CN108047235A - 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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CN108047235A
CN108047235A CN201711484681.3A CN201711484681A CN108047235A CN 108047235 A CN108047235 A CN 108047235A CN 201711484681 A CN201711484681 A CN 201711484681A CN 108047235 A CN108047235 A CN 108047235A
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compound
reaction
atom
aromatic heterocyclic
heterocyclic compounds
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CN108047235B (en
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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 represented by general formula (1), in formula, Y1For oxygen atom or sulphur atom；Y2For oxygen atom, sulphur atom, NR3Or CR1R2, wherein R1、R2One kind respectively in hydrogen atom, methyl, ethyl, propyl, tertiary butyl, phenyl, R3For hydrogen atom or phenyl；X11~X20Respectively nitrogen-atoms or CR4, and X11~X20In at least one be and L1With the carbon atom that singly-bound combines, wherein, R4For hydrogen atom, halogen atom or cyano；X17~X20In it is 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, electron-transporting can be improved, it can realize that organic EL element high brightness, low-voltage, high efficiency, service life are long, can be widely used in OLED luminescent devices 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 technology
As a kind of self luminous electronic component, organic electroluminescent OLED (Organic Light Emission Diodes the luminescence mechanism for) showing illumination component is under the action of DC electric field, by organic semiconductor functional material by electricity One kind of the novel photoelectric information technology of luminous energy can be converted into.Its luminous color can be individual red, green, blue, yellow light or Person is combination white light.The maximum feature of OLED luminescence display technologies is 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 this two class of phosphorescence type. Apply voltage for organic EL element, inject hole from anode and the electronics from cathode, they in luminescent layer again Combine to form exciton.According to electron spin statistic law, singlet exciton is with triplet exciton with 25%:75% ratio generation. 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 poor (Δ Est) with smaller singlet-triplet, 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 reach 100%, while material structure is controllable, and property is stablized, cheap without precious metal, in OLEDs fields It has a extensive future.
It is corresponding in order to prepare high performance OLED luminescent devices, it is necessary to select and using high performance OLED functional materials Not, it is necessary to which the basic demand possessed is as follows for the OLED functional materials of same-action：
1st, there is good thermal stability, i.e., will not be decomposed in long-time vapor deposition process in which materials, while material is required to have There is good process reproducibility；
2nd, the OLED luminescent devices that OLED functional materials make of arranging in pairs or groups have good performance, that is, require better effect Rate, longer service life and lower voltage.This requires material need to have suitable HOMO, LUMO, suitable triplet state energy Amount.
In recent years, although the development of OLED functional materials achieves some breakthroughs, applied as illumination or display, Excavation and the better material of innovation performance are needed, phosphorescent OLED system is particularly can be applied to and having for TADF systems is grown Service life, the organic functional material of efficient more preferable performance.
The content of the invention
The purpose of the present invention is overcoming the deficiencies in the prior art, organic electroluminescence can be improved by providing one kind The aromatic heterocyclic compounds of part service efficiency and service life.
A kind of aromatic heterocyclic compounds provided by the invention are represented 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 kind in 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 represented by the following general formula (2) or (3),
[changing 2]
-HAr (2)
[changing 3]
In formula (3), L1For the linking group of divalent~sexavalence, n is 1~5 integer；
In formula (2) or (3), HAr is the nitrogenous polycyclic group represented by the following general formula (4),
[changing 4]
In formula (4), Ar1And Ar2Respectively triaryl；X1~X3Respectively nitrogen-atoms or CR5；Wherein, R5For hydrogen atom, Halogen atom, cyano, the first aryl, substituted or unsubstituted into 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 number are 1~30, substituted or unsubstituted Alkynyl that alkenyl that carbon number is 2~30, substituted or unsubstituted carbon number are 2~30, substituted or unsubstituted carbon are former Arylsilyl groups that subnumber is 3~30, substituted or unsubstituted carbon number are one kind in 6~30 aryloxy group.
Preferably, the linking group be substituted or unsubstituted cyclization C atomicities be 6~30 the second aryl, substitution Or unsubstituted cyclization C atomicities are 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, L1For three The linking group of valency~sexavalence.
Preferably, in the general formula (1), X17~X20In it is 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 it is 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 material 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 device, including:
Anode and cathode relative to each other；
At least one organic layer between the anode and the cathode；
Wherein described organic layer includes luminescent layer, and the luminescent layer is made comprising aromatic heterocyclic compounds described above Material.
Preferably, the organic layer further includes hole blocking layer and electron transfer layer；Wherein, the hole blocking layer or electricity Sub- transport layer includes material made of aromatic heterocyclic compounds described above respectively.
Aromatic heterocyclic compounds described above have similar with dibenzofuran derivative, dibenzothiophene derivatives Structure.
The present invention also provides a kind of organic electroluminescent device 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 improve electron-transporting, can realize that organic EL element highlights Degree, low-voltage, high efficiency and service life are long, meanwhile, material made of the compound of the present invention has higher thermostabilization Property, the stability of photoluminescence of luminescent device is remarkably improved, can be widely used in OLED luminescent devices and display device as hair Photosphere material of main part uses.
Description of the drawings
Fig. 1 is a kind of structure diagram of organic electroluminescent device of the present invention.
Reference sign：
1- cathodes；2- transparent conductive films；3- hole injection layers；
4- hole transmission layers；5- luminescent layers；6- hole blocking layers；
7- electron transfer layers；8- electron injecting layers；9- anodes.
Specific embodiment
It, below will be in the embodiment of the present invention to make the purpose, technical scheme and advantage of the embodiment of the present invention clearer Technical solution be explicitly described, it is clear that described embodiment be part of the embodiment 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, belongs to the scope of protection of the invention.Unless otherwise specified, technological means used is in embodiment Conventional means well-known to those skilled in the art.
Hereinafter, each group in the general formula (1)~(4) is illustrated.
Substituted or unsubstituted ring carbons number is the first aryl that C atomicities are 6~30 and the second aryl group point Not for example there are：Phenyl, 1- naphthalenes, 2- naphthalenes, 1- anthryls, 2- anthryls, 9- anthryls, 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- benzos phenanthryl, 3-9,10- benzos phenanthryl, 4-9,10- benzos phenanthryl, 1- fluorenyls, 2- fluorenyls, 3- fluorenes Base, 4- fluorenyls, o- terphenyl, m- terphenyl, benzo fluorenyl, dibenzo fluorenyl, 2- biphenylyls, 3- biphenylyls, 4- biphenylyls, o- terphenyl, m- terphenyl -4- bases, m- terphenyl -3- bases, m- terphenyl -2- bases, p- three Benzene -4- bases, p- terphenyl -3- bases, p- terphenyl -2- bases, m- tetraphenyl, 3- fluoranthene base, 4- fluoranthene base, 8- fluoranthene base, 9- Fluoranthene base, benzofluoranthrene base, o- tolyl, m- tolyl, p- tolyl, 2,3- xylyls, 3,4- xylyls, 2, 5- xylyls, 2,4,6- trimethylphenyls, o- cumenyl, m- cumenyl, p- cumenyl, p- tertiary butyl, 9,9- Dimethyl -1- fluorenyls, 9,9- dimethyl -2- fluorenyls, 9,9- dimethyl -4- fluorenyls, 9,9- phenylbenzene -2- fluorenyls, 9,9- di-s Benzene -3- fluorenyls, 9,9- phenylbenzene -4- fluorenyls.
Triaryl group, for example there are：Phenyl, 1,2- xenyls, 1,3- xenyls, 1,4- xenyls, 1- naphthalenes, 2- naphthalenes Base, 1- anthryls, 2- anthryls, 9- anthryls, 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- benzos phenanthryl, 2-9,10- benzos phenanthryl, 3- 9,10- benzo phenanthryl, 4-9,10- benzos phenanthryl, 1- fluorenyls, 2- fluorenyls, 3- fluorenyls, 4- fluorenyls, o- terphenyl, m- three Phenyl, benzo fluorenyl, dibenzo fluorenyl, 2- biphenylyls, 3- biphenylyls, 4- biphenylyls, o- terphenyl, m- three Benzene -4- bases, m- terphenyl -3- bases, m- terphenyl -2- bases, p- terphenyl -4- bases, p- terphenyl -3- bases, p- three Benzene -2- bases, m- tetraphenyl, 3- fluoranthene base, 4- fluoranthene base, 8- fluoranthene base, 9- fluoranthene base, benzofluoranthrene base, o- tolyl, It is m- tolyl, p- tolyl, 2,3- xylyls, 3,4- xylyls, 2,5- xylyls, 2,4,6- trimethylphenyls, o- Cumenyl, m- cumenyl, p- cumenyl, p- tertiary butyl, 9,9- dimethyl -1- fluorenyls, 9,9- dimethyl -2- fluorenes Base, 9,9- dimethyl -4- fluorenyls, 9,9- phenylbenzene -2- fluorenyls, 9,9- phenylbenzene -3- fluorenyls, 9,9- phenylbenzene -4- fluorenyls.
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 Base, phenazinyl, phenothiazinyl, fen Dumb piperazines base, Dumb oxazolyls, Dumb di azolies, furan a word used for translation base, benzothienyl and pyridine ring, pyrazine Ring, pyrimidine ring, pyridazine ring, indole ring, quinoline ring, acridine ring, pyrrolidine ring, carbazole ring, furan nucleus, thiphene ring, Dumb azoles ring, Dumb 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 Fen 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.
Substituted or unsubstituted carbon number is 1~30 alkyl, for example there are：Methyl, ethyl, propyl, isopropyl, fourth Base, isobutyl group, tertiary butyl, amyl, hexyl, cyclopropyl, cyclobutyl, cyclopenta, cyclohexyl etc..
Substituted or unsubstituted carbon number is 2~30 alkenyl, for example there are：Vinyl, acrylic, cyclobutenyl, oil base, Eicosapentaenoic base, 26 carbon, six alkenyl, styryl, 2,2- diphenylacetylenes, 1,2,2- triphenyl vinyls, 2- benzene Base -2- acrylic etc..Preferred vinyl in above-mentioned alkenyl.
Substituted or unsubstituted carbon number be 2~30 alkynyl for example there are：Acetenyl, propinyl, 2- phenylacetylene bases etc.. Preferred acetenyl in above-mentioned alkynyl.
Substituted or unsubstituted carbon number be 3~30 arylsilyl groups for example there are：Dialkyl silyl, alkyl Diarylsilyl, diarye silyl.
Substituted or unsubstituted carbon number for 6~30 aryloxy group for example there are：Phenoxy group.
It is as follows by the concrete example of singly linked group with group A in general formula (1)：
[changing 5]
A is the group represented by general formula (2) or (3) in general formula (1)；Wherein, L in general formula (3)1Linking group it is specific It is such as lower shown：
[changing 6]
The concrete example of group represented by general formula (3) is as follows：
[changing 7]
HAr is by the nitrogenous polycyclic group of general formula (4) expression, the nitrogenous polycyclic group of general formula (4) in its formula of (2) or (3) Concrete example is as follows：
[changing 8]
The concrete example of general formula (1) compound represented of the invention is as follows：
[changing 9]
[changing 10]
[changing 11]
[changing 12]
[changing 13]
[changing 14]
A kind of organic electroluminescent device provided by the invention, wherein the heteroaromatic chemical combination shown in containing general formula (1) Object, in the case of no specific limitation, the organic electroluminescent device can be that phosphorescent devices can also be fluorescent device Either comprising thermal activities delayed fluorescence (TADF) material devices.
Fig. 1 shows an example of organic electroluminescence device.According to the organic electroluminescent member of an embodiment Part includes anode 9, organic layer and cathode 1 successively, and organic layer includes transparent conductive film 2, hole injection layer 3, hole biography successively 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 use as 5 main body of luminescent layer, when being used as 5 main body of luminescent layer It can the individually compound or the other organic materials composition hybrid agents uses of compound collocation.As master The fluorescent material that can arrange in pairs or groups during body use uses, and the phosphor material that can also arrange in pairs or groups uses or collocation TADF materials'uses.It is described Compound can also be used as hole blocking layer 6 to use or be used 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)
30g O-methoxies this boric acid, 43g bromophenyl first are sequentially added in the 1L there-necked flasks equipped with thermometer, condenser pipe Sour methyl esters, 55g k2CO3With 13g TBABA, 300ml toluene, 100ml ethyl alcohol and 50ml water are then sequentially added, uses nitrogen displacement Air in reaction bulb adds in 1.15g Pd (PPH under nitrogen guard mode3)4, heating is opened, magnetic agitation is heated to (78 ~80 DEG C) back flow reaction, detection is sampled after reacting 8h, until raw material stops reaction when the reaction was complete, is cooled to after room temperature carries out Reason, by reacting liquid 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 drier 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 analysis results are：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 are added in 500ml there-necked flasks, 40g intermediates 2 are then added in, in nitrogen displacement reaction bulb Air, reaction system are cooled to 0 DEG C, and MeMgBr (3M in THF) 110ml is slowly added dropwise under nitrogen guard mode, 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, adds in saturation NH4Cl Reaction is quenched in solution, the reaction solution stratification that will be obtained, and aqueous layer is extracted 2 times, each 50ml with dichloromethane, merges organic Phase, with saturated common salt washing once, anhydrous Na2SO4Dry 1h is filtered to remove drier, 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 analysis results are：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 are added in 1L there-necked flasks, then add in 33g intermediates 3, are cooled to 0 DEG C of stirring 10min, then Phosphatase 24 00ml is added in, reaction system, which is warming up to, is stirred at room temperature 3h, after the reaction completely of TLC monitorings raw material, is added in 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 crossing silicagel column after concentration filtrate obtains target product intermediate 4.
Intermediate 4 be white solid 25g, yield 80%,1H NMR spectra analysis results are：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 intermediates 4 are added in the 500ml there-necked flasks equipped with 150ml DCM, with the sky in nitrogen displacement reaction bulb Gas is down to -5 DEG C, by BBr3DCM is dissolved in, reaction system is slowly added under nitrogen protection, this temperature is kept to continue after being added dropwise Reaction, until TLC monitorings raw material stops reaction when the reaction was complete；Under condition of ice bath slowly plus water quenching is gone out reaction, stratification, water It is mutually extracted with DCM, merges organic phase, washed once with saturated common salt, then anhydrous Na2SO4Dry 1h, is filtered to remove drier, Silicagel column, which is crossed, after filtrate concentration obtains target product intermediate 5.
Intermediate 5 is white solid 23g, and yield 96%, 1H NMR spectra analysis results are：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 flasks equipped with thermometer, condenser pipe, then sequentially adds 23g intermediates 5,31g K2CO3, 3g 18- crown-s 6, bis- iodo- 4 aminopyridine of 38g 3,5- with the air in reaction system with nitrogen, protects in nitrogen Lower addition CuI stops stirring after being heated to the reaction completely of 100 DEG C of reaction 6h, TLC monitoring raw materials, is down to room temperature.In reaction system Adding in the water of 3 times of volumes makes product precipitate, and filters, and gained crude product is washed 3 times, each 400ml after being completely dissolved with DCM, It is concentrated after organic phase drying, crude product crosses silicagel column and obtains target product intermediate 6.
Intermediate 6 be faint yellow solid 41g, yield 87%,1H NMR spectra analysis results are：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 flasks, then adds in 40g intermediates 6, reaction 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 stops reaction when monitoring raw material reacts completely, is down to room temperature.It is 9 to add in NaOH solution and adjust PH ~10, reaction solution is extracted 3 times, each 100ml with DCM, merges organic phase, and with saturated common salt washing once, 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 analysis results are：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) synthesis compound 1
15g intermediates 7,10g 3,5- diphenyl benzene boron are added in the 500ml there-necked flasks equipped with thermometer, condenser pipe Acid, 11g K2CO3, then 2.4g TBAB sequentially add 120ml toluene, 40ml ethyl alcohol, 20ml water, with nitrogen displacement reaction bulb In air, 0.21g Pd (PPH are added under nitrogen guard mode3)4, heating is opened, magnetic agitation is heated to (78~80 DEG C) Back flow reaction samples detection after 6h, until raw material stops reaction when the reaction was complete, is cooled to room temperature and is post-processed, 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 Drier 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 analysis results are：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 intermediates 7,10g 1,3,5-triazines -4,6- are added in the 500ml there-necked flasks equipped with thermometer, condenser pipe Diphenyl -2- boric acid, 11g K2CO3, then 2.4g TBAB sequentially add 120ml toluene, 40ml ethyl alcohol, 20ml water uses nitrogen The air in reaction bulb is replaced, 0.21g Pd (PPH are added under nitrogen guard mode3)4, open heating.Magnetic agitation is heated to (78-80 DEG C) back flow reaction samples detection after 6h, until raw material stops reaction when the reaction was complete, is cooled to room temperature and is post-processed, Reacting liquid 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 drier, 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 analysis results are：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)
Sequentially add 15g intermediates 8 in the 1L there-necked flasks equipped with thermometer, condenser pipe, 30g c pyridine -4- boric acid, The bromo- 3- methoxyl groups methyl formates of 60g 2-, 51g K2CO3, then 1.3g TBAB sequentially add 300ml toluene, 100ml ethyl alcohol, 50ml water with the air in nitrogen displacement reaction bulb, adds in 1.15g Pd (PPH under nitrogen guard mode3)4, open heating, magnetic Power stirs, and is heated to (78~80 DEG C) back flow reaction, detection is sampled after 8h, until raw material stops reaction when the reaction was complete, be cooled to Room temperature is post-processed, reacting liquid filtering, stratification.Water is mutually extracted with 100ml toluene, is merged organic phase, is washed to neutrality, Anhydrous Na2SO41h is dried, is filtered to remove drier, filter cake is eluted with a small amount of toluene, merging filtrate, during silicagel column obtains excessively after concentration Mesosome 9.
Intermediate 9 be white solid 53g, yield 89%,1H NMR spectra analysis results are：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 are sequentially added in 1L there-necked flasks, 53g intermediates 9 are then added in, in nitrogen displacement reaction bulb Air, reaction system are down to 0 DEG C, and MeMgBr (3M in THF) 200ml is slowly added dropwise under nitrogen guard mode, keeps this temperature It is warming up to after reaction 1h and is stirred to react 12h under room temperature, monitoring raw material stops reaction when the reaction was complete, adds in saturation NH4Cl Reaction is quenched in solution, stands liquid separation, and water is mutually extracted 2 times, each 100ml with dichloromethane, 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 analysis results are：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 are added in 1L there-necked flasks, 43g intermediates 10 is then added in and is cooled to 0 DEG C of stirring 10min, then Phosphoric acid 500ml is added in, reaction system, which is warmed to room temperature, stirs 3h, and TLC monitorings after raw material reaction completely into reaction system until add Enter NaOH solution and adjust PH to neutrality, then extracted 3 times, each 500ml with DCM, merge organic phase and wash one with saturated common salt 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 analysis results are：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 intermediates 11 are added in the 500ml there-necked flasks equipped with 200ml THF, then with nitrogen displacement reaction bulb 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, then add in dissolved with 17g B (OCH3)3THF 50ml, keep this temperature anti- 2h is answered, warms naturally to room temperature the reaction was continued 1h, TCL monitorings are until raw material stops reaction when the reaction was complete, into reaction system Addition dilute hydrochloric acid adjusting pH value to acidity, stratification, water is mutually extracted with DCM, merges organic phase, then anhydrous Na2SO4It is dry 1h is filtered to remove drier, and petroleum ether elutes to obtain target product intermediate 12. after filtrate concentration
Intermediate 12 be white solid 26g, yield 72%,1H NMR spectra analysis results are：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 intermediates 12, bis- chloro- 2- of 26.5g 1,3- are sequentially added in the 1L there-necked flasks equipped with thermometer, condenser pipe Iodobenzene, 27g K2CO3, then 3g TBAB sequentially add 300ml toluene, 100ml ethyl alcohol, 50ml water, with nitrogen displacement reaction bulb In air, 0.56g Pd (PPH are added under nitrogen guard mode3)4, heating is opened, magnetic agitation is heated to (78~80 DEG C) Back flow reaction samples detection after 6h, until raw material stops reaction when the reaction was complete, is cooled to room temperature and is post-processed, reaction solution mistake Filter, stratification.Water is mutually extracted with 100ml toluene, merges organic phase, ultrapure to be washed to neutrality, anhydrous Na2SO4Dry 1h, mistake Drier 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 analysis results are：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 intermediates 13 are added in the 500ml there-necked flasks equipped with 300ml DCM, in nitrogen displacement reaction bulb Air is down to -5 DEG C, by BBr3DCM is dissolved in, nitrogen protection is lower to add in reaction system, this temperature is kept to continue after being added dropwise anti- Should, until TLC monitoring raw materials stop reaction when reacting completely, under condition of ice bath slowly plus water quenching is gone out reaction, stratification.Water phase It is extracted with DCM, merges organic phase, with saturated common salt washing once, then use anhydrous Na2SO4Dry 1h, is filtered to remove drier, Silicagel column is crossed after concentration and obtains intermediate 14.
Intermediate 14 be white solid 30g, yield 97%,1H NMR spectra analysis results are：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)
Sequentially add 30g intermediates 14 in the 500ml there-necked flasks equipped with thermometer, condenser pipe, 12g sodium tert-butoxides, 250ml toluene then with the air in nitrogen displacement reaction bulb, adds in 0.19g Pd (OAc) under nitrogen guard mode2, open Heating.Magnetic agitation is heated to (110~115 DEG C) back flow reaction, detection is sampled after 8h, until raw material stops anti-when the reaction was complete Should, it being cooled to room temperature and is post-processed, reacting liquid filtering, filter cake is eluted with a small amount of toluene, is merged organic phase, is washed to neutrality, Anhydrous Na2SO4Dry 1h, is filtered to remove drier, and silicagel column is crossed after concentration and obtains intermediate 15.
Intermediate 15 be white solid 20g, yield 74%,1H NMR spectra analysis results are：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) synthesis compound 3
10g intermediates 15,8.6g 3,5- diphenyl are sequentially added in the 250ml there-necked flasks equipped with thermometer, condenser pipe Phenyl boric acid, 8.7g K2CO3, then 1.0g TBAB sequentially add 80ml toluene, 20ml ethyl alcohol, and 10ml water is anti-with nitrogen displacement The air in bottle is answered, 0.36g Pd (PPH are added under nitrogen guard mode3)4, open heating.Magnetic agitation is heated to (78~80 DEG C) back flow reaction, detection is sampled after 8h, until raw material stops reaction when the reaction was complete, room temperature is cooled to and is post-processed.
Reacting liquid filtering, stratification.Water is mutually extracted with 20ml toluene, merges organic phase, ultrapure to be washed to neutrality, anhydrous Na2SO4Dry 1h, is filtered to remove drier, 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 analysis results are：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：
Sequentially added in the 250ml there-necked flasks equipped with thermometer, condenser pipe 15,8.6g1,3,5- triazine of 10g intermediates- - 2 boric acid of 4,6- diphenyl, 8.7g K2CO3, then 1.0g TBAB sequentially add 80ml toluene, 20ml ethyl alcohol, 10ml water is used Air in nitrogen displacement reaction bulb adds in 0.36g Pd (PPH under nitrogen guard mode3)4, open heating.Magnetic agitation adds Heat samples detection to (78~80 DEG C) back flow reaction after 8h, until raw material stops reaction when the reaction was complete, be cooled to after room temperature carries out Processing, reacting liquid filtering, stratification, water are mutually extracted with 20ml toluene, merge organic phase, ultrapure to be washed to neutrality, anhydrous Na2SO4Dry 1h, is filtered to remove drier, 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 analysis results are：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 intermediates 16,27.4g 4- dibenzo are sequentially added in the 250ml there-necked flasks equipped with thermometer, condenser pipe Furan boronic acid, 36g K2CO3, then 4g TBAB sequentially add 240ml toluene, 80ml ethyl alcohol, and 40ml water is anti-with nitrogen displacement The air in bottle is answered, 0.75g Pd (PPH are added under nitrogen guard mode3)4, heating is opened, magnetic agitation is heated to (78~80 DEG C) back flow reaction, detection is sampled after 8h, until raw material stops reaction when the reaction was complete, room temperature is cooled to and is post-processed, reaction solution Filtering, stratification.Water is mutually extracted with 50ml toluene, merges organic phase, ultrapure to be washed to neutrality, anhydrous Na2SO4Dry 1h, mistake Drier 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 analysis results are：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 intermediates 17 are added in the 500ml there-necked flasks equipped with 250ml DCM, go out reaction system with nitrogen displacement In air, -5 DEG C are down to, by BBr3DCM is dissolved in, lower add in of nitrogen protection answers system, this temperature is kept to continue after being added dropwise Reaction until TLC monitorings are until raw material stops reaction when reacting completely, under condition of ice bath slowly plus water quenching is gone out reaction, stand and divides Layer, water are mutually 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 analysis results are：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 intermediates 18,150ml DMI, 150ml are sequentially added in the 500ml there-necked flasks equipped with thermometer, condenser pipe Toluene with the air in nitrogen displacement reaction bulb, adds in 0.67g PHCO under nitrogen guard mode3T-Bu and 022g palladiums, Heating magnetic agitation is opened, (110~115 DEG C) back flow reaction is heated to, detection is sampled after 8h, until raw material stops when the reaction was complete Reaction, is cooled to room temperature and is post-processed, and reaction solution directly filters, and crossing silicagel column after filtrate concentration obtains intermediate 19.
Intermediate 19 be white solid 20.3g, yield 68%,1H NMR spectra analysis results are：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 intermediates 19,200ml THF, 10g zinc are sequentially added in the 500ml there-necked flasks 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 detects, until raw material stops reaction when the reaction was complete, is cooled to room temperature and is post-processed, and NaOH solution is added in reaction solution and is adjusted PH value is neutrality, and stratification, water is mutually with DCM extractions 3 times, each 100ml, merging organic phase, after anhydrous sodium sulfate dries 1h Filtering crosses silicagel column after filtrate concentration and obtains intermediate 20.
Intermediate 20 be white solid 17.3g, yield 96%,1H NMR spectra analysis results are：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)
Sequentially add 17g intermediates 20 in the 250ml there-necked flasks equipped with thermometer, condenser pipe, 180ml 1M dilute hydrochloric acid, - 5~0 DEG C is cooled to, 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, inspection is sampled after being heated to (60-75 DEG C) reaction 6h It surveys, until raw material stops reaction when the reaction was complete, is cooled to room temperature and is post-processed.
Reacting liquid filtering, filter cake water wash, is then dissolved in DCM.Filtrate is extracted 3 times with DCM, and each 50ml is associated with Machine phase, saturated common salt are washed once, are filtered after anhydrous sodium sulfate drying 1h, and crossing silicagel column after filtrate concentration obtains intermediate 2.
Intermediate 20 be white solid 16.2g, yield 68%,1H NMR spectra analysis results are：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) synthesis compound 5
16g intermediates 21,11.5g1,3,5- tri- are sequentially added in the 250ml there-necked flasks equipped with thermometer, condenser pipe Piperazine -4,6- diphenyl -2- boric acid, 11.5g K2CO3, then 1.3g TBAB sequentially add 120ml toluene, 40ml ethyl alcohol, 20ml Water with the air in nitrogen displacement reaction bulb, adds in Pb (PPH under nitrogen guard mode3)4, open heating.Magnetic agitation, heating Detection is sampled after to (78~80 DEG C) back flow reaction 8h, until raw material stops reaction when the reaction was complete, after being cooled to room temperature progress Reason, reacting liquid filtering, stratification.Water is mutually extracted with 50ml toluene, is merged organic phase, is washed to neutrality, anhydrous sodium sulfate is done It is filtered after dry 1h, crossing silicagel column after filtrate concentration obtains compound 5.
Compound 5 be white solid 17.7g, yield 87%,1H NMR spectra analysis results are：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 intermediates 22,26.4g O-methoxy benzene are sequentially added in the 250ml there-necked flasks equipped with thermometer, condenser pipe Boric acid, 48g K2CO3, then 5.6g TBAB sequentially add 240ml toluene, 60ml ethyl alcohol, 30ml water is reacted with nitrogen displacement Air in bottle adds in 1g Pb (PPH under nitrogen guard mode3)4, open heating.Magnetic agitation is heated to (78~80 DEG C) and returns Detection is sampled after stream reaction 8h, until raw material stops reaction when the reaction was complete, room temperature is cooled to and is post-processed, reacting liquid filtering, Stratification.Water is mutually extracted with 50ml toluene, merges organic phase, ultrapure to be washed to neutrality, is filtered after anhydrous sodium sulfate drying 1h, Drier is filtered to remove, 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 analysis results are：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 intermediates 23,150ml DMI, 150ml are sequentially added in the 250ml there-necked flasks equipped with thermometer, condenser pipe Toluene with the air in nitrogen displacement reaction bulb, adds in 0.9g PHCO under nitrogen guard mode2Ot-Bu and 0.35g palladiums, Open heating.Magnetic agitation is heated to (110~115 DEG C) back flow reaction, detection is sampled after 8h, until raw material stops when the reaction was complete It only reacts, is cooled to room temperature and is post-processed, reacting liquid filtering crosses silicagel column after filtrate concentration and obtains intermediate 24.
Intermediate 24 be white solid 20.2g, yield 66%,1H NMR spectra analysis results are：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 intermediates 24 are added in the 250ml there-necked flasks equipped with 150ml DCM, go out reaction system with nitrogen displacement In air, -5 DEG C are down to, by BBr3DCM is dissolved in, lower add in of nitrogen protection answers system, this temperature is kept to continue after being added dropwise Reaction until TLC monitorings are until raw material stops reaction when reacting completely, under condition of ice bath slowly plus water quenching is gone out reaction, stand and divides Layer, water are mutually 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 analysis results are：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 are sequentially added in the 250ml there-necked flasks equipped with thermometer, condenser pipe, then sequentially add 17g Intermediate 25,25.5g K2CO3, 2.5g 18- crown-s 6, bis- iodo- 4-aminopyridine of 32g 3,5-, in nitrogen displacement reaction bulb Air adds in 5.3g CuI under nitrogen guard mode, stops stirring after being heated to the reaction completely of 100 DEG C of reaction 6h, TCL monitoring raw materials It mixes, is down to room temperature.The water of 3 times of volumes is added in reaction system is precipitated out product, filters.Water is mutually 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 drying, 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 analysis results are：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 flasks, then adds in 26g intermediates 26, reaction 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.Add in NaOH solution tune It is 9~10 to save pH value, and reaction solution is extracted 3 times with DCM, each 100ml.Merge organic phase, it is with saturated common salt washing once, organic It is concentrated after mutually being dried with anhydrous sodium sulfate, 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 analysis results are：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) synthesis compound 6
15g intermediates 27,10.8g K are sequentially added in the 250ml there-necked flasks 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 bulb, nitrogen protection 0.23g Pd (PPH are added under state3)4, open heating.Magnetic agitation is heated to (78~80 DEG C) back flow reaction, is sampled after 6h Detection until raw material stops reaction when the reaction was complete, is cooled to room temperature and is post-processed, reacting liquid filtering, stratification, and water is mutually used 50ml toluene extracts, and merges organic phase, ultrapure to be washed to neutrality, anhydrous Na2SO4After dry 1h, drier, filter cake are filtered to remove 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 analysis results are：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 flasks equipped with thermometer, condenser pipe, 46g t-BuOK use nitrogen The air in reaction bulb is replaced, 7.8g CuI is added under nitrogen guard mode, stirs 1h, then add in 23g 1,3- dinitrobenzenes Pyridine solution 50ml, solution becomes red turbid, continuously adds 30g intermediates 28, and it is anti-to be heated to (110~115 DEG C) reflux Should, detection is sampled after 5h, until raw material stops reaction when the reaction was complete, room temperature is cooled to and is post-processed, reacting liquid filtering adds in The hydrochloric acid solution of 1M adjusts pH value as neutrality, stratification.Water is mutually extracted with 100ml toluene, merges organic phase, saturated salt solution It washes once, anhydrous Na2SO4After dry 1h, drier is filtered to remove, 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 analysis results are：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 intermediates 29,150ml THF, 15g zinc are sequentially added in the 250ml there-necked flasks 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 detects, until raw material stops reaction when the reaction was complete, is cooled to room temperature and is post-processed, and NaOH solution is added in reaction solution and is adjusted PH value is neutral, stratification.Water is mutually extracted 2 times with 100ml DCM, merges organic phase, anhydrous Na2SO4After dry 1h, filtering Drier 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 analysis results are：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 intermediates 30,130ml 2M dilute hydrochloric acid solutions are sequentially added in 250ml there-necked flasks.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 solutions dissolved with 21g K xanthate, detection is sampled after being heated to (60~65 DEG C) reaction 3h, until former Material stops reaction when the reaction was complete, is cooled to room temperature and is post-processed, and DCM is added in reaction solution and is extracted 3 times, each 300ml.It closes And organic phase, saturated common salt are washed once, 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 analysis results are：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 flasks equipped with thermometer, condenser pipe, then sequentially adds 10g intermediates 31, 13.8g K2CO3, 1.6g 18- crown-s 6, bis- iodo- 4-aminopyridine of 17.3g 3,5-, with the air in nitrogen displacement reaction bulb, nitrogen 2.9g CuI are added under gas shielded state, adds in 120 DEG C of reaction 10h, TLC monitoring raw materials and stops stirring, drop when the reaction was complete It warms to room temperature.The water of 3 times of volumes is 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 drying, crude product crosses silicagel column and obtains target product intermediate 32.
Intermediate 32 be faint yellow solid 16.9g, yield 81%,1H NMR spectra analysis results are：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 flasks, 16g intermediates 32 are added in, with the sky in nitrogen displacement reaction bulb Gas is slowly added to 4.4g t-BuONO under nitrogen guard mode, and 70 DEG C of reaction 5h, TLC prisons are heated to after stirring at normal temperature reaction 1h Stop stirring after surveying raw material reaction completely, be down to room temperature.Na is added in reaction system2CO3Solution adjusts pH value to neutrality, adds in DCM is extracted 3 times, each 150ml.Merge organic phase, use 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 analysis results are：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) synthesis compound 7
11g intermediates 33,7.6g 1,3,5- tri- are sequentially added in the 250ml there-necked flasks 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 Air in nitrogen displacement reaction bulb adds in 0.16g Pd (PPH under nitrogen guard mode3)4, open heating.Magnetic agitation adds Heat samples detection to (78~80 DEG C) back flow reaction after 6h, until raw material stops reaction when the reaction was complete, be cooled to after room temperature carries out Processing, reacting liquid 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 drier, 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 analysis results are：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 intermediates 34 are sequentially added in the 250ml there-necked flasks equipped with thermometer, condenser pipe, 25.6g and benzofuran Boric acid, 33.4g K2CO3, then 3.9g TBAB sequentially add 240ml toluene, 60ml ethyl alcohol, and 30ml water is anti-with nitrogen displacement The air in bottle is answered, Pd (PPH are added under nitrogen guard mode3)4, open heating.Magnetic agitation is heated to (78~80 DEG C) and returns Stream reacts, and detection is sampled after 8h, until raw material stops reaction when the reaction was complete, is cooled to room temperature and is post-processed, reacting liquid filtering, Stratification.Water is mutually extracted with 50ml toluene, merges organic phase, ultrapure to be washed to neutrality, anhydrous Na2SO4Dry 1h, crosses and filters out Drier 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 analysis results are：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 intermediates 35 are added in 150ml propylamine solution, are down to 0 DEG C, with the air in nitrogen displacement reaction bulb, so Afterwards with 7.5g ethylenediamines and 0.9g lithiums is added under nitrogen guard mode, reaction 3h, which drops back, at a temperature of this removes ice bath, rises to room naturally Temperature the reaction was continued 5h, TLC monitoring raw material stops reaction when reacting completely, reaction solution is poured into the dilute hydrochloric acid of ice, DCM extractions 3 Secondary, each 100ml merges organic phase, anhydrous Na2SO4Dry 1h is filtered to remove drier, silica gel column purification is crossed after filtrate concentration Obtain intermediate 36.
Intermediate 36 be faint yellow solid 26.2g, yield 78%,1H NMR spectra analysis results are：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 flasks equipped with thermometer, condenser pipe, 120ml toluene with the air in nitrogen displacement reaction bulb, adds in 0.5g PHCO under nitrogen guard mode3T-Bu and 0.18g vinegar Sour palladium is heated to (110~115 DEG C) back flow reaction, detection is sampled after 8h, until raw material stops reaction when the reaction was complete, is cooled to Room temperature is post-processed, and reaction solution directly filters, and crossing silica gel column purification after filtrate concentration obtains intermediate 37.
Intermediate 37 be faint yellow solid 16.3g, yield 63%,1H NMR spectra analysis results are：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 intermediates 37,120ml THF, 7.2g zinc powders are added in 250ml there-necked flasks.6.6g glacial acetic acid is slowly dripped It is added in reaction system, (78~80 DEG C) back flow reaction is heated to after being added dropwise, detection is sampled after 6h, until the reaction was complete for raw material When stop reaction, be cooled to room temperature and post-processed, reacting liquid filtering adds in NaOH solution in filtrate and adjusts PH as neutrality, quiet Layering is put, water is mutually 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 analysis results are：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 intermediates 38 are added in the 250ml there-necked flasks 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 solutions be slowly dropped in reaction system, rear insulation reaction 1h is added dropwise, will Reaction solution is added drop-wise in the 30ml aqueous solutions dissolved with 9g KI, detection is sampled after being heated to (60~75 DEG C) reaction 6h, until raw material is anti- Stop reaction when answering complete, be cooled to room temperature and post-processed, reacting liquid filtering, filter cake water wash is then dissolved in DCM, filter Liquid is extracted 3 times with DCM, each 80ml.Merge organic phase, saturated common salt is washed once, 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 analysis results are：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) synthesis compound 8
Sequentially added in the 250ml there-necked flasks equipped with thermometer, condenser pipe 39,8.3g1,3,5- triazine of 12g intermediates- 4,6- diphenyl -2- boric acid, 8.5g K2CO3, then 1g TBABA sequentially add 100ml toluene, 30ml ethyl alcohol, 15ml water is used Air in nitrogen displacement reaction bulb adds in 0.18g Pd (PPH under nitrogen guard mode3)4, open heating.Magnetic agitation adds Heat samples detection to (78~80 DEG C) back flow reaction after 8h, until raw material stops reaction when the reaction was complete, be cooled to after room temperature carries out Processing, reacting liquid filtering, stratification.Water is mutually extracted with 30ml toluene, merges organic phase, ultrapure to be washed to neutrality, anhydrous Na2SO4Dry 1h, is filtered to remove drier, 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 analysis results are：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 process 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, thickness 10nm are deposited by vacuum evaporation mode, This layer is as hole injection layer；
3) hole mobile material NPB, thickness 60nm are deposited by vacuum evaporation mode on hole injection layer, which makees For hole transmission layer；
4) on hole transmission layer, luminescent layer is deposited by vacuum evaporation mode, using 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%, thickness 30nm；
5) on luminescent layer, hole barrier materials TPBI, thickness 15nm are deposited by way of vacuum evaporation, this Layer is used as hole blocking layer；
6) electron transport material ET-1, thickness 30nm on the hole blocking layer, are deposited by way of vacuum evaporation, this One layer is used as electron transfer layer；
7) electron injection material Liq, thickness 2nm on the electron transport layer, are deposited by way of vacuum evaporation, this Layer is used as electron injecting layer；
8) on electron injecting layer, the evaporation cathode Al by way of vacuum evaporation, thickness 120nm, the layer is as cloudy Pole conductive electrode uses.
Embodiment 10
It is same as Example 9, the difference is that：Using 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：Using compound 3 as material of main part alternative compounds 2.
Embodiment 12
It is same as in Example 10, the difference is that：Using compound 4 as material of main part alternative compounds 2.
Embodiment 13
It is same as in Example 10, the difference is that：Using compound 5 as material of main part alternative compounds 2.
Embodiment 14
It is identical with embodiment 13, the difference is that：Using compound 7 as hole barrier materials alternative compounds 1.
Embodiment 15
It is identical with embodiment 13, the difference is that：Using compound 7 as material of main part alternative compounds 5.
Embodiment 16
It is identical with embodiment 15, the difference is that：Using 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 as hole barrier materials alternative compounds 1.
Embodiment 18
It is same as in Example 10, the difference is that：Compound 2 is 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 with 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, the device of comparative example 2 device compared with device embodiments 9 Manufacture craft it is identical, and employ 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 Conversion.OLED luminescent devices described above, cathode and anode are connected, pass through the method for standard with well known driving circuit Test voltage-efficiency-current density relation 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, is 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 the aromatic heterocyclic compounds of the present invention, LUMO can be reduced, is reduced Band gap so as to extend light abstraction width, can improve electronic transmission performance, beneficial 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, this is added in hole blocking layer After invention compound, luminous efficiency and service life get a promotion.
Meanwhile five-membered ring N heterocyclic groups are a kind of rigid radicals, double in aromatic heterocyclic compounds of the present invention and five yuan Ring heterocyclic group containing N is to connect the group formed by two five-membered ring structures and two N heterocycle structures intervals, unit structure tool There is larger 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 Glass transition temperature (the T of compound can be improvedg), 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 has higher glass transition temperature (Tg), in higher temperature section Interior deformation is stablized relatively, that is, has higher thermal stability, applied to the hair that luminescent device is remarkably improved in luminescent device Photostability.The material property of compound 3 is optimal it can be seen from table 2 and table 3, has higher glass transition temperature 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 The present invention is described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that：It still may be used To modify to the technical solution recorded in foregoing embodiments or carry out equivalent substitution to which part technical characteristic； And these modification or replace, do not make appropriate technical solution essence depart from various embodiments of the present invention technical solution spirit and Scope.

Claims (10)

1. a kind of aromatic heterocyclic compounds, which is characterized in that represented by the following general formula (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 butyl, benzene One kind in base, R3For hydrogen atom or phenyl；
X11~X20Respectively nitrogen-atoms or CR4, and X11~X20In at least one be and L1With the carbon atom that singly-bound combines, wherein, R4For hydrogen atom, halogen atom or cyano；
A is the group represented by the following general formula (2) or (3),
-HAr (2)
In formula (3), L1For the linking group of divalent~sexavalence, n is 1~5 integer；
In formula (2) or (3), HAr is the nitrogenous polycyclic group represented by the following general formula (4),
In formula (4), Ar1And Ar2Respectively triaryl；
X1~X3Respectively nitrogen-atoms or CR5；Wherein, R5For hydrogen atom, halogen atom, cyano, substituted or unsubstituted former into ring carbon The first aryl that subnumber is 6~30, the first heterocycle that substituted or unsubstituted ring carbons number is 5~30, substitution or not Alkenyl that alkyl that substituted carbon number is 1~30, substituted or unsubstituted carbon number are 2~30, substitution or unsubstituted Carbon number be 2~30 alkynyl, substituted or unsubstituted carbon number be 3~30 arylsilyl groups, substitution or not Substituted carbon number is one kind in 6~30 aryloxy group.
2. aromatic heterocyclic compounds as described in claim 1, which is characterized in that the linking group is substitution or unsubstituted Ring carbons number be 6~30 the second aryl, the second heterocycle that substituted or unsubstituted ring carbons number is 5~30 The group that base or 2~3 aryl and 2~3 heterocycles combine.
3. aromatic heterocyclic compounds as claimed in claim 1 or 2, which is characterized in that in the general formula (3), when n is 1, L1 For the linking group of divalent；When n is 2~5, L1For the linking group of trivalent~sexavalence.
4. aromatic heterocyclic compounds as described in claim 1, which is characterized in that in the general formula (1), X17~X20In at least One is nitrogen-atoms；
5. aromatic heterocyclic compounds as described in claim 1, which is characterized in that Y1For oxygen atom or sulphur atom；Y2It is former for oxygen Son or CR1R2, wherein R1For methyl, R2For methyl；X11~X20Respectively CR4, wherein, R4For hydrogen atom；
X1~X3Respectively nitrogen-atoms；Ar1And Ar2Respectively phenyl.
6. aromatic heterocyclic compounds as described in claim 1, which is characterized in that Y1For oxygen atom；Y2For CR1R2, wherein R1 For methyl, R2For methyl；X17~X20In it is at least one for nitrogen-atoms, remaining is CR4, X11~X16Respectively CR4, wherein, R4For Hydrogen atom；X1~X3Respectively nitrogen-atoms；Ar1And Ar2Respectively phenyl.
7. material is in organic electroluminescent made of a kind of aromatic heterocyclic compounds according to any one of claims 1 to 6 Application in element.
8. a kind of organic electroluminescent device, which is characterized in that including：
Anode and cathode relative to each other；
At least one organic layer between the anode and the cathode；
Wherein described organic layer includes luminescent layer, and it is miscellaneous that the luminescent layer includes aromatic series according to any one of claims 1 to 6 Material made of cycle compound.
9. organic electroluminescent device as claimed in claim 8, 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 are respectively comprising any one of claim 1~6 Aromatic heterocyclic compounds made of material.
It is 10. a kind of if 8 or 9 any one of them organic electroluminescent device of claim is in organic electroluminescence display device and method of manufacturing same Application.
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