CN108440543A - Perimidine derivative - Google Patents

Perimidine derivative Download PDF

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Publication number
CN108440543A
CN108440543A CN201710084022.4A CN201710084022A CN108440543A CN 108440543 A CN108440543 A CN 108440543A CN 201710084022 A CN201710084022 A CN 201710084022A CN 108440543 A CN108440543 A CN 108440543A
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compound
difference
replaced
organic electroluminescence
base
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范洪涛
张亚光
张向慧
任雪艳
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Beijing Eternal Material Technology Co Ltd
Guan Eternal Material Technology Co Ltd
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Beijing Eternal Material Technology Co Ltd
Guan Eternal Material Technology Co Ltd
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    • C07D487/12—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains three hetero rings
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    • H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
    • H10K85/633—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine comprising polycyclic condensed aromatic hydrocarbons as substituents on the nitrogen atom
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    • H10K85/636—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine comprising heteroaromatic hydrocarbons as substituents on the nitrogen atom
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Abstract

The present invention relates to perimidine derivatives, the invention discloses a kind of organic electroluminescent compounds and include purposes of the compound in preparing organic electroluminescence device, the present invention also provides a kind of organic electroluminescence device, which includes the organic electroluminescent compounds.Organic electroluminescent compounds provided by the invention can effectively reduce the operating voltage of organic electroluminescence device, and improve the luminous efficiency of organic electroluminescence device.

Description

Perimidine derivative
Technical field
The present invention relates to a kind of novel compounds, further relate to the organic electroluminescence device for having used the compound.
Background technology
Display of organic electroluminescence (hereinafter referred to as OLED) has from main light emission, low-voltage direct-current driving, all solidstate, regards Angular width, light-weight, composition and a series of advantage such as simple for 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 less 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, the organic electroluminescence device of an excellent in efficiency long lifespan be typically device architecture with The result of the optimization collocation of various organic materials.In 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..
Currently, hole mobile material and hole-injecting material are mostly aromatic multi-amine class compound, as NPB, TPD, TCTA, TNATA, copper phthalocyanine (CuPc).Although these materials play critically important effect in the evolution of OLED technology, some Material is still widely used so far in laboratory and PMOLED producing lines, but with display and lighting area pair The continuous promotion in OLED device photoelectric properties and service life, these materials cannot be met the requirements, and be used at present existing organic The luminescent device of material either needs higher driving voltage or the luminous efficiency of organic electroluminescence device can be caused low, And device lifetime can not be satisfactory.Therefore exploitation has high stability, high efficiency and all kinds of hole proximate matters of long-life Material has a very important significance.
What the generation of organic electroluminescent was leaned on is the weight of the carrier (electrons and holes) transmitted in organic electroluminescence material Group, it is well known that the electric conductivity of organic material is very poor, does not have continuity unlike inorganic semiconductor, in organic semiconductor Energy band, the transmission of carrier commonly use jump theory to describe, i.e., under the driving of an electric field, electronics is being excited or is being injected into point In the lumo energy of son, achieve the purpose that charge transmits via the lumo energy for jumping to another molecule.In order to make have Organic electroluminescence devices reach breakthrough in application aspect, it is necessary to overcome the difficulty of the injection of organic material charge and transmittability difference. Scientists are by the adjustment of device architecture, such as increase the number of device organic material layer, and different organic layers is made to play the part of Different roles is drilled, such as the functional material having helps electronics to be injected from cathode and hole from anode, some materials help electricity The transmission of lotus, the material played the role of then plays blocking electronics and hole transport, most important certainly in organic electroluminescent The luminescent material of a variety of colors will also achieve the purpose that match with adjacent functional material, the Organic Electricity of an excellent in efficiency long lifespan Electroluminescence device is typically the optimization collocation of device architecture and various organic materials as a result, this is just designed out for chemists The functionalization material for sending out structure various provides great opportunities and challenges.
Invention content
To solve the above problems, the present invention provides a kind of novel compound for organic electroluminescence device.The chemical combination Object introduces fragrant amino or heteroaryl amino in the specific position of perimidine structural unit, realizes good hole note Enter, transmission performance.The compound of the present invention is indicated by leading to formula (I) as follows：
Wherein, A1、A2And A3Respectively stand alone as hydrogen orDotted line indicates link position, and A1、A2And A3When different For hydrogen；
Above-mentioned R1、R2It is identical or different, it is each independently selected from substituted or unsubstituted C6~C30Aryl replaces or does not take The C in generation2~C30Heteroaryl, C6~C30Arylamino or heteroaryl amino；The C6~C30Aryl or C2~C30On heteroaryl Substituent group be selected from C1~C6Alkyl, C1~C6Alkoxy, F, Cl, Br, I, cyano.
The compound of the present invention can be used as hole-injecting material, can effectively have been injected holes into from ito anode In machine material, additionally it is possible to it is used as hole mobile material, can preferably matches with the HOMO energy levels of luminescent layer material of main part, from And it can effectively reduce device operating voltages and improve device light emitting efficiency.
Specific implementation mode
In the present invention, Ca-CbExpression way represent the carbon atom number that the group has as a~b, unless specifically indicated, one As for the carbon atom number do not include the carbon atom number of substituent group.
In the present invention, include the concept of the identical isotope of chemical property for the statement of chemical element, such as " hydrogen " Statement also includes chemical property identical " deuterium ", the concept of " tritium ".
Hetero atom in the present invention is often referred to selected from B, N, O, S, P, P (=O), Si and the atom in Se or atomic group.
The compound of the present invention is indicated by leading to formula (I) as follows：
Wherein, A1、A2And A3Respectively stand alone as hydrogen or(dotted line expression link position), and A1、A2And A3When different For hydrogen；
Above-mentioned R1、R2It is identical or different, it is each independently selected from substituted or unsubstituted C6~C30Aryl replaces or does not take The C in generation2~C30Heteroaryl, C6~C30Arylamino or heteroaryl amino；The C6~C30Aryl or C2~C30On heteroaryl Substituent group be selected from C1~C6Alkyl, C1~C6Alkoxy, F, Cl, Br, I, cyano.
Specifically, in above-mentioned logical formula (I), R1、R2The substituted or unsubstituted C being respectively and independently selected from6~C30Aryl, preferably With 6-20 ring skeleton carbon atom, the preferably described aryl is by phenyl, xenyl, terphenyl, naphthalene, anthryl, phenanthryl, indenes Base, fluorenyl and its derivative, fluoranthene base, triphenylene, pyrenyl, base,Group in the group that base and aphthacene base are formed. The xenyl be selected from by 2- xenyls, 3- xenyls and 4- xenyls, the terphenyl include p- terphenyl -4- bases, P- terphenyl -3- bases, p- terphenyl -2- bases, m- terphenyl -4- bases, m- terphenyl -3- bases and m- three Phenyl -2- bases；In the group that the naphthalene is made of 1- naphthalenes and 2- naphthalenes；The anthryl be selected from by 1- anthryls, 2- anthryls and In the group that 9- anthryls are formed；The fluorenyl is selected from and is made of 1- fluorenyls, 2- fluorenyls, 3- fluorenyls, 4- fluorenyls and 9- fluorenyls In group；The fluorenyl derivative is selected from the group being made of 9,9 '-dimethyl fluorenes, 9,9 '-spiral shell, two fluorenes and benzfluorene；The pyrene Base is in the group being made of 1- pyrenyls, 2- pyrenyls and 4- pyrenyls；The aphthacene base is selected from by 1- aphthacenes base, 2- and four In the group that phenyl and 9- aphthacene bases are formed.
In logical formula (I), R1、R2The substituted or unsubstituted C being respectively and independently selected from2~C30Heteroaryl, it is miscellaneous in the heteroaryl Atom is preferably one or more hetero atoms for being selected from O, S and N, is preferably substituted or unsubstituted C as the heteroaryl5-C20 Heteroaryl can be enumerated as the preferred example of heteroaryl herein selected from by furyl, thienyl, pyrrole radicals, benzofuran Base, benzothienyl, isobenzofuran-base, indyl, dibenzofuran group, dibenzothiophene, carbazyl and its derivative At least one of group of composition, wherein the carbazole radical derivative can include but is not limited to 9- phenyl carbazoles, 9- naphthalene clicks At least one of azoles benzo carbazole, dibenzo-carbazole and indolocarbazole.
In logical formula (I), R1、R2The C being respectively and independently selected from6~C30Arylamino or heteroaryl amino, two (miscellaneous) can be enumerated Arylamino, three (miscellaneous) arylaminos, the expression way of " (miscellaneous) aryl " includes both aryl and heteroaryl herein, as specific Example can be enumerated selected from tri- phenylaminos of 4-, tri- phenylaminos of 3-, 4- [N- phenyl-N- (dibenzofurans -3- bases)] phenyl amino, 4- Group in the group that [N- phenyl-N- (dibenzothiophenes -3- bases)] phenyl amino is formed, tri- phenylaminos of more preferable 4-.
As substitution C6~C30Aryl or substitution C2~C30The C of heteroaryl1~C6Alkyl, can enumerate methyl, ethyl, N-propyl, isopropyl, normal-butyl, n-hexyl, n-octyl, isobutyl group, tertiary butyl, cyclopenta, cyclohexyl etc., more preferable methyl, Ethyl, isopropyl, cyclohexyl.
As substitution C6~C30Aryl or substitution C2~C30The C of heteroaryl1~C6Alkoxy, preferred methoxyl group.
Parent nucleus of the compounds of this invention with perimidine structure, the triplet for determining parent nucleus are 2.78eV, in addition perimidine structure itself is with stronger Hole injection capacity, based on such specific electronics Cloud density and distribution, present invention is especially suitable for the hole-injecting material of organic electroluminescent device and hole mobile materials.
In addition, the crystalline growth when position of compound substituent and symmetric relation will be to arrangement, the film forming of electron cloud It has an impact.On this basis, the present inventor's sharp study finds the adjustment by symmetric relation and selects substitution appropriate Base location can inject transmittability to the hole of the compound of the present invention and be finely adjusted, further optimize electricity as needed Performance, and summarize following rule：
1 of parent nucleus perimidine or 4 connection (miscellaneous) arylamino can finely tune the compounds of this invention HOMO energy levels, it is 5.4-5.7eV or so that can make the HOMO energy levels for the compound to be formed, and is very beneficial for as hole mobile material It uses.
Parent nucleus perimidine connects two (miscellaneous) arylaminos or parent nucleus naphthalene embedding two with 4 ' positions by 4 Pyridine connects three (miscellaneous) arylaminos by 1,4 and 4 ' positions so that molecule has shallower HOMO energy levels, Ke Yida To 5.1-5.2eV, there is very strong Hole injection capacity, such compound to come particularly suitable as the material of hole injection layer It uses.In addition, the identical compound of parent nucleus substituent group, is more easily-synthesized.
Therefore,
As a kind of preferred embodiment of the present invention, lead in formula (I), A1ForA2And A3For hydrogen.
As a kind of preferred embodiment of the present invention, lead in formula (I), A1And A2For hydrogen, A3For
As a kind of preferred embodiment of the present invention, lead in formula (I), A3For hydrogen, A1With A2ForIt is highly preferred that A1With A2It is identical.
As a kind of preferred embodiment of the present invention, lead in formula (I), A1、A2And A3It isIt is highly preferred that A1、A2With A3All same.
Specifically, as the further preferably following concrete structure compounds of the compounds of this invention：
The present invention also provides purposes of the above-mentioned compound selected from logical formula (I) in preparing organic electroluminescence device.
Specifically, the compound in the logical formula (I) can be, but not limited to be used as hole in organic electroluminescence device Injection material or hole mobile material also can be used as the material of main part and fluorescence luminescent material of luminescent layer.
Organic electroluminescence device
The present invention also provides a kind of organic electroluminescence device, which includes first electrode, second electrode and insertion One or more layers organic layer between the first electrode and second electrode, the organic layer include at least one chemical combination of the present invention Object.
As the organic layer between first electrode and second electrode, usually there is electron injecting layer, electron transfer layer, shines The organic layers such as layer, hole transmission layer, hole injection layer.The compound of the present invention may be used as but be not limited to hole-injecting material/ Hole mobile material.
Wherein, the preferred example as the organic electroluminescence device of the present invention, can enumerate compound A1~A15, B1 ~B15 is used as the organic electroluminescence device of hole transport layer material, and above compound C1~C19, D1 and D2 are used as The organic electroluminescence device of the material of hole injection layer.The organic electroluminescence device of the present invention is based on the compounds of this invention Excellent properties can reduce device and play bright and operating voltage, improve device efficiency, extend device lifetime.
Embodiment
Below with reference to following examples set forth the preparation methods of the representation compound of the present invention.Due to the compounds of this invention Skeleton having the same, those skilled in the art be based on these preparation methods, can by known functional group's conversion method, readily Synthesize other the compound of the present invention.Hereinafter, also providing the preparation method and photism of the luminescent device comprising the compound Matter measures.
Synthetic example
Illustrate the synthetic method of representation compound of the present invention briefly below.
Various chemicals used in synthetic example for example petroleum ether, ethyl acetate, n-hexane, toluene, tetrahydrofuran, Bis- (bromomethyl) benzene of dichloromethane, carbon tetrachloride, acetone, 1,2-, CuI, o-phthaloyl chloride, phenylhydrazine hydrochloride, trifluoroacetic acid, second Sour, trans--diaminocyclohexane, iodobenzene, cesium carbonate, potassium phosphate, ethylenediamine, benzophenone, cyclopentanone, 9-Fluorenone, the tert-butyl alcohol The bromo- 2- methyl naphthalenes of sodium, Loprazolam, 1-, o-dibromobenzene, Bromofume, o-dibromobenzene, benzoyl peroxide, 1- (2- bromobenzenes Base) -2- methyl naphthalenes, N- bromo-succinimides, methoxyl methyl San Jia Ji phosphonium chlorides, tris(dibenzylideneacetone) dipalladium, 1,3- Pairs of 2-phenyl-phosphine oxide nickel chloride, diphenylamines, N- phenyl-2-naphthylamines, 4- bromine dibenzofurans, 2- bromine dibenzofurans, 2- bromines Dibenzothiophenes, 4- bromodiphenylthiophenes, the basic chemical industries raw material such as 9- bromine phenanthrene chemical products can be commercially available at home.This hair The compound intermediate of not detailed description synthetic method is all the raw produce obtained by commercial sources in bright.
The analysis detection of intermediate and compound in the present invention uses AB SCIEX mass spectrographs (4000QTRAP) and cloth Shandong Gram Nuclear Magnetic Resonance (400M).
The synthesis of 1. intermediate M1 of synthetic example
1,8-, bis- amido -4- bromonaphthalenes (50mmol, 11.86g) and acetone (300mmol, 17.43g) are mixed, solution is down to 0 DEG C, boron trifluoride hydrate (12.5g, 145mmol) is added dropwise with constant pressure funnel, after being added dropwise, stirs at room temperature, TLC Reaction end is monitored, is reacted 12 hours.Reaction finishes, and reaction solution is poured into ice water, and sodium carbonate adjusts reaction solution to neutrality, uses Ethyl acetate extracts, extract liquor concentration.Silica gel chromatography method (solvent Shi You Mi ﹕ ethyl acetate=50 ﹕ 1), rotation are steamed Hair removes solvent, obtains intermediate M1-a (11.1g, yield 80.1%).
By intermediate M1-a (11.1g, 40.1mmol), o-iodonitrobenzene (24.9g, 100.2mmol), sodium tert-butoxide (15.4g, 160.5mmol) is mixed in 220mL toluene, nitrogen protection, and 0.66 gram of Pd2 (dba) 3, tri-tert-butylphosphine is added (45ml, 10% toluene solution) opens stirring, is heated to 100 DEG C of reflux, reacts 12h, and reaction solution is washed, organic phase concentration, and two Silica gel chromatography (solvent Shi You Mi ﹕ ethyl acetate=50 ﹕ 1) concentrates eluent, obtains M1-b (17.2g, yield 82.6%).
Intermediate M1-b (17.2g, 33.1mmol), 770ml ethyl alcohol, iron powder (9.5g, 170mmol), 4.5ml hydrochloric acid rise Temperature arrives back flow reaction 6h, and point board monitoring, which is reacted, to be completed, filtering, elutes filter cake with ethyl acetate, filtrate, which is received, does, and obtains intermediate M1-c (15.2g, yield 100%).
Intermediate M1-c (15.2g, 33mmol), is dissolved in 35ml acetic acid, and 2.2g copper powders are added, and stirring, which cools to, to be not more than It 10 DEG C, with acetic acid (17ml) dissolving isoamyl nitrite (10.5g, 101.6mmol), is slowly added drop-wise in system, is added dropwise It being stirred at room temperature, reaction end is controlled in contact plate, after the completion of reaction, liquid separation, organic phase is washed one time with aqueous sodium carbonate, dry, Silica gel is mixed, pillar is crossed with petroleum ether, obtains product intermediate M1 (10g, yield 71.4%).
Product MS (m/e)：424；Elemental analysis (C56H34S)：Theoretical value C, 70.60；H,4.03；N,6.59；Measured value C, 70.50%, H, 4.00%, N, 6.50%.
The magnetic resonance spectroscopy data of intermediate M1,1H NMR (500MHz, Chloroform)：δ8.34(s,1H),8.17(s, 2H), 7.77 (s, 1H), 7.62 (s, 2H), 7.41 (s, 1H), 7.36-7.18 (m, 3H), 7.18 (d, J=6.4Hz, 5H), 7.14 (s,1H),1.73(s,6H).
The synthesis of 2. intermediate M2 of synthetic example
1,8- bis- amido naphthalene (20mmol, 3.1g) is mixed with acetone (120mmol, 7g), and mixed liquor is down to 0 DEG C, uses constant pressure Boron trifluoride hydrate (5g, 58mmol) is added dropwise in dropping funel, after being added dropwise, stirs at room temperature, and TLC monitors reaction end, Reaction is overnight.Reaction finishes, and reaction solution is poured into ice water, sodium carbonate adjusts reaction solution to neutrality, extracted with dichloromethane, extracted Liquid concentrates, and crosses silicagel column, and eluent is the ﹕ 1 of Shi You Mi ﹕ ethyl acetate=50, concentrates eluent, obtain intermediate M2-a (3.7g, Yield 93.4%).
Intermediate M2-a (3.7g, 18.7mmol) and o-iodonitrobenzene (4.7g, 18.7mmol), sodium tert-butoxide (3.6g, 37.4mmol), toluene 60mL, nitrogen protection, Pd2 (dba) 3 (0.17g), tri-tert-butylphosphine (11ml, 10% toluene solution) are opened Stirring is opened, 100 DEG C of reflux are heated to, reacts 12h, reaction solution washing, silicagel column is crossed in organic phase concentration, and eluent is Shi You Mi ﹕ The ﹕ 1 of ethyl acetate=50 concentrates eluent, obtains intermediate M2-b (4.8g products, yield 80.0%).
The iodo- 5- bromo nitrobenzenes (5.9g, 18mmol) of intermediate M2-b (4.8g, 15mmol), 2-, sodium tert-butoxide (2.9g, 30mmol), toluene 50mL, nitrogen protection, 0.17 gram of Pd2 (dba) 3, tri-tert-butylphosphine (11ml, 10% toluene solution) are opened Stirring is heated to 100 DEG C of reflux, reacts 12h, reaction solution washing, and silicagel column is crossed in organic phase concentration, and eluent is Shi You Mi ﹕ second The ﹕ 1 of acetoacetic ester=50 concentrates eluent, obtains intermediate M2-c (6.6g, yield 84.6%).
Intermediate M2-c (6.6g, 12.7mmol), ethyl alcohol (300ml), iron powder (3.6g, 63.5mmol), hydrochloric acid (2ml), It is warming up to back flow reaction 5h, point board monitoring, which is reacted, to be completed, filtering, elutes filter cake with ethyl acetate, filtrate, which is received, does, and obtains intermediate M2-d (5.9g, yield 100%).
Intermediate M2-d (5.9g, 12.8mmol), is dissolved in 10ml acetic acid, and 1g copper powders are added, and stirring, which cools to, to be not more than It 10 DEG C, with 6ml acetic acids isoamyl nitrite (4.5g, 38.4mmol), is slowly added drop-wise in system, room temperature is added dropwise and stirs It mixes, reaction end is controlled in contact plate, after the completion of reaction, liquid separation, organic phase is washed one time with aqueous sodium carbonate, dry, mixes silica gel, Pillar is crossed with petroleum ether, obtains intermediate M2 (2.6g, yield 48.1%).
m/z:426.06 (100.0%)
Elemental analysis (theoretical value):C,70.60；H,4.03；Br,18.79；N, 6.59. measured value C, 70.50, H, 4.00, N, 6.50
The magnetic resonance spectroscopy data of intermediate M2：
1H NMR (500MHz, Chloroform) δ 8.34 (s, 1H), 7.78 (d, J=10.2Hz, 2H), 7.62 (d, J= 4.0Hz, 3H), 7.55 (s, 1H), 7.41 (s, 1H), 7.16 (d, J=16.0Hz, 2H), 7.08 (s, 1H), 1.73 (s, 6H)
The synthesis of 3. intermediate M3 of synthetic example
Intermediate M3-a (3.7g, 18.6mmol) and the iodo- 5- bromo nitrobenzenes (15.3g, 46.7mmol) of 2-, sodium tert-butoxide (7.1g, 74.4mmol), toluene 100mL, nitrogen protection, Pd2(dba)3(0.3g), (20ml, 10% toluene are molten for tri-tert-butylphosphine Liquid), stirring is opened, 100 DEG C of reflux are heated to, reacts 12h, reaction solution washing, silicagel column is crossed in organic phase concentration, and eluent is The ﹕ 1 of Shi You Mi ﹕ ethyl acetate=50 concentrates eluent, obtains intermediate M3-b (9.2g, yield 82.7%).
Intermediate M3-b (9.2g, 15.4mmol), ethyl alcohol (450ml), iron powder (4.3g, 77mmol), hydrochloric acid (2ml) rise Temperature arrives back flow reaction 5h, and point board monitoring reaction response is completed, and filtering elutes filter cake with ethyl acetate, and filtrate receives dry be directly used in It reacts in next step.Obtain intermediate M3-c (8.3g, yield 100%).
M3-c (8.3g, 15.4mmol), is dissolved in 16ml acetic acid, and copper powder is added in 1g, and stirring is cooled to no more than 10 DEG C, used 8ml acetic acids isoamyl nitrite (504g, 46.2mmol), is slowly added drop-wise in system, is added dropwise and is stirred at room temperature, contact plate Middle control reaction end, liquid separation after the completion of reaction, organic phase are washed one time with aqueous sodium carbonate, dry, are mixed silica gel, are used petroleum ether Pillar is crossed, intermediate M3 (3.9g, yield 50%) is obtained.
Product MS (m/e)：503；Elemental analysis (C25H16Br2N2)：Theoretical value C, 59.55；H,3.20；N, 5.56 actual measurements Value C, 60.01%, H, 3.18%, N, 5.34%.
The magnetic resonance spectroscopy data of intermediate M3：
1H NMR (500MHz, Chloroform) δ 7.88 (d, J=12.0Hz, 2H), 7.81 (s, 1H), 7.61-7.45 (m, 3H), 7.44 (s, 1H), 7.29 (s, 1H), 7.20 (d, J=12.0Hz, 2H), 1.73 (s, 6H)
The synthesis of 4. intermediate M4 of synthetic example
1,8-, bis- amido -4- bromonaphthalenes (20mmol, 4.7g) and acetone (120mmol, 7g) are mixed, solution is down to 0 DEG C, uses Boron trifluoride hydrate (5g, 58mmol) is added dropwise in constant pressure funnel, after being added dropwise, stirs at room temperature, and TLC monitoring reaction is eventually Point reacts 12 hours.Reaction finishes, and reaction solution is poured into ice water, sodium carbonate adjusts reaction solution to neutrality, extracted with dichloromethane It takes, extract liquor concentration.Silica gel chromatography method (solvent Shi You Mi ﹕ ethyl acetate=50 ﹕ 1), rotary evaporation remove solvent, Obtain intermediate M4-a (5.1g, yield 91.4%).
Intermediate M4-a (5.1g, 18.4mmol) and the iodo- 5- bromo nitrobenzenes (15.3g, 46.7mmol) of 2-, sodium tert-butoxide (7.1g, 74.4mmol), toluene 100mL, nitrogen protection, 0.3gPd2(dba)3, (20ml, 10% toluene are molten for tri-tert-butylphosphine Liquid), stirring is opened, 100 DEG C of reflux are heated to, reacts 12h, reaction solution washing, silicagel column is crossed in organic phase concentration, and eluent is The ﹕ 1 of Shi You Mi ﹕ ethyl acetate=50 concentrates eluent, obtains intermediate M4-b (9.2g, yield 73.9%).
Intermediate M4-b (9.2g, 13.6mmol), ethyl alcohol (450ml), iron powder (3.8g, 68mmol), hydrochloric acid (2ml) rise Temperature arrives back flow reaction 5h, and point board monitoring reaction response is completed, and filtering elutes filter cake with ethyl acetate, and filtrate receives dry be directly used in It reacts in next step.Obtain intermediate M4-c (8.5g, yield 100%).
Intermediate M4-c (8.5g, 13.8mmol), is dissolved in 16ml acetic acid, and 1g copper powders are added, and stirring, which cools to, to be not more than It 10 DEG C, with 8ml acetic acids isoamyl nitrite (4.8g, 41.4mmol), is slowly added drop-wise in system, room temperature is added dropwise and stirs It mixes, reaction end is controlled in contact plate, after reaction liquid separation, organic phase is washed one time with aqueous sodium carbonate, dry, mixes silica gel, Pillar is crossed with petroleum ether, obtains intermediate M4 (3.1g, yield 52%).
Product MS (m/e)：581；Elemental analysis (C56H34S)：Theoretical value C, 51.49；H,2.59；N, 4.80, measured value C, 51.70%, H, 2.80%, N, 4.50%.
The magnetic resonance spectroscopy data of intermediate M4：1H NMR(500MHz,Chloroform)δ8.17(s,1H),8.05(s, 1H),7.80(s,1H),7.62(s,2H),7.55(s,1H),7.42(s,1H),7.36(s,1H),7.18(s,1H),1.73(s, 6H).
The synthesis of 5. compound A1 of synthetic example
By intermediate M1 (4.3g, 10mmol), diphenylamines (2.1g, 12mmol), toluene (80ml), Pd2 (dba) 3 (0.1g), 50% toluene solution of tri-tert-butylphosphine (0.12mL), sodium tert-butoxide (2.3g, 24mmol), are added to 250ml there-necked flasks In, nitrogen is replaced twice, is warming up to 120 DEG C, is stirred to react 10 hours.After reaction, distilled water washing reaction system, then use Ethyl acetate extracts, and detaches organic layer, uses MgSO4Dry organic layer, Rotary Evaporators remove most of solvent, residue silica gel Column chromatography detaches (Shi You Mi ﹕ ethyl acetate=50 ﹕, 1~5 ﹕ 1), obtains faint yellow solid 3.6g, yield 70.1%.
The magnetic resonance spectroscopy data of compound A1：
1H NMR (500MHz, Chloroform) δ 8.17 (s, 27H), 7.71 (d, J=78.2Hz, 27H), 7.33 (s, 30H), 7.29 (s, 4H), 7.24 (s, 60H), 7.22 (s, 4H), 7.14 (d, J=60.0Hz, 100H), 7.00 (s, 24H), 1.73(s,78H).
The synthesis of 6. compound A2 of synthetic example
Synthesis step is to replace with diphenylamines into the N- phenyl-1-naphthylamines of equivalent, reacts and tie with compound A1, difference Shu Hou, isolated white solid 3.9g, yield 69.2%.
The magnetic resonance spectroscopy data of compound A2：
1H NMR(500MHz,Chloroform)δ8.22(s,13H),8.17(s,28H),7.84(s,14H),7.69(s, 14H),7.63(s,19H),7.58(s,19H),7.50(s,27H),7.44(s,7H),7.33(s,30H),7.29(s,4H), 7.28 (d, J=3.6Hz, 18H), 7.22 (d, J=20.0Hz, 50H), 7.08 (s, 42H), 7.00 (s, 12H), 1.73 (s, 79H).
The synthesis of 7. compound A-13 of synthetic example
With compound A1, difference is to replace with diphenylamines into 4, the 4- diisopropyl diphenylamines of equivalent synthesis step, After reaction, isolated white solid 4.5g, yield 75.3%.
The magnetic resonance spectroscopy data of compound A-13：
1H NMR (500MHz, Chloroform) δ 8.17 (s, 12H), 7.71 (d, J=76.7Hz, 12H), 7.33 (s, 13H), 7.29 (s, 9H), 7.13 (dd, J=60.0,10.0Hz, 66H), 2.87 (s, 4H), 1.73 (s, 35H), 1.20 (s, 72H).
The synthesis of 8. compound A4 of synthetic example
Synthesis step is with compound A1, after difference is the N- phenyl terphenyl amine that diphenylamines is replaced with to equivalent, point From obtaining white solid 4.9g, yield 73.6%.
The magnetic resonance spectroscopy data of compound A4：
1H NMR(500MHz,Chloroform)δ8.17(s,31H),7.83(s,15H),7.75(s,31H),7.71– 7.65(m,1H),7.63(s,18H),7.63(s,17H),7.71–7.39(m,94H),7.37(s,35H),7.33(s,37H), 7.29 (s, 25H), 7.24 (d, J=5.0Hz, 90H), 7.20 (s, 25H), 7.08 (s, 48H), 7.00 (s, 14H), 1.73 (s, 90H).
The synthesis of 9. compound A-45 of synthetic example
With compound A1, difference is to replace with diphenylamines into 4, the 4- dimethoxy diphenylamines of equivalent synthesis step, After reaction, isolated white solid 4.5g, yield 78.4.
The magnetic resonance spectroscopy data of compound A-45：
1H NMR (500MHz, Chloroform) δ 8.17 (s, 1H), 7.70 (d, J=74.1Hz, 1H), 7.33 (s, 1H), 7.29(s,1H),7.23–7.03(m,3H),6.79(s,2H),3.79(s,3H),1.73(s,3H).
The synthesis of 10. compound A6 of synthetic example
Synthesis step is with compound A1, and difference is to replace with diphenylamines into 3, the 3- dimethylbenzidines of equivalent, instead After answering, isolated white solid 3.7g, yield 68.3%.
The magnetic resonance spectroscopy data of compound A6：
1H NMR (500MHz, Chloroform) δ 8.17 (s, 2H), 7.80 (s, 1H), 7.63 (s, 1H), 7.31 (d, J= 20.0Hz,4H),7.25(s,2H),7.20(s,2H),7.15(s,2H),7.08(s,2H),6.98(s,1H),6.79(s,2H), 2.27(s,6H),1.73(s,6H).
The synthesis of 11. compound A7 of synthetic example
Synthesis step is to replace with diphenylamines into the A7-1 of equivalent, after reaction, detach with compound A1, difference Obtain white solid 4.4g, yield 73.6%.
The magnetic resonance spectroscopy data of compound A7：
1H NMR (500MHz, Chloroform) δ 8.17 (s, 8H), 7.63 (d, J=3.7Hz, 8H), 7.33 (s, 9H), 7.29(s,6H),7.20(s,5H),7.08(s,4H),6.76(s,16H),2.26(s,24H),2.13(s,48H),1.73(s, 24H) the synthesis of 12. compound A-28 of synthetic examples
Synthesis step is to replace with diphenylamines into the A8-1 of equivalent, after reaction, detach with compound A1, difference Obtain white solid 4.9g, yield 79.8%.
The magnetic resonance spectroscopy data of compound A-28：
1H NMR (500MHz, Chloroform) δ 8.20 (d, J=25.0Hz, 24H), 7.84 (s, 12H), 7.76 (s, 6H),7.63(s,11H),7.58(s,11H),7.50(s,24H),7.44(s,6H),7.33(s,13H),7.29(s,9H), 7.20(s,7H),7.08(s,6H),1.73(s,35H).
The synthesis of 13. compound A9 of synthetic example
Synthesis step is to replace with diphenylamines into the A9-1 of equivalent, after reaction, detach with compound A1, difference Obtain white solid 4.9g, yield 79.8%.
The magnetic resonance spectroscopy data of compound A9：
1H NMR(500MHz,Chloroform)δ8.98(s,13H),8.84(s,38H),8.17(s,52H),8.11(s, 23H), 8.09-7.98 (m, 2H), 8.09-7.76 (m, 78H), 7.68 (s, 28H), 7.62 (d, J=5.0Hz, 68H), 7.33 (s,56H),7.29(s,43H),7.24(s,50H),7.20(s,41H),7.08(s,78H),7.00(s,23H),1.73(s, 147H).
The synthesis of 14. compound A10 of synthetic example
Synthesis step is to replace with diphenylamines into the A10-1 of equivalent, after reaction, divide with compound A1, difference From obtaining white solid 4.7g, yield 75.8%.
The magnetic resonance spectroscopy data of compound A10：
1H NMR (500MHz, Chloroform) δ 8.45 (s, 35H), 8.17 (s, 70H), 7.85 (d, J=10.5Hz, 69H), 7.60 (dd, J=20.0,15.0Hz, 139H), 7.32 (d, J=10.0Hz, 102H), 7.29 (s, 4H), 7.29 (s, 57H), 7.26 (d, J=25.0Hz, 99H), 7.30-6.96 (m, 369H), 1.73 (s, 201H)
The synthesis of 15. compound A11 of synthetic example
Synthesis step is to replace with diphenylamines into the A11-1 of equivalent, after reaction, divide with compound A1, difference From obtaining white solid 4.7g, yield 77.9%.
The magnetic resonance spectroscopy data of compound A11：
1H NMR (500MHz, Chloroform) δ 8.17 (s, 2H), 7.98 (s, 1H), 7.85 (s, 1H), 7.63 (d, J= 5.0Hz, 2H), 7.54 (s, 1H), 7.38 (d, J=9.5Hz, 2H), 7.35-7.27 (m, 5H), 7.24 (s, 2H), 7.19 (d, J =10.0Hz, 3H), 7.08 (s, 3H), 7.00 (s, 1H), 1.73 (s, 6H)
The synthesis of 16. compound A12 of synthetic example
Synthesis step is to replace with diphenylamines into the A12-1 of equivalent, after reaction, divide with compound A1, difference From obtaining white solid 4.9g, yield 72.2%.
The magnetic resonance spectroscopy data of compound A12：
1H NMR (500MHz, Chloroform) δ 8.55 (s, 1H), 8.18 (d, J=10.0Hz, 3H), 7.86 (s, 1H), 7.69(s,2H),7.63(s,1H),7.52(s,1H),7.40(s,1H),7.38–7.27(m,6H),7.24(s,2H),7.22– 7.14 (m, 5H), 7.09 (d, J=15.0Hz, 4H), 7.00 (s, 1H), 1.73 (s, 6H)
The synthesis of 17. compound A13 of synthetic example
Synthesis step is to replace with diphenylamines into the A13-1 of equivalent, after reaction, divide with compound A1, difference From obtaining white solid 4.3g, yield 68.3%.
The magnetic resonance spectroscopy data of compound A13：
1H NMR (500MHz, Chloroform) δ 8.17 (s, 2H), 7.90 (s, 1H), 7.82 (d, J=3.0Hz, 2H), 7.85-7.30 (m, 10H), 7.29 (s, 1H), 7.24 (d, J=1.4Hz, 4H), 7.20 (s, 2H), 7.08 (s, 3H), 7.00 (s, 1H),1.73(s,6H),1.69(s,6H).
The synthesis of 19. compound A14 of synthetic example
Synthesis step is to replace with diphenylamines into the A14-1 of equivalent, after reaction, divide with compound A1, difference From obtaining white solid 4.5g, yield 70.6%.
The magnetic resonance spectroscopy data of compound A14：
1H NMR (500MHz, Chloroform) δ 8.17 (s, 34H), 7.98-7.60 (m, 101H), 7.66 (d, J= 9.9Hz,4H),7.63(s,21H),7.63(s,20H),7.29(s,5H),7.29–7.27(m,26H),7.67–6.75(m, 307H), 7.17 (dd, J=45.0,35.0Hz, 124H), 7.30-6.75 (m, 195H), 7.00 (s, 15H), 6.93 (s, 18H), 1.73(s,97H).
The synthesis of 19. compound A15 of synthetic example
Synthesis step is with compound A1, and difference is to replace with diphenylamines into the dibenzofurans -2- boric acid of equivalent, instead After answering, isolated white solid 3.9g, yield 69.2%.
The magnetic resonance spectroscopy data of compound A15：
1H NMR (500MHz, Chloroform) δ 8.45 (s, 2H), 8.17 (s, 2H), 7.88 (d, J=15.4Hz, 3H), 7.60 (q, J=15.0Hz, 7H), 7.28 (dd, J=37.5,27.5Hz, 9H), 7.18-7.09 (m, 1H), 7.08 (s, 1H), 7.01(s,2H),1.73(s,6H).
The synthesis of 20. compound B-11 of synthetic example
Synthesis step is to replace with intermediate M1 into the M2 of equivalent, diphenylamines is replaced with compound A1, difference The N- phenyl-2-naphthylamines of equivalent, after reaction, isolated white solid 4.1g, yield 72.7%
The magnetic resonance spectroscopy data of compound B-11：
1H NMR (500MHz, Chloroform) δ 8.17 (s, 5H), 7.67 (d, J=40.0Hz, 17H), 7.63 (s, 7H), 7.64-7.52 (m, 20H), 7.43 (d, J=15.0Hz, 10H), 7.52-7.36 (m, 15H), 7.52-7.27 (m, 30H), 7.24 (s, 9H), 7.20 (s, 6H), 7.10 (d, J=15.0Hz, 25H), 7.00 (s, 5H), 6.57 (s, 5H), 1.73 (s, 29H).
The synthesis of 21. compound B2 of synthetic example
Synthesis step is to replace with intermediate M1 into the M2 of equivalent, diphenylamines is replaced with compound A1, difference The B2-1 of equivalent, after reaction, isolated white solid 4.9g, yield 73.6%
The magnetic resonance spectroscopy data of compound B2：
1H NMR(500MHz,Chloroform)δ8.17(s,5H),7.75(s,26H),7.63(s,11H),7.55(s, 18H),7.49(s,21H),7.41(s,7H),7.39–7.31(m,30H),7.29(s,6H),7.20(s,3H),7.08(s, 11H),6.57(s,5H),1.73(s,30H).
The synthesis of 22. compound B3 of synthetic example
Synthesis step is to replace with intermediate M1 into the M2 of equivalent, diphenylamines is replaced with compound A1, difference N- (2- aminomethyl phenyls) -2-aminotoluene of equivalent, after reaction, isolated white solid 4.1g, yield is 75.7%
The magnetic resonance spectroscopy data of compound B3：
1H NMR(500MHz,Chloroform)δ8.17(s,1H),7.63(s,3H),7.48–7.27(m,3H),7.19 (d, J=5.0Hz, 3H), 7.14 (d, J=10.0Hz, 4H), 7.08 (s, 2H), 6.90 (s, 2H), 6.57 (s, 1H), 2.13 (s, 6H),1.73(s,6H).
The synthesis of 23. compound B4 of synthetic example
Synthesis step is to replace with intermediate M1 into the M2 of equivalent, diphenylamines is replaced with compound A1, difference 4, the 4- dimethyl diphenylamines of equivalent, after reaction, isolated white solid 4.2g, yield 77.5%
The magnetic resonance spectroscopy data of compound B4：
1H NMR(500MHz,Chloroform)δ8.17(s,1H),7.63(s,3H),7.48–7.27(m,3H),7.20 (s, 1H), 7.14 (d, J=10.0Hz, 8H), 7.08 (s, 2H), 6.57 (s, 1H), 2.32 (s, 6H), 1.73 (s, 6H)
The synthesis of 24. compound B5 of synthetic example
Synthesis step is to replace with intermediate M1 into the M2 of equivalent, diphenylamines is replaced with compound A1, difference N- (2,4- 3,5-dimethylphenyl) -2,4- dimethylanilines of equivalent, after reaction, isolated white solid 4.5g is received Rate is 79.0%
The magnetic resonance spectroscopy data of compound B5：
1H NMR (500MHz, Chloroform) δ 8.17 (s, 2H), 7.63 (s, 6H), 7.34 (d, J=5.0Hz, 4H), 7.29 (s, 3H), 7.20 (s, 1H), 7.07 (d, J=15.0Hz, 12H), 6.86 (s, 4H), 6.57 (s, 2H), 2.24 (s, 12H),2.13(s,12H),1.73(s,12H).
The synthesis of 25. compound B-26 of synthetic example
Synthesis step is to replace with intermediate M1 into the M2 of equivalent, diphenylamines is replaced with compound A1, difference 2, the 2- dinaphthylamines of equivalent, after reaction, isolated white solid 4.2g, yield 68.4%
The magnetic resonance spectroscopy data of compound B-26：
1H NMR (500MHz, Chloroform) δ 8.17 (s, 1H), 7.71 (s, 2H), 7.62 (d, J=5.0Hz, 6H), 7.54 (s, 2H), 7.43 (d, J=15.0Hz, 5H), 7.38 (s, 2H), 7.36-7.27 (m, 4H), 7.20 (s, 1H), 7.10 (d, J=15.0Hz, 5H), 6.57 (s, 1H), 1.73 (s, 7H)
The synthesis of 26. compound B7 of synthetic example
Synthesis step is to replace with intermediate M1 into the M2 of equivalent, diphenylamines is replaced with compound A1, difference The B7-4 of equivalent, after reaction, isolated white solid 4.3g, yield 70.1%
The magnetic resonance spectroscopy data of compound B7：
1H NMR(500MHz,Chloroform)δ8.84(s,1H),8.63(s,1H),8.17(s,1H),8.07(s, 1H),7.90(s,1H),7.77–7.66(m,3H),7.63(s,3H),7.47–7.29(m,2H),7.24(s,2H),7.20(s, 1H),7.08(s,3H),7.00(s,1H),6.57(s,1H),1.73(s,5H).
The synthesis of 27. compound B8 of synthetic example
Synthesis step is to replace with intermediate M1 into the M2 of equivalent, diphenylamines is replaced with compound A1, difference The B8-1 of equivalent, after reaction, isolated white solid 4.4g, yield 72.9%
The magnetic resonance spectroscopy data of compound B8：
1H NMR (500MHz, Chloroform) δ 8.20 (d, J=25.0Hz, 10H), 7.98 (s, 5H), 7.63 (s, 15H), 7.50 (d, J=40.0Hz, 8H), 7.37 (d, J=18.8Hz, 11H), 7.35-7.27 (m, 21H), 7.24 (s, 9H), 7.20(s,6H),7.08(s,20H),7.00(s,5H),6.57(s,5H),1.73(s,29H).
The synthesis of 28. compound B9 of synthetic example
Synthesis step is to replace with intermediate M1 into the M2 of equivalent, diphenylamines is replaced with compound A1, difference The B9-1 of equivalent, after reaction, isolated white solid 4.5g, yield 71.5%
The magnetic resonance spectroscopy data of compound B9：
1H NMR (500MHz, Chloroform) δ 8.17 (s, 1H), 7.88 (d, J=20.0Hz, 2H), 7.64 (dd, J= 4.0,2.9Hz, 1H), 7.53 (dd, J=78.9,60.1Hz, 5H), 7.34 (t, J=3.2Hz, 2H), 7.29 (s, 1H), 7.24 (d, J=1.4Hz, 3H), 7.20 (s, 1H), 7.08 (s, 4H), 7.00 (s, 1H), 6.57 (s, 1H), 1.73 (s, 6H), 1.69 (s,6H).
The synthesis of 29. compound B-11 0 of synthetic example
Synthesis step is to replace with intermediate M1 into the M2 of equivalent, diphenylamines is replaced with compound A1, difference The B10-1 of equivalent, after reaction, isolated white solid 4.3g, yield 69.3%
The magnetic resonance spectroscopy data of compound B-11 0：
1H NMR (500MHz, Chloroform) δ 8.45 (s, 1H), 8.14 (d, J=30.0Hz, 2H), 7.86 (s, 1H), 7.63 (s, 3H), 7.56 (s, 1H), 7.32 (dd, J=17.5,7.5Hz, 5H), 7.24 (s, 2H), 7.20 (s, 1H), 7.08 (s, 2H), 7.01 (d, J=5.0Hz, 4H), 6.57 (s, 1H), 1.73 (s, 6H)
The synthesis of 30 compound B-11 1 of synthetic example
Synthesis step is to replace with intermediate M1 into the M2 of equivalent, diphenylamines is replaced with compound A1, difference N- (2,4- 3,5-dimethylphenyl) -2,4- dimethylanilines of equivalent, after reaction, isolated white solid 4.7g is received Rate is 69.2%
The magnetic resonance spectroscopy data of compound B-11 1：
1H NMR(500MHz,Chloroform)δ8.55(s,27H),8.17(s,27H),7.77(s,26H),7.62(d, J=5.0Hz, 114H), 7.58 (s, 39H), 7.51 (d, J=10.0Hz, 73H), 7.35 (dd, J=10.0,5.0Hz, 101H), 7.29 (s, 16H), 7.24 (s, 64H), 7.20 (s, 34H), 7.16 (s, 20H), 7.13-6.98 (m, 155H), 6.97 (d, J= 3.1Hz,4H),6.57(s,27H),1.73(s,156H).
The synthesis of 31. compound B-11 2 of synthetic example
Synthesis step is to replace with intermediate M1 into the M2 of equivalent, diphenylamines is replaced with compound A1, difference The B12-1 of equivalent, after reaction, isolated white solid 4.6g, yield 66.3%
The magnetic resonance spectroscopy data of compound B-11 2：
1H NMR(500MHz,Chloroform)δ8.22(s,2H),8.17(s,1H),7.98(s,2H),7.63(s, 3H), 7.50 (d, J=40.0Hz, 3H), 7.45 (s, 1H), 7.40 (d, J=13.4Hz, 4H), 7.36-7.23 (m, 5H), 7.20 (s,1H),7.08(s,2H),6.57(s,1H),1.74(s,6H).
The synthesis of 32. compound B-11 3 of synthetic example
Synthesis step is to replace with intermediate M1 into the M2 of equivalent, diphenylamines is replaced with compound A1, difference The B13-1 of equivalent, after reaction, isolated white solid 4.6g, yield 67.6%
The magnetic resonance spectroscopy data of compound B-11 3：
1H NMR (500MHz, Chloroform) δ 8.17 (s, 20H), 7.63 (s, 57H), 7.34 (d, J=5.0Hz, 36H), 7.29 (s, 12H), 7.22 (d, J=20.0Hz, 142H), 7.19 (d, J=6.5Hz, 6H), 7.14 (s, 78H), 7.08 (s,135H),7.00(s,53H),6.57(s,20H),1.73(s,115H).
The synthesis of 33. compound B-11 4 of synthetic example
Synthesis step is to replace with intermediate M1 into the M2 of equivalent, diphenylamines is replaced with compound A1, difference The B14-1 of equivalent, after reaction, isolated white solid 5.1g, yield 68.4%
The magnetic resonance spectroscopy data of compound B-11 4：
1H NMR(500MHz,Chloroform)δ8.17(s,1H),7.90(s,2H),7.78(s,2H),7.65–7.51 (m,7H),7.51–7.27(m,7H),7.24(s,2H),7.20(s,1H),7.08(s,2H),6.57(s,1H),1.73(s, 6H),1.69(s,12H).
The synthesis of 34. compound B-11 5 of synthetic example
Synthesis step is to replace with intermediate M1 into the M2 of equivalent, diphenylamines is replaced with compound A1, difference The B15-1 of equivalent, after reaction, isolated white solid 4.1g, yield 69.5%
The magnetic resonance spectroscopy data of compound B-11 5：
1H NMR (500MHz, Chloroform) δ 8.14 (d, J=35.0Hz, 2H), 7.63 (s, 3H), 7.48-7.26 (m, 8H), 7.27 (t, J=3.4Hz, 1H), 7.24 (s, 2H), 7.20 (s, 1H), 7.11 (d, J=30.0Hz, 6H), 7.00 (s, 1H),6.57(s,1H),1.73(s,6H).
The synthesis of 35. compound B-11 6 of synthetic example
Synthesis step is to replace with intermediate M1 into the M2 of equivalent, diphenylamines is replaced with compound A1, difference N- phenyl -4- the benzidine of equivalent, after reaction, isolated white solid 4.2g, yield 71.2%
The magnetic resonance spectroscopy data of compound B-11 6：
1H NMR (500MHz, Chloroform) δ 8.17 (s, 1H), 7.75 (s, 2H), 7.63 (d, J=2.9Hz, 1H), 7.63–7.45(m,6H),7.41(s,1H),7.39–7.31(m,4H),7.29(s,1H),7.24(s,2H),7.20(s,1H), 7.08(s,4H),7.00(s,1H),6.57(s,1H),1.73(s,6H).
The synthesis of 36. compound C1 of synthetic example
By intermediate M3 (4.3g, 10mmol), diphenylamines (4.2g, 24mmol), toluene (80ml), Pd2 (dba) 3 (0.2g), 50% toluene solution of tri-tert-butylphosphine (0.24mL), sodium tert-butoxide (4.6g, 48mmol), are added to 250ml there-necked flasks In, nitrogen is replaced twice, is warming up to 120 DEG C, is stirred to react 10 hours.After reaction, distilled water washing reaction system, then use Ethyl acetate extracts, and detaches organic layer, uses MgSO4Dry organic layer, Rotary Evaporators remove most of solvent, residue silica gel Column chromatography detaches (Shi You Mi ﹕ ethyl acetate=50 ﹕, 1~5 ﹕ 1), obtains faint yellow solid 4.4g, yield 64.6%.
The magnetic resonance spectroscopy data of compound C1：
1H NMR(500MHz,Chloroform)δ7.63(s,2H),7.34(s,1H),7.24(s,4H),7.08(s, 5H),7.00(s,2H),6.57(s,1H),1.73(s,3H).
The synthesis of 37. compound C2 of synthetic example
With compound C1, difference is to be difference that diphenylamines to be replaced with to the N- (2,4- bis- of equivalent synthesis step Aminomethyl phenyl) -2,4- dimethylanilines obtain faint yellow solid 5.2g, yield 65.6%.
The magnetic resonance spectroscopy data of compound C2：
1H NMR (500MHz, Chloroform) δ 7.63 (s, 2H), 7.34 (s, 1H), 7.07 (d, J=15.0Hz, 5H), 6.86(s,2H),6.57(s,1H),2.24(s,6H),2.13(s,6H),1.73(s,3H).
The synthesis of 38. compound C3 of synthetic example
With compound C1, difference is to be difference that diphenylamines to be replaced with to the N- phenyl -2- of equivalent synthesis step Naphthylamines obtains faint yellow solid 4.8g, yield 61.5%.
The magnetic resonance spectroscopy data of compound C3：
1H NMR (500MHz, Chloroform) δ 7.71 (s, 1H), 7.62 (d, J=5.0Hz, 3H), 7.54 (s, 1H), 7.43 (d, J=15.0Hz, 2H), 7.38 (s, 1H), 7.34 (s, 1H), 7.24 (s, 2H), 7.10 (d, J=15.0Hz, 4H), 7.00(s,1H),6.57(s,1H),1.73(s,3H).
The synthesis of 39. compound C4 of synthetic example
With compound C1, difference is to be difference that diphenylamines to be replaced with to the B8-1 of equivalent synthesis step, obtains Faint yellow solid 5.2g, yield 60.4%.
The magnetic resonance spectroscopy data of compound C4：
1H NMR(500MHz,Chloroform)δ8.22(s,50H),7.98(s,51H),7.65(s,2H),7.66– 7.49 (m, 200H), 7.46 (s, 50H), 7.39 (s, 44H), 7.33 (d, J=15.0Hz, 100H), 7.24 (s, 107H), 7.08 (s,141H),7.00(s,45H),6.57(s,51H),1.72(s,147H).
The synthesis of 40. compound C5 of synthetic example
With compound C1, difference is to be difference that diphenylamines to be replaced with to the A10-1 of equivalent synthesis step, obtains Faint yellow solid 6.1g, yield 68.3%.
The magnetic resonance spectroscopy data of compound C5：
1H NMR (500MHz, Chloroform) δ 8.45 (s, 1H), 7.86 (s, 1H), 7.60 (dd, J=20.0, 15.0Hz, 5H), 7.33 (d, J=15.0Hz, 2H), 7.24 (s, 2H), 7.08 (s, 3H), 7.01 (d, J=5.0Hz, 2H), 6.57(s,1H),1.72(s,3H).
The synthesis of 41. compound C6 of synthetic example
With compound C1, difference is to be difference that diphenylamines to be replaced with to the B9-1 of equivalent synthesis step, obtains Faint yellow solid 5.5g, yield 60.2%.
The magnetic resonance spectroscopy data of compound C6：
1H NMR (500MHz, Chloroform) δ 7.88 (d, J=20.0Hz, 14H), 7.71-7.61 (m, 27H), 7.61-7.26 (m, 26H), 7.30-7.26 (m, 5H), 7.24 (d, J=1.4Hz, 17H), 7.08 (s, 22H), 7.00 (s, 6H), 6.57 (s, 7H), 1.71 (d, J=17.8Hz, 60H)
The synthesis of 42. compound C7 of synthetic example
With compound C1, difference is difference being that the B11-1 that diphenylamines is replaced with to equivalent is obtained synthesis step Faint yellow solid 7.1g, yield 70.2%.
The magnetic resonance spectroscopy data of compound C7：
1H NMR (500MHz, Chloroform) δ 8.55 (s, 7H), 8.26 (s, 7H), 7.62 (d, J=5.0Hz, 23H), 7.58 (s, 10H), 7.51 (d, J=10.0Hz, 19H), 7.35 (t, J=5.0Hz, 21H), 7.24 (s, 14H), 7.16 (s, 4H), 7.10 (d, J=15.0Hz, 26H), 7.00 (s, 6H), 6.57 (s, 7H), 1.74 (s, 20H)
The synthesis of 43. compound C8 of synthetic example
With compound C1, difference is difference being that the B12-1 that diphenylamines is replaced with to equivalent is obtained synthesis step Faint yellow solid 7.3g, yield 70.1%.
The magnetic resonance spectroscopy data of compound C8：
1H NMR(500MHz,Chloroform)δ8.41(s,2H),8.22(s,2H),7.98(s,2H),7.63(s, 2H), 7.54 (s, 2H), 7.46 (s, 2H), 7.39 (s, 2H), 7.33 (d, J=15.0Hz, 3H), 7.08 (s, 1H), 6.57 (s, 1H),1.79(s,3H).
The synthesis of 44. compound C9 of synthetic example
With compound C1, difference is difference being that the B13-1 that diphenylamines is replaced with to equivalent is obtained synthesis step Faint yellow solid 7.2g, yield 70.9%.
The magnetic resonance spectroscopy data of compound C9：
1H NMR(500MHz,Chloroform)δ7.63(s,2H),7.34(s,1H),7.24(s,6H),7.14(s, 4H),7.08(s,6H),7.00(s,3H),6.57(s,1H),1.73(s,3H).
The synthesis of 45. compound C10 of synthetic example
With compound C1, difference is to be difference that diphenylamines to be replaced with to the N- phenyl -4- of equivalent synthesis step Benzidine obtains faint yellow solid 5.4g, yield 64.8%.
The magnetic resonance spectroscopy data of compound C10：
1H NMR(500MHz,Chloroform)δ7.75(s,6H),7.63(s,2H),7.55(s,4H),7.49(s, 4H),7.43–7.22(m,11H),7.24(s,3H),7.24(s,4H),7.08(s,6H),7.00(s,2H),6.57(s,2H), 1.72(s,6H).
The synthesis of 46. compound C11 of synthetic example
With compound C1, difference is difference being that the A14-1 that diphenylamines is replaced with to equivalent is obtained synthesis step Faint yellow solid 6.1g, yield 65.7%.
The magnetic resonance spectroscopy data of compound C11：
1H NMR(500MHz,Chloroform)δ7.94–7.60(m,12H),7.63(s,3H),7.63(s,4H),7.61 (dd, J=8.4,6.9Hz, 1H), 7.62-7.32 (m, 9H), 7.24 (s, 4H), 7.18 (s, 2H), 7.08 (s, 6H), 7.00 (s, 2H),6.93(s,2H),6.57(s,2H),1.76(s,6H).
The synthesis of 47. compound C12 of synthetic example
With compound C1, difference is to be difference that diphenylamines to be replaced with to the N- (2,4- bis- of equivalent synthesis step Aminomethyl phenyl) -2,4- dimethylanilines obtain faint yellow solid 6.8g, yield 67.4%.
The magnetic resonance spectroscopy data of compound C12：
1H NMR(500MHz,Chloroform)δ7.63(s,8H),7.34(s,4H),7.31–7.01(m,38H),7.04 (s,1H),6.57(s,4H),2.47(s,3H),1.94(s,10H),1.71(s,12H),1.60(s,22H),1.40(s,10H), 1.12(s,22H).
The synthesis of 48. compound C13 of synthetic example
With compound C1, difference is difference being that the A9-1 that diphenylamines is replaced with to equivalent is obtained light synthesis step Yellow solid 5.8g, yield 65.8%.
The magnetic resonance spectroscopy data of compound C13：
1H NMR(500MHz,Chloroform)δ8.98(s,4H),8.84(s,12H),8.25(s,5H),8.11(s, 11H), 7.90 (s, 8H), 7.68 (s, 9H), 7.62 (d, J=5.0Hz, 29H), 7.34 (s, 8H), 7.24 (s, 16H), 7.08 (s,22H),7.00(s,7H),6.57(s,8H),1.77(s,23H).
The synthesis of 49. compound C14 of synthetic example
By intermediate M3 (4.3g, 10mmol), diphenylamines (1.7g, 10mmol), toluene (80ml), Pd2 (dba) 3 (0.1g), 50% toluene solution of tri-tert-butylphosphine (0.12mL), sodium tert-butoxide (1.9g, 20mmol), are added to 250ml there-necked flasks In, nitrogen is replaced twice, is warming up to 120 DEG C, is stirred to react 10 hours.After reaction, distilled water washing reaction system, then use Ethyl acetate extracts, and detaches organic layer, uses MgSO4Dry organic layer, Rotary Evaporators remove most of solvent, residue silica gel Column chromatography detaches (Shi You Mi ﹕ ethyl acetate=50 ﹕, 1~5 ﹕ 1), obtains faint yellow solid 4.2g, yield 70.9%.
By intermediate C14-1 (4.2g, 7.1mmol), N- (2,4- 3,5-dimethylphenyl) -2,4- dimethylanilines (1.9g, 8.5mmol), toluene (80ml), Pd2 (dba) 3 (0.1g), 50% toluene solution of tri-tert-butylphosphine (0.11mL), sodium tert-butoxide (1.7g, 17mmol) is added in 250ml there-necked flasks, and nitrogen is replaced twice, is warming up to 120 DEG C, is stirred to react 10 hours.Instead After answering, distilled water washing reaction system, then be extracted with ethyl acetate, organic layer is detached, MgSO is used4Dry organic layer, rotation Turn evaporimeter and remove most of solvent, residue silica gel column chromatography detaches (Shi You Mi ﹕ ethyl acetate=50 ﹕, 1~5 ﹕ 1), obtains To faint yellow solid 3.3g, yield 63.2%.Two step total recoverys 44.8%.
The magnetic resonance spectroscopy data of compound C14：
1H NMR (500MHz, Chloroform) δ 7.63 (s, 2H), 7.34 (s, 1H), 7.24 (s, 2H), 7.07 (d, J= 15.0Hz,5H),7.00(s,1H),6.86(s,1H),6.57(s,1H),2.24(s,3H),2.13(s,3H),1.73(s,3H).
The synthesis of 50. compound C15 of synthetic example
Synthesis step is to replace with diphenylamines into the B8-1 of equivalent, N- (2,4- dimethyl with compound C14, difference Phenyl) -2,4- dimethylanilines replace with the A10-1 of equivalent, obtain faint yellow solid 3.9g, yield 44.5%
The magnetic resonance spectroscopy data of compound C15：
1H NMR(500MHz,Chloroform)δ8.45(s,3H),8.22(s,3H),8.11–7.66(m,9H),7.65– 7.52 (m, 23H), 7.46 (s, 3H), 7.39 (s, 6H), 7.33 (d, J=15.0Hz, 8H), 7.28-7.27 (m, 2H), 7.24 (s,8H),7.27–6.96(m,37H),6.57(s,6H),1.72(s,17H).
The synthesis of 51. compound C16 of synthetic example
Synthesis step is to replace with diphenylamines into the B9-1 of equivalent, N- (2,4- dimethyl with compound C14, difference Phenyl) -2,4- dimethylanilines replace with the C16-1 of equivalent, obtain faint yellow solid 3.6g, yield 40.6%
The magnetic resonance spectroscopy data of compound C16：
1H NMR(500MHz,Chloroform)δ8.03(s,15H),7.98(s,8H),7.92–7.59(m,94H), 7.62 (d, J=7.6Hz, 57H), 7.62 (d, J=7.6Hz, 59H), 7.55 (d, J=5.0Hz, 25H), 7.44 (s, 5H), 7.39 (s, 16H), 7.34 (d, J=1.4Hz, 37H), 7.26 (dd, J=18.8,17.4Hz, 76H), 7.08 (s, 69H), 7.00 (s, 21H), 6.57 (s, 24H), 1.71 (d, J=17.5Hz, 139H)
The synthesis of 52. compound C17 of synthetic example
Synthesis step is to replace with diphenylamines into the B11-1 of equivalent, N- (2,4- dimethyl with compound C14, difference Phenyl) -2,4- dimethylanilines replace with the C17-1 of equivalent, obtain faint yellow solid 3.8g, yield 37.6%
The magnetic resonance spectroscopy data of compound C17：
1H NMR (500MHz, Chloroform) δ 8.55 (s, 2H), 8.24 (s, 1H), 8.19 (s, 1H), 7.62 (d, J= 5.0Hz, 7H), 7.58 (s, 3H), 7.51 (d, J=10.0Hz, 6H), 7.35 (t, J=5.0Hz, 4H), 7.29-7.20 (m, 6H), 7.16 (s, 1H), 7.09 (d, J=15.0Hz, 8H), 7.00 (s, 2H), 6.57 (s, 2H), 1.73 (s, 6H)
The synthesis of 53. compound C18 of synthetic example
With compound C14, difference is to replace with N- (2,4- 3,5-dimethylphenyl) -2,4- dimethylanilines synthesis step The N- phenyl-2-naphthylamines of equivalent obtain faint yellow solid 2.7g, yield 36.9%
The magnetic resonance spectroscopy data of compound C18：
1H NMR (500MHz, Chloroform) δ 7.78-7.62 (m, 5H), 7.62 (d, J=5.0Hz, 4H), 7.65- 7.48 (m, 6H), 7.48-7.19 (m, 11H), 7.34 (s, 2H), 7.29 (d, J=50.0Hz, 8H), 7.24 (s, 6H), 7.10 (d, J=15.0Hz, 9H), 7.00 (s, 3H), 6.57 (s, 2H), 1.74 (s, 6H)
The synthesis of 54. compound C19 of synthetic example
With compound C14, difference is to replace with N- (2,4- 3,5-dimethylphenyl) -2,4- dimethylanilines synthesis step The A12-1 of equivalent obtains faint yellow solid 3.3g, yield 38.9%
The magnetic resonance spectroscopy data of compound C19：
1H NMR(500MHz,Chloroform)δ7.63(s,2H),7.34(s,1H),7.24(s,5H),7.14(s, 2H),7.08(s,5H),7.00(s,2H),6.57(s,1H),1.72(s,3H).
The synthesis of 55. compound D1 of synthetic example
By intermediate M4 (4.3g, 10mmol), diphenylamines (6.1g, 36mmol), toluene (80ml), Pd2 (dba) 3 (0.3g), 50% toluene solution of tri-tert-butylphosphine (0.35mL), sodium tert-butoxide (6.9g, 72mmol), are added to 250ml there-necked flasks In, nitrogen is replaced twice, is warming up to 120 DEG C, is stirred to react 10 hours.After reaction, distilled water washing reaction system, then use Ethyl acetate extracts, and detaches organic layer, uses MgSO4Dry organic layer, Rotary Evaporators remove most of solvent, residue silica gel Column chromatography detaches (Shi You Mi ﹕ ethyl acetate=50 ﹕, 1~5 ﹕ 1), obtains faint yellow solid 5.9g, yield 69.6%.
The magnetic resonance spectroscopy data of compound D1：
1H NMR(500MHz,Chloroform)δ7.69(s,6H),7.63(s,17H),7.34(s,12H),7.24(s, 69H),7.08(s,74H),7.00(s,32H),6.57(s,12H),1.73(s,35H).
The synthesis of 56. compound D2 of synthetic example
Synthesis step is to replace with diphenylamines into the N- phenyl-2-naphthylamines of equivalent, obtain light with compound D1, difference Yellow solid 6.9g, yield 69.1%
The magnetic resonance spectroscopy data of compound D2：
1H NMR (500MHz, Chloroform) δ 7.71 (s, 11H), 7.62 (d, J=5.0Hz, 25H), 7.54 (s, 11H), 7.43 (d, J=15.0Hz, 26H), 7.38 (s, 9H), 7.34 (s, 10H), 7.24 (s, 24H), 7.10 (d, J= 15.0Hz,38H),7.00(s,11H),6.89(s,4H),6.57(s,8H),1.73(s,24H).
The analysis detecting data row of specific preferably synthetic structural compounds disclosed in the embodiment of the present invention are in table 1 below：
Device embodiments
OLED device evaluation and test is carried out using following device architecture：ITO/HIL/HTL/EML/ETL/LiF/Al (above-mentioned abbreviations Correspond to ito anode/hole injection layer/hole transmission layer/luminescent layer/electron transfer layer/electron injecting layer/LiF's and Al respectively Cathode, the meaning of above-mentioned abbreviation is identical below), it is (all that the following formulae illustrate the structural formulas of the used material of each functional layer in device Material is purchased from lark prestige reagent, purity>99.9%)：
1. the compound of the present invention of device embodiments is as hole mobile material
The glass plate for being coated with ITO (150nm) transparency conducting layer is ultrasonically treated in commercial detergent, in deionized water Middle flushing, in acetone: ultrasonic oil removing in alcohol mixed solvent (volume ratio 1: 1) is baked under clean environment and removes water completely Part, with ultraviolet light and ozone clean, the low energy cation beam bombarded surface of Satella (ULVAC) is used in combination；
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 compound 2-TNATA on anode tunic forms the hole injection layer that thickness is 60nm；It is true on hole injection layer Sky vapor deposition compound A1, forms the hole transmission layer that thickness is 20nm, evaporation rate 0.1nm/s；
Electroluminescence layer is formed on above-mentioned hole transmission layer, concrete operations are:By as the CBP of luminous layer main body [4, Bis- carbazoles of 4'-N, N'--biphenyl] it is placed in the cell of vacuum phase deposition equipment, it will be as the CBP/Ir of dopant (ppy) 3 It is placed in another room of vacuum phase deposition equipment, two kinds of materials is evaporated with different rates simultaneously, CBP/Ir's (ppy) 3 A concentration of 10%, vapor deposition total film thickness is 30nm；Vacuum evaporation Bphen forms the electron-transport that thick film is 20nm on luminescent layer Layer, evaporation rate 0.1nm/s；
The LiF of vacuum evaporation 0.5nm is as the Al layer conducts that electron injecting layer and thickness are 150nm on the electron transport layer The cathode of device.
2. the compounds of this invention of device embodiments is as hole mobile material
Organic electroluminescence device is prepared using method same as Example 1, difference is, compound A1 is replaced It is changed to compound A2.
3. the compounds of this invention of device embodiments is as hole mobile material
Organic electroluminescence device is prepared using method same as Example 1, difference is, compound A1 is replaced It is changed to compound A-13.
4. the compounds of this invention of device embodiments is as hole mobile material
Organic electroluminescence device is prepared using method same as Example 1, difference is, compound A1 is replaced It is changed to compound A7.
5. the compounds of this invention of device embodiments is as hole mobile material
Organic electroluminescence device is prepared using method same as Example 1, difference is, compound A1 is replaced It is changed to compound A-28.
6. the compounds of this invention of device embodiments is as hole mobile material
Organic electroluminescence device is prepared using method same as Example 1, difference is, compound A1 is replaced It is changed to compound A9.
7. the compounds of this invention of device embodiments is as hole mobile material
Organic electroluminescence device is prepared using method same as Example 1, difference is, compound A1 is replaced It is changed to compound A10.
8. the compounds of this invention of device embodiments is as hole mobile material
Organic electroluminescence device is prepared using method same as Example 1, difference is, compound A1 is replaced It is changed to compound A13.
9. the compounds of this invention of device embodiments is as hole mobile material
Organic electroluminescence device is prepared using method same as Example 1, difference is, compound A1 is replaced It is changed to compound B4.
10. the compounds of this invention of device embodiments is as hole mobile material
Organic electroluminescence device is prepared using method same as Example 1, difference is, compound A1 is replaced It is changed to compound B-11 1.
11. the compounds of this invention of device embodiments is as hole mobile material
Organic electroluminescence device is prepared using method same as Example 1, difference is, compound A1 is replaced It is changed to compound B-11 3.
12. the compounds of this invention of device embodiments is as hole mobile material
Organic electroluminescence device is prepared using method same as Example 1, difference is, compound A1 is replaced It is changed to compound B-11 5.
13. the compounds of this invention of device embodiments is as hole-injecting material
Organic electroluminescence device is prepared using method same as Example 1, difference is, compound B-11 is replaced It is changed to NPB, 2-TNATA is replaced with into compound C1.
14. the compounds of this invention of device embodiments is as hole-injecting material
Organic electroluminescence device is prepared using method same as Example 1, difference is, compound B-11 is replaced It is changed to NPB, 2-TNATA is replaced with into compound C2.
15. the compounds of this invention of device embodiments is as hole-injecting material
Organic electroluminescence device is prepared using method same as Example 1, difference is, compound B-11 is replaced It is changed to NPB, 2-TNATA is replaced with into compound C3.
16. the compounds of this invention of device embodiments is as hole-injecting material
Organic electroluminescence device is prepared using method same as Example 1, difference is, compound B-11 is replaced It is changed to NPB, 2-TNATA is replaced with into compound C4.
17. the compounds of this invention of device embodiments is as hole-injecting material
Organic electroluminescence device is prepared using method same as Example 1, difference is, compound B-11 is replaced It is changed to NPB, 2-TNATA is replaced with into compound C6.
18. the compounds of this invention of device embodiments is as hole-injecting material
Organic electroluminescence device is prepared using method same as Example 1, difference is, compound B-11 is replaced It is changed to NPB, 2-TNATA is replaced with into compound C7.
19. the compounds of this invention of device embodiments is as hole-injecting material
Organic electroluminescence device is prepared using method same as Example 1, difference is, compound B-11 is replaced It is changed to NPB, 2-TNATA is replaced with into compound C9.
20. the compounds of this invention of device embodiments is as hole-injecting material
Organic electroluminescence device is prepared using method same as Example 1, difference is, compound B-11 is replaced It is changed to NPB, 2-TNATA is replaced with into compound C10.
21. the compounds of this invention of device embodiments is as hole-injecting material
Organic electroluminescence device is prepared using method same as Example 1, difference is, compound B-11 is replaced It is changed to NPB, 2-TNATA is replaced with into compound C12.
22. the compounds of this invention of device embodiments is as hole-injecting material
Organic electroluminescence device is prepared using method same as Example 1, difference is, compound B-11 is replaced It is changed to NPB, 2-TNATA is replaced with into compound C14.
23. the compounds of this invention of device embodiments is as hole-injecting material
Organic electroluminescence device is prepared using method same as Example 1, difference is, compound B-11 is replaced It is changed to NPB, 2-TNATA is replaced with into compound C16.
24. the compounds of this invention of device embodiments is as hole-injecting material
Organic electroluminescence device is prepared using method same as Example 1, difference is, compound B-11 is replaced It is changed to NPB, 2-TNATA is replaced with into compound C18.
25. the compounds of this invention of device embodiments is as hole-injecting material
Organic electroluminescence device is prepared using method same as Example 1, difference is, compound B-11 is replaced It is changed to NPB, 2-TNATA is replaced with into compound C19.
26. the compounds of this invention of device embodiments is as hole-injecting material
Organic electroluminescence device is prepared using method same as Example 1, difference is, compound B-11 is replaced It is changed to NPB, 2-TNATA is replaced with into compound D1.
27. the compounds of this invention of device embodiments is as hole-injecting material
Organic electroluminescence device is prepared using method same as Example 1, difference is, compound B-11 is replaced It is changed to NPB, 2-TNATA is replaced with into compound D2.
28. the compounds of this invention D1 of device embodiments is used as hole-injecting material, and compound B-11 1 is used as hole transport material Material.
Comparative example 1.2-TNATA is as hole-injecting material, and NPB is as hole mobile material, and CBP is as green phosphorus Light material of main part.
Organic electroluminescence device is prepared using method same as Example 1, difference is, compound B-11 is replaced It is changed to NPB.
Testing example 1
Green device is in brightness 2000cd/m2Under, using 2602 digital sourcemeter luminance meters of Keithley, (Beijing is pedagogical big Learn photoelectric instrument factory) measure the driving of the organic electroluminescence device being prepared in device embodiments 26-27 and comparative example 2 Voltage and current efficiency, the results are shown in Table 2.
Table 2：
Device embodiments 1-12 and comparative example 1, the identical feelings of other materials in organic electroluminescence device structure Under condition, series compound of the present invention is instead of NPB in comparative device embodiment 1 as hole mobile material.Make parent nucleus HOMO energy levels It is slightly promoted, it is made more to be matched with main body energy level, relatively higher triplet allows to play exciton barrier-layer simultaneously Effect, improve the injection transmission performance of single carrier, and there is stronger cavity transmission ability, obtain higher electric current Efficiency and lower driving voltage improve the luminous efficiency of luminescent device under same device architecture.
Device embodiments 13-27 and comparative device embodiment 1, other materials is identical in organic electroluminescence device structure In the case of, present invention compound as described in table replaces 2-TNATA in comparative device embodiment 1 to inject material as hole Material, current efficiency are promoted to 40cd/A from 30cd/A, have and be extremely obviously improved effect, work at the same time voltage and also obtain Significantly reduce.Show the superiority of the compounds of this invention.
Device embodiments 28 use this hair respectively compared with comparative device embodiment 1 in organic electroluminescence device Bright middle material substitution 2-TNATA and NPB is used as hole injection and hole mobile material, and other materials is identical in the device structure In the case of, the operating voltage of device is reduced to 4.4V from 5.1V, and current efficiency is promoted from 30cd/A to 42cd/A, has ten Divide and be obviously improved effect, works at the same time voltage and also obtained significantly reducing.Show the good sky of the compounds of this invention The better matching mutual with the superiority of transporting and this series material is injected in cave.
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 can carry out a variety of simple variants to technical scheme of the present invention within the scope of the technical concept of the present invention, this A little simple variants all belong to the scope of protection of the present invention.

Claims (12)

1. a kind of compound is indicated by leading to formula (I) as follows：
Wherein, A1、A2And A3Respectively stand alone as hydrogen orAnd A1、A2And A3It is asynchronously hydrogen；
Above-mentioned R1、R2It is identical or different, it is each independently selected from substituted or unsubstituted C6~C30Aryl, it is substituted or unsubstituted C2~C30Heteroaryl, C6~C30Arylamino or heteroaryl amino；The C6~C30Aryl or C2~C30Taking on heteroaryl It is selected from C for group1~C6Alkyl, C1~C6Alkoxy, F, Cl, Br, I, cyano.
2. compound according to claim 1, which is characterized in that
The C6~C30Aryl includes phenyl, xenyl, terphenyl, naphthalene, anthryl, phenanthryl, indenyl, 9,9 '-dimethyl fluorenes Base, fluoranthene base, triphenylene, pyrenyl, base,Base and aphthacene base；
The C2~C30Heteroaryl includes furyl, thienyl, pyrrole radicals, benzofuranyl, benzothienyl, isobenzofuran Base, indyl, dibenzofuran group, dibenzothiophene, 9- phenyl carbazoles base, dibenzo-carbazole base, indolocarbazole base, three Phenylamino；
The C6~C30Arylamino or heteroaryl amino include tri- phenylaminos of 4-, tri- phenylaminos of 3-, 4- [N- phenyl-N- (two Benzofuran -3- bases)] phenyl amino, 4- [N- phenyl-N- (dibenzothiophenes -3- bases)] phenyl amino；
The C6~C30Aryl or C2~C30Substituent group on heteroaryl is selected from methyl, ethyl, isopropyl, cyclohexyl, methoxy Base.
3. compound according to claim 1 or 2, which is characterized in that A1With A2For hydrogen.
4. compound according to claim 1 or 2, which is characterized in that A2And A3For hydrogen.
5. compound according to claim 1 or 2, which is characterized in that A3For hydrogen, A1With A2It is identical.
6. compound according to claim 1 or 2, which is characterized in that A1、A2And A3All same.
7. compound according to claim 1 or 2 is selected from following concrete structure formulas：
8. application of the claim 1~7 any one of them compound in organic electroluminescence device.
9. application according to claim 8, which is characterized in that the compound is used as hole mobile material and/or hole Injection material.
10. a kind of organic electroluminescence device, including first electrode, second electrode and it is located at the first electrode and second electrode Between one or more layers organic layer, the organic layer includes any compound of at least one claim 1~7.
11. organic electroluminescence device according to claim 10, the organic layer includes hole injection layer, the hole Implanted layer includes compound according to any one of claims 1 to 7.
12. organic electroluminescence device according to claim 10, the organic layer includes hole transmission layer, the hole Transport layer includes compound according to any one of claims 1 to 7.
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