CN108976212A - Fluorene derivative and its application in luminous organic material - Google Patents

Fluorene derivative and its application in luminous organic material Download PDF

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CN108976212A
CN108976212A CN201710408047.5A CN201710408047A CN108976212A CN 108976212 A CN108976212 A CN 108976212A CN 201710408047 A CN201710408047 A CN 201710408047A CN 108976212 A CN108976212 A CN 108976212A
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condensed
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邢其锋
李之洋
刘叔尧
任雪艳
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Beijing Eternal Material Technology Co Ltd
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Abstract

The present invention relates to a kind of compounds that one kind is indicated by general formula (I):In formula (I), L is selected from the inferior heteroaryl or sub- condensed hetero ring aromatic hydrocarbon group of chemical bond, the arlydene of C6~C12 or sub- condensed-nuclei aromatics group, C3~C12, and n is 1 or 2, and Hy is indicated by following formula (Hy1) or (Hy2):In formula (Hy1) and formula (Hy2): X is selected from chemical bond ,-C (R3)2‑、‑NR4,-O- or-S-；Y is selected from-C (R3) 2‑、‑NR4,-O- or-S-.It include at least one compound stated by above-mentioned general formula in organic luminous layer the invention further relates to a kind of organic electroluminescence device.

Description

Fluorene derivative and its application in luminous organic material
Technical field
The present invention relates to a kind of new substituted fluorene derivative organic compounds, more particularly to one kind to be used for organic electroluminescent The compound of device and the application in organic electroluminescence device.
Background technique
Display of organic electroluminescence (hereinafter referred to as OLED) has from main light emission, low-voltage direct-current driving, all solidstate, view The a series of advantages such as angular width, light-weight, composition and simple process, compared with liquid crystal display, display of organic electroluminescence Backlight is not needed, visual angle is big, and power is low, and up to 1000 times of liquid crystal display, manufacturing cost is but lower than response speed The liquid crystal display of same resolution ratio, therefore, organic electroluminescence device has broad application prospects.
As OLED technology is in the continuous propulsion for illuminating and showing two big fields, people are for influencing OLED device performance The research of efficient organic material focuses more on, an excellent in efficiency service life long organic electroluminescence device be usually device architecture with The result of the optimization collocation of various organic materials.In the most common OLED device structure, the organic of following type is generally included Material: hole-injecting material, hole mobile material, electron transport material, and assorted luminescent material (dyestuff or doping visitor Body material) and corresponding material of main part etc..Main body luminescent material has important shadow to the luminescent properties of phosphorescence or TADF device It rings, the material of main part applied at present is all often with single carrier transmittability, such as hole class transmission main body and electricity Subclass transmits main body.Single carrier transport ability will cause the mismatch of electrons and holes in luminescent layer, to cause tight The efficiency roll-off and the lost of life of weight；In addition the material of main part thermal stability applied at present is poor, to the performance of device with And there is detrimental effect in the service life；In addition, light emitting host material triplet energy is not high enough, can generate energy from object to The passback of main body causes the reduction of luminous efficiency.
Summary of the invention
The shortcomings that in order to overcome the above material of convention body in the prior art, the offer present invention of the invention provide a kind of new Type is used for the compound of organic electroluminescence device.
The compound of the present invention is indicated by following general formula (I):
In formula (I),
Ar1And Ar2It is respectively and independently selected from the substituted or non-substituted aryl or condensed-nuclei aromatics group, C3~C60 of C6~C60 Substituted or non-substituted heteroaryl or condensed hetero ring aromatic hydrocarbon group, work as Ar1And Ar2It is respectively and independently selected from substituted aryl, condensed ring virtue When hydrocarbyl group, heteroaryl or condensed hetero ring aromatic hydrocarbon group, the substituent group thereon is independently selected from halogen, cyano, nitro, or choosing From the alkyl or cycloalkyl of C1~C10, alkenyl, the alkoxy of C1~C6 or thio alkoxy group, or be independently selected from containing Hetero atom selected from N, O, S, Si and monocycle or fused ring aryl with 4~15 ring carbon atoms；
L is selected from the inferior heteroaryl or sub- thick miscellaneous of chemical bond, the arlydene of C6~C12 or sub- condensed-nuclei aromatics group, C3~C12 Aromatic hydrocarbon group；
N is 1 or 2；
Hy is indicated by following formula (Hy1) or (Hy2):
In formula (Hy1) and formula (Hy2):
* the connection site with L is indicated；
X is selected from chemical bond ,-C (R3)2-、-NR4,-O- or-S-；Y is selected from-C (R3) 2-、-NR4,-O- or-S-；
The R3And R4It is respectively and independently selected from the aryl or thick of hydrogen, the alkyl of C1~C5, halogen, cyano, nitro, C6~C10 Aromatic hydrocarbon group, the heteroaryl of C3~C30 or condensed hetero ring aromatic hydrocarbon group；
And the Ar when X is selected from chemical bond, in formula (I)1Substituted or non-substituted heteroaryl or thick miscellaneous selected from C3~C60 Aromatic hydrocarbon group, Ar2The substitution or non-of substituted or non-substituted aryl or condensed-nuclei aromatics group, C3~C60 selected from C6~C60 Substituted heteroaryl or condensed hetero ring aromatic hydrocarbon group；
R1And R2It is respectively and independently selected from hydrogen, the alkylidene of C1~C10, halogen, cyano, nitro, the substitution of C6~C30 or not The substituted or unsubstituted heteroaryl or condensed hetero ring aromatic hydrocarbon group of substituted aryl or condensed-nuclei aromatics group, C3~C30, work as R1With R2When being respectively and independently selected from substituted aryl, condensed-nuclei aromatics group, heteroaryl or condensed hetero ring aromatic hydrocarbon group, the substitution thereon Group is independently selected from halogen, cyano, nitro, or the alkyl or cycloalkyl selected from C1~C30, alkenyl, C1~C6 alkoxy or Thio alkoxy group, or be independently selected from containing the hetero atom selected from N, O, S, Si and with the list of 4~60 ring carbon atoms Ring or fused ring aryl.
Specifically, as the above-mentioned Ar of definition1With Ar2、R1With R2Refer to when being respectively and independently selected from aryl selected from certain amount Aromatics ring system of ring skeleton carbon atom, including single ring architecture substituent group such as phenyl etc. also include the virtue for being covalently attached structure Ring substitute group such as xenyl, terphenyl etc..
Specifically, as the above-mentioned Ar of definition1With Ar2、L、R1With R2Refer to when being respectively and independently selected from condensed-nuclei aromatics group with one The aromatics ring system, including condensed cyclic structure substituent group such as naphthalene, anthryl etc. of fixed number mesh ring skeleton carbon atom also include condensed ring knot Building stone that structure substituent group is connected with single ring architecture aryl such as benzene binaphthyl, naphthalene xenyl, biphenyl dianthranide base etc., also Thick aromatic ring substituents including being covalently attached structure are rolled into a ball such as binaphthyl.
Specifically, as the above-mentioned Ar of definition1With Ar2、L、R1With R2When being respectively and independently selected from heteroaryl or condensed hetero ring aromatic hydrocarbon group Refer to include that one or more is selected from B, N, O, S, P (=O), the hetero atom of Si and P and monocycle or condensed ring with ring carbon atom Aryl.
Further, in formula (I), Ar1And Ar2It is respectively and independently selected from the substituted aryl or condensed-nuclei aromatics base of C6~C15 It rolls into a ball, the substituted or non-substituted heteroaryl or condensed hetero ring aromatic hydrocarbon group of C4~C15.
Further, in formula (I), work as Ar1And Ar2It is respectively and independently selected from substituted aryl, condensed-nuclei aromatics group, heteroaryl Or when condensed hetero ring aromatic hydrocarbon group, the substituent group thereon preferably independently is selected from F, cyano, or alkyl or cycloalkanes selected from C1~C10 Base, alkenyl, alkoxy or thio alkoxy group, or be independently selected from containing selected from N, O, S, Si hetero atom and have 4~ The monocycle or fused ring aryl of 15 ring carbon atoms.
Further, in formula (I), work as Ar1And Ar2It is respectively and independently selected from substituted aryl, condensed-nuclei aromatics group, heteroaryl When base or condensed hetero ring aromatic hydrocarbon group, the substituent group thereon preferably independently be selected from cyano, methyl, ethyl, isopropyl, alkoxy, Phenyl, naphthalene, pyridyl group, pyrrole radicals.
Further, in formula (I), Ar1And Ar2It is respectively and independently selected from following aryl or fused ring aryl group: phenyl, connection Phenyl, terphenyl, naphthalene, anthryl, phenanthryl, indenyl, fluoranthene base, triphenylene, pyrenyl, base,Base or aphthacene base；Quilt The phenyl that furyl, thienyl, pyrrole radicals and/or pyridyl group replace.
Above-mentioned xenyl is preferably 2- xenyl, 3- xenyl and 4- xenyl, and above-mentioned terphenyl is preferably p- three Phenyl -4- base, p- terphenyl -3- base, p- terphenyl -2- base, m- terphenyl -4- base, m- terphenyl -3- base With m- terphenyl -2- base；Above-mentioned naphthalene is preferably 1- naphthalene and/or 2- naphthalene；Above-mentioned anthryl is preferably 1- anthryl, 2- anthracene Base or 9- anthryl；Above-mentioned pyrenyl is preferably 1- pyrenyl, 2- pyrenyl or 4- pyrenyl；Above-mentioned aphthacene base be preferably 1- aphthacene base, 2- aphthacene base or 9- aphthacene base.
Further, in formula (I), Ar1And Ar2It is respectively and independently selected from following heteroaryls or thick heteroaryl groups: furans Base, benzofurane base, thienyl, tolylthiophene base, pyrrole radicals, phenylpyrrole base, pyridyl group, phenylpyridyl, pyrazinyl, fluorenes Base, indeno fluorenyl, quinoline, triazine radical, benzofuranyl, benzothienyl, phentriazine, benzopyrazines, isobenzofuran-base, Indyl, benzoquinoline, dibenzofuran group, dibenzothiophene, dibenzopyrrole base, carbazyl and its derivative, phenyl At least one of substituted diazole, coffee quinoline base, coffee quinoline benzothiazolyl and benzodioxole group, wherein the click Preparation of azolyl-derivatives can include but is not limited to 9- phenyl carbazole, 9- naphthyl carbazole benzo carbazole, dibenzo-carbazole and indoles and click At least one of azoles.
As a kind of preferred embodiment of general formula (I), Ar1And Ar2At least one of selected from nitrogenous heteroaryl or nitrogenous thick Heterocyclic arene group.
Further, in formula (Hy1), R1And R2Independently preferably be selected from hydrogen, the alkyl of C1~C5, halogen, cyano, nitro, The substituted or unsubstituted heteroaryl or thick miscellaneous of the substituted or unsubstituted aryl or condensed-nuclei aromatics group of C6~C15, C3~C15 Aromatic hydrocarbon group.
Further, in formula (Hy1), R1And R2It is respectively and independently selected from following radicals: methyl, ethyl, isopropyl, tertiary fourth Base, cyclopenta, cyclohexyl, cyano, nitro, phenyl, naphthalene, triphenylene, 9,9 dimethyl fluorenes, two fluorenyl of spiral shell, furyl, benzene Base furyl, thienyl, tolylthiophene base, pyrrole radicals, phenylpyrrole base, pyridyl group, phenylpyridyl, pyrazinyl, fluorenyl, indenes And fluorenyl, quinoline, triazine radical, benzofuranyl, benzothienyl, phentriazine, benzopyrazines, isobenzofuran-base, indoles Base, benzoquinoline, dibenzofuran group, dibenzothiophene, dibenzopyrrole base, carbazyl and its derivative, phenyl replace At least one of diazole, coffee quinoline base, coffee quinoline benzothiazolyl and benzodioxole group, wherein the carbazyl Derivative can include but is not limited in 9- phenyl carbazole, 9- naphthyl carbazole benzo carbazole, dibenzo-carbazole and indolocarbazole At least one.
In formula (Hy1), X is selected from-C (R3)2When, R3Preferably methyl or phenyl；X is selected from-NR4When, R4Preferably methyl Or phenyl.
Further, the exemplary construction as formula (Hy2) is preferably following formula (Hy2-1) to (Hy2-6):
The definition of Y is as described in (Hy2).
Further, the exemplary construction as formula (Hy2) is preferably formula (Hy2-7) to (Hy2-12):
The expression way of above-mentioned Ca~Cb represents the carbon atom number that the group has as a~b, unless specifically indicated, generally For the carbon atom number do not include substituent group carbon atom number.
The above-mentioned statement for chemical element includes the concept of the identical isotope of chemical property, such as the statement of " hydrogen ", It also include the concept of chemical property identical " deuterium ", " tritium ".
In a preferred embodiment of the present invention, for filming performance and processing performance aspect the considerations of, described The molecular weight of compound is between 400~1200, between preferably 450~1100.
Further, following specific knots can preferably be gone out in conjunction with logical formula (I) of the invention and general formula (Hy1) and (Hy2) Structure compound: A1~A38, these compounds are only representative.
The present invention also provides above-mentioned organic electroluminescent compounds to prepare the purposes in organic electroluminescence device.Have Organic electroluminescence devices generally comprise first electrode, second electrode and one layer between the first electrode and second electrode Or multilayer organic function layer usually has electron injecting layer, electron-transport as the organic layer between first electrode and second electrode The organic layers such as layer, luminescent layer, hole transmission layer, hole injection layer.The compound of the present invention may be used as but be not limited to the master that shines Body material.
The present invention also provides a kind of organic electroluminescence device, which includes first electrode, second electrode and is located at One or more layers organic layer between the first electrode and second electrode includes at least one in the organic layer by general formula (I) a kind of compound indicated:
In formula (I):
Ar1And Ar2It is respectively and independently selected from the substituted or non-substituted aryl or condensed-nuclei aromatics group, C3~C60 of C6~C60 Substituted or non-substituted heteroaryl or condensed hetero ring aromatic hydrocarbon group, work as Ar1And Ar2It is respectively and independently selected from substituted aryl, condensed ring virtue When hydrocarbyl group, heteroaryl or condensed hetero ring aromatic hydrocarbon group, the substituent group thereon is independently selected from halogen, cyano, nitro, or choosing From the alkyl or cycloalkyl of C1~C10, alkenyl, the alkoxy of C1~C6 or thio alkoxy group, or be independently selected from containing Hetero atom selected from N, O, S, Si and monocycle or fused ring aryl with 4~15 ring carbon atoms；
L is selected from the inferior heteroaryl or sub- thick miscellaneous of chemical bond, the arlydene of C6~C12 or sub- condensed-nuclei aromatics group, C3~C12 Aromatic hydrocarbon group；
N is 1 or 2；
Hy is indicated by following formula (Hy1) or (Hy2):
In formula (Hy1) and formula (Hy2):
* the connection site with L is indicated；
X is selected from chemical bond ,-C (R3)2-、-NR4,-O- or-S-；Y is selected from-C (R3) 2-、-NR4,-O- or-S-；
The R3And R4It is respectively and independently selected from the aryl or thick of hydrogen, the alkyl of C1~C5, halogen, cyano, nitro, C6~C10 Aromatic hydrocarbon group, the heteroaryl of C3~C30 or condensed hetero ring aromatic hydrocarbon group；
And the Ar when X is selected from chemical bond, in formula (I)1Substituted or non-substituted heteroaryl or thick miscellaneous selected from C3~C60 Aromatic hydrocarbon group, Ar2The substitution or non-of substituted or non-substituted aryl or condensed-nuclei aromatics group, C3~C60 selected from C6~C60 Substituted heteroaryl or condensed hetero ring aromatic hydrocarbon group；
R1 and R2 is respectively and independently selected from hydrogen, the alkylidene of C1~C10, halogen, cyano, nitro, the substitution of C6~C30 or not The substituted or unsubstituted heteroaryl or condensed hetero ring aromatic hydrocarbon group of substituted aryl or condensed-nuclei aromatics group, C3~C30, as R1 and When R2 is respectively and independently selected from substituted aryl, condensed-nuclei aromatics group, heteroaryl or condensed hetero ring aromatic hydrocarbon group, the taking thereon Halogen, cyano, nitro, or the alkoxy of the alkyl or cycloalkyl selected from C1~C30, alkenyl, C1~C6 are independently selected from for group Or thio alkoxy group, or be independently selected from containing the hetero atom selected from N, O, S, Si and there are 4~60 ring carbon atoms Monocycle or fused ring aryl.
The compounds of this invention devises a kind of new compound by introducing novel substituted fluorene derivative structure.Fluorene structured Flatness, which makes material integrally, has the possibility of part accumulation, while the introducing of substituent group is so that whole structure realizes one Determine the distortion of degree, whole structure is due to part wreath piece flatness, so that material has very high vitrifying temperature Degree, while there is very high thermal stability.
Present invention employs the Molecular Design thinkings of innovation, in this way can be with first in 2 introducing substituent groups of fluorenes Realize the performance of the hole transport of material；Simultaneously in 9 introducing electron-withdrawing groups of fluorenes, material can be promoted to electronics simultaneously in this way Transmission performance, thus the compound of fluorenes substitution has the performance of the bipolar transmission of simultaneous transmission hole and electronics.When by this When class replaces fluorene derivative to be applied in organic electroluminescence device, so that it may play the property of its efficiently balanced transmission carrier It can advantage.In addition, the triplet of such substitution fluorene derivative of the invention is higher, can be suitable for efficiently panchromatic organic Electroluminescent device.
2 power supplying groups of such fluorenes substituted compound and 9 electron-withdrawing groups are real on space structure using fluorenes as carrier Very high warping property is showed, Figure of description 1 and attached drawing 2 are it will be clear that the HOMO of compound is main through the invention It is distributed on 2 bit substituents, and LUMO is distributed on 9 substituent groups, the distortion that the HOMO and LUMO of molecule pass through space It realizes and is totally separated from, the compound that such fluorenes replaces can in device application process with the property of potential TADF Realize the more efficient utilization to exciton, thus luminous efficiency improves.
When the compound of the present invention is used as the light emitting host material in organic electroluminescence device, because of the substituted fluorene of invention Interatomic bond energy is high in derivative precursor structure, ensures that material has good thermal stability, and then improve and adopt With the service life of the organic electroluminescence device of the compounds of this invention.Meanwhile because the compound of the present invention has bipolarity Feature, good transmission characteristic is all had to electrons and holes, to improve the organic electroluminescence using the compounds of this invention The device efficiency of luminescent device.
In addition, preparation is simple for the compounds of this invention, raw material is easy to get, and is suitable for volume production amplification.
Detailed description of the invention
From the detailed description with reference to the accompanying drawing to the embodiment of the present invention, these and/or other aspects of the invention and Advantage will become clearer and be easier to understand, in which:
Fig. 1 is the HOMO energy diagram of the compounds of this invention A4；
Fig. 2 is the lumo energy figure of the compounds of this invention A4.
Specific embodiment
In order to make those skilled in the art more fully understand the present invention, with reference to the accompanying drawings and detailed description to this hair It is bright to be described in further detail.
The compound for the synthetic method that do not mention in the present invention is all the raw produce being obtained through commercial channels.Implement Various chemicals such as petroleum ether, ethyl acetate, n-hexane, toluene, tetrahydrofuran, methylene chloride, four chlorinations used in example Bis- (bromomethyl) benzene of carbon, acetone, 1,2-, CuI, o-phthaloyl chloride, phenylhydrazine hydrochloride, trifluoroacetic acid, acetic acid, trans--diamino Hexamethylene, iodobenzene, cesium carbonate, potassium phosphate, ethylenediamine, benzophenone, cyclopentanone, 9-Fluorenone, sodium tert-butoxide, Loprazolam, 1- Bromo- 2- methyl naphthalene, o-dibromobenzene, butyl lithium, Bromofume, o-dibromobenzene, benzoyl peroxide, 1- (2- bromophenyl) -2- first Base naphthalene, N- bromo-succinimide, methoxyl methyl San Jia Ji phosphonium chloride, tris(dibenzylideneacetone) dipalladium, four (triphenylphosphines) Palladium, 1,3- pairs of 2-phenyl-phosphine oxide nickel chloride, carbazole, 3,6- di-t-butyl carbazole, N- phenyl carbazole -3- bromine, 2- bromine Fluorenone, The basic chemical industries raw materials such as 2- (4- bromobenzene) -4,6- diphenyl triazine chemical products can be commercially available at home.
The analysis detection of intermediate and compound in the present invention uses ABSCIEX mass spectrograph (4000QTRAP) and cloth Shandong Gram Nuclear Magnetic Resonance (400M).
The synthetic example of compound:
The synthesis of 1. compound A1 of synthetic example
Select 2- bromine Fluorenone as starting material, under nitrogen protection, be added into 1L there-necked flask carbazole (0.05mol, 1.0eq), 2- bromine Fluorenone (0.1mol) (1.05eq), sodium tert-butoxide (1.5eq), toluene 500mL add Pd2 (dba) 3 (0.5%eq) injects 10% tri-tert-butylphosphine (1%eq) with syringe, opens stirring, be heated to 100 degrees Celsius, reacted Night is cooled to 50 degrees centigrades, adds 2L dilution with toluene, and water 3000ml is added to wash, liquid separation, and organic phase is dry, rushes quick column, elutes Liquid is in black, and M1 yellow solid powder 14.2g, yield 74% is obtained by filtration in concentration.
Under nitrogen protection, 2- (4- bromobenzene) -4,6- diphenyl triazine is dissolved in 1L tetrahydrofuran, is cooled to subzero 78 degree, The butyl lithium of equivalent is added dropwise, keeps the temperature 1h, intermediate M1 is dissolved in tetrahydrofuran, is added dropwise to reaction solution, temperature control is added dropwise, Naturally it heats up, is stirred overnight.Aqueous ammonium chloride solution is added in reaction solution, liquid separation, organic layer washing is dry, is concentrated to get centre Body M2 is pale yellow powder 15g, yield 63.2%.
15g intermediate M2 is dissolved in 200ml acetic acid, is heated to 80 DEG C, and 30mlHI is added dropwise, and reacts 5h. end of reaction, adds water, Ethyl acetate extraction, organic phase washing is dry, and concentration obtains yellow powder
20g intermediate M3 is dissolved in 200mlDMF, and 1.2eq bromobenzene is added, and potassium carbonate l0g is added dropwise, and reaction solution is heated to 80 DEG C, react 12h.Ethyl acetate is added in end of reaction, reaction solution, washes, dry, and concentration obtains 19.4g yellow powder A1, receives Rate 93.5%.
1HNMR (400MHz, Chloroform) δ 8.56 (d, J=4.0Hz, 3H), 8.35 (d, J=4.0Hz, 5H), 8.19 (s, 1H), 8.14 (s, 1H), 8.04 (d, J=1.7Hz, 2H), 7.90 (s, 1H), 7.51 (d, J=8.0Hz, 7H), 7.41 (d, J=12.0Hz, 4H), 7.34 (s, 1H), 7.31-7.07 (m, 11H)
The synthesis of 2. compound A2 of synthetic example
With compound A1, difference is 2- (4- bromobenzene) -4,6- diphenyl triazine replacing with equivalent synthesis step Bromobenzene is replaced with the 2- bromopyridine of equivalent by 2- bromopyridine, carbazole is replaced with to 3, the 6- diisopropyl carbazole of equivalent, instead After answering, isolated yellow solid 17.1g, yield 72.3%.
1HNMR (400MHz, Chloroform) δ 8.55 (d, J=4.0Hz, 1H), 8.27 (s, 1H), 8.19 (s, 1H), 8.03 (d, J=11.1Hz, 2H), 7.92 (d, J=14.0Hz, 2H), 7.51 (d, J=8.0Hz, 3H), 7.40 (s, 7H), 7.34(s,1H),7.27–7.09 (m,10H).
The synthesis of 3. compound A-13 of synthetic example
With compound A1, difference is to replace with carbazole into 3,6- diphenyl carbazole synthesis step, and bromobenzene is replaced with The 4- bromo biphenyl of equivalent, after reaction, isolated yellow solid 17.1g, yield 72.3%.
1HNMR (400MHz, Chloroform) δ 8.56 (s, 2H), 8.36 (s, 3H), 8.03 (d, J=8.8Hz, 3H), 7.88 (d, J=12.0Hz, 2H), 7.73 (d, J=16.0Hz, 9H), 7.61 (d, J=12.8Hz, 2H), 7.56-7.36 (m, 12H), (s, 1H) .. of 7.35 (t, J=2.8 Hz, 3H), 7.34 (s, 7H), 7.21 (t, J=10.8Hz, 21H), 6.22
The synthesis of 4. compound A4 of synthetic example
Synthesis step is with compound A1, and difference is to replace with carbazole into 3, the 6- phenyl carbazole of equivalent, by 2- (4- bromine Benzene) -4,6- diphenyl triazine replaces with 5- (4- bromophenyl) -2- cyanopyrimidine of equivalent, and it is after reaction, isolated Yellow solid 9.6g, yield 46.7%.
1HNMR (400MHz, Chloroform) δ 9.68 (s, 6H), 8.95 (s, 3H), 8.34 (d, J=18.6Hz, 6H), 8.05 (t, J=8.4Hz, 9H), 7.90 (s, 3H), 7.43 (d, J=4.0Hz, 8H), 7.69-6.82 (m, 45H), 7.37- 7.30 (m, 9H), 7.51-6.82 (m, 36H), 7.25 (d, J=6.9Hz, 8H), 7.18 (s, 2H), 7.10 (s, 5H)
The synthesis of 5. compound A-45 of synthetic example
The same compound A-13 of synthesis step, difference are 2- (4- bromobenzene) -4,6- diphenyl triazine replacing with equivalent 2- (4- bromobenzene) -4,6- diphenylpyrimidin, after reaction, isolated yellow solid 11.9g, yield 60.5%.
The synthesis of 6. compound A6 of synthetic example
Synthesis step is with compound A1, and difference is to replace with carbazole into 1, the 8- Dimethylcarbazole of equivalent, by 2- (4- Bromobenzene) -4,6- diphenyl triazine replaces with the 2- bromopyridine of equivalent, bromobenzene is replaced with to the N- phenyl -3- bromine click of equivalent Azoles, after reaction, isolated yellow solid 11.5g, yield 74.3%.
1HNMR (400MHz, Chloroform) δ 8.82 (s, 1H), 8.49 (d, J=12.0Hz, 2H), 8.24-8.13 (m, 5H), 8.12-7.82 (m, 6H), 7.82-7.67 (m, 3H), 7.85-7.67 (m, 7H), 7.60 (d, J=16.0Hz, 3H), 7.51 (d, J=4.0Hz, 3H), 7.42 (d, J=14.7Hz, 3H), 7.34 (s, 1H), 7.27-7.11 (m, 5H), 7.09- 6.96(m,3H),6.92(s,1H),2.50(s, 6H).
The synthesis of 7. compound A7 of synthetic example
Synthesis step is with compound A1, and difference is to replace with carbazole into 3- (2- triphenylene) carbazole of equivalent, instead After answering, isolated yellow solid 9.9g, yield 65.6%.
1HNMR (400MHz, Chloroform) δ 8.55 (d, J=8.0Hz, 3H), 8.23 (s, 1H), 8.12 (s, 1H), 8.02-7.75 (m, 7H), 7.52 (dd, J=12.0,8.0Hz, 8H), 7.39 (d, J=12.0Hz, 3H), 7.32 (s, 2H), 7.27–7.10(m,10H),6.94(s, 2H),1.69(s,6H).
The synthesis of 8. compound A-28 of synthetic example
Synthesis step is to replace with carbazole into 3- (9- phenyl -3- carbazyl) click of equivalent with compound A1, difference Azoles, after reaction, isolated yellow solid 9.9g, yield 65.6%.
1HNMR (400MHz, Chloroform) δ 8.55 (d, J=8.0Hz, 3H), 8.23 (s, 1H), 8.12 (s, 1H), 8.02-7.75 (m, 7H), 7.52 (dd, J=12.0,8.0Hz, 8H), 7.39 (d, J=12.0Hz, 3H), 7.32 (s, 2H), 7.27–7.10(m,10H),6.94(s, 2H),1.69(s,6H).
The synthesis of 9. compound A9 of synthetic example
Synthesis step is to replace with carbazole into 3- (N- carbazyl) carbazole of equivalent, react with compound A1, difference After, isolated yellow solid 9.5g, yield 62.1%.
1HNMR (400MHz, Chloroform) δ 8.55 (d, J=8.0Hz, 3H), 8.23 (s, 1H), 8.12 (s, 1H), 8.02-7.75 (m, 7H), 7.52 (dd, J=12.0,8.0Hz, 8H), 7.39 (d, J=12.0Hz, 3H), 7.32 (s, 2H), 7.27–7.10(m,10H),6.94(s, 2H),1.69(s,6H).
The synthesis of 10. compound A10 of synthetic example
Synthesis step is to replace with carbazole into 4- (2- dibenzofuran group) click of equivalent with compound A1, difference Azoles, after reaction, isolated yellow solid 10.5g, yield 71.3%.
1HNMR (400MHz, Chloroform) δ 8.55 (d, J=8.0Hz, 3H), 8.23 (s, 1H), 8.12 (s, 1H), 8.02-7.75 (m, 7H), 7.52 (dd, J=12.0,8.0Hz, 8H), 7.39 (d, J=12.0Hz, 3H), 7.32 (s, 2H), 7.27–7.10(m,10H),6.94(s, 2H),1.69(s,6H).
The synthesis of 11. compound A11 of synthetic example
Synthesis step is to replace with carbazole into 2- (2- (9,9- dimethyl fluorene) click of equivalent with compound A1, difference Azoles, after reaction, isolated yellow solid 9.0g, yield 58.9%.
1HNMR (400MHz, Chloroform) δ 8.55 (d, J=8.0Hz, 3H), 8.23 (s, 1H), 8.12 (s, 1H), 8.02-7.75 (m, 7H), 7.52 (dd, J=12.0,8.0Hz, 8H), 7.39 (d, J=12.0Hz, 3H), 7.32 (s, 2H), 7.27–7.10(m,10H),6.94(s, 2H),1.69(s,6H).
The synthesis of 12. compound A12 of synthetic example
Synthesis step is to replace with carbazole into 3- (2- spiro fluorene) carbazole of equivalent, reacts and tie with compound A1, difference Shu Hou, isolated yellow solid 11.6g, yield 76.8%.
1HNMR (400MHz, Chloroform) δ 8.55 (d, J=8.0Hz, 3H), 8.23 (s, 1H), 8.12 (s, 1H), 8.02-7.75 (m, 7H), 7.52 (dd, J=12.0,8.0Hz, 8H), 7.39 (d, J=12.0Hz, 3H), 7.32 (s, 2H), 7.27–7.10(m,10H),6.94(s, 2H),1.69(s,6H).
The synthesis of 13. compound A13 of synthetic example
Synthesis step is with compound A1, and difference is to replace with carbazole into 3, the 3- diphenyl carbazole of equivalent, by bromobenzene The 2- bromo- (9,9- dimethyl fluorene) of equivalent is replaced with, after reaction, isolated yellow solid 12.5g, yield is 79.3%.
1HNMR (400MHz, Chloroform) δ 8.55 (d, J=8.0Hz, 3H), 8.23 (s, 1H), 8.12 (s, 1H), 8.02-7.75 (m, 7H), 7.52 (dd, J=12.0,8.0Hz, 8H), 7.39 (d, J=12.0Hz, 3H), 7.32 (s, 2H), 7.27–7.10(m,10H),6.94(s, 2H),1.69(s,6H).
The synthesis of 14. compound A14 of synthetic example
Synthesis step is with compound A1, and difference is to replace with carbazole into 1, the 8- Dimethylcarbazole of equivalent, by 2- (4- Bromobenzene) -4,6- diphenyl triazine replaces with the 2- bromopyridine of equivalent, bromobenzene is replaced with to the N- phenyl -3- bromine click of equivalent Azoles, after reaction, isolated yellow solid 8.5g, yield 47.5%.
1HNMR (400MHz, Chloroform) δ 8.55 (d, J=8.0Hz, 3H), 8.23 (s, 1H), 8.12 (s, 1H), 8.02-7.75 (m, 7H), 7.52 (dd, J=12.0,8.0Hz, 8H), 7.39 (d, J=12.0Hz, 3H), 7.32 (s, 2H), 7.27–7.10(m,10H),6.94(s, 2H),1.69(s,6H).
The synthesis of 15. compound A15 of synthetic example
With compound A1, difference is 2- (4- bromobenzene) -4,6- diphenyl triazine replacing with equivalent synthesis step Bromo- 1, the 10- ferrosin of 3-, the bromo- triphenylene of the 2- that bromobenzene is replaced with into equivalent, after reaction, isolated yellow solid 13.5g, yield 72.8%.
1HNMR (400MHz, Chloroform) δ 9.67 (s, 1H), 9.08 (s, 1H), 8.78 (d, J=16.0Hz, 2H), 8.53 (dd, J=12.8,8.0Hz, 3H), 8.43 (d, J=2.4Hz, 1H), 8.33 (s, 1H), 8.21-8.01 (m, 5H), 7.88 (d, J=16.0Hz, 2H), 7.64 (s, 2H), 7.79-7.34 (m, 10H), 7.59-7.46 (m, 3H), 7.69-7.34 (m,8H),7.40(s,1H),7.34(s,1H),7.27 –7.09(m,4H).
The synthesis of 16. compound A16 of synthetic example
Synthesis step is to replace with carbazole into N- (4- phenylboric acid) -3,6- bis- of equivalent with compound A1, difference Phenyl carbazole, after reaction, isolated yellow solid 11.0g, yield 65.4%.
1HNMR (400MHz, Chloroform) δ 9.67 (s, 1H), 9.08 (s, 1H), 8.78 (d, J=16.0Hz, 2H), 8.53 (dd, J=12.8,8.0Hz, 3H), 8.43 (d, J=2.4Hz, 1H), 8.33 (s, 1H), 8.21-8.01 (m, 5H), 7.88 (d, J=16.0Hz, 2H), 7.64 (s, 2H), 7.79-7.34 (m, 10H), 7.59-7.46 (m, 3H), 7.69-7.34 (m,8H),7.40(s,1H),7.34(s,1H),7.27 –7.09(m,4H).
The synthesis of 17. compound A17 of synthetic example
Synthesis step is to replace with carbazole into N- (4- phenylboric acid) -1,8- bis- of equivalent with compound A1, difference Methyl carbazole, after reaction, isolated yellow solid 12.6g, yield 71.8%.
1HNMR (400MHz, Chloroform) δ 9.67 (s, 1H), 9.08 (s, 1H), 8.78 (d, J=16.0Hz, 2H), 8.53 (dd, J=12.8,8.0Hz, 3H), 8.43 (d, J=2.4Hz, 1H), 8.33 (s, 1H), 8.21-8.01 (m, 5H), 7.88 (d, J=16.0Hz, 2H), 7.64 (s, 2H), 7.79-7.34 (m, 10H), 7.59-7.46 (m, 3H), 7.69-7.34 (m,8H),7.40(s,1H),7.34(s,1H),7.27 –7.09(m,4H).
The synthesis of 18. compound A18 of synthetic example
Synthesis step is to replace with carbazole into N- (3- phenylboric acid) -3,6- bis- of equivalent with compound A1, difference Phenyl carbazole, after reaction, isolated yellow solid 10.8g, yield 58.7%.
1HNMR (400MHz, Chloroform) δ 9.67 (s, 1H), 9.08 (s, 1H), 8.78 (d, J=16.0Hz, 2H), 8.53 (dd, J=12.8,8.0Hz, 3H), 8.43 (d, J=2.4Hz, 1H), 8.33 (s, 1H), 8.21-8.01 (m, 5H), 7.88 (d, J=16.0Hz, 2H), 7.64 (s, 2H), 7.79-7.34 (m, 10H), 7.59-7.46 (m, 3H), 7.69-7.34 (m,8H),7.40(s,1H),7.34(s,1H),7.27 –7.09(m,4H).
The synthesis of 19. compound A19 of synthetic example
Synthesis step is with compound A1, and difference is to replace with carbazole into 3,5-, bis- carbazoles-phenylboric acid of equivalent, instead After answering, isolated yellow solid 14.6g, yield 75.2%.
1HNMR (400MHz, Chloroform) δ 9.67 (s, 1H), 9.08 (s, 1H), 8.78 (d, J=16.0Hz, 2H), 8.53 (dd, J=12.8,8.0Hz, 3H), 8.43 (d, J=2.4Hz, 1H), 8.33 (s, 1H), 8.21-8.01 (m, 5H), 7.88 (d, J=16.0Hz, 2H), 7.64 (s, 2H), 7.79-7.34 (m, 10H), 7.59-7.46 (m, 3H), 7.69-7.34 (m,8H),7.40(s,1H),7.34(s,1H),7.27 –7.09(m,4H).
The synthesis of 20. compound A20 of synthetic example
Synthesis step is to replace with carbazole into the N- (4- biphenylboronic) -3,6- of equivalent with compound A1, difference Diphenyl carbazole, after reaction, isolated yellow solid 14.8g, yield 78.8%.
1HNMR (400MHz, Chloroform) δ 9.67 (s, 1H), 9.08 (s, 1H), 8.78 (d, J=16.0Hz, 2H), 8.53 (dd, J=12.8,8.0Hz, 3H), 8.43 (d, J=2.4Hz, 1H), 8.33 (s, 1H), 8.21-8.01 (m, 5H), 7.88 (d, J=16.0Hz, 2H), 7.64 (s, 2H), 7.79-7.34 (m, 10H), 7.59-7.46 (m, 3H), 7.69-7.34 (m,8H),7.40(s,1H),7.34(s,1H),7.27 –7.09(m,4H).
The synthesis of 21. compound A21 of synthetic example
Synthesis step is to replace with carbazole into the N- (3- biphenylboronic) -3,6- of equivalent with compound A1, difference Diphenyl carbazole, after reaction, isolated yellow solid 10.9g, yield 61.5%.
1HNMR (400MHz, Chloroform) δ 9.67 (s, 1H), 9.08 (s, 1H), 8.78 (d, J=16.0Hz, 2H), 8.53 (dd, J=12.8,8.0Hz, 3H), 8.43 (d, J=2.4Hz, 1H), 8.33 (s, 1H), 8.21-8.01 (m, 5H), 7.88 (d, J=16.0Hz, 2H), 7.64 (s, 2H), 7.79-7.34 (m, 10H), 7.59-7.46 (m, 3H), 7.69-7.34 (m,8H),7.40(s,1H),7.34(s,1H),7.27 –7.09(m,4H).
The synthesis of 22. compound A22 of synthetic example
Synthesis step is to replace with carbazole into (2,6- dimethyl -4- bromobenzene)-click of equivalent with compound A1, difference Azoles, the bromo- 9- phenyl-pyridin a pair of horses going side by side indoles of the 7- that 2- (4- bromobenzene) -4,6- diphenyl triazine is replaced with equivalent, bromobenzene is replaced It is changed to the bromo- dibenzofurans of 4- of equivalent, after reaction, isolated yellow solid 14.3g, yield 67.9%.
1HNMR (400MHz, Chloroform) δ 8.72-8.45 (m, 3H), 8.41 (d, J=12.0Hz, 2H), 8.19 (s, 1H), 8.09 (s, 1H), 8.05-7.97 (m, 2H), 7.89 (d, J=8.0Hz, 3H), 7.80 (d, J=16.0Hz, 3H), 7.64-7.47 (m, 9H), 7.36 (dd, J=12.8,8.4Hz, 4H), 7.28-7.05 (m, 7H), 2.50 (s, 6H)
The synthesis of 23. compound A23 of synthetic example
Synthesis step is to replace with carbazole into bromo- 12- phenyl -2, the 3- indoles of 11- of equivalent with compound A4, difference And carbazole, 2- (4- bromobenzene) -4,6- diphenyl triazine is replaced with to 1- (4- bromobenzene)-indazole of equivalent, bromobenzene is replaced with The 2- bromopyridine of equivalent, after reaction, isolated yellow solid 10.4g, yield 67.8%.
1HNMR(400MHz,Chloroform)δ8.85(s,1H),8.66–8.55(m,2H),8.55–7.97(m,7H), 8.22-7.97 (m, 3H), 7.97 (d, J=16.0,4.2Hz, 7H), 7.67-7.46 (m, 8H), 7.45 (s, 1H), 7.34 (s, 1H), 7.24 (d, J=10.0Hz, 1H), 7.18-6.88 (m, 6H)
The synthesis of 24. compound A24 of synthetic example
Synthesis step is with compound A1, and difference is to replace with carbazole into the benzofuran of equivalent and carbazole, by 2- (4- Bromobenzene) -4,6- diphenyl triazine replaces with the 3- bromobenzene of equivalent, and the 2- bromine that bromobenzene is replaced with equivalent is luxuriant and rich with fragrance, and reaction terminates Afterwards, isolated yellow solid 13.0g, yield 75.4%.
1HNMR (400MHz, Chloroform) δ 8.80 (d, J=12.0Hz, 2H), 8.68 (s, 1H), 8.57 (d, J= 13.5Hz, 2H), 8.49-8.38 (m, 4H), 8.11 (dd, J=10.8,6.4Hz, 6H), 7.98 (s, 1H), 7.91 (d, J= 8.0Hz, 2H), 7.78-7.62 (m, 2H), 7.59 (s, 1H), 7.53 (d, J=8.0Hz, 2H), 7.46 (s, 1H), 7.44- 7.28 (m, 3H), 7.24 (d, J=5.2Hz, 3H), 7.13 (d, J=10.0Hz, 4H)
The synthesis of 25. compound A25 of synthetic example
Synthesis step is to replace with carbazole into 5- phenyl -5,11- Dihydro-indole of equivalent with compound A1, difference And carbazole, 2- (4- bromobenzene) -4,6- diphenyl triazine is replaced with to 5- (4- bromophenyl)-nicotinonitrile of equivalent, is reacted After, isolated yellow solid 12.7g, yield 58.3%.
1HNMR (400MHz, Chloroform) δ 9.74 (s, 5H), 9.18 (s, 5H), 8.55 (d, J=2.4Hz, 14H), 8.23 (d, J=2.3Hz, 10H), 8.04 (s, 5H), 7.94 (d, J=35.0Hz, 10H), 7.87-7.66 (m, 1H), 7.65- 7.48 (m, 49H), 7.43 (s, 11H), 7.34 (s, 4H), 7.25 (d, J=6.9Hz, 15H), 7.14 (dd, J=26.0, 6.0Hz,32H),7.00(s,5H).
The synthesis of 26. compound A26 of synthetic example
The same compound A-13 of synthesis step, different 11, the 11- dimethyl-indols for being to replace with carbazole into equivalent and fluorenes, 1- (4- bromobenzene)-pyrazoles that 2- (4- bromobenzene) -4,6- diphenyl triazine is replaced with to equivalent, replaces with equivalent for bromobenzene 4- bromopyridine, after reaction, isolated yellow solid 10.6g, yield 69.8%.
1HNMR(400MHz,Chloroform)δ8.55(s,2H),8.43(s,2H),8.37–8.01(m,5H),7.92 (d, J=16.0Hz, 3H), 7.79 (s, 1H), 7.72 (s, 1H), 7.70-7.49 (m, 6H), 7.24 (s, 1H), 7.43-6.91 (m, 8H), 7.14 (dd, J=12.8,6.4Hz, 4H), 7.13 (d, J=10.0Hz, 2H), 7.03 (s, 2H), 6.46 (s, 1H), 1.69(s,6H).
The synthesis of 27. compound A27 of synthetic example
With compound A1, difference is to replace with carbazole into 10- (4- naphthalene boronic acids)-phenoxazine of equivalent synthesis step, Bromobenzene is replaced with etc. and is worked as by 8- (4- bromobenzene)-quinoxaline that 2- (4- bromobenzene) -4,6- diphenyl triazine is replaced with to equivalent The 2- bromonaphthalene of amount, after reaction, isolated yellow solid 15.4g, yield 76.1%.
1HNMR (400MHz, Chloroform) δ 9.74 (s, 2H), 9.35 (d, J=7.1Hz, 4H), 8.95 (s, 2H), 8.66 (s, 2H), 8.27 (s, 1H), 8.19 (s, 2H), 8.09 (s, 2H), 7.97 (s, 2H), 7.93 (d, J=8.0Hz, 1H), 7.87 (d, J=12.0Hz, 4H), 7.75 (dd, J=13.2,5.6Hz, 6H), 7.63-7.32 (m, 8H), 7.42 (d, J= 4.0Hz, 4H), 7.46-7.32 (m, 6H), 7.39-7.30 (m, 6H), 7.24 (s, 1H), 7.14 (s, 2H), 6.99 (d, J= 12.0Hz, 4H), 6.96 (d, J=6.4Hz, 1H), 6.83 (d, J=8.0Hz, 4H)
The synthesis of 28. compound A28 of synthetic example
With compound A1, difference is to replace with carbazole into the phenoxazine of equivalent synthesis step, by 2- (4- bromobenzene) -4, 6- diphenyl triazine replaces with 6- (4- bromobenzene)-quinoxaline of equivalent, and bromobenzene is replaced with to the 2- bromonaphthalene of equivalent, reaction knot Shu Hou, isolated yellow solid 16.4g, yield 82.4%.
1HNMR(400MHz,Chloroform)δ8.95–8.90(m,4H),8.41(s,2H),8.32(s,2H),8.18 (s, 2H), 8.29-7.93 (m, 6H), 8.29-7.79 (m, 12H), 8.29-7.59 (m, 12H), 7.52 (d, J=8.0Hz, 6H), 7.40 (t, J=17.5Hz, 6H), 7.31 (s, 1H), 7.24 (s, 1H), 7.14 (s, 3H), 7.00 (d, J=12.0Hz, 6H),6.93(s,4H).
The synthesis of 29. compound A29 of synthetic example
Synthesis step is with compound A1, and difference is to replace with carbazole into 9, the 9- dimethyl acridinium of equivalent, by 2- (4- Bromobenzene) -4,6- diphenyl triazine replaces with 2- (4- bromophenyl) -4,6- diphenylpyrimidin of equivalent, after reaction, point From obtaining yellow solid 9.9g, yield 65.6%.
1HNMR (400MHz, Chloroform) δ 8.55 (d, J=8.0Hz, 3H), 8.23 (s, 1H), 8.12 (s, 1H), 8.02-7.75 (m, 7H), 7.52 (dd, J=12.0,8.0Hz, 8H), 7.39 (d, J=12.0Hz, 3H), 7.32 (s, 2H), 7.27–7.10(m,10H),6.94(s, 2H),1.69(s,6H).
The synthesis of 30. compound A-13 0 of synthetic example
Synthesis step is to replace with carbazole into the phenthazine of equivalent, bromobenzene is replaced with compound A1, difference The 2- bromonaphthalene of equivalent, after reaction, isolated yellow solid 11.9g, yield 60.5%.
1HNMR(400MHz,Chloroform)δ9.12(s,10H),8.56(s,19H),8.49(s,11H),8.37(d,J =8.6Hz, 45H), 8.18 (s, 10H), 7.88 (d, J=16.0Hz, 20H), 7.74 (t, J=6.8Hz, 29H), 7.61 (s, 9H), 7.51 (d, J=4.0Hz, 62H), 7.40 (t, J=17.5Hz, 35H), 7.31 (s, 2H), 7.20 (dd, J=18.5, 14.5Hz,69H),6.97(s,13H).
The synthesis of 31. compound A-13 1 of synthetic example
Synthesis step is to replace with carbazole into the phenthazine of equivalent, bromobenzene is replaced with compound A1, difference The 2- bromonaphthalene of equivalent, after reaction, isolated yellow solid 10.3g, yield 58.5%.
1HNMR(400MHz,Chloroform)δ9.12(s,10H),8.56(s,19H),8.49(s,11H),8.37(d,J =8.6Hz, 45H), 8.18 (s, 10H), 7.88 (d, J=16.0Hz, 20H), 7.74 (t, J=6.8Hz, 29H), 7.61 (s, 9H), 7.51 (d, J=4.0Hz, 62H), 7.40 (t, J=17.5Hz, 35H), 7.31 (s, 2H), 7.20 (dd, J=18.5, 14.5Hz,69H),6.97(s,13H).
The synthesis of 32. compound A-13 2 of synthetic example
Synthesis step is to replace with carbazole into N- methyl-azophenlyene of equivalent, bromobenzene is replaced with compound A1, difference For the 2- bromonaphthalene of equivalent, after reaction, isolated yellow solid 12.7g, yield 69.8%.
1HNMR(400MHz,Chloroform)δ9.12(s,10H),8.56(s,19H),8.49(s,11H),8.37(d,J =8.6Hz, 45H), 8.18 (s, 10H), 7.88 (d, J=16.0Hz, 20H), 7.74 (t, J=6.8Hz, 29H), 7.61 (s, 9H), 7.51 (d, J=4.0Hz, 62H), 7.40 (t, J=17.5Hz, 35H), 7.31 (s, 2H), 7.20 (dd, J=18.5, 14.5Hz,69H),6.97(s,13H).
The synthesis of 33. compound A-13 3 of synthetic example
With compound A4, difference is to replace with 3,6- diphenyl carbazole into the phenthazine of equivalent synthesis step, reaction After, isolated yellow solid 13.5g, yield 65.4%.
1HNMR(400MHz,Chloroform)δ9.12(s,10H),8.56(s,19H),8.49(s,11H),8.37(d,J =8.6Hz, 45H), 8.18 (s, 10H), 7.88 (d, J=16.0Hz, 20H), 7.74 (t, J=6.8Hz, 29H), 7.61 (s, 9H), 7.51 (d, J=4.0Hz, 62H), 7.40 (t, J=17.5Hz, 35H), 7.31 (s, 2H), 7.20 (dd, J=18.5, 14.5Hz,69H),6.97(s,13H).
The synthesis of 34. compound A-13 4 of synthetic example
Synthesis step is to replace with carbazole into the acridine of equivalent, will separate after reaction with compound A1, difference Obtain yellow solid 16.8g, yield 76.2%.
1HNMR(400MHz,Chloroform)δ9.12(s,10H),8.56(s,19H),8.49(s,11H),8.37(d,J =8.6Hz, 45H), 8.18 (s, 10H), 7.88 (d, J=16.0Hz, 20H), 7.74 (t, J=6.8Hz, 29H), 7.61 (s, 9H), 7.51 (d, J=4.0Hz, 62H), 7.40 (t, J=17.5Hz, 35H), 7.31 (s, 2H), 7.20 (dd, J=18.5, 14.5Hz,69H),6.97(s,13H).
The synthesis of 35. compound A-13 5 of synthetic example
Synthesis step is with compound A1, and difference is to replace with carbazole into 3- tert-butyl-phenoxazine of equivalent, by bromobenzene The 2- bromonaphthalene of equivalent is replaced with, after reaction, isolated yellow solid 13.5g, yield 67.9%.
1HNMR(400MHz,Chloroform)δ9.12(s,10H),8.56(s,19H),8.49(s,11H),8.37(d,J =8.6Hz, 45H), 8.18 (s, 10H), 7.88 (d, J=16.0Hz, 20H), 7.74 (t, J=6.8Hz, 29H), 7.61 (s, 9H), 7.51 (d, J=4.0Hz, 62H), 7.40 (t, J=17.5Hz, 35H), 7.31 (s, 2H), 7.20 (dd, J=18.5, 14.5Hz,69H),6.97(s,13H).
The synthesis of 36. compound A-13 6 of synthetic example
Synthesis step is to replace with carbazole into the phenthazine of equivalent, bromobenzene is replaced with compound A1, difference Bromo- 9, the 9- dimethyl fluorene of the 2- of equivalent, after reaction, isolated yellow solid 12.4g, yield 67.3%.
1HNMR(400MHz,Chloroform)δ9.12(s,10H),8.56(s,19H),8.49(s,11H),8.37(d,J =8.6Hz, 45H), 8.18 (s, 10H), 7.88 (d, J=16.0Hz, 20H), 7.74 (t, J=6.8Hz, 29H), 7.61 (s, 9H), 7.51 (d, J=4.0Hz, 62H), 7.40 (t, J=17.5Hz, 35H), 7.31 (s, 2H), 7.20 (dd, J=18.5, 14.5Hz,69H),6.97(s,13H).
The synthesis of 37. compound A-13 7 of synthetic example
Synthesis step is to replace with carbazole into N- methyl-azophenlyene of equivalent, bromobenzene is replaced with compound A1, difference For the bromo- dibenzofurans of 2- of equivalent, after reaction, isolated yellow solid 13.8g, yield 67.8%.
1HNMR(400MHz,Chloroform)δ9.12(s,10H),8.56(s,19H),8.49(s,11H),8.37(d,J =8.6Hz, 45H), 8.18 (s, 10H), 7.88 (d, J=16.0Hz, 20H), 7.74 (t, J=6.8Hz, 29H), 7.61 (s, 9H), 7.51 (d, J=4.0Hz, 62H), 7.40 (t, J=17.5Hz, 35H), 7.31 (s, 2H), 7.20 (dd, J=18.5, 14.5Hz,69H),6.97(s,13H).
The synthesis of 38. compound A-13 8 of synthetic example
With compound A1, difference is to replace with (2,6- dimethyl -4- bromobenzene)-carbazole into the 4- of equivalent synthesis step Bromophenyl-acridine, after reaction, isolated yellow solid 14.6g, yield 75.6%.
1HNMR(400MHz,Chloroform)δ9.12(s,10H),8.56(s,19H),8.49(s,11H),8.37(d,J =8.6Hz, 45H), 8.18 (s, 10H), 7.88 (d, J=16.0Hz, 20H), 7.74 (t, J=6.8Hz, 29H), 7.61 (s, 9H), 7.51 (d, J=4.0Hz, 62H), 7.40 (t, J=17.5Hz, 35H), 7.31 (s, 2H), 7.20 (dd, J=18.5, 14.5Hz,69H),6.97(s,13H).
The analysis detecting data of concrete preferred structure compound disclosed in synthetic example of the present invention is listed in the following table 1 In:
Table 1
Device embodiments prepared by compound:
The typical structure of the OLED organic electroluminescence device prepared in device embodiments are as follows:
Substrate/anode/hole injection layer (HIL)/hole transmission layer (HTL)/organic luminous layer (EL)/electron transfer layer (ETL)/electron injecting layer (EIL)/cathode
Above-mentioned "/" indicates to be laminated in order between different function layer.
Invention compound can be, but not limited to for luminescent layer material of main part and luminescent layer dye materials.
Device embodiments 1-1 (comparative example)
The structure of organic electroluminescence device in device embodiments of the present invention are as follows:
ITO/2-TNATA(30nm)/NPB(20nm)/EML(20nm)/Bphen(50nm)/LiF(1nm)/Al。
Emitting layer material uses green phosphorescent coloring Ir (ppy)3Dyestuff, arrange in pairs or groups main body CBP.Each functional layer material molecular structure It is as follows:
Organic electroluminescence device preparation process is as follows in the present embodiment:
The glass substrate that surface is coated with transparent conductive film is cleaned by ultrasonic in cleaning solution, in deionized water Ultrasonic treatment, in ethyl alcohol: ultrasonic oil removing in acetone mixed solution is baked under clean environment and completely removes moisture, use is ultraviolet Lamp performs etching and ozone treatment, and with low energy cation beam bombarded surface；
The above-mentioned glass substrate with anode is placed in vacuum chamber, is evacuated to 1 × 10-5~9 × 10-3Pa, above-mentioned Vacuum evaporation 2-TNATA on anode tunic, adjusting evaporation rate are 0.1nm/s, form the hole injection layer with a thickness of 30nm；? Vacuum evaporation compound N PB on hole injection layer forms the hole transmission layer with a thickness of 20nm, evaporation rate 0.1nm/s； Luminescent layer of the vacuum evaporation EML as device on hole transmission layer, EML include material of main part and dye materials, using more The method that source is steamed altogether, adjusting material of main part CBP evaporation rate are 0.1nm/s, and 3 evaporation rate of dye materials Ir (ppy) is according to mixing Miscellaneous ratio (5%) setting, vapor deposition total film thickness are 20nm；
Bphen is used to transmit layer material, evaporation rate 0.1nm/s as device electronic, vapor deposition total film thickness is 50nm；
On electron transfer layer (ETL) vacuum evaporation with a thickness of the LiF of 1nm as electron injecting layer, with a thickness of 150nm's The Al layers of cathode as device.
Device embodiments 1-2. the compounds of this invention is as light emitting host material
Organic electroluminescence device is prepared using method same as Example 1, difference is, CBP is replaced with The compound of the present invention A1.
Device embodiments 1-3. the compounds of this invention is as light emitting host material
Organic electroluminescence device is prepared using method same as Example 1, difference is, CBP is replaced with The compound of the present invention A5.
Device embodiments 1-4. the compounds of this invention is as light emitting host material
Organic electroluminescence device is prepared using method same as Example 1, difference is, CBP is replaced with The compound of the present invention A7.
Device embodiments 1-5. the compounds of this invention is as light emitting host material
Organic electroluminescence device is prepared using method same as Example 1, difference is, CBP is replaced with The compound of the present invention A8.
Device embodiments 1-6. the compounds of this invention is as light emitting host material
Organic electroluminescence device is prepared using method same as Example 1, difference is, CBP is replaced with The compound of the present invention A14.
Device embodiments 1-7. the compounds of this invention is as light emitting host material
Organic electroluminescence device is prepared using method same as Example 1, difference is, CBP is replaced with The compound of the present invention A17.
Device embodiments 1-8. the compounds of this invention is as light emitting host material
Organic electroluminescence device is prepared using method same as Example 1, difference is, CBP is replaced with The compound of the present invention A18.
Device embodiments 1-9. the compounds of this invention is as light emitting host material
Organic electroluminescence device is prepared using method same as Example 1, difference is, CBP is replaced with The compound of the present invention A22.
Device embodiments 1-10. the compounds of this invention is as light emitting host material
Organic electroluminescence device is prepared using method same as Example 1, difference is, CBP is replaced with The compound of the present invention A25.
Device embodiments 1-11. the compounds of this invention is as light emitting host material
Organic electroluminescence device is prepared using method same as Example 1, difference is, CBP is replaced with The compound of the present invention A28.
Device embodiments 1-12. the compounds of this invention is as light emitting host material
Organic electroluminescence device is prepared using method same as Example 1, difference is, CBP is replaced with The compound of the present invention A30.
Under 10000nit brightness, the Organic Electricity that device embodiments 1-1 is prepared into device embodiments 1-12 is measured The performance parameter of electroluminescence device, detection data are detailed in the following table 2:
Table 2
As can be seen from Table 2, the present invention devises totally 11 embodiments for being parallel to device embodiments 1-1, design scheme are as follows: In the case that other function material is all the same in organic electroluminescence device structure, spread out using this kind of substituted fluorene disclosed by the invention Typical Representative compound in biology replaces the material C BP in comparative device embodiment 1 as luminescent layer material of main part, in table 2 It is specific statistics indicate that, for device embodiments 1-2 into 1-12, the operating voltage of each device is respectively less than comparative example device embodiments 5.0V in 1-1, the current efficiency of each device are all larger than the 48cd/A in comparative example device embodiments 1-1, each device Service life is all larger than the 8h in comparative example device embodiments 1-1.Thus it proves, the present invention this kind of typical generation replaced in fluorene derivative Table compound is compared with the material C BP that comparative example uses, the stability of the compounds of this invention and when as material of main part Carrier transmission performance, which all has, is extremely obviously improved effect, so the compounds of this invention has ideal practical valence Value.
The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above Detail within the scope of the technical concept of the present invention can be with various simple variants of the technical solution of the present invention are made, this A little simple variants all belong to the scope of protection of the present invention.
It is further to note that specific technical features described in the above specific embodiments, in not lance In the case where shield, can be combined in any appropriate way, in order to avoid unnecessary repetition, the present invention to it is various can No further explanation will be given for the combination of energy.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally The thought of invention, it should also be regarded as the disclosure of the present invention.

Claims (10)

1. a kind of compound is indicated by general formula (I):
In formula (I):
Ar1And Ar2The substituted or non-substituted aryl or condensed-nuclei aromatics group, C3~C60 for being respectively and independently selected from C6~C60 take Generation or non-substituted heteroaryl or condensed hetero ring aromatic hydrocarbon group, work as Ar1And Ar2It is respectively and independently selected from substituted aryl, condensed-nuclei aromatics base When group, heteroaryl or condensed hetero ring aromatic hydrocarbon group, the substituent group thereon is independently selected from halogen, cyano, nitro, or is selected from C1 Alkyl or cycloalkyl, alkenyl, the alkoxy of C1~C6 or the thio alkoxy group of~C10, or be independently selected from containing being selected from N, the hetero atom of O, S, Si and monocycle or fused ring aryl with 4~15 ring carbon atoms；
L is selected from the inferior heteroaryl or sub- condensed hetero ring virtue of chemical bond, the arlydene of C6~C12 or sub- condensed-nuclei aromatics group, C3~C12 Hydrocarbyl group；
N is 1 or 2；
Hy is indicated by following formula (Hy1) or (Hy2):
In formula (Hy1) and formula (Hy2):
* the connection site with L is indicated；
X is selected from chemical bond ,-C (R3)2-、-NR4,-O- or-S-；Y is selected from-C (R3) 2-、-NR4,-O- or-S-；
The R3And R4It is respectively and independently selected from hydrogen, the alkyl of C1~C5, halogen, cyano, nitro, the aryl of C6~C10 or condensed ring virtue Hydrocarbyl group, the heteroaryl of C3~C30 or condensed hetero ring aromatic hydrocarbon group；
And the Ar when X is selected from chemical bond, in formula (I)1Substituted or non-substituted heteroaryl or condensed hetero ring virtue selected from C3~C60 Hydrocarbyl group, Ar2Substituted or non-substituted aryl or condensed-nuclei aromatics group, C3~C60 selected from C6~C60 it is substituted or non-substituted Heteroaryl or condensed hetero ring aromatic hydrocarbon group；
R1And R2Be respectively and independently selected from hydrogen, the alkyl of C1~C10, halogen, cyano, nitro, C6~C30 it is substituted or unsubstituted The substituted or unsubstituted heteroaryl or condensed hetero ring aromatic hydrocarbon group of aryl or condensed-nuclei aromatics group, C3~C30, work as R1And R2Respectively When being independently selected from substituted aryl, condensed-nuclei aromatics group, heteroaryl or condensed hetero ring aromatic hydrocarbon group, the substituent group thereon is only It is vertical to be selected from halogen, cyano, nitro, or the alkoxy or thio alkane of the alkyl or cycloalkyl selected from C1~C30, alkenyl, C1~C6 Oxygroup group, or it is independently selected from containing the hetero atom selected from N, O, S, Si and has the monocycle or thick of 4~60 ring carbon atoms Cyclophane base.
2. compound according to claim 1, wherein in formula (I), Ar1And Ar2It is respectively and independently selected from the substitution of C6~C15 Or the substituted or non-substituted heteroaryl or condensed hetero ring aromatic hydrocarbon group of non-substituted aryl or condensed-nuclei aromatics group, C4~C15, when Ar1And Ar2When being respectively and independently selected from substituted aryl, condensed-nuclei aromatics group, heteroaryl or condensed hetero ring aromatic hydrocarbon group, it is described thereon Substituent group be independently selected from F, cyano, or the alkyl or cycloalkyl selected from C1~C10, alkenyl, alkoxy or thio alkoxy base Group, or be independently selected from containing the hetero atom selected from N, O, S, Si and with the monocycle or fused ring aryl of 4~15 ring carbon atoms；
In formula (Hy1), R1And R2Be respectively and independently selected from hydrogen, the alkyl of C1~C5, halogen, cyano, nitro, C6~C15 substitution or The substituted or unsubstituted heteroaryl or condensed hetero ring aromatic hydrocarbon group of unsubstituted aryl or condensed-nuclei aromatics group, C3~C15, work as R1 And R2When being respectively and independently selected from substituted aryl, condensed-nuclei aromatics group, heteroaryl or condensed hetero ring aromatic hydrocarbon group, the taking thereon Dai Ji is independently selected from F, cyano, or the alkyl or cycloalkyl selected from C1~C10, alkenyl, alkoxy or thio alkoxy group, or Person is independently selected from containing the hetero atom selected from N, O, S, Si and with the monocycle or fused ring aryl of 4~15 ring carbon atoms；
The structure of formula (Hy2) is selected from following formula (Hy2-1) to (Hy2-6):
3. compound according to claim 1, wherein in formula (I), Ar1And Ar2It is respectively and independently selected from the substitution of C6~C15 Or the substituted or non-substituted heteroaryl or condensed hetero ring aromatic hydrocarbon group of non-substituted aryl or condensed-nuclei aromatics group, C4~C15, when Ar1And Ar2When being respectively and independently selected from substituted aryl, condensed-nuclei aromatics group, heteroaryl or condensed hetero ring aromatic hydrocarbon group, taking thereon Dai Ji is independently selected from cyano, methyl, ethyl, isopropyl, alkoxy, phenyl, naphthalene, pyridyl group or pyrrole radicals；
The structure of formula (Hy2) is selected from following formula (Hy2-7) to (Hy2-12):
4. compound according to claim 1 or 2, wherein in formula (I), Ar1Selected from the substituted or non-substituted of C4~C15 Nitrogenous heteroaryl or nitrogenous condensed hetero ring aromatic hydrocarbon group.
5. compound described in any one of -4 according to claim 1,
Wherein in formula (I), Ar1And Ar2It is respectively and independently selected from phenyl, 2- xenyl, 3- xenyl and 4- xenyl, p- terphenyl Base -4- base, p- terphenyl -3- base, p- terphenyl -2- base, m- terphenyl -4- base, m- terphenyl -3- base and M- terphenyl -2- base, naphthalene, anthryl, phenanthryl, indenyl, fluoranthene base, triphenylene, pyrenyl, base,Base, 1- aphthacene Base, 2- aphthacene base or 9- aphthacene base aphthacene base, or be selected from and replaced by furyl, thienyl, pyrrole radicals and/or pyridyl group Phenyl；Or it is respectively and independently selected from furyl, benzofurane base, thienyl, tolylthiophene base, pyrrole radicals, phenylpyrrole base, pyrrole Piperidinyl, phenylpyridyl, pyrazinyl, fluorenyl, indeno fluorenyl, quinoline, triazine radical, benzofuranyl, benzothienyl, benzo three Piperazine, benzopyrazines, isobenzofuran-base, indyl, benzoquinoline, dibenzofuran group, dibenzothiophene, dibenzopyrrole Base, 9- phenyl carbazole, 9- naphthyl carbazole benzo carbazole, dibenzo-carbazole, indolocarbazole, phenyl replace diazole, coffee quinoline base, Coffee quinoline benzothiazolyl or benzodioxole group；
Wherein in formula (Hy1), R1And R2It is respectively and independently selected from methyl, ethyl, isopropyl, tert-butyl, cyclopenta, cyclohexyl, cyanogen Base, nitro, phenyl, naphthalene, triphenylene, 9,9 dimethyl fluorenes, two fluorenyl of spiral shell, furyl, benzofurane base, thienyl, phenyl Thienyl, pyrrole radicals, phenylpyrrole base, pyridyl group, phenylpyridyl, pyrazinyl, fluorenyl, indeno fluorenyl, quinoline, triazine radical, Benzofuranyl, benzothienyl, phentriazine, benzopyrazines, isobenzofuran-base, indyl, benzoquinoline, dibenzo furan It mutters base, dibenzothiophene, dibenzopyrrole base, carbazyl, 9- phenyl carbazole base, 9- naphthyl carbazole benzo carbazole, dibenzo Diazole, coffee quinoline base, coffee quinoline benzothiazolyl or the benzodioxole group that carbazole, indolocarbazole base, phenyl replace.
6. general formula compound according to any one of claims 1 to 3 is selected from following concrete structure formulas:
7. application of the general formula compound according to claim 1 to 3 in organic electroluminescence device.
8. application of the structural compounds according to claim 6 in organic electroluminescence device.
9. a kind of organic electroluminescence device, which includes first electrode, second electrode and is located at the first electrode and the One or more layers organic layer between two electrodes, which is characterized in that include at least one in the organic layer by general formula (I) expression A kind of compound:
In formula (I):
Ar1And Ar2The substituted or non-substituted aryl or condensed-nuclei aromatics group, C3~C60 for being respectively and independently selected from C6~C60 take Generation or non-substituted heteroaryl or condensed hetero ring aromatic hydrocarbon group, work as Ar1And Ar2It is respectively and independently selected from substituted aryl, condensed-nuclei aromatics base When group, heteroaryl or condensed hetero ring aromatic hydrocarbon group, the substituent group thereon is independently selected from halogen, cyano, nitro, or is selected from C1 Alkyl or cycloalkyl, alkenyl, the alkoxy of C1~C6 or the thio alkoxy group of~C10, or be independently selected from containing being selected from N, the hetero atom of O, S, Si and monocycle or fused ring aryl with 4~15 ring carbon atoms；
L is selected from the inferior heteroaryl or sub- condensed hetero ring virtue of chemical bond, the arlydene of C6~C12 or sub- condensed-nuclei aromatics group, C3~C12 Hydrocarbyl group；
N is 1 or 2；
Hy is indicated by following formula (Hy1) or (Hy2):
In formula (Hy1) and formula (Hy2):
* the connection site with L is indicated；
X is selected from chemical bond ,-C (R3)2-、-NR4,-O- or-S-；Y is selected from-C (R3) 2-、-NR4,-O- or-S-；
The R3And R4It is respectively and independently selected from hydrogen, the alkyl of C1~C5, halogen, cyano, nitro, the aryl of C6~C10 or condensed ring virtue Hydrocarbyl group, the heteroaryl of C3~C30 or condensed hetero ring aromatic hydrocarbon group；
And the Ar when X is selected from chemical bond, in formula (I)1Substituted or non-substituted heteroaryl or condensed hetero ring virtue selected from C3~C60 Hydrocarbyl group, Ar2Substituted or non-substituted aryl or condensed-nuclei aromatics group, C3~C60 selected from C6~C60 it is substituted or non-substituted Heteroaryl or condensed hetero ring aromatic hydrocarbon group；
R1And R2Be respectively and independently selected from hydrogen, the alkylidene of C1~C10, halogen, cyano, nitro, C6~C30 it is substituted or unsubstituted Aryl or condensed-nuclei aromatics group, C3~C30 substituted or unsubstituted heteroaryl or condensed hetero ring aromatic hydrocarbon group, work as R1And R2Point When not being independently selected from substituted aryl, condensed-nuclei aromatics group, heteroaryl or condensed hetero ring aromatic hydrocarbon group, the substituent group thereon It is independently selected from halogen, cyano, nitro, or the alkoxy or thio of the alkyl or cycloalkyl selected from C1~C30, alkenyl, C1~C6 Alkoxy base, or be independently selected from containing the hetero atom selected from N, O, S, Si and the monocycle with 4~60 ring carbon atoms or Fused ring aryl.
10. a kind of organic electroluminescence device, which includes first electrode, second electrode and is located at the first electrode and the One or more layers organic layer between two electrodes, which is characterized in that comprising at least one selected from following specific in the organic layer The compound of structure:
CN201710408047.5A 2017-06-02 2017-06-02 Fluorene derivative and its application in luminous organic material Pending CN108976212A (en)

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