3M in THF) 200ml is slowly added dropwise under nitrogen protection state, keeps this temperature It is warming up to after reaction 1h and is stirred to react 12h under room temperature, stop reaction when monitoring raw material fully reacting, saturation NH is added4Cl Solution quenching reaction stands liquid separation, and water phase is extracted with dichloromethane 2 times, each 100ml, merges organic phase, saturated common salt washing Once, anhydrous Na2SO4Dry 1h, filtration drying agent cross silicagel column after filtrate concentration and obtain intermediate 10.
Intermediate 10 be white solid 43g, yield 81%,1H NMR spectra analyzes result are as follows:1H NMR (400MHz, CDC13) δ 8.66 (dd, J=7.7,2H), 7.62 (dd, J=7.7,2H), 7.04 (td, J=6.2,1H), 6.81 (dd, J= 6.2,1H), 6.76 (dd, J=6.2,1H), 3.73 (s, 3H), 1.54 (s, 6H).
(3) intermediate 10 (compound 10) synthetic intermediate 11 (compound 11)
AcOH 300ml is added in 1L there-necked flask, 43g intermediate 10 is then added and is cooled to 0 DEG C of stirring 10min, then Phosphoric acid 500ml is added, reaction system is warmed to room temperature stirring 3h, TLC monitoring until raw material adds after reacting completely into reaction system Enter NaOH solution and adjust PH to neutrality, is then extracted 3 times, each 500ml with DCM, merge organic phase with saturated common salt and wash one It is secondary, anhydrous Na2SO4Dry 1h, filtering, concentrated solvent cross silicagel column and obtain target product intermediate 11.
Intermediate 11 be white solid 30g, yield 75%,1H NMR spectra analyzes result are as follows:1H NMR (400MHz, CDC13) δ 8.63 (m, 2H), 7.51 (d, J=7.6,1H), 7.03 (t, J=6.2,1H), 6.75 (dd, J=6.2,1H), 6.65 (dd, J=6.2,1H), 3.73 (s, 3H), 1.67 (s, 6H).
(4) intermediate 11 (compound 11) synthetic intermediate 12 (compound 12)
30g intermediate 11 is added in the 500ml there-necked flask equipped with 200ml THF, then with nitrogen displacement reaction flask In air, be down to -78 DEG C, slowly 53ml n-BuLi (2.5M in THF) be added drop-wise in reaction system under nitrogen protection, This temperature is kept after being added dropwise the reaction was continued 1h, is then added dissolved with 17g B (OCH3)3THF 50ml, keep this temperature anti- Answer 2h, warm naturally to room temperature the reaction was continued 1h, TCL monitoring until when raw material fully reacting stop reaction, into reaction system Addition dilute hydrochloric acid adjusting pH value to acidity, stratification, water phase is extracted with DCM, merges organic phase, then anhydrous Na2SO4It is dry 1h is filtered to remove desiccant, and petroleum ether elutes to obtain target product intermediate 12. after filtrate concentration
Intermediate 12 be white solid 26g, yield 72%,1H NMR spectra analyzes result are as follows:1H NMR (400MHz, CDC13) δ 8.63 (m, 2H), 7.51 (dd, J=7.6,1H), 7.12 (dd, J=6.2,1H), 6.84 (dd, J=6.2,1H), 3.73 (s, 3H), 2.02 (s, 2H), 1.67 (s, 6H).
(5) intermediate 12 (compound 12) synthetic intermediate 13 (compound 13)
26g intermediate 12, the chloro- 2- of 26.5g 1,3- bis- are sequentially added in the 1L there-necked flask equipped with thermometer, condenser pipe Iodobenzene, 27g K2CO3, then 3g TBAB sequentially adds 300ml toluene, 100ml ethyl alcohol, 50ml water, with nitrogen displacement reaction flask In air, 0.56g Pd (PPH is added under nitrogen protection state3)4, heating is opened, magnetic agitation is heated to (78~80 DEG C) Back flow reaction, sample detection after 6h are cooled to room temperature and are post-processed until stopping reaction when raw material fully reacting, reaction solution mistake Filter, stratification.Water phase is extracted with 100ml toluene, merges organic phase, ultrapure to be washed to neutrality, anhydrous Na2SO4Dry 1h, mistake Desiccant is filtered out, filter cake is eluted with a small amount of toluene, merging filtrate, and silicagel column is crossed after concentration and obtains intermediate 13.
Intermediate 13 be white solid 32g, yield 89%,1H NMR spectra analyzes result are as follows:1H NMR (400MHz, CDC13) δ 8.63 (m, 2H), 7.51 (d, J=7.4,1H), 7.25 (d, J=7.6,1H), 7.21 (dd, J=6.2,2H), 7.10 (t, J=6.2,1H), 6.81 (d, J=7.6,1H), 3.73 (s, 3H), 1.67 (s, 6H).
(6) intermediate 13 (compound 13) synthetic intermediate 14 (compound 14)
32g intermediate 13 is added in the 500ml there-necked flask equipped with 300ml DCM, in nitrogen displacement reaction flask Air is down to -5 DEG C, by BBr3It is dissolved in DCM, reaction system is added under nitrogen protection, keeps this temperature to continue after being added dropwise anti- It answers, until TLC monitoring raw material stops reaction when reacting completely, slowly adds water quenching reaction, stratification under condition of ice bath.Water phase It is extracted with DCM, merges organic phase, washed once with saturated common salt, then use anhydrous Na2SO4Dry 1h, is filtered to remove desiccant, Silicagel column is crossed after concentration obtains intermediate 14.
Intermediate 14 be white solid 30g, yield 97%,1H NMR spectra analyzes result are as follows:1H NMR (400MHz, CDC13) δ 8.63 (m, 2H), 7.51 (d, J=7.4,1H), 7.18-7.21 (m, 3H), 7.10 (t, J=6.2,1H), 6.81 (d, J=7.6,1H), 1.67 (s, 6H).
(7) intermediate 14 (compound 14) synthetic intermediate 15 (compound 15)
30g intermediate 14 is sequentially added in the 500ml there-necked flask equipped with thermometer, condenser pipe, 12g sodium tert-butoxide, 0.19g Pd (OAc) is added under nitrogen protection state then with the air in nitrogen displacement reaction flask in 250ml toluene2, open Heating.Magnetic agitation is heated to (110~115 DEG C) back flow reaction, sample detection after 8h, until stopping when raw material fully reacting anti- It answers, is cooled to room temperature and is post-processed, reaction solution filtering, filter cake is eluted with a small amount of toluene, and merge organic phase, is washed to neutrality, Anhydrous Na2SO4Dry 1h, is filtered to remove desiccant, and silicagel column is crossed after concentration and obtains intermediate 15.
Intermediate 15 be white solid 20g, yield 74%,1H NMR spectra analyzes result are as follows:1H NMR (400MHz, CDC13) δ 8.63 (m, 2H), 7.51 (d, J=7.4,1H), 7.37 (d, J=7.2,1H), 7.30 (d, J=7.4,1H), 7.13 (m, 2H), 7.06 (t, J=7.2,1H), 1.67 (s, 6H).
(8) intermediate 15 (compound 15) synthesizes compound 3
10g intermediate 15,8.6g 3,5- diphenyl are sequentially added in the 250ml there-necked flask equipped with thermometer, condenser pipe Phenyl boric acid, 8.7g K2CO3, then 1.0g TBAB sequentially adds 80ml toluene, 20ml ethyl alcohol, 10ml water is replaced anti-with nitrogen The air in bottle is answered, 0.36g Pd (PPH is added under nitrogen protection state3)4, open heating.Magnetic agitation is heated to (78~80 DEG C) back flow reaction, sample detection after 8h is cooled to room temperature and post-processed until stopping reaction when raw material fully reacting.
Reaction solution filtering, stratification.Water phase is extracted with 20ml toluene, merges organic phase, ultrapure to be washed to neutrality, anhydrous Na2SO4Dry 1h, is filtered to remove desiccant, and filter cake is eluted with a small amount of toluene, merging filtrate, and silicagel column is crossed after concentration and obtains compound 3。
Compound 3 be white solid 13g, yield 82%,1H NMR spectra analyzes result are as follows:1H NMR (400MHz, CDC13) δ 8.63 (m, 2H), 7.66 (s, 3H), 7.51 (d, J=7.4,1H), 7.48 (dd, J=7.2,4H), 7.32-7.37 (m, 7H), 7.22-7.25 (m, 3H), 7.06 (d, J=7.2,1H), 1.67 (s, 6H).
Embodiment 4: compound 4
The synthesis of compound 4:
15,8.6g1,3,5- triazine of 10g intermediate-is sequentially added in the 250ml there-necked flask equipped with thermometer, condenser pipe - 2 boric acid of 4,6- diphenyl, 8.7g K2CO3, then 1.0g TBAB sequentially adds 80ml toluene, 20ml ethyl alcohol, 10ml water is used 0.36g Pd (PPH is added under nitrogen protection state for air in nitrogen displacement reaction flask3)4, open heating.Magnetic agitation adds Heat is to (78~80 DEG C) back flow reaction, sample detection after 8h, until stop reaction when raw material fully reacting, is cooled to after room temperature carries out Processing, reaction solution filtering, stratification, water phase are extracted with 20ml toluene, merge organic phase, ultrapure to be washed to neutrality, anhydrous Na2SO4Dry 1h, is filtered to remove desiccant, and filter cake is eluted with a small amount of toluene, merging filtrate, and silicagel column is crossed after concentration and obtains compound 4。
Compound 4 be white solid 13.7g, yield 85%,1H NMR spectra analyzes result are as follows:1H NMR (400MHz, CDC13) δ 8.63 (m, 2H), 7.51 (d, J=7.4,1H), 7.48 (dd, J=7.2,4H), 7.32-7.37 (m, 7H), 7.22- 7.25 (m, 3H), 7.06 (d, J=7.2,1H), 1.67 (s, 6H).
Embodiment 5: compound 5
The synthesis of compound 5:
(1) intermediate 16 (compound 16) synthetic intermediate 17 (compound 17)
30g intermediate 16,27.4g 4- dibenzo are sequentially added in the 250ml there-necked flask equipped with thermometer, condenser pipe Furan boronic acid, 36g K2CO3, then 4g TBAB sequentially adds 240ml toluene, 80ml ethyl alcohol, 40ml water is replaced anti-with nitrogen The air in bottle is answered, 0.75g Pd (PPH is added under nitrogen protection state3)4, heating is opened, magnetic agitation is heated to (78~80 DEG C) back flow reaction, sample detection after 8h is cooled to room temperature and post-processed until stopping reaction when raw material fully reacting, reaction solution Filtering, stratification.Water phase is extracted with 50ml toluene, merges organic phase, ultrapure to be washed to neutrality, anhydrous Na2SO4Dry 1h, mistake Desiccant is filtered out, filter cake is eluted with a small amount of toluene, merging filtrate, and silicagel column is crossed after concentration and obtains intermediate 17.
Intermediate 17 be white solid 34.3g, yield 83%,1H NMR spectra analyzes result are as follows:1H NMR (400MHz, CDC13) δ 7.81 (dd, J=7.7,1H), 7.38-7.42 (m, 3H), 7.49 (dd, J=6.2,1H), 7.45 (dd, J=6.2, 1H), 7.17-7.22 (m, 4H), 3.73 (s, 3H).
(2) intermediate 17 (compound 17) synthetic intermediate 18 (compound 18)
34g intermediate 17 is added in the 500ml there-necked flask equipped with 250ml DCM, displaces reaction system with nitrogen In air, -5 DEG C are down to, by BBr3It is dissolved in DCM, is added under nitrogen protection and answers system, this temperature is kept to continue after being added dropwise Reaction stands and divides up to slowly adding water quenching reaction under TLC monitoring stopping reaction when raw material reacts completely, condition of ice bath Layer, water phase are extracted with DCM, merge organic phase, are washed once with saturated common salt, then anhydrous Na2SO4Dry 1h, is filtered to remove dry Drying prescription crosses silicagel column after filtrate concentration and obtains target product intermediate 18.
Intermediate 18 be white solid 30.2g, yield 93%,1H NMR spectra analyzes result are as follows:1H NMR (400MHz, CDC13) δ 7.81 (dd, J=7.7,1H), 7.49 (dd, J=6.2,1H), 7.45 (dd, J=6.2,1H), 7.42 (dd, J= 7.7,3H), 7.39 (dd, J=7.7,3H), 7.31 (td, J=7.7,1H), 7.17-7.22 (m, 4H).
(3) intermediate 18 (compound 18) synthetic intermediate 19 (compound 19)
30g intermediate 18,150ml DMI, 150ml are sequentially added in the 500ml there-necked flask equipped with thermometer, condenser pipe 0.67g PHCO is added with the air in nitrogen displacement reaction flask in toluene under nitrogen protection state3T-Bu and 022g palladium acetate, Heating magnetic agitation is opened, (110~115 DEG C) back flow reaction, sample detection after 8h, until stopping when raw material fully reacting are heated to Reaction, is cooled to room temperature and is post-processed, and reaction solution directly filters, and crosses silicagel column after filtrate concentration and obtains intermediate 19.
Intermediate 19 be white solid 20.3g, yield 68%,1H NMR spectra analyzes result are as follows:1H NMR (400MHz, CDC13) δ 8.06 (dd, J=7.7,1H), 7.81 (dd, J=7.7,1H), 7.49 (dd, J=6.2,1H), 7.38-7.42 (m, 3H), 7.15-7.19 (m, 3H).
(4) intermediate 19 (compound 19) synthetic intermediate 20 (compound 20)
20g intermediate 19,200ml THF, 10g zinc are sequentially added in the 500ml there-necked flask equipped with thermometer, condenser pipe Powder.10g glacial acetic acid is slowly dropped in reaction system, (70~80 DEG C) back flow reaction is heated to after being added dropwise, is taken after 5h Sample detection is cooled to room temperature and is post-processed until stopping reaction when raw material fully reacting, and NaOH solution is added in reaction solution and adjusts PH value is neutral, stratification, and water phase is extracted 3 times, each 100ml with DCM, merging organic phase, after the dry 1h of anhydrous sodium sulfate Filtering crosses silicagel column after filtrate concentration and obtains intermediate 20.
Intermediate 20 be white solid 17.3g, yield 96%,1H NMR spectra analyzes result are as follows:1H NMR (400MHz, CDC13) δ 7.49 (dd, J=6.2,1H), 7.38-7.42 (m, 3H), 6.94 (td, J=6.2,1H), 6.78 (dd, J=6.2, 1H), 4.12 (s, 2H).
(5) intermediate 20 (compound 20) synthetic intermediate 21 (compound 21)
17g intermediate 20 is sequentially added in the 250ml there-necked flask equipped with thermometer, condenser pipe, 180ml 1M dilute hydrochloric acid, It is cooled to -5~0 DEG C, it will be dissolved with 4.8g NaNO2Aqueous solution 15ml be slowly dropped in reaction system, kept the temperature after being added dropwise 1h is reacted, reaction solution is added drop-wise in the aqueous solution 50ml dissolved with 11g KI, samples inspection after being heated to (60-75 DEG C) reaction 6h It surveys, until stopping reaction when raw material fully reacting, is cooled to room temperature and is post-processed.
Reaction solution filtering, filter cake are eluted with water, are then dissolved in DCM.Filtrate is extracted 3 times with DCM, and each 50ml is associated with Machine phase, saturated common salt washing is primary, filters after the dry 1h of anhydrous sodium sulfate, crosses silicagel column after filtrate concentration and obtain intermediate 2.
Intermediate 20 be white solid 16.2g, yield 68%,1H NMR spectra analyzes result are as follows:1H NMR (400MHz, CDC13) δ 7.51 (dd, J=6.2,1H), 7.49 (dd, J=6.2,1H), 7.41-7.42 (m, 3H), 6.96-7.15 (m, 4H).
(6) intermediate 21 (compound 21) synthesizes compound 5
16g intermediate 21,11.5g1,3,5- tri- is sequentially added in the 250ml there-necked flask equipped with thermometer, condenser pipe Piperazine -4,6- diphenyl -2- boric acid, 11.5g K2CO3, then 1.3g TBAB sequentially adds 120ml toluene, 40ml ethyl alcohol, 20ml Pb (PPH is added with the air in nitrogen displacement reaction flask in water under nitrogen protection state3)4, open heating.Magnetic agitation, heating Sample detection after to (78~80 DEG C) back flow reaction 8h, until stopping reaction when raw material fully reacting, after being cooled to room temperature progress Reason, reaction solution filtering, stratification.Water phase is extracted with 50ml toluene, merges organic phase, is washed to neutrality, and anhydrous sodium sulfate is dry It is filtered after dry 1h, crosses silicagel column after filtrate concentration and obtain compound 5.
Compound 5 be white solid 17.7g, yield 87%,1H NMR spectra analyzes result are as follows:1H NMR (400MHz, CDC13) δ 7.48-7.50 (m, 5H), 7.42 (m, 2H), 7.35-7.38 (m, 6H), 7.19-7.22 (m, 5H), 7.12 (td, J= 6.2,1H).
Embodiment 6: compound 6
The synthesis of compound 6:
(1) intermediate 22 (compound 22) synthetic intermediate 23 (compound 23)
30g intermediate 22,26.4g O-methoxy benzene are sequentially added in the 250ml there-necked flask equipped with thermometer, condenser pipe Boric acid, 48g K2CO3, then 5.6g TBAB sequentially adds 240ml toluene, 60ml ethyl alcohol, 30ml water is replaced with nitrogen and reacted 1g Pb (PPH is added under nitrogen protection state for air in bottle3)4, open heating.Magnetic agitation is heated to (78~80 DEG C) and returns Sample detection is cooled to room temperature and is post-processed until stopping reaction when raw material fully reacting after stream reaction 8h, reaction solution filtering, Stratification.Water phase is extracted with 50ml toluene, merges organic phase, ultrapure to be washed to neutrality, is filtered after the dry 1h of anhydrous sodium sulfate, It is filtered to remove desiccant, filter cake is eluted with a small amount of toluene, merging filtrate, and silicagel column is crossed after concentration and obtains intermediate 23.
Intermediate 23 be colourless liquid 31g, yield 89%,1H NMR spectra analyzes result are as follows:1H NMR (400MHz, CDC13) δ 6.75-7.30 (m, 4H), 7.16 (dd, J=7.5,7.5Hz, 1H), 7.03-7.12 (m, 3H), 6.34 (s, 1H), 3.92 (s, 3H).
(2) intermediate 23 (compound 23) synthetic intermediate 24 (compound 24)
31g intermediate 23,150ml DMI, 150ml are sequentially added in the 250ml there-necked flask equipped with thermometer, condenser pipe 0.9g PHCO is added with the air in nitrogen displacement reaction flask in toluene under nitrogen protection state2Ot-Bu and 0.35g palladium acetate, Open heating.Magnetic agitation is heated to (110~115 DEG C) back flow reaction, sample detection after 8h, until stopping when raw material fully reacting It only reacts, is cooled to room temperature and is post-processed, reaction solution filtering crosses silicagel column after filtrate concentration and obtains intermediate 24.
Intermediate 24 be white solid 20.2g, yield 66%,1H NMR spectra analyzes result are as follows:1H NMR (400MHz, CDC13) δ 8.14 (d, J=7.8Hz, 1H), 7.55 (d, J=8.2Hz, 1H), 7.44-7.32 (m, 3H), 7.20 (d, J= 8.1Hz, 1H), 4.06 (s, 3H).
(3) intermediate 24 (compound 24) synthetic intermediate 25 (compound 25)
20g intermediate 24 is added in the 250ml there-necked flask equipped with 150ml DCM, displaces reaction system with nitrogen In air, -5 DEG C are down to, by BBr3It is dissolved in DCM, is added under nitrogen protection and answers system, this temperature is kept to continue after being added dropwise Reaction stands and divides up to slowly adding water quenching reaction under TLC monitoring stopping reaction when raw material reacts completely, condition of ice bath Layer, water phase are extracted with DCM, merge organic phase, are washed once with saturated common salt, then anhydrous Na2SO4Dry 1h, is filtered to remove dry Drying prescription crosses silicagel column after filtrate concentration and obtains target product intermediate 25.
Intermediate 25 be white solid 17.8g, yield 96%,1H NMR spectra analyzes result are as follows:1H NMR (400MHz, CDC13) δ 7.81 (dd, J=7.7,1H), 7.52 (dd, J=6.2,1H), 7.47 (td, J=6.2,1H), 7.32-7.38 (m, 2H), 7.23 (dd, J=7.1,1H), 6.98 (dd, J=7.7,1H).
(4) intermediate 25 (compound 25) synthetic intermediate 26 (compound 26)
120ml DMSO is sequentially added in the 250ml there-necked flask equipped with thermometer, condenser pipe, then sequentially adds 17g Intermediate 25,25.5g K2CO3, 2.5g 18- crown- 6, the iodo- 4-aminopyridine of 32g 3,5- bis-, in nitrogen displacement reaction flask 5.3g CuI is added under nitrogen protection state for air, is heated to 100 DEG C of reaction 6h, TCL, which is monitored after raw materials react completely, to be stopped stirring It mixes, is down to room temperature.The water that 3 times of volumes are added in reaction system is precipitated out product, filters.Water phase is extracted with 100ml DCM, Filter cake merges organic phase after being completely dissolved with 200ml DCM, wash 3 times, each 80ml.It is concentrated after organic phase is dry, crude product It crosses silicagel column and obtains target product intermediate 26.
Intermediate 26 be faint yellow solid 26.7g, yield 72%,1H NMR spectra analyzes result are as follows:1H NMR (400MHz, CDC13) δ 8.62 (s, 1H), 8.45 (s, 1H), 7.86 (dd, J=7.7,1H), 7.42-7.46 (m, 2H), 7.19 (td, J= 7.7,1H), 7.13 (td, J=7.7,1H), 6.98-7.02 (m, 2H), 4.13 (s, 2H).
(5) intermediate 26 (compound 26) synthetic intermediate 27 (compound 27)
The dilute sulfuric acid 150ml of mass fraction 25% is added in 500ml there-necked flask, 26g intermediate 26, reaction is then added System is cooled to -5~0 DEG C, and being slowly added to will be dissolved with 5g NaNO2Aqueous solution 20ml, be added dropwise after rear insulation reaction 2h plus Heat continues to be stirred to react 2h to 80 DEG C.TCL stops reaction when monitoring raw material reacts completely, is down to room temperature.NaOH solution tune is added Saving pH value is 9~10, and reaction solution is extracted 3 times with DCM, each 100ml.Merge organic phase, is washed once with saturated common salt, it is organic Mutually with being concentrated after anhydrous sodium sulfate drying, crude product crosses silica gel column purification and obtains target product intermediate 27.
Intermediate 27 be gray solid 15.7g, yield 63%,1H NMR spectra analyzes result are as follows:1H NMR (400MHz, CDC13) δ 8.97 (s, 1H), 8.58 (s, 1H), 7.51 (dd, J=7.7,1H), 7.42-7.44 (m, 2H), 7.18-7.22 (m, 2H), 7.11 (td, J=7.7,1H).
(5) intermediate 27 (compound 27) synthesizes compound 6
15g intermediate 27,10.8g K are sequentially added in the 250ml there-necked flask equipped with thermometer, condenser pipe2CO3, 1.2g Then TBAB sequentially adds 120ml toluene, 40ml ethyl alcohol, 20ml water, with the air in nitrogen displacement reaction flask, nitrogen protection 0.23g Pd (PPH is added under state3)4, open heating.Magnetic agitation is heated to (78~80 DEG C) back flow reaction, samples after 6h Detection is cooled to room temperature and is post-processed until stopping reaction when raw material fully reacting, reaction solution filtering, stratification, and water phase is used The extraction of 50ml toluene merges organic phase, ultrapure to be washed to neutrality, anhydrous Na2SO4After dry 1h, it is filtered to remove desiccant, filter cake It is eluted with a small amount of toluene, merging filtrate, silica gel column purification is crossed after concentration and obtains target product compound 6.
Compound 6 be white solid 16.2g, yield 85%,1H NMR spectra analyzes result are as follows:1H NMR (400MHz, CDC13) δ 8.81 (s, 1H), 8.55 (s, 1H), 7.46-7.51 (m, 5H), 7.42 (m, 2H), 7.35 (td, J=6.2,4H), 7.19-7.22 (m, 5H).
Embodiment 7: compound 7
The synthesis of compound 7:
(1) intermediate 28 (compound 28) synthetic intermediate 29 (compound 29)
200ml toluene is sequentially added in the 500ml there-necked flask equipped with thermometer, condenser pipe, 46g t-BuOK uses nitrogen The air in reaction flask is replaced, 7.8g CuI is added under nitrogen protection state, stirs 1h, 23g 1,3- dinitrobenzene is then added Pyridine solution 50ml, solution becomes red turbid, continuously adds 30g intermediate 28, and it is anti-to be heated to (110~115 DEG C) reflux It answers, sample detection after 5h, until stopping reaction when raw material fully reacting, is cooled to room temperature and is post-processed, reaction solution filtering is added It is neutrality, stratification that the hydrochloric acid solution of 1M, which adjusts pH value,.Water phase is extracted with 100ml toluene, merges organic phase, saturated salt solution Wash primary, anhydrous Na2SO4After dry 1h, it is filtered to remove desiccant, silica gel column purification is crossed after concentration and obtains intermediate 29.
Intermediate 29 be faint yellow solid 22.1g, yield 76%,1H NMR spectra analyzes result are as follows:1H NMR (400MHz, CDC13) δ 8.68 (dd, 1H, J=8.0,1H) .8.23 (dd, J=8.0,1H), 7.91 (dd, J=8.0,1H), 7.62 (m, 3H), 7.46 (dd, J=8.0,1H).
(2) intermediate 29 (compound 29) synthetic intermediate 30 (compound 30)
22g intermediate 29,150ml THF, 15g zinc are sequentially added in the 250ml there-necked flask equipped with thermometer, condenser pipe Powder.14g glacial acetic acid is slowly added into reaction system, (10~80 DEG C) back flow reaction is heated to after being added dropwise, is taken after 6h Sample detection is cooled to room temperature and is post-processed until stopping reaction when raw material fully reacting, and NaOH solution is added in reaction solution and adjusts PH value is neutrality, stratification.Water phase is extracted 2 times with 100ml DCM, merges organic phase, anhydrous Na2SO4After dry 1h, filtering Desiccant is removed, silica gel column purification is crossed after concentration and obtains intermediate 30.
Intermediate 30 be white solid 16.3g, yield 86%,1H NMR spectra analyzes result are as follows:1H NMR (400MHz, CDC13) δ 7.69 (dd, J=6.2,1H), 7.62 (dd, J=6.2,1H), 7.48 (td, J=6.2,1H), 7.38-7.43 (m, 2H), 6.92 (dd, J=6.2,1H), 6.70 (dd, J=6.2,1H), 4.07 (s, 2H).
(3) intermediate 30 (compound 30) synthetic intermediate 31 (compound 31)
16g intermediate 30,130ml 2M dilute hydrochloric acid solution are sequentially added in 250ml there-necked flask.Being cooled to -5~0 DEG C will Dissolved with 7.2g NaNO2Aqueous solution 20ml be slowly dropped in reaction system, rear insulation reaction 1h is added dropwise, by reaction solution It is added drop-wise in the 50ml aqueous solution dissolved with 21g K xanthate, is heated to sample detection after (60~65 DEG C) reaction 3h, until former Expect to stop reaction when fully reacting, is cooled to room temperature and is post-processed, DCM is added in reaction solution and extracts 3 times, each 300ml.It closes And organic phase, saturated common salt washing is primary, anhydrous Na2SO4It is filtered after drying 1h, mistake silica gel column purification obtains intermediate after filtering and concentrating Body 31.
Intermediate 31 be faint yellow solid 10.7g, yield 61%,1H NMR spectra analyzes result are as follows:1H NMR (400MHz, CDC13) δ 7.49 (dd, J=6.2,1H), 7.42 (dd, J=6.2,1H), 7.18-7.20 (m, 2H), 7.13 (m, 1H), 7.03- 7.05 (m, 2H), 3.15 (s, 1H).
(4) intermediate 31 (compound 31) synthetic intermediate 32 (compound 32)
DMSO is added in the 250ml there-necked flask equipped with thermometer, condenser pipe, then sequentially adds 10g intermediate 31, 13.8g K2CO3, 1.6g 18- crown- 6, the iodo- 4-aminopyridine of 17.3g 3,5- bis-, with the air in nitrogen displacement reaction flask, nitrogen 2.9g CuI is added under gas shielded state, is added to 120 DEG C of reactions 10h, TLC and stops stirring, drop when monitoring raw material fully reacting It warms to room temperature.The water that 3 times of volumes are added in reaction system is precipitated out product, filters.After gained crude product is completely dissolved with DCM Washing 3 times, each 400ml.It is concentrated after organic phase is dry, crude product crosses silicagel column and obtains target product intermediate 32.
Intermediate 32 be faint yellow solid 16.9g, yield 81%,1H NMR spectra analyzes result are as follows:1H NMR (400MHz, CDC13) δ 8.56 (s, 1H) .8.37 (s, 1H), 7.49 (dd, J=7.7,1H), 7.42 (dd, J=7.7,1H), 7.18-7.20 (m, 2H), 7.13 (td, J=7.7,1H), 7.03-7.05 (m, 2H), 4.05 (s, 2H).
(5) intermediate 32 (compound 32) synthetic intermediate 33 (compound 33)
120ml glacial acetic acid is added in 250ml there-necked flask, 16g intermediate 32 is added, with the sky in nitrogen displacement reaction flask Gas is slowly added to 4.4g t-BuONO under nitrogen protection state, and 70 DEG C of reaction 5h are heated to after stirring at normal temperature reaction 1h, and TLC is supervised It surveys after raw material reacts completely and stops stirring, be down to room temperature.Na is added in reaction system2CO3Solution adjusts pH value to neutrality, is added DCM is extracted 3 times, each 150ml.Merge organic phase, uses anhydrous Na2SO4It is concentrated after drying, crude product crosses silicagel column and obtains intermediate 33。
Intermediate 33 be faint yellow solid 11.2g, yield 73%,1H NMR spectra analyzes result are as follows:1H NMR (400MHz, CDC13) δ 8.97 (s, 1H), 7.78 (dd, J=7.7,1H), 7.49 (dd, J=7.7,1H), 7.38-7.42 (m, 2H), 7.16- 7.19 (m, 2H).
(6) intermediate 33 (compound 33) synthesizes compound 7
11g intermediate 33,7.6g 1,3,5- tri- are sequentially added in the 250ml there-necked flask equipped with thermometer, condenser pipe Piperazine -4,6- diphenyl -2- boric acid, 7.8g K2CO3, 0.7g TBAB, then addition 80ml toluene, 20ml ethyl alcohol, 10ml water are used 0.16g Pd (PPH is added under nitrogen protection state for air in nitrogen displacement reaction flask3)4, open heating.Magnetic agitation adds Heat is to (78~80 DEG C) back flow reaction, sample detection after 6h, until stop reaction when raw material fully reacting, is cooled to after room temperature carries out Processing, reaction solution filtering, stratification.It is extracted with water phase 30ml toluene, merges organic phase, it is ultrapure to be washed to neutrality, it is anhydrous Na2SO4Dry 1h, is filtered to remove desiccant, and filter cake is eluted with a small amount of toluene, merging filtrate, and silica gel column purification is crossed after concentration to be changed Close object 7.Compound 7 be faint yellow solid 12.2g, yield 88%,1H NMR spectra analyzes result are as follows:1H NMR (400MHz, CDC13) δ 8.81 (s, 1H) .8.55 (s, 1H), 7.79 (dd, J=7.7,1H), 7.48-7.50 (m, 5H), 7.42 (dd, J= 7.7,1H), 7.32 (m, 5H), 7.19-7.22 (m, 3H), 7.13 (td, J=7.7,1H).
Embodiment 8: compound 8
The synthesis of compound 8:
(1) intermediate 34 (compound 34) synthetic intermediate 35 (compound 35)
30g intermediate 34 is sequentially added in the 250ml there-necked flask equipped with thermometer, condenser pipe, 25.6g and benzofuran Boric acid, 33.4g K2CO3, then 3.9g TBAB sequentially adds 240ml toluene, 60ml ethyl alcohol, 30ml water is replaced anti-with nitrogen The air in bottle is answered, Pd (PPH is added under nitrogen protection state3)4, open heating.Magnetic agitation is heated to (78~80 DEG C) and returns Stream reacts, and sample detection after 8h is cooled to room temperature and is post-processed until stopping reaction when raw material fully reacting, reaction solution filtering, Stratification.Water phase is extracted with 50ml toluene, merges organic phase, ultrapure to be washed to neutrality, anhydrous Na2SO4Dry 1h, crosses and filters out Desiccant is removed, filter cake is eluted with a small amount of toluene, merging filtrate, and silica gel column purification is crossed after concentration and obtains intermediate 35.
Intermediate 35 be faint yellow solid 35.2g, yield 82%,1H NMR spectra analyzes result are as follows:1H NMR (400MHz, CDC13) δ 8.01 (dd, J=7.7,1H), 7.63 (dd, J=7.7,1H), 7.45-7.49 (m, 4H), 7.38 (td, J=6.2, 1H), 7.19 (td, J=6.2,1H), 7.13 (td, J=6.2,1H), 2.47 (s, 3H).
(2) intermediate 35 (compound35) synthetic intermediate 36 (compound 36)
35g intermediate 35 is added in 150ml propylamine solution, is down to 0 DEG C, with the air in nitrogen displacement reaction flask, so Afterwards with 7.5g ethylenediamine and 0.9g lithium are added under nitrogen protection state, ice bath is removed in reaction 3h recession at a temperature of this, rises to room naturally Temperature the reaction was continued 5h, TLC monitoring raw material stops reaction when react completely, reaction solution is poured into the dilute hydrochloric acid of ice, DCM extracts 3 Secondary, each 100ml merges organic phase, anhydrous Na2SO4Dry 1h is filtered to remove desiccant, crosses silica gel column purification after filtrate concentration Obtain intermediate 36.
Intermediate 36 be faint yellow solid 26.2g, yield 78%,1H NMR spectra analyzes result are as follows:1H NMR (400MHz, CDC13) δ 8.03 (dd, J=7.7,1H), 7.63 (dd, J=7.7,1H), 7.49 (dd, J=6.2,3H), 7.42-7.45 (m, 3H), 7.32 (td, J=6.2,1H), 7.19 (td, J=6.2,1H), 7.13 (td, J=6.2,1H), 2.33 (s, 1H).
(3) intermediate 36 (compound36) synthetic intermediate 37 (compound 37)
26g compound 32,120ml DMI are sequentially added in the 500ml there-necked flask equipped with thermometer, condenser pipe, 0.5g PHCO is added with the air in nitrogen displacement reaction flask in 120ml toluene under nitrogen protection state3T-Bu and 0.18g vinegar Sour palladium, is heated to (110~115 DEG C) back flow reaction, and sample detection after 8h is cooled to until stopping reaction when raw material fully reacting Room temperature is post-processed, and reaction solution directly filters, and is crossed silica gel column purification after filtrate concentration and is obtained intermediate 37.
Intermediate 37 be faint yellow solid 16.3g, yield 63%,1H NMR spectra analyzes result are as follows:1H NMR (400MHz, CDC13) δ 8.26 (m, 2H), 7.78 (dd, J=7.7,1H), 7.57 (dd, J=6.5,1H), 7.49 (dd, J=6.2,1H), 7.42 (dd, J=6.2,1H), 7.33 (dd, J=7.7,1H), 7.19 (td, J=6.2,1H), 7.13 (td, J=6.2,1H).
(4) intermediate 37 (compound37) synthetic intermediate 38 (compound 38)
16g intermediate 37,120ml THF, 7.2g zinc powder are added in 250ml there-necked flask.6.6g glacial acetic acid is slowly dripped It is added in reaction system, (78~80 DEG C) back flow reaction, sample detection after 6h, until raw material fully reacting is heated to after being added dropwise When stop reaction, be cooled to room temperature and post-processed, reaction solution filtering, it is neutrality that NaOH solution is added in filtrate and adjusts PH, quiet Layering is set, water phase is extracted 3 times, each 150ml with DCM, merges organic phase, anhydrous Na2SO4It is filtered after dry 1h, after filtrate concentration It crosses silica gel column purification and obtains intermediate 38.
Intermediate 38 be faint yellow solid 13.3g, yield 92%,1H NMR spectra analyzes result are as follows:1H NMR (400MHz, CDC13) δ 7.78 (dd, J=6.2,1H), 7.49 (dd, J=6.2,1H), 7.42 (dd, J=6.2,1H), 7.33 (dd, J= 7.7,1H), 7.22 (dd, J=6.2,1H), 7.19 (td, J=6.2,1H), 7.13 (td, J=6.2,1H), 7.06 (dd, J= 6.2,1H), 6.53 (td, J=6.2,1H), 3.65 (s, 2H).
(5) intermediate 38 (compound38) synthetic intermediate 39 (compound 39)
13g intermediate 38 is added in the 250ml there-necked flask equipped with low-reading thermometer, 70ml 2M dilute hydrochloric acid is cooled to -5 ~0 DEG C will be dissolved with 3.7g NaNO210ml aqueous solution be slowly dropped in reaction system, rear insulation reaction 1h is added dropwise, will Reaction solution is added drop-wise in the 30ml aqueous solution dissolved with 9g KI, sample detection after (60~75 DEG C) reaction 6h is heated to, until raw material is anti- Stop reaction when answering complete, be cooled to room temperature and post-processed, reaction solution filtering, filter cake is eluted with water, is then dissolved in DCM, is filtered Liquid is extracted 3 times with DCM, each 80ml.Merge organic phase, saturated common salt washing is primary, anhydrous Na2SO4It filters, filters after dry 1h Silica gel column purification, which is crossed, after liquid concentration obtains intermediate 39.
Intermediate 39 be faint yellow solid 12.8g, yield 71%,1H NMR spectra analyzes result are as follows:1H NMR (400MHz, CDC13) δ 7.85 (dd, J=7.7,1H), 7.73-7.75 (m, 2H), 7.49 (dd, J=6.5,1H), 7.42 (dd, J=6.2, 1H), 7.33 (dd, J=7.7,1H), 7.19 (td, J=6.2,1H), 7.09-7.12 (m, 2H).
(6) intermediate 39 (compound39) synthesizes compound 8
39,8.3g1,3,5- triazine of 12g intermediate-is sequentially added in the 250ml there-necked flask equipped with thermometer, condenser pipe 4,6- diphenyl -2- boric acid, 8.5g K2CO3, then 1g TBABA sequentially adds 100ml toluene, 30ml ethyl alcohol, 15ml water is used 0.18g Pd (PPH is added under nitrogen protection state for air in nitrogen displacement reaction flask3)4, open heating.Magnetic agitation adds Heat is to (78~80 DEG C) back flow reaction, sample detection after 8h, until stop reaction when raw material fully reacting, is cooled to after room temperature carries out Processing, reaction solution filtering, stratification.Water phase is extracted with 30ml toluene, merges organic phase, ultrapure to be washed to neutrality, anhydrous Na2SO4Dry 1h, is filtered to remove desiccant, and filter cake is eluted with a small amount of toluene, merging filtrate, and silica gel column purification is crossed after concentration to be changed Close object 8.
Compound 8 be white solid 12.6g, yield 83%,1H NMR spectra analyzes result are as follows:1H NMR (400MHz, CDC13) δ 7.78-7.82 (m, 2H), 7.48-7.53 (m, 6H), 7.42 (dd, J=6.2,1H), 7.33-7.36 (m, 6H), 7.19-7.22 (m, 3H), 7.13 (td, J=6.2,1H).
Embodiment 9
A kind of organic electroluminescence device, device preparation step include:
1) ito anode on transparent glass substrate is cleaned, is respectively cleaned by ultrasonic 20 points with deionized water, acetone, ethyl alcohol respectively Then clock carries out Plasma under oxygen atmosphere and handles 5 minutes；
2) on ito anode layer, hole injection layer material HAT-CN is deposited by vacuum evaporation mode, with a thickness of 10nm, This layer is as hole injection layer；
3) hole mobile material NPB is deposited by vacuum evaporation mode on hole injection layer, with a thickness of 60nm, which makees For hole transmission layer；
4) luminescent layer on the hole transport layer, is deposited by vacuum evaporation mode, uses the compounds of this invention 1 as main body Material, Ir (ppy) 3 are used as dopant material, and material doped mass ratio is 10%, with a thickness of 30nm；
5) on luminescent layer, hole barrier materials TPBI is deposited by way of vacuum evaporation, with a thickness of 15nm, this Layer is used as hole blocking layer；
6) electron transport material ET-1 on the hole blocking layer, is deposited by way of vacuum evaporation, with a thickness of 30nm, this One layer is used as electron transfer layer；
7) electron injection material Liq on the electron transport layer, is deposited by way of vacuum evaporation, with a thickness of 2nm, this Layer is used as electron injecting layer；
8) on electron injecting layer, the evaporation cathode Al by way of vacuum evaporation, with a thickness of 120nm, the layer is as yin Pole conductive electrode uses.
Embodiment 10
It is same as Example 9, the difference is that: it regard compound 2 as material of main part, compound 1 is used as hole barrier Material.
Embodiment 11
It is same as in Example 10, the difference is that: it regard compound 3 as material of main part alternative compounds 2.
Embodiment 12
It is same as in Example 10, the difference is that: it regard compound 4 as material of main part alternative compounds 2.
Embodiment 13
It is same as in Example 10, the difference is that: it regard compound 5 as material of main part alternative compounds 2.
Embodiment 14
It is identical as embodiment 13, the difference is that: it regard compound 7 as hole barrier materials alternative compounds 1.
Embodiment 15
It is identical as embodiment 13, the difference is that: it regard compound 7 as material of main part alternative compounds 5.
Embodiment 16
It is identical as embodiment 15, the difference is that: it regard compound 8 as material of main part alternative compounds 7.
Embodiment 17
It is same as Example 9, the difference is that: compound 2 is used as hole barrier materials alternative compounds 1.
Embodiment 18
It is same as in Example 10, the difference is that: compound 2 is used as hole barrier materials alternative compounds 1.
Comparative example 1
It is same as Example 9, the difference is that: CBP is as material of main part alternative compounds 1.
Comparative example 2
It is identical as comparative example 1, the difference is that: compound 1 substitutes TPBI as hole barrier materials.
The different components list of table 1 embodiment of the present invention 9~18, comparative example 1, comparative example 2
Embodiment Hole injection layer Hole transmission layer Luminescent layer HB ET
9 HAT-CN(10nm) NPB(60nm) Compound 1:Ir (ppy) 3 TPBI ET-1
10 HAT-CN(10nm) NPB(60nm) Compound 2:Ir (ppy) 3 Compound 1 ET-1
11 HAT-CN(10nm) NPB(60nm) Compound 3:Ir (ppy) 3 Compound 1 ET-1
12 HAT-CN(10nm) NPB(60nm) Compound 4:Ir (ppy) 3 Compound 1 ET-1
13 HAT-CN(10nm) NPB(60nm) Compound 5:Ir (ppy) 3 Compound 1 ET-1
14 HAT-CN(10nm) NPB(60nm) Compound 5:Ir (ppy) 3 Compound 7 ET-1
15 HAT-CN(10nm) NPB(60nm) Compound 7:Ir (ppy) 3 Compound 7 ET-1
16 HAT-CN(10nm) NPB(60nm) Compound 8:Ir (ppy) 3 Compound 7 ET-1
17 HAT-CN(10nm) NPB(60nm) Compound 1:Ir (ppy) 3 Compound 2 ET-1
18 HAT-CN(10nm) NPB(60nm) Compound 2:Ir (ppy) 3 Compound 2 ET-1
Comparative example 1 HAT-CN(10nm) NPB(60nm) CBP:Ir (ppy) 3 TPBI ET-1
Comparative example 2 HAT-CN(10nm) NPB(60nm) CBP:Ir (ppy) 3 Compound 1 ET-1
The embodiment of the present invention 9~18, comparative example 1, comparative example 2 the device compared with device embodiments 9 device Manufacture craft it is identical, and use identical baseplate material and electrode material, the film thickness of electrode material also keeps phase Together, except that device 9~18, comparative example 1, comparative example 2 do the material of main part hole barrier materials of device luminescent layer Transformation.Such as above-mentioned OLED luminescent device, cathode and anode are connected with well known driving circuit, pass through the method for standard Test voltage-efficiency-current density relationship of OLED device；The service life of device is tested by constant flow method, and original intensity is 3000cd/m2, test brightness decays to 95% time of original intensity, as device LT95Service life.Test result such as 2 institute of table Show.
2 different components embodiment performance graph of table
Containing double and five-membered ring heterocyclic group containing N in aromatic heterocyclic compounds of the invention, LUMO can reduce, reduce Band gap can be improved electronic transmission performance to extend light abstraction width, conducive to the injection and transmission of electronics, be applied to luminous Can effectively improve the luminous efficiency of light-emitting component in layer main body material or hole barrier materials, realize significantly low-voltage, Long-life.As shown in Table 2, compound of the present invention is applied to OLED as the material of main part and hole barrier materials of luminescent layer In photophore, chroma stability, compared with comparative example 1, luminous efficiency and service life have obtained significant raising, luminous efficiency 26% or so is improved, service life improves 22% or so；Comparative example 2 is compared with comparative example 1, adds this in hole blocking layer After invention compound, luminous efficiency and service life get a promotion.
Meanwhile five-membered ring N heterocyclic group is a kind of rigid radical, double simultaneously five yuan in aromatic heterocyclic compounds of the present invention Ring heterocyclic group containing N is to connect the group formed by two five-membered ring structures and two N heterocycle structure intervals, unit structure tool There is biggish rigidity, and double and five-membered ring heterocyclic group containing N molecular weight is big, then introduces double and five-membered ring heterocyclic group containing N also It can be improved the glass transition temperature (T of compoundg), glass transition temperature is carried out to the material of the compound containing Examples 1 to 8 (Tg) test experiments, the results are shown in Table 3 for test.
Glass transition temperature (the T of 3 compound 1~8 of tableg)
Material Glass transition temperature (Tg)
Compound 1 155℃
Compound 2 142℃
Compound 3 165℃
Compound 4 159℃
Compound 5 138℃
Compound 6 129℃
Compound 7 156℃
Compound 8 148℃
CBP 62℃
As shown in Table 3, the compound of the present invention material glass transition temperature (T with higherg), in higher temperature section Interior deformation is relatively stable, i.e., thermal stability with higher, applied to the hair for being remarkably improved luminescent device in luminescent device Photostability.The material property of compound 3 is optimal it can be seen from table 2 and table 3, glass transition temperature with higher and longevity Order characteristic.
Finally, it should be noted that the above embodiments are merely illustrative of the technical solutions of the present invention, rather than its limitations；Although Present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that: it still may be used To modify the technical solutions described in the foregoing embodiments or equivalent replacement of some of the technical features； And these are modified or replaceed, technical solution of various embodiments of the present invention that it does not separate the essence of the corresponding technical solution spirit and Range.

Claims (5)

1. a kind of aromatic heterocyclic compounds, which is characterized in that indicated by the following general formula (1):
In formula (1),
Y1For oxygen atom, Y2For oxygen atom, sulphur atom；Or Y1For sulphur atom, Y2For oxygen atom；
X11~X20In, X12Or X18For nitrogen-atoms, remaining is CH；
A is the group indicated by the following general formula (2),
In formula (2), HAr is the nitrogenous polycyclic group indicated by the following general formula (4),
In formula (4), Ar1And Ar2Respectively phenyl；
X1~X3Respectively nitrogen-atoms or CH.
2. material answering in organic electroluminescent device made of a kind of aromatic heterocyclic compounds described in claim 1 With.
3. a kind of organic electroluminescent device characterized by comprising
Anode and cathode relative to each other；
At least one organic layer between the anode and the cathode；
Wherein the organic layer includes luminescent layer, and the luminescent layer includes aromatic heterocyclic compounds system described in claim 1 At material.
4. organic electroluminescent device as claimed in claim 3, which is characterized in that the organic layer further includes hole blocking layer And electron transfer layer；Wherein, the hole blocking layer or electron transfer layer separately include heteroaromatic described in claim 1 Material made of compound.
5. a kind of application of the organic electroluminescent device in organic electroluminescence display device and method of manufacturing same as described in claim 3 or 4.
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